Isoxazolin-5-one derivative and herbicide containing same as active ingredient
11109593 · 2021-09-07
Assignee
Inventors
- Jun SUZUKI (Kanagawa, JP)
- Keiyo Nakai (Kanagawa, JP)
- Kohei KOYAMA (Kanagawa, JP)
- Yutaro Tanaka (Kanagawa, JP)
- Tsunehiro Kido (Kanagawa, JP)
Cpc classification
A01N43/80
HUMAN NECESSITIES
C07D413/06
CHEMISTRY; METALLURGY
C07D413/12
CHEMISTRY; METALLURGY
International classification
A01N43/80
HUMAN NECESSITIES
C07D413/12
CHEMISTRY; METALLURGY
Abstract
An isoxazolin-5-one derivative represented by the following (1): ##STR00001##
wherein R.sup.1 represents a C1-C6 haloalkyl group, and R.sup.2 to R.sup.4 and X each represents a certain substituent or the like; and n represents an integer of 1 to 4, wherein X's may be different from each other when n represents an integer of 2 to 4, and an herbicide containing the isoxazolin-5-one derivative as an active ingredient are provided.
Claims
1. An isoxazolin-5-one derivative of formula (1): ##STR00014## wherein, R.sup.1 is a C1-C6 haloalkyl group; R.sup.2 is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxy C1-C6 alkyl group, a C1-C6 haloalkoxy C1-C6 alkyl group, a C1-C6 alkoxy C1-C6 alkoxy C1-C6 alkyl group, a C1-C6 alkylthio C1-C6 alkyl group, a C1-C6 alkylcarbonyl C1-C6 alkyl group, a C7-C11 aralkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a phenoxy C1-C6 alkyl group, a C7-C11 aralkyloxy C1-C6 alkyl group, a phenylcarbonyl C1-C6 alkyl group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkylcarbonyl group, a C2-C6 alkenylcarbonyl group, a C2-C6 alkynylcarbonyl group, a C3-C6 cycloalkylcarbonyl group, a C3-C6 cycloalkyl C1-C6 alkylcarbonyl group, a C1-C6 alkoxy C1-C6 alkylcarbonyl group, a C1-C6 haloalkoxy C1-C6 alkylcarbonyl group, a C1-C6 alkoxy C1-C6 alkoxy C1-C6 alkylcarbonyl group, a C1-C6 alkylthio C1-C6 alkylcarbonyl group, a C1-C6 haloalkylthio C1-C6 alkylcarbonyl group, a benzoyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C7-C11 aralkylcarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a heterocyclic carbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a heterocyclic C1-C6 alkylcarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 haloalkoxycarbonyl group, a C2-C6 alkenyloxycarbonyl group, a C2-C6 alkynyloxycarbonyl group, a C3-C6 cycloalkyloxycarbonyl group, a C3-C6 cycloalkyl C1-C6 alkoxycarbonyl group, a C1-C6 alkoxy C1-C6 alkoxycarbonyl group, a C1-C6 haloalkoxy C1-C6 alkoxycarbonyl group, a C1-C6 alkoxy C1-C6 alkoxy C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio C1-C6 alkoxycarbonyl group, a C1-C6 haloalkylthio C1-C6 alkoxycarbonyl group, a phenoxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C7-C11 aralkyloxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a phenoxy C1-C6 alkoxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a heterocyclic oxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a heterocyclic C1-C6 alkoxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C1-C6 alkylthiocarbonyl group, a C1-C6 haloalkylthiocarbonyl group, a C1-C6 alkylaminocarbonyl group, a C1-C6 haloalkylaminocarbonyl group, a di-C1-C6 alkylaminocarbonyl group wherein the di-C1-C6 alkyl groups may be same or different, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylsulfonyl group, a C2-C6 alkenylsulfonyl group, a C2-C6 alkynylsulfonyl group, a C3-C6 cycloalkylsulfonyl group, a C3-C6 cycloalkyl C1-C6 alkylsulfonyl group, a C1-C6 alkoxy C1-C6 alkylsulfonyl group, a phenylsulfonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C7-C11 aralkylsulfonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C1-C6 alkylaminosulfonyl group, or a di-C1-C6 alkylaminosulfonyl group wherein the di-C1-C6 alkyl groups may be same or different; R.sup.3 is a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 cycloalkyl group, a phenyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, an amino group, a C1-C6 alkylamino group, or a di-C1-C6 alkylamino group wherein the di-C1-C6 alkyl groups may be same or different; R.sup.4 is a hydrogen atom, a C1-C15 alkyl group, a C1-C15 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C2-C6 alkynyl group, a C2-C6 haloalkynyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyl C1-C6 alkyl group, a C1-C6 alkoxy C1-C6 alkyl group, a C1-C6 haloalkoxy C1-C6 alkyl group, a C1-C6 alkoxy C1-C6 alkoxy C1-C6 alkyl group, a C1-C6 alkylthio C1-C6 alkyl group, a C1-C6 haloalkylthio C1-C6 alkyl group, a C1-C6 alkylsulfinyl C1-C6 alkyl group, a C1-C6 alkylsulfonyl C1-C6 alkyl group, a C1-C6 alkylamino C1-C6 alkyl group, a di-C1-C6 alkylamino C1-C6 alkyl group wherein the di-C1-C6 alkyl groups may be same or different, a C1-C6 alkylcarbonyl C1-C6 alkyl group, a phenyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C7-C11 aralkyl group which may be monosubstituted or polysubstituted with a halogen atom, cyano, nitro, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C1-C6 alkylthio group or a C1-C6 haloalkylthio group, an indanyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a tetrahydronaphthyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a heterocyclic C1-C6 alkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a phenoxy C1-C6 alkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C7-C11 aralkyloxy C1-C6 alkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a phenylcarbonyl C1-C6 alkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group; a benzoyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C7-C11 aralkylcarbonyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylaminocarbonyl group, a di-C1-C6 alkylaminocarbonyl group wherein the di-C1-C6 alkyl groups may be same or different, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylsulfonyl group, a phenylsulfonyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, or a C7-C11 aralkylsulfonyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group; X is a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group; and n is an integer of 1 to 4, wherein X's may be different from each other when n represents an integer of 2 to 4.
2. The isoxazolin-5-one derivative according to claim 1, wherein R.sup.1 is a C1-C6 fluoroalkyl group.
3. The isoxazolin-5-one derivative according to claim 1, wherein R.sup.1 is a trifluoromethyl group.
4. The isoxazolin-5-one derivative according to claim 1, wherein R.sup.1 is a trifluoromethyl group; R.sup.2 is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy C1-C6 alkyl group, a C7-C11 aralkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkylcarbonyl group, a C3-C6 cycloalkylcarbonyl group, a C1-C6 alkoxy C1-C6 alkylcarbonyl group, a benzoyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C7-C11 aralkylcarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a heterocyclic carbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a heterocyclic C1-C6 alkylcarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C1-C6 alkoxycarbonyl group, a C2-C6 alkenyloxycarbonyl group, a C1-C6 alkoxy C1-C6 alkoxycarbonyl group, a phenoxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C7-C11 aralkyloxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a heterocyclic C1-C6 alkoxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C1-C6 alkylaminocarbonyl group, a di-C1-C6 alkylaminocarbonyl group wherein the di-C1-C6 alkyl groups may be same or different, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylsulfonyl group, a C3-C6 cycloalkylsulfonyl group, a phenylsulfonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, or a C7-C11 aralkylsulfonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group; R.sup.3 is a hydrogen atom, a C1-C6 alkyl group which may be substituted with a fluorine atom, or a C3-C6 cycloalkyl group; R.sup.4 is a hydrogen atom, a C1-C15 alkyl group, a C1-C15 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyl C1-C6 alkyl group, a C1-C6 alkoxy C1-C6 alkyl group, a C1-C6 alkylthio C1-C6 alkyl group, a phenyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C7-C11 aralkyl group which may be monosubstituted or polysubstituted with a halogen atom, cyano, nitro, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C1-C6 alkylthio group or a C1-C6 haloalkylthio group, an indanyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a tetrahydronaphthyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a heterocyclic C1-C6 alkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a phenoxy C1-C6 alkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C7-C11 aralkyloxy C1-C6 alkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group, a di-C1-C6 alkylaminocarbonyl group wherein the di-C1-C6 alkyl groups may be same or different, a C1-C6 alkylsulfonyl group, or a phenylsulfonyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group; X is a hydrogen atom or a halogen atom; and n is an integer of 1 to 4 wherein X's may be different from each other when n represents an integer of 2 to 4.
5. A herbicide comprising the isoxazolin-5-one derivative according to claim 1 as an active ingredient.
6. The isoxazolin-5-one derivative according to claim 2, wherein R.sup.1 is a trifluoromethyl group.
7. The isoxazolin-5-one derivative according to claim 2, wherein R.sup.1 is a trifluoromethyl group; R.sup.2 is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy C1-C6 alkyl group, a C7-C11 aralkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkylcarbonyl group, a C3-C6 cycloalkylcarbonyl group, a C1-C6 alkoxy C1-C6 alkylcarbonyl group, a benzoyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C7-C11 aralkylcarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a heterocyclic carbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a heterocyclic C1-C6 alkylcarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C1-C6 alkoxycarbonyl group, a C2-C6 alkenyloxycarbonyl group, a C1-C6 alkoxy C1-C6 alkoxycarbonyl group, a phenoxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C7-C11 aralkyloxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a heterocyclic C1-C6 alkoxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C1-C6 alkylaminocarbonyl group; a di-C1-C6 alkylaminocarbonyl group wherein the di-C1-C6 alkyl groups may be same or different, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylsulfonyl group, a C3-C6 cycloalkylsulfonyl group, a phenylsulfonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, or a C7-C11 aralkylsulfonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, R.sup.3 is a hydrogen atom, a C1-C6 alkyl group which may be substituted with a fluorine atom, or a C3-C6 cycloalkyl group; R.sup.4 is a hydrogen atom, a C1-C15 alkyl group, a C1-C15 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyl C1-C6 alkyl group, a C1-C6 alkoxy C1-C6 alkyl group, a C1-C6 alkylthio C1-C6 alkyl group, a phenyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C7-C11 aralkyl group which may be monosubstituted or polysubstituted with a halogen atom, cyano, nitro, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C1-C6 alkylthio group or a C1-C6 haloalkylthio group, an indanyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a tetrahydronaphthyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a heterocyclic C1-C6 alkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a phenoxy C1-C6 alkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C7-C11 aralkyloxy C1-C6 alkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group, a di-C1-C6 alkylaminocarbonyl group wherein the di-C1-C6 alkyl groups may be same or different, a C1-C6 alkylsulfonyl group, or a phenylsulfonyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group; X is a hydrogen atom or a halogen atom; and n is an integer of 1 to 4 wherein X's may be different from each other when n represents an integer of 2 to 4.
8. The isoxazolin-5-one derivative according to claim 3, wherein in the formula (1), R.sup.1 is a trifluoromethyl group; R.sup.2 is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy C1-C6 alkyl group, a C7-C11 aralkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkylcarbonyl group, a C3-C6 cycloalkylcarbonyl group, a C1-C6 alkoxy C1-C6 alkylcarbonyl group, a benzoyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C7-C11 aralkylcarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a heterocyclic carbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a heterocyclic C1-C6 alkylcarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C1-C6 alkoxycarbonyl group, a C2-C6 alkenyloxycarbonyl group, a C1-C6 alkoxy C1-C6 alkoxycarbonyl group, a phenoxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C7-C11 aralkyloxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a heterocyclic C1-C6 alkoxycarbonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, a C1-C6 alkylaminocarbonyl group, a di-C1-C6 alkylaminocarbonyl group wherein the di-C1-C6 alkyl groups may be same or different, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylsulfonyl group, a C3-C6 cycloalkylsulfonyl group, a phenylsulfonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group, or a C7-C11 aralkylsulfonyl group which may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group; R.sup.3 is a hydrogen atom, a C1-C6 alkyl group which may be substituted with a fluorine atom, or a C3-C6 cycloalkyl group; R.sup.4 is a hydrogen atom, a C1-C15 alkyl group, a C1-C15 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyl C1-C6 alkyl group, a C1-C6 alkoxy C1-C6 alkyl group, a C1-C6 alkylthio C1-C6 alkyl group, a phenyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C7-C11 aralkyl group which may be monosubstituted or polysubstituted with a halogen atom, cyano, nitro, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C1-C6 alkylthio group or a C1-C6 haloalkylthio group, an indanyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a tetrahydronaphthyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a heterocyclic C1-C6 alkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a phenoxy C1-C6 alkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C7-C11 aralkyloxy C1-C6 alkyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group, a C1-C6 alkylcarbonyl group, a di-C1-C6 alkylaminocarbonyl group wherein the di-C1-C6 alkyl groups may be same or different, a C1-C6 alkylsulfonyl group, or a phenylsulfonyl group which may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group; X is a hydrogen atom or a halogen atom; and n is an integer of 1 to 4 wherein X's may be different from each other when n represents an integer of 2 to 4.
9. A herbicide comprising the isoxazolin-5-one derivative according to claim 2 as an active ingredient.
10. A herbicide comprising the isoxazolin-5-one derivative according to claim 3 as an active ingredient.
11. A herbicide comprising the isoxazolin-5-one derivative according to claim 4 as an active ingredient.
Description
DESCRIPTION OF EMBODIMENTS
(1) The isoxazolin-5-one derivatives related to the compounds of the invention, the production methods thereof and the herbicides containing the compounds as active ingredients are explained specifically.
(2) The carbon atom number described in each of a group below does not include the carbon in the cyano group when the group has a cyano group. Moreover, the carbonyl carbon in a group containing carbonyl, such as a C1-C6 alkylcarbonyl group or a (C1-C6) alkoxycarbonyl group, is not included, either.
(3) In the isoxazolin-5-one derivatives represented by the formula (1) of the invention, examples of the halogen atom or the halogen atom as a substituent include elements of fluorine, chlorine, bromine or iodine. The number of the halogen atom(s) as a substituent may be one, or two or more, and when the number is two or more, the halogen atoms may be the same or different from each other. The position of substitution with the halogen atom may be any position.
(4) Examples of the C1-C6 haloalkyl group represented by R.sup.1, R.sup.2 or R.sup.3 or the C1-C6 haloalkyl group as a substituent include monochloromethyl group, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2-chloroethyl group, trichloromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, 6-fluorohexyl group and the like. The number of the C1-C6 haloalkyl group(s) as a substituent may be one, two or more, and when the number is two or more, the C1-C6 haloalkyl groups may be the same or different from each other. The position of substitution with the C1-C6 haloalkyl group may be any position.
(5) Examples of the C1-C6 alkyl group represented by R.sup.2, R.sup.3 or X or the C1-C6 alkyl group as a substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, 2-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 2-hexyl group, 3-hexyl group and the like. The number of the C1-C6 alkyl group(s) as a substituent may be one, two or more, and when the number is two or more, the C1-C6 alkyl groups may be the same or different from each other. The position of substitution with the C1-C6 alkyl group may be any position.
(6) Examples of the C2-C6 alkenyl group represented by R.sup.2 or R.sup.4 include vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like.
(7) Examples of the C2-C6 alkynyl group represented by R.sup.2 or R.sup.4 include ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 2-methyl-3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 2-methyl-3-pentynyl group, 1-hexynyl group, 1,1-dimethyl-2-butynyl group and the like.
(8) Examples of the C1-C6 alkoxy C1-C6 alkyl group represented by R.sup.2 or R.sup.4 include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, sec-butoxymethyl group, tert-butoxymethyl group, 1-pentyloxymethyl group, 1-hexyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-isopropoxyethyl group, 2-isobutoxyethyl group, 3-methoxypropyl group, 2-methoxypropyl group, 2-methoxy-1-methylethyl group, 2-methoxy-1-ethylethyl group, 2-ethoxy-1-methylethyl group, 2-ethoxy-propyl group, 3-methoxy-1-methylpropyl group and the like.
(9) Examples of the C1-C6 haloalkoxy C1-C6 alkyl group represented by R.sup.2 or R.sup.4 include trifluoromethoxymethyl group, 2,2,2-trifluoroethoxymethyl group, 2-(2,2,2-trifluoroethoxy)ethyl group and the like.
(10) Examples of the C1-C6 alkoxy C1-C6 alkoxy C1-C6 alkyl group represented by R.sup.2 or R.sup.4 include methoxyethoxymethyl group, ethoxyethoxymethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group and the like.
(11) Examples of the C1-C6 alkylthio C1-C6 alkyl group represented by R.sup.2 or R.sup.4 include methylthiomethyl group, ethylthiomethyl group, n-propylthiomethyl group, isopropylthiomethyl group, n-butylthiomethyl group, sec-butylthiomethyl group, tert-butylthiomethyl group, 1-pentylthiomethyl group, 1-hexylthiomethyl group, 2-methylthioethyl group, 2-ethylthioethyl group, 2-isopropylthioethyl group, 2-isobutylthioethyl group, 3-methylthiopropyl group, 2-methylthiopropyl group, 2-methylthio-1-methylethyl group, 2-methylthio-1-methylpropyl group and the like.
(12) Examples of the C1-C6 alkylcarbonyl C1-C6 alkyl group represented by R.sup.2 or R.sup.4 include 2-oxopropyl group, 2-oxobutyl group, 3-oxobutyl group and the like.
(13) Examples of the C7-C11 aralkyl group moiety of the C7-C11 aralkyl group which may be substituted and is represented by R.sup.2 or R.sup.4 include benzyl group, 1-phenethyl group, 2-phenethyl group, 1-phenylpropyl group, 2-phenylpropyl group, 3-phenylpropyl group, 1-phenyl-2-methylpropyl group, 1-phenylbutyl group, 1-phenylpentyl group, 1-phenylhexyl group, 2-phenyl-1-methylethyl group and the like.
(14) Examples of the phenoxy C1-C6 alkyl group moiety of the phenoxy C1-C6 alkyl group which may be substituted and is represented by R.sup.2 or R.sup.4 include 2-phenoxyethyl group, 2-phenoxypropyl group, 3-phenoxypropyl group, 2-phenoxybutyl group, 3-phenoxybutyl group, 4-phenoxybutyl group and the like.
(15) Examples of the C7-C11 aralkyloxy C1-C6 alkyl group moiety of the C7-C11 aralkyloxy C1-C6 alkyl group which may be substituted and is represented by R.sup.2 or R.sup.4 include benzyloxymethyl group, 1-phenethyloxymethyl group, 2-phenethyloxymethyl group, 1-phenylpropoxymethyl group, 2-phenylpropoxymethyl group, 3-phenylpropoxymethyl group, benzyloxyethyl group and the like.
(16) Examples of the phenylcarbonyl C1-C6 alkyl group moiety of the phenylcarbonyl C1-C6 alkyl group which may be substituted and is represented by R.sup.2 or R.sup.4 include phenacyl group, 1-phenyl-1-oxopropyl group, 1-phenyl-2-oxopropyl group and the like.
(17) Examples of the C1-C6 alkylcarbonyl group represented by R.sup.2 or R.sup.4 include acetyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, sec-butylcarbonyl group, tert-butylcarbonyl group, 1-pentylcarbonyl group, 1-hexylcarbonyl group and the like.
(18) Examples of the C1-C6 haloalkylcarbonyl group represented by R.sup.2 include monofluoromethylcarbonyl group, difluoromethylcarbonyl group, trifluoromethylcarbonyl group, 2,2,2-trifluoroethylcarbonyl group, 2-chloroethylcarbonyl group, trichloromethylcarbonyl group, 1-fluoroethylcarbonyl group, 2-fluoroethylcarbonyl group, 6-fluorohexylcarbonyl group and the like.
(19) Examples of the C2-C6 alkenylcarbonyl group represented by R.sup.2 include acryloyl group, methacryloyl group and the like.
(20) Examples of the C2-C6 alkynylcarbonyl group represented by R.sup.2 include propiolyl group, methylpropiolyl group and the like.
(21) Examples of the C3-C6 cycloalkylcarbonyl group represented by R.sup.2 include cyclopropanecarbonyl group, 1-methylcyclopropanecarbonyl group, 2-methylcyclopropanecarbonyl group, 2,2-dimethylcyclopropanecarbonyl group, cyclobutanecarbonyl group, cyclopentanecarbonyl group, cyclohexanecarbonyl group and the like.
(22) Examples of the C3-C6 cycloalkyl C1-C6 alkylcarbonyl group represented by R.sup.2 include cyclopropylmethylcarbonyl group, cyclopropylethylcarbonyl group, 1-methylcyclopropylmethylcarbonyl group, 2-methylcyclopropylmethylcarbonyl group, 2,2-dimethylcyclopropylmethylcarbonyl group, cyclobutylmethylcarbonyl group, cyclopentylmethylcarbonyl group, cyclohexylmethylcarbonyl group and the like.
(23) Examples of the C1-C6 alkoxy C1-C6 alkylcarbonyl group represented by R.sup.2 include methoxymethylcarbonyl group, ethoxymethylcarbonyl group, n-propoxymethylcarbonyl group, isopropoxymethylcarbonyl group, n-butoxymethylcarbonyl group, sec-butoxymethylcarbonyl group, tert-butoxymethylcarbonyl group, 1-pentyloxymethylcarbonyl group, 1-hexyloxymethylcarbonyl group, 2-methoxyethylcarbonyl group, 2-ethoxyethylcarbonyl group, 2-isopropoxyethylcarbonyl group, 2-isobutoxyethylcarbonyl group, 3-methoxypropylcarbonyl group, 2-methoxypropylcarbonyl group, 2-methoxy-1-methylethylcarbonyl group and the like.
(24) Examples of the C1-C6 haloalkoxy C1-C6 alkylcarbonyl group represented by R.sup.2 include trifluoromethoxymethylcarbonyl group, 2,2,2-trifluoroethoxymethylcarbonyl group, 2-(2,2,2-trifluoroethoxy)ethylcarbonyl group and the like.
(25) Examples of the C1-C6 alkoxy C1-C6 alkoxy C1-C6 alkylcarbonyl group represented by R.sup.2 include methoxyethoxymethylcarbonyl group, ethoxyethoxymethylcarbonyl group, methoxyethoxyethylcarbonyl group, ethoxyethoxyethylcarbonyl group and the like.
(26) Examples of the C1-C6 alkylthio C1-C6 alkylcarbonyl group represented by R.sup.2 include methylthiomethylcarbonyl group, ethylthiomethylcarbonyl group, n-propylthiomethylcarbonyl group, isopropylthiomethylcarbonyl group, n-butylthiomethylcarbonyl group, sec-butylthiomethylcarbonyl group, tert-butylthiomethylcarbonyl group, 1-pentylthiomethylcarbonyl group, 1-hexylthiomethylcarbonyl group, 2-methylthioethylcarbonyl group, 2-ethylthioethylcarbonyl group, 2-isopropylthioethylcarbonyl group, 2-isobutylthioethylcarbonyl group, 3-methylthiopropylcarbonyl group, 2-methylthiopropylcarbonyl group, 2-methylthio-1-methylethylcarbonyl group, 2-methylthio-1-methylpropylcarbonyl group and the like.
(27) Examples of the C1-C6 haloalkylthio C1-C6 alkylcarbonyl group represented by R.sup.2 include monofluoromethylthiomethylcarbonyl group, difluoromethylthiomethylcarbonyl group, trifluoromethylthiomethylcarbonyl group, 2,2,2-trifluoroethylthiomethylcarbonyl group, 2-chloroethylthiomethylcarbonyl group, trichloromethylthiomethylcarbonyl group, 1-fluoroethylthiomethylcarbonyl group, 2-fluoroethylthiomethylcarbonyl group, 6-fluorohexylthiomethylcarbonyl group and the like.
(28) Examples of the C7-C11 aralkylcarbonyl group moiety of the C7-C11 aralkylcarbonyl group which may be substituted and is represented by R.sup.2 or R.sup.4 include benzylcarbonyl group, 1-phenethylcarbonyl group, 2-phenethylcarbonyl group, 1-phenylpropylcarbonyl group, 2-phenylpropylcarbonyl group, 3-phenylpropylcarbonyl group, 1-phenyl-2-methylpropylcarbonyl group, 1-phenylbutylcarbonyl group, 1-phenylpentylcarbonyl group and the like.
(29) Examples of the heterocyclic carbonyl group moiety of the heterocyclic carbonyl group which may be substituted and is represented by R.sup.2 include 2-pyridylcarbonyl group, 3-pyridylcarbonyl group, 4-pyridylcarbonyl group, 2-thienylcarbonyl group, 3-thienylcarbonyl group, 2-tetrahydrofurylcarbonyl group, 3-tetrahydrofurylcarbonyl group and the like.
(30) Examples of the heterocyclic C1-C6 alkylcarbonyl group moiety of the heterocyclic C1-C6 alkylcarbonyl group which may be substituted and is represented by R.sup.2 include 2-pyridylmethylcarbonyl group, 3-pyridylmethylcarbonyl group, 4-pyridylmethylcarbonyl group, 2-thienylmethylcarbonyl group, 3-thienylmethylcarbonyl group, 2-tetrahydrofurfurylcarbonyl group, 3-tetrahydrofurfurylcarbonyl group and the like.
(31) Examples of the C1-C6 alkoxycarbonyl group represented by R.sup.2 or R.sup.4 include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, 2-pentyloxycarbonyl group, 3-pentyloxycarbonyl group, n-hexyloxycarbonyl group and the like.
(32) Examples of the C1-C6 haloalkoxycarbonyl group represented by R.sup.2 include trifluoromethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group and the like.
(33) Examples of the C2-C6 alkenyloxycarbonyl group represented by R.sup.2 include vinyloxycarbonyl group, 1-propenyloxycarbonyl group, 2-propenyloxycarbonyl group, 1-butenyloxycarbonyl group, 2-butenyloxycarbonyl group, 3-butenyloxycarbonyl group and the like.
(34) Examples of the C2-C6 alkynyloxycarbonyl group represented by R.sup.2 include ethynyloxycarbonyl group, 1-propynyloxycarbonyl group, propargyloxycarbonyl group, 1-butynyloxycarbonyl group, 2-butynyloxycarbonyl group, 3-butynyloxycarbonyl group, 1-methyl-2-propynyloxycarbonyl group, 2-methyl-3-butynyloxycarbonyl group and the like.
(35) Examples of the C3-C6 cycloalkyloxycarbonyl group represented by R.sup.2 include cyclopropyloxycarbonyl group, 1-methylcyclopropyloxycarbonyl group, 2-methylcyclopropyloxycarbonyl group, 2,2-dimethylcyclopropyloxycarbonyl group, cyclobutyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group and the like.
(36) Examples of the C3-C6 cycloalkyl C1-C6 alkoxycarbonyl group represented by R.sup.2 include cyclopropylmethoxycarbonyl group, 1-methylcyclopropylmethoxycarbonyl group, 2-methylcyclopropylmethoxycarbonyl group, 2,2-dimethylcyclopropylmethoxycarbonyl group, cyclobutylmethoxycarbonyl group, cyclopentylmethoxycarbonyl group, cyclohexylmethoxycarbonyl group and the like.
(37) Examples of the C1-C6 alkoxy C1-C6 alkoxycarbonyl group represented by R.sup.2 include methoxymethoxycarbonyl group, ethoxymethoxycarbonyl group, n-propoxymethoxycarbonyl group, isopropoxymethoxycarbonyl group, n-butoxymethoxycarbonyl group, sec-butoxymethoxycarbonyl group, tert-butoxymethoxycarbonyl group, 1-pentyloxymethoxycarbonyl group, 1-hexyloxymethoxycarbonyl group, 2-methoxyethoxycarbonyl group, 2-ethoxyethoxycarbonyl group, 2-isopropoxyethoxycarbonyl group, 2-isobutoxyethoxycarbonyl group, 3-methoxypropoxycarbonyl group, 2-methoxypropoxycarbonyl group, 2-methoxy-1-methylethoxycarbonyl group and the like.
(38) Examples of the C1-C6 haloalkoxy C1-C6 alkoxycarbonyl group represented by R.sup.2 include trifluoromethoxymethoxycarbonyl group, 2,2,2-trifluoroethoxymethoxycarbonyl group, 2-(2,2,2-trifluoroethoxy)ethoxycarbonyl group and the like.
(39) Examples of the C1-C6 alkoxy C1-C6 alkoxy C1-C6 alkoxycarbonyl group represented by R.sup.2 include methoxyethoxymethoxycarbonyl group, ethoxyethoxymethoxycarbonyl group, methoxyethoxyethoxycarbonyl group, ethoxyethoxyethoxycarbonyl group and the like.
(40) Examples of the C1-C6 alkylthio C1-C6 alkoxycarbonyl group represented by R.sup.2 include methylthiomethoxycarbonyl group, ethylthiomethoxycarbonyl group, n-propylthiomethoxycarbonyl group, isopropylthiomethoxycarbonyl group, n-butylthiomethoxycarbonyl group, sec-butylthiomethoxycarbonyl group, tert-butylthiomethoxycarbonyl group, 1-pentylthiomethoxycarbonyl group, 1-hexylthiomethoxycarbonyl group, 2-methylthioethoxycarbonyl group, 2-ethylthioethoxycarbonyl group, 2-isopropylthioethoxycarbonyl group, 2-isobutylthioethoxycarbonyl group, 3-methylthiopropoxycarbonyl group, 2-methylthiopropoxycarbonyl group, 2-methylthio-1-methylethoxycarbonyl group, 2-methylthio-1-methylpropoxycarbonyl group and the like.
(41) Examples of the C1-C6 haloalkylthio C1-C6 alkoxycarbonyl group represented by R.sup.2 include monofluoromethylthiomethoxycarbonyl group, difluoromethylthiomethoxycarbonyl group, trifluoromethylthiomethoxycarbonyl group, 2,2,2-trifluoroethylthiomethoxycarbonyl group, 2-chloroethylthiomethoxycarbonyl group, trichloromethylthiomethoxycarbonyl group, 1-fluoroethylthiomethoxycarbonyl group, 2-fluoroethylthiomethoxycarbonyl group, 6-fluorohexylthiomethoxycarbonyl group, 2-(2,2,2-trifluoroethylthio)ethoxycarbonyl group and the like.
(42) Examples of the C7-C11 aralkyloxycarbonyl group moiety of the C7-C11 aralkyloxycarbonyl group which may be substituted and is represented by R.sup.2 include benzyloxycarbonyl group, 1-phenethyloxycarbonyl group, 2-phenethyloxycarbonyl group, 1-phenylpropoxycarbonyl group, 2-phenylpropoxycarbonyl group, 3-phenylpropoxycarbonyl group, 1-phenyl-2-methylpropoxycarbonyl group, 1-phenylbutoxycarbonyl group, 1-phenylpentyloxycarbonyl group and the like.
(43) Examples of the phenoxy C1-C6 alkoxycarbonyl group moiety of the phenoxy C1-C6 alkoxycarbonyl group which may be substituted and is represented by R.sup.2 include 2-phenoxyethoxycarbonyl group, 2-phenoxypropoxycarbonyl group, 3-phenoxypropoxycarbonyl group, 2-phenoxybutoxycarbonyl group, 3-phenoxybutoxycarbonyl group, 4-phenoxybutoxycarbonyl group and the like.
(44) Examples of the heterocyclic oxycarbonyl group moiety of the heterocyclic oxycarbonyl group which may be substituted and is represented by R.sup.2 include 2-pyridyloxycarbonyl group, 3-pyridyloxycarbonyl group, 4-pyridyloxycarbonyl group, 2-thienyloxycarbonyl group, 3-thienyloxycarbonyl group, 2-tetrahydrofuryloxycarbonyl group, 3-tetrahydrofuryloxycarbonyl group and the like.
(45) Examples of the heterocyclic C1-C6 alkoxycarbonyl group moiety of the heterocyclic C1-C6 alkoxycarbonyl group which may be substituted and is represented by R.sup.2 include 2-pyridylmethyloxycarbonyl group, 3-pyridylmethyloxycarbonyl group, 4-pyridylmethyloxycarbonyl group, 2-thienylmethyloxycarbonyl group, 3-thienylmethyloxycarbonyl group, 2-tetrahydrofurfuryloxycarbonyl group, 3-tetrahydrofurfuryloxycarbonyl group and the like.
(46) Examples of the C1-C6 alkylthiocarbonyl group represented by R.sup.2 include methylthiocarbonyl group, ethylthiocarbonyl group, n-propylthiocarbonyl group, isopropylthiocarbonyl group, n-butylthiocarbonyl group, isobutylthiocarbonyl group, sec-butylthiocarbonyl group, tert-butylthiocarbonyl group and the like.
(47) Examples of the C1-C6 haloalkylthiocarbonyl group represented by R.sup.2 include trifluoromethylthiocarbonyl group, 2,2,2-trifluoroethylthiocarbonyl group and the like.
(48) Examples of the C1-C6 alkylaminocarbonyl group represented by R.sup.2 or R.sup.4 include methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, isopropylaminocarbonyl group, n-butylaminocarbonyl group, isobutylaminocarbonyl group, sec-butylaminocarbonyl group, tert-butylaminocarbonyl group and the like.
(49) Examples of the C1-C6 haloalkylaminocarbonyl group represented by R.sup.2 include trifluoromethylaminocarbonyl group, 2,2,2-trifluoroethylaminocarbonyl group and the like.
(50) Examples of the di-C1-C6 alkylaminocarbonyl group wherein the di-C1-C6 alkyl groups may be same or different and the di-C1-C6 alkylaminocarbonyl group is represented by R.sup.2 or R.sup.4 include dimethylaminocarbonyl group, methylethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, methyl n-propylaminocarbonyl group, ethyl n-propylaminocarbonyl group, diisopropylaminocarbonyl group, di-n-butylaminocarbonyl group, diisobutylaminocarbonyl group, di-sec-butylaminocarbonyl group, di-tert-butylaminocarbonyl group and the like.
(51) Examples of the C1-C6 alkylsulfonyl group represented by R.sup.2 or R.sup.4 include methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, isopropanesulfonyl group, n-butanesulfonyl group, isobutanesulfonyl group, sec-butanesulfonyl group, tert-butanesulfonyl group, n-pentanesulfonyl group and the like.
(52) Examples of the C1-C6 haloalkylsulfonyl group represented by R.sup.2 or R.sup.4 include monofluoromethylsulfonyl group, difluoromethylsulfonyl group, trifluoromethylsulfonyl group, monochloromethylsulfonyl group, trichloromethylsulfonyl group, 2,2,2-trifluoroethylsulfonyl group and the like.
(53) Examples of the C2-C6 alkenylsulfonyl group represented by R.sup.2 include vinylsulfonyl group, 1-propenylsulfonyl group, 2-propenylsulfonyl group, 1-butenylsulfonyl group, 2-butenylsulfonyl group, 3-butenylsulfonyl group and the like.
(54) Examples of the C2-C6 alkynylsulfonyl group represented by R.sup.2 include ethynylsulfonyl group, 1-propynylsulfonyl group, propargylsulfonyl group, 1-butynylsulfonyl group, 2-butynylsulfonyl group, 3-butynylsulfonyl group, 1-methyl-2-propynylsulfonyl group, 2-methyl-3-butynylsulfonyl group and the like.
(55) Examples of the C3-C6 cycloalkylsulfonyl group represented by R.sup.2 include cyclopropanesulfonyl group, 1-methylcyclopropanesulfonyl group, 2-methylcyclopropanesulfonyl group, 2,2-dimethylpropanesulfonyl group, cyclobutanesulfonyl group, cyclopentanesulfonyl group, cyclohexanesulfonyl group and the like.
(56) Examples of the C3-C6 cycloalkyl C1-C6 alkylsulfonyl group represented by R.sup.2 include cyclopropylmethylsulfonyl group, 1-methylcyclopropylmethylsulfonyl group, 2-methylcyclopropylmethylsulfonyl group, 2,2-dimethylpropylmethylsulfonyl group, cyclobutylmethylsulfonyl group, cyclopentylmethylsulfonyl group, cyclohexylmethylsulfonyl group and the like.
(57) Examples of the C1-C6 alkoxy C1-C6 alkylsulfonyl group represented by R.sup.2 include methoxymethylsulfonyl group, ethoxymethylsulfonyl group, n-propoxymethylsulfonyl group, isopropoxymethylsulfonyl group, n-butoxymethylsulfonyl group, sec-butoxymethylsulfonyl group, tert-butoxymethylsulfonyl group, 1-pentyloxymethylsulfonyl group, 1-hexyloxymethylsulfonyl group, 2-methoxyethylsulfonyl group, 2-ethoxyethylsulfonyl group, 2-isopropoxyethylsulfonyl group, 2-isobutoxyethylsulfonyl group, 3-methoxypropylsulfonyl group, 2-methoxypropylsulfonyl group, 2-methoxy-1-methylethylsulfonyl group and the like.
(58) Examples of the C7-C11 aralkylsulfonyl group moiety of the C7-C11 aralkylsulfonyl group which may be substituted and is represented by R.sup.2 or R.sup.4 include benzylsulfonyl group, 1-phenethylsulfonyl group, 2-phenethylsulfonyl group, 1-phenylpropylsulfonyl group, 2-phenylpropylsulfonyl group, 3-phenylpropylsulfonyl group, 1-phenyl-2-methylpropylsulfonyl group, 1-phenylbutylsulfonyl group, 1-phenylpentylsulfonyl group and the like.
(59) Examples of the C1-C6 alkylaminosulfonyl group represented by R.sup.2 include methylaminosulfonyl group, ethylaminosulfonyl group, n-propylaminosulfonyl group, isopropylaminosulfonyl group, n-butylaminosulfonyl group, isobutylaminosulfonyl group, sec-butylaminosulfonyl group, tert-butylaminosulfonyl group and the like.
(60) Examples of the di-C1-C6 alkylaminosulfonyl group wherein the di-C1-C6 alkyl groups may be same or different and the di-C1-C6 alkylaminosulfonyl group is represented by R.sup.2 include dimethylaminosulfonyl group, methylethylaminosulfonyl group, diethylaminosulfonyl group, di-n-propylaminosulfonyl group, methyl n-propylaminosulfonyl group, ethyl n-propylaminosulfonyl group, diisopropylaminosulfonyl group, di-n-butylaminosulfonyl group, diisobutylaminosulfonyl group, di-sec-butylaminosulfonyl group, di-tert-butylaminosulfonyl group and the like.
(61) Examples of the C3-C6 cycloalkyl group represented by R.sup.3 or R.sup.4 include cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylpropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
(62) Examples of the C1-C6 alkylamino group represented by R.sup.3 include methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, sec-butylamino group, tert-butylamino group and the like.
(63) Examples of the di-C1-C6 alkylamino group wherein the di-C1-C6 alkyl groups may be same or different and the di-C1-C6 alkylamino group is represented by R.sup.3 include dimethylamino group, methylethylamino group, diethylamino group, di-n-propylamino group, methyl n-propylamino group, ethyl n-propylamino group, diisopropylamino group, di-n-butylamino group, diisobutylamino group, di-sec-butylamino group, di-tert-butylamino group and the like.
(64) Examples of the C1-C15 alkyl group represented by R.sup.4 include methyl group, ethyl group, n-propyl group, isopropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethyl-2-methylbutyl group, n-pentyl group, neopentyl group, 2-pentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, n-hexyl group, 1-methylhexyl group, 2-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group and the like.
(65) Examples of the C1-C15 haloalkyl group represented by R.sup.4 include monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2-chloroethyl group, trichloromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, 5,5,5-trifluoropentyl group, 6-fluorohexyl group, 6,6,6-trifluorohexyl group, 7,7,7-trifluoroheptyl group and the like.
(66) Examples of the C2-C6 haloalkenyl group represented by R.sup.4 include bromovinyl group, chlorovinyl group, 3,3-dichloro-2-propenyl group, 3,3,3-trifluoro-1-propenyl group, 4,4-difluoro-3-butenyl group, 3,4,4-trifluoro-3-butenyl group and the like.
(67) Examples of the C2-C6 haloalkynyl group represented by R.sup.4 include fluoroethynyl group, 3-fluoro-2-propynyl group, 3-chloro-2-propynyl group, 3-chloro-1-propynyl group, 5-chloro-4-pentynyl group, 3,3,3-trifluoro-1-propynyl group, 3,3-difluoro-1-propynyl group, 4,4,4-trifluoro-2-butynyl group and the like.
(68) Examples of the C3-C6 cycloalkyl C1-C6 alkyl group represented by R.sup.4 include cyclopropylmethyl group, cyclopropylethyl group, 1-methylcyclopropylmethyl group, 2-methylcyclopropylmethyl group, 2,2-dimethylcyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group and the like.
(69) Examples of the C1-C6 haloalkylthio C1-C6 alkyl group represented by R.sup.4 include monofluoromethylthiomethyl group, difluoromethylthiomethyl group, trifluoromethylthiomethyl group, 2,2,2-trifluoroethylthiomethyl group, 2-(2,2,2-trifluoroethylthio)ethyl group, 2-chloroethylthiomethyl group, trichloromethylthiomethyl group, 1-fluoroethylthiomethyl group, 2-fluoroethylthiomethyl group, 6-fluorohexylthiomethyl group and the like.
(70) Examples of the C1-C6 alkylsulfinyl C1-C6 alkyl group represented by R.sup.4 include methylsulfinylmethyl group, ethylsulfinylmethyl group, n-propylsulfinylmethyl group, isopropylsulfinylmethyl group, n-butylsulfinylmethyl group, isobutylsulfinylmethyl group, sec-butylsulfinylmethyl group, tert-butylsulfinylmethyl group, methylsulfinylethyl group, ethylsulfinylethyl group, n-propyl sulfinylethyl group, isopropyl sulfinylethyl group, methylsulfinylpropyl group and the like.
(71) Examples of the C1-C6 alkylsulfonyl C1-C6 alkyl group represented by R.sup.4 include methylsulfonylmethyl group, ethylsulfonylmethyl group, n-propylsulfonylmethyl group, isopropylsulfonylmethyl group, n-butylsulfonylmethyl group, isobutylsulfonylmethyl group, sec-butylsulfonylmethyl group, tert-butylsulfonylmethyl group, methylsulfonylethyl group, ethylsulfonylethyl group, n-propylsulfonylethyl group, isopropyl sulfonylethyl group, methylsulfonylpropyl group and the like.
(72) Examples of the C1-C6 alkylamino C1-C6 alkyl group represented by R.sup.4 include methylaminomethyl group, methylaminoethyl group, ethylaminoethyl group, n-propylaminoethyl group, isopropylaminoethyl group, n-butylaminoethyl group, isobutylaminoethyl group, sec-butylaminoethyl group, tert-butylaminoethyl group and the like.
(73) Examples of the di-C1-C6 alkylamino C1-C6 alkyl group wherein the di-C1-C6 alkyl groups may be same or different and the di-C1-C6 alkylamino C1-C6 alkyl group is represented by R.sup.4 include dimethylaminomethyl group, dimethylaminoethyl group, methylethylaminoethyl group, diethylaminoethyl group, di-n-propylaminoethyl group, methyl n-propylaminoethyl group, ethyl n-propylaminoethyl group, diisopropylaminoethyl group, di-n-butylaminoethyl group, diisobutylaminoethyl group, di-sec-butylaminoethyl group, di-tert-butylaminoethyl group and the like.
(74) Examples of the indanyl group moiety of the indanyl group which may be substituted and is represented by R.sup.4 include 1-indanyl group, 2-indanyl group and the like.
(75) Examples of the tetrahydronaphthyl group moiety of the tetrahydronaphthyl group which may be substituted and is represented by R.sup.4 include 1-(1,2,3,4-tetrahydronaphthyl) group, 2-(1,2,3,4-tetrahydronaphthyl) group and the like.
(76) Examples of the heterocyclic C1-C6 alkyl group moiety of the heterocyclic C1-C6 alkyl group which may be substituted and is represented by R.sup.4 include (2-oxiranyl)methyl group, (3-oxetanyl)methyl group, (2-methyl-2-oxiranyl)methyl group, (3-methyl-3-oxetanyl)methyl group, (2-tetrahydrofuryl)methyl group, (3-tetrahydrofuryl)methyl group, (2-thienyl)methyl group, (3-thienyl)methyl group, (2-pyridyl)methyl group, (3-pyridyl)methyl group, (4-pyridyl)methyl group, 1-(2-thienyl)ethyl group, 2-(2-thienyl)ethyl group, 1-(3-thienyl)ethyl group, 2-(3-thienyl)ethyl group, 1-(2-pyridyl)ethyl group, 2-(2-pyridyl)ethyl group, 1-(3-pyridyl)ethyl group, 2-(3-pyridyl)ethyl group, 1-(4-pyridyl)ethyl group, 2-(4-pyridyl)ethyl group and the like.
(77) Examples of the C1-C6 alkoxy group represented by X or the C1-C6 alkoxy group as a substituent include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group and the like. The number of the C1-C6 alkoxy group(s) as a substituent may be one, two or more, and when the number is two or more, the C1-C6 alkoxy groups may be the same or different from each other. The position of substitution with the C1-C6 alkoxy group may be any position.
(78) Examples of the C1-C6 haloalkoxy group as a substituent include monofluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2-chloroethoxy group, trichloromethoxy group, 1-fluoroethoxy group, 2-fluoroethoxy group and the like. The number of the C1-C6 haloalkoxy group(s) as a substituent may be one, two or more, and when the number is two or more, the C1-C6 haloalkoxy groups may be the same or different from each other. The position of substitution with the C1-C6 haloalkoxy group may be any position.
(79) Examples of the C1-C6 alkylthio group as a substituent include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group and the like. The number of the C1-C6 alkylthio group(s) as a substituent may be one, or two or more, and when the number is two or more, the C1-C6 alkylthio groups may be the same or different from each other. The position of substitution with the C1-C6 alkylthio group may be any position.
(80) Examples of the C1-C6 haloalkylthio group as a substituent include trifluoromethylthio group, 2,2,2-trifluoroethylthio group and the like.
(81) The number of the C1-C6 haloalkylthio group(s) as a substituent may be one, or two or more, and when the number is two or more, the C1-C6 haloalkylthio groups may be the same or different from each other. The position of substitution with the C1-C6 haloalkylthio group may be any position.
(82) In the isoxazolin-5-one derivatives represented by the formula (1), although the combination of R.sup.1 to R.sup.4, X and n is not particularly limited, for example, an embodiment is as follows.
(83) In the formula (1) above, R.sup.1 is a trifluoromethyl group; R.sup.2 is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy C1-C6 alkyl group, a C7-C11 aralkyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group), a C1-C6 alkylcarbonyl group, a C1-C6 haloalkylcarbonyl group, a C3-C6 cycloalkylcarbonyl group, a C1-C6 alkoxy C1-C6 alkylcarbonyl group, a benzoyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group), a C7-C11 aralkylcarbonyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group), a heterocyclic carbonyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group), a heterocyclic C1-C6 alkylcarbonyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group), a C1-C6 alkoxycarbonyl group, a C2-C6 alkenyloxycarbonyl group, a C1-C6 alkoxy C1-C6 alkoxycarbonyl group, a phenoxycarbonyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group), a C7-C11 aralkyloxycarbonyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group), a heterocyclic C1-C6 alkoxycarbonyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group), a C1-C6 alkylaminocarbonyl group, a di-C1-C6 alkylaminocarbonyl group wherein the di-C1-C6 alkyl groups may be same or different, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylsulfonyl group, a C3-C6 cycloalkylsulfonyl group, a phenylsulfonyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group) or a C7-C11 aralkylsulfonyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom or a C1-C6 alkyl group); R.sup.3 is a hydrogen atom, a C1-C6 alkyl group which may be substituted with a fluorine atom or a C3-C6 cycloalkyl group; R.sup.4 is a hydrogen atom, a C1-C15 alkyl group, a C1-C15 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkyl C1-C6 alkyl group, a C1-C6 alkoxy C1-C6 alkyl group, a C1-C6 alkylthio C1-C6 alkyl group, a phenyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group), a C7-C11 aralkyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom, cyano, nitro, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C1-C6 alkylthio group or a C1-C6 haloalkylthio group), an indanyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group), a tetrahydronaphthyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group), a heterocyclic C1-C6 alkyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group), a phenoxy C1-C6 alkyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group), a C7-C11 aralkyloxy C1-C6 alkyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group), a C1-C6 alkylcarbonyl group, a di-C1-C6 alkylaminocarbonyl group wherein the di-C1-C6 alkyl groups may be same or different, a C1-C6 alkylsulfonyl group or a phenylsulfonyl group which may be substituted (the group may be monosubstituted or polysubstituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 alkoxy group); X is a hydrogen atom or a halogen atom; and n is an integer of 1 to 4 (wherein X's may be different from each other when n represents an integer of 2 to 4.)
(84) Representative examples of the isoxazolin-5-one derivatives represented by the formula (1) are shown together in Table 1 below, but the isoxazolin-5-one derivatives are not limited to these compounds. These compounds include compounds including optical isomers, an E-form and a Z-form. The compound numbers are referred to in the following paragraphs.
(85) The symbols below in the tables stand for the corresponding groups as follows: “H” stands for hydrogen atom; “Me” stands for methyl group; “Et” stands for ethyl group; “n-Pr” stands for normal propyl group; “i-Pr” stands for isopropyl group; “c-Pr” stands for cyclopropyl group; “n-Bu” stands for normal butyl group; “s-Bu” stands for sec-butyl group; “i-Bu” stands for isobutyl group; “t-Bu” stands for tert-butyl group; “c-Bu” stands for cyclobutyl group; “n-Pen” stands for normal pentyl group; “c-Pen” stands for cyclopentyl group; “n-Hex” stands for normal hexyl group; “c-Hex” stands for cyclohexyl group; “Ph” stands for phenyl group; “Bz” stands for benzoyl group; and “Np” stands for naphthyl group.
(86) TABLE-US-00001 TABLE 1
(87) Next, although production methods of the isoxazolin-5-one derivatives represented by the formula (1) of the invention are explained in detail, the production methods are not limited to these methods. In this regard, regarding the reaction devices, reaction using a microwave synthesis device is also possible in addition to reaction using a magnetic stirrer or a mechanical stirrer.
(88) ##STR00004##
(89) (R.sup.3, X and n have the same meanings as those described above. Y represents a leaving group such as a halogen atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a toluenesulfonyloxy group. R.sup.5 represents a C1-C6 alkyl group.)
(90) The step-1 is a step of reacting a nitrobenzene derivative represented by the formula (2) and a β-ketoester derivative represented by the formula (3) in the presence of a base and thus producing a 2-(2-nitrobenzyl)-β-ketoester derivative (4). The nitrobenzene derivative represented by the formula (2) and the β-ketoester derivative represented by the formula (3) are sometimes known and can be obtained from Tokyo Chemical Industry Co., Ltd. or the like. Alternatively, the derivatives can also be easily produced from an available reagent according to a known method described in Courses in Experimental Chemistry, Organic Syntheses or the like.
(91) It is necessary to conduct the reaction in the presence of a base, and as the base, an organic base such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline and lutidine, an alkali metal salt such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium-tert-butoxide, sodium hydride, potassium hydride, sodium amide, butyllithium, tert-butyllithium, lithium diisopropylamide, trimethylsilyl lithium and lithium hexamethyldisilazide or the like can be used. Of these bases, a metal base such as sodium methoxide and sodium ethoxide is preferable in view of the high yield. By conducting the reaction using the base in an amount of 0.1 to 5 equivalents based on the substrates, the target material can be obtained with a high yield. The reaction substrate (3) is generally used in an amount of 1 to 5 equivalents based on the substrate (2).
(92) The reaction is preferably conducted in the presence of a solvent. A solvent which does not adversely affect the reaction can be used as the solvent used, and an aromatic hydrocarbon-based solvent such as benzene, toluene, xylene and chlorobenzene, an aliphatic hydrocarbon-based solvent such as pentane, hexane and octane, an ether-based solvent such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane and 1,4-dioxane, a ketone such as acetone, methyl ethyl ketone and cyclohexanone, a halogen-based solvent such as chloroform and dichloromethane, a nitrile-based solvent such as acetonitrile and propionitrile, an ester-based solvent such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate, an amide-based solvent such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, an alcohol-based solvent such as methanol, ethanol, 1-propanol, 2-propanol and tert-butanol, dimethyl sulfoxide, water or a mixed solvent thereof can be used. To promote the progress of the reaction, a phase-transfer catalyst such as a quaternary ammonium salt can also be added.
(93) The reaction can be conducted at a temperature which is appropriately determined in the range of from −78° C. to 200° C., although the temperature varies with the reaction conditions. After the reaction, although the target material can be obtained by a general post-treatment operation, the target material can also be purified by column chromatography, recrystallization or the like if necessary.
(94) ##STR00005##
(95) (R.sup.3, X, n and R.sup.5 have the same meanings as those described above.)
(96) The step-2 is a step of reacting the 2-(2-nitrobenzyl)-3-ketoester derivative represented by the formula (4) and hydroxylamine represented by the formula (5) and thus producing an isoxazolin-5-one derivative (6). The hydroxylamine represented by the formula (5) may be a quaternary salt such as a hydrochloride or a sulfate.
(97) The reaction may be conducted in the presence of a base, and as the base, an organic base such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline and lutidine, an alkali metal salt such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium-tert-butoxide, sodium hydride, potassium hydride, sodium amide, butyllithium, tert-butyllithium, lithium diisopropylamide, trimethylsilyl lithium and lithium hexamethyldisilazide or the like can be used. By conducting the reaction using the base in an amount of 0.1 to 5 equivalents based on the substrates, the target material can be obtained with a high yield. The reaction substrate (5) is generally used in an amount of 1 to 5 equivalents based on the substrate (4).
(98) The reaction is preferably conducted in a solvent. A solvent which does not adversely affect the reaction can be used as the solvent, and an aromatic hydrocarbon-based solvent such as benzene, toluene, xylene and chlorobenzene, an aliphatic hydrocarbon-based solvent such as pentane, hexane and octane, an ether-based solvent such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane and 1,4-dioxane, a ketone such as acetone, methyl ethyl ketone and cyclohexanone, a halogen-based solvent such as chloroform and dichloromethane, a nitrile-based solvent such as acetonitrile and propionitrile, an ester-based solvent such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate, an amide-based solvent such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, an alcohol-based solvent such as methanol, ethanol, 1-propanol, 2-propanol and tert-butanol, dimethyl sulfoxide, water or a mixed solvent thereof can be used.
(99) The reaction can be conducted at a temperature which is appropriately determined in the range of from −78° C. to 200° C., although the temperature varies with the base used and the reaction conditions. After the reaction, although the target material can be obtained by a general post-treatment operation, the target material can also be purified by column chromatography, recrystallization or the like if necessary.
(100) ##STR00006##
(101) (R.sup.3, R.sup.4, X, n and Y have the same meanings as those described above.)
(102) The step-3 is a step of introducing R.sup.4 to the nitrogen atom at the 2-position of the isoxazolin-5-one derivative represented by the formula (6) and thus producing an isoxazolin-5-one derivative represented by the formula (7).
(103) It is necessary to conduct the reaction in the presence of a base, and as the base, an organic base such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline and lutidine, an alkali metal salt such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium-tert-butoxide, sodium hydride, potassium hydride, sodium amide, butyllithium, tert-butyllithium, lithium diisopropylamide, trimethylsilyl lithium and lithium hexamethyldisilazide or the like can be used. Of these bases, a metal base such as potassium carbonate and sodium hydride is preferable in view of the high yield. By conducting the reaction using the base in an amount of 0.1 to 5 equivalents based on the substrates, the target material can be obtained with a high yield. The reaction substrate (8) is generally used in an amount of 1 to 5 equivalents based on the substrate (6).
(104) The reaction is preferably conducted in a solvent. A solvent which does not adversely affect the reaction can be used as the solvent, and an aromatic hydrocarbon-based solvent such as benzene, toluene, xylene and chlorobenzene, an aliphatic hydrocarbon-based solvent such as pentane, hexane and octane, an ether-based solvent such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane and 1,4-dioxane, a ketone such as acetone, methyl ethyl ketone and cyclohexanone, a halogen-based solvent such as chloroform and dichloromethane, a nitrile-based solvent such as acetonitrile and propionitrile, an ester-based solvent such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate, an amide-based solvent such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, an alcohol-based solvent such as methanol, ethanol, 1-propanol, 2-propanol and tert-butanol, dimethyl sulfoxide, water or a mixed solvent thereof can be used.
(105) The reaction can be conducted at a temperature which is appropriately determined in the range of from −78° C. to 200° C., although the temperature varies with the base used and the reaction conditions. After the reaction, although the target material can be obtained by a general post-treatment operation, the target material can also be purified by column chromatography, recrystallization or the like if necessary. Additionally, an O-substitution product may be generated in the reaction but can be easily separated and purified by column chromatography or the like.
(106) ##STR00007##
(107) (R.sup.3, R.sup.4, X and n have the same meanings as those described above.)
(108) The step-4 is a step of reducing the nitro group of the isoxazolin-5-one derivative represented by the formula (7) and thus producing an isoxazolin-5-one derivative (9) having an amino group.
(109) The method for reducing the nitro group in the step can be a method using a reducing agent such as zinc powder, reduced iron, tin powder, stannous chloride and titanium chloride, a method using a hydrogen donor such as hydrazine in the presence of Raney nickel, catalytic hydrogenation reduction or catalytic hydrogen transfer reduction in the presence of a catalyst such as Raney nickel, palladium on carbon, palladium hydroxide and platinum oxide or the like.
(110) The reaction is preferably conducted in a solvent. A solvent which does not adversely affect the reaction can be used as the solvent, and an aromatic hydrocarbon-based solvent such as benzene, toluene, xylene and chlorobenzene, an aliphatic hydrocarbon-based solvent such as pentane, hexane and octane, an ether-based solvent such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane and 1,4-dioxane, a ketone such as acetone, methyl ethyl ketone and cyclohexanone, a halogen-based solvent such as chloroform and dichloromethane, a nitrile-based solvent such as acetonitrile and propionitrile, an ester-based solvent such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate, an amide-based solvent such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, an alcohol-based solvent such as methanol, ethanol, 1-propanol, 2-propanol and tert-butanol, dimethyl sulfoxide, water, hydrochloric acid, acetic acid or a mixed solvent thereof can be used.
(111) The reaction can be conducted at a temperature which is appropriately determined in the range of from 0° C. to 200° C., although the temperature varies with the base used and the reaction conditions. After the reaction, although the target material can be obtained by a general post-treatment operation, the target material can also be purified by column chromatography, recrystallization or the like if necessary.
(112) ##STR00008##
(113) (R.sup.1, R.sup.3, R.sup.4, X, n and Y have the same meanings as those described above. R.sup.22 represents a hydrogen atom or R.sup.1SO.sub.2.)
(114) The step-5 is a step of reacting the isoxazolin-5-one derivative having an amino group represented by the formula (9) and a compound represented by the formula (10) and thus producing an isoxazolin-5-one derivative (la).
(115) The reaction may be conducted in the presence of a base, and as the base, an organic base such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline and lutidine, an alkali metal salt such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium-tert-butoxide, sodium hydride, potassium hydride, sodium amide, butyllithium, tert-butyllithium, lithium diisopropylamide, trimethylsilyl lithium and lithium hexamethyldisilazide or the like can be used. Of these bases, an organic base such as triethylamine and diisopropylethylamine is preferable in view of the high yield. By conducting the reaction using the base in an amount of 0.1 to 5 equivalents based on the substrates, the target material can be obtained with a high yield.
(116) The reaction is preferably conducted in a solvent. A solvent which does not adversely affect the reaction can be used as the solvent, and an aromatic hydrocarbon-based solvent such as benzene, toluene, xylene and chlorobenzene, an aliphatic hydrocarbon-based solvent such as pentane, hexane and octane, an ether-based solvent such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane and 1,4-dioxane, a ketone such as acetone, methyl ethyl ketone and cyclohexanone, a halogen-based solvent such as chloroform and dichloromethane, a nitrile-based solvent such as acetonitrile and propionitrile, an ester-based solvent such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate, an amide-based solvent such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, an alcohol-based solvent such as methanol, ethanol, 1-propanol, 2-propanol and tert-butanol, dimethyl sulfoxide, water or a mixed solvent thereof can be used.
(117) The reaction can be conducted at a temperature which is appropriately determined in the range of from −78° C. to 200° C., although the temperature varies with the base used and the reaction conditions. After the reaction, although the target material can be obtained by a general post-treatment operation, the target material can also be purified by column chromatography, recrystallization or the like if necessary.
(118) ##STR00009##
(119) (R.sup.1, R.sup.3, R.sup.4, X, n and Y have the same meanings as those described above. R.sup.23 represents any of the groups in R.sup.2 except for hydrogen atom.)
(120) The step-6 is a step of reacting a compound represented by the formula (11) with an isoxazolin-5-one derivative represented by the formula (1b) and thus producing an isoxazolin-5-one derivative (1c).
(121) It is necessary to conduct the reaction in the presence of a base depending on the kind of the compound (11), and as the base, an organic base such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline and lutidine, an alkali metal salt such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium-tert-butoxide, sodium hydride, potassium hydride, sodium amide, butyllithium, tert-butyllithium, lithium diisopropylamide, trimethylsilyl lithium and lithium hexamethyldisilazide or the like can be used. By conducting the reaction using the base in an amount of 0.1 to 5 equivalents based on the substrates, the target material can be obtained with a high yield.
(122) The reaction is preferably conducted in a solvent. A solvent which does not adversely affect the reaction can be used as the solvent, and an aromatic hydrocarbon-based solvent such as benzene, toluene, xylene and chlorobenzene, an aliphatic hydrocarbon-based solvent such as pentane, hexane and octane, an ether-based solvent such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane and 1,4-dioxane, a ketone such as acetone, methyl ethyl ketone and cyclohexanone, a halogen-based solvent such as chloroform and dichloromethane, a nitrile-based solvent such as acetonitrile and propionitrile, an ester-based solvent such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate, an amide-based solvent such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, an alcohol-based solvent such as methanol, ethanol, 1-propanol, 2-propanol and tert-butanol, dimethyl sulfoxide, water or a mixed solvent thereof can be used.
(123) The reaction can be conducted at a temperature which is appropriately determined in the range of from −78° C. to 200° C., although the temperature varies with the base used and the reaction conditions. After the reaction, although the target material can be obtained by a general post-treatment operation, the target material can also be purified by column chromatography, recrystallization or the like if necessary.
(124) ##STR00010##
(125) (R.sup.1, R.sup.3, R.sup.4, R.sup.23, X, n and Y have the same meanings as those described above.)
(126) The step-7 is a step of reacting the sulfonyl compound represented by the formula (10) with an isoxazolin-5-one derivative represented by the formula (1d) and thus producing the isoxazolin-5-one derivative (1c).
(127) The reaction may be conducted in the presence of a base, and as the base, an organic base such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline and lutidine, an alkali metal salt such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium-tert-butoxide, sodium hydride, potassium hydride, sodium amide, butyllithium, tert-butyllithium, lithium diisopropylamide, trimethylsilyl lithium and lithium hexamethyldisilazide or the like can be used. By conducting the reaction using the base in an amount of 0.1 to 5 equivalents based on the substrates, the target material can be obtained with a high yield.
(128) The reaction is preferably conducted in a solvent. A solvent which does not adversely affect the reaction can be used as the solvent, and an aromatic hydrocarbon-based solvent such as benzene, toluene, xylene and chlorobenzene, an aliphatic hydrocarbon-based solvent such as pentane, hexane and octane, an ether-based solvent such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane and 1,4-dioxane, a ketone such as acetone, methyl ethyl ketone and cyclohexanone, a halogen-based solvent such as chloroform and dichloromethane, a nitrile-based solvent such as acetonitrile and propionitrile, an ester-based solvent such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate, an amide-based solvent such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, an alcohol-based solvent such as methanol, ethanol, 1-propanol, 2-propanol and tert-butanol, dimethyl sulfoxide, water or a mixed solvent thereof can be used.
(129) The reaction can be conducted at a temperature which is appropriately determined in the range of from −78° C. to 200° C., although the temperature varies with the base used and the reaction conditions. After the reaction, although the target material can be obtained by a general post-treatment operation, the target material can also be purified by column chromatography, recrystallization or the like if necessary.
(130) ##STR00011##
(131) (X, n, Y and R.sup.5 have the same meanings as those described above.)
(132) The step-8 is a step of reacting the nitrobenzene derivative represented by the formula (2) and a phosphonium ylide derivative represented by the formula (12) and thus producing a phosphonium salt derivative (13). The phosphonium ylide derivative represented by the formula (12) is sometimes known and can be obtained from Tokyo Chemical Industry Co., Ltd. or the like. Alternatively, the derivative can also be easily produced from an available reagent according to a known method described in Courses in Experimental Chemistry, Organic Syntheses or the like.
(133) The reaction is preferably conducted in the presence of a solvent. A solvent which does not adversely affect the reaction can be used as the solvent used, and an aromatic hydrocarbon-based solvent such as benzene, toluene, xylene and chlorobenzene, an aliphatic hydrocarbon-based solvent such as pentane, hexane and octane, an ether-based solvent such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane and 1,4-dioxane, a halogen-based solvent such as chloroform, dichloromethane and 1,2-dichloroethane, an ester-based solvent such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate, an amide-based solvent such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, dimethyl sulfoxide or a mixed solvent thereof can be used. To promote the progress of the reaction, a phase-transfer catalyst such as a quaternary ammonium salt can also be added.
(134) The reaction can be conducted at a temperature which is appropriately determined in the range of from −78° C. to 200° C., although the temperature varies with the reaction conditions. After the reaction, although the target material can be obtained by a general post-treatment operation, the target material can also be purified by column chromatography, recrystallization or the like if necessary.
(135) ##STR00012##
(136) (X, n, Y and R.sup.5 have the same meanings as those described above. Z represents a halogen atom. R.sup.6 represents a hydrogen atom or a C1-C6 alkyl group. R.sup.7 represents a hydrogen atom or a C1-C6 alkyl group.)
(137) The step-9 is a step of reacting the phosphonium salt derivative represented by the formula (13) and an acyl halide derivative represented by the formula (14) in the presence of a base and thus producing an allenoate derivative (15).
(138) It is necessary to conduct the reaction in the presence of a base, and as the base, an organic base such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline and lutidine, an alkali metal salt such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium-tert-butoxide, sodium hydride, potassium hydride, sodium amide, butyllithium, tert-butyllithium, lithium diisopropylamide, trimethylsilyl lithium and lithium hexamethyldisilazide or the like can be used. Of these bases, an organic base such as triethylamine and diisopropylethylamine is preferable in view of the high yield. By conducting the reaction using the base in an amount of 0.1 to 5 equivalents based on the substrates, the target material can be obtained with a high yield. The reaction substrate (14) is generally used in an amount of 1 to 5 equivalents based on the substrate (13).
(139) The reaction is preferably conducted in the presence of a solvent. A solvent which does not adversely affect the reaction can be used as the solvent used, and an aromatic hydrocarbon-based solvent such as benzene, toluene, xylene and chlorobenzene, an aliphatic hydrocarbon-based solvent such as pentane, hexane and octane, an ether-based solvent such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane and 1,4-dioxane, a halogen-based solvent such as chloroform and dichloromethane or a mixed solvent thereof can be used.
(140) The reaction can be conducted at a temperature which is appropriately determined in the range of from −78° C. to 200° C., although the temperature varies with the reaction conditions. After the reaction, although the target material can be obtained by a general post-treatment operation, the target material can also be purified by column chromatography, recrystallization or the like if necessary.
(141) ##STR00013##
(142) (X, n, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 have the same meanings as those described above.)
(143) The step-10 is a step of reacting the allenoate derivative represented by the formula (15) and a hydroxylamine derivative represented by the formula (16) and thus producing an isoxazolin-5-one derivative (17). The hydroxylamine derivative represented by the formula (16) is sometimes known and can be obtained from Tokyo Chemical Industry Co., Ltd. or the like. Alternatively, the derivative can also be easily produced from an available reagent according to a known method described in Courses in Experimental Chemistry, Organic Syntheses or the like. The hydroxylamine derivative represented by the formula (16) may be a quaternary salt such as a hydrochloride or a sulfate.
(144) The reaction may be conducted in the presence of a base, and as the base, an organic base such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline and lutidine, an alkali metal salt such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium-tert-butoxide, sodium hydride, potassium hydride, sodium amide, butyllithium, tert-butyllithium, lithium diisopropylamide, trimethylsilyl lithium and lithium hexamethyldisilazide or the like can be used. Of these bases, an organic base such as triethylamine and diisopropylamine is preferable in view of the high yield. By conducting the reaction using the base in an amount of 0.1 to 5 equivalents based on the substrates, the target material can be obtained with a high yield. The reaction substrate (16) is generally used in an amount of 1 to 5 equivalents based on the substrate (15).
(145) The reaction is preferably conducted in the presence of a solvent. A solvent which does not adversely affect the reaction can be used as the solvent used, and an aromatic hydrocarbon-based solvent such as benzene, toluene, xylene and chlorobenzene, an aliphatic hydrocarbon-based solvent such as pentane, hexane and octane, an ether-based solvent such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane and 1,4-dioxane, a ketone such as acetone, methyl ethyl ketone and cyclohexanone, a halogen-based solvent such as chloroform and dichloromethane, a nitrile-based solvent such as acetonitrile and propionitrile, an ester-based solvent such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate, an amide-based solvent such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, an alcohol-based solvent such as methanol, ethanol, 1-propanol, 2-propanol and tert-butanol, dimethyl sulfoxide, water or a mixed solvent thereof can be used.
(146) The reaction can be conducted at a temperature which is appropriately determined in the range of from −78° C. to 200° C., although the temperature varies with the reaction conditions. After the reaction, although the target material can be obtained by a general post-treatment operation, the target material can also be purified by column chromatography, recrystallization or the like if necessary.
(147) The compounds of the invention can be analyzed, confirmed or identified by the melting points, the infrared absorption spectra, .sup.1H-NMR, .sup.13C-NMR, mass spectrometry, X-ray structure analysis or the like, if necessary.
(148) The production methods are not limited to those described above, and the compounds of the invention can be produced by any organic synthesis methods.
(149) As also shown in Test Examples described below, the compounds of the invention exhibit an excellent herbicidal activity and exhibit an excellent selective weed killing activity distinguishing the weeds and the crops below. Thus, the compounds can be used for a wide range of targets such as weeds and the like in paddy rice fields and dry field. Specific examples of the weeds are as follows.
(150) Specifically, for example, the following harmful weeds can be controlled: Gramineae weeds such as Echinochloa crus-galli, Echinochloa oryzicola, southern crabgrass (Digitaria sanguinalis, Digitaria ischaem, Digitaria adscendens, Digitaria microbachne or Digitaria horizontalis), Setaria viridis, Setaria faberi, Setaria lutescens, Eleusine indica, Avena fatua, Sorghum halepense, Aropyron repens, Brachiaria plantaginea, Panicum maximum, Panicum purpurascens, Panicum dichotomiflorum, Leptochloa chinensis, Leptochloa panicea, Poa annua, Alopecurus aequalis, Alopecurus myosuroides, Agropyron tsukushiense, Bracharia platyphylla, Cenchrus echinatus, Lolium multiflorum, Cynodon dactylon, Beckmannia syzigache, Bromus catharticus, Leersia japonica, Leersia sayanuka, Lolium rigidum, Paspalum distichum and Phleum pratense; Cyperaceae weeds such as Cyperus iria, Cyperus rotundus, Cyperus esculentus, Scirpus hotarui, Cyperus serotinus, Cyperus serotinus, Eleocharis acicularis, Eleocharis kuroguwai, Cyperus flaccidus, Kyllinga brevifolia and Scirpus juncoides; Alismataceae weeds such as Sagittaria pygmaea, Sagittaria trifolia and Alisma canaliculatum; Pontderiaceae weeds such as Monochoria vaginalis, Heteranthera limosa and Monochoria kosakowii; Linderniaceae weeds such as Lindernia pyxidaria; Plantaginaceae weeds such as Plantago asiatica, Gratiola japonica, Dopatrium junceum and Veronica polita; Lythraceae weeds such as Rotala india, Ammannia multifflora and Rotala indica; Elatinaceae weeds such as Elatine triandra; Malvaceae weeds such as Abutiol theophrsti and Sida spinosa; Compositae weeds such as Xanthium strumarim, Ambrosia elatior, Breea serosa, Galinsoga ciliata, Matricaria chamomilla, Taraxacum officinale, Erigeron canadensis, Bidens frondosa, Bidens pilosa, Bidens tripartita, Gnaphalium affine and Senecio vulgaris; Lamiaceae weeds such as Lamium amplexinale weber; Solanaceae weeds such as Solanum nigrum and Datura stramonium; Amaranthaceae weeds such as Amaranthus viridis, Chenopodium album, Kochia scoparia and Amaranthus hybridus; Polygonaceeae weeds such as Polygonum lapathifolium, Polygonum persicaria, Polygonum convolvulus, Polygonum aviculare, Persicaria longiseta and Persicaria nepalensis; Crpurea weeds such as Cardamine flexuosa, Capsella bursapastoris, Brassica juncea and Rorippa indica; Convolvulaceae weeds such as Ipomoea purpurea, Convolvulus arvensis, Ipomoea hederacea, Calystegia pubescens and Ipomoea coccinea; Portulacaceae weeds such as Portulaca oleracea; Fabaceae weeds such as Cassia obtusifolia, Aeschynomene indica, Sesbania exaltata, Trifolium repens and Vicia sativa; Caryophyllaceae weeds such as Stellaria media, Stellaria neglecta and Stellaria uliginosa; Euphoribiaceae weeds such as Euphorbia helioscopia and Acalypha australis; Commelinaceae weeds such as Commelina communis and Murdannia keisak; Potamogetonaceae weeds such as Potamogeton distinctus; Araceae weeds such as Spirodela polyrhiza; Cucurbitaceae weeds such as Sicyos angulatus; Rubiaceae weeds such as Galium spurium; Apiaceae weeds such as Oenanthe javanica; Violaceae weeds such as Viola mandshuria; Onagraceae weeds such as Ludwigia epilobioides and Oenothera odorata; Oxalidaceae weeds such as Oxalis corniculata; Equisetaceae weeds such as Equisetum arvense; Zygnemataceae weeds such as Spirogyra sp. and the like. Accordingly, the compounds are effectively used for a case of selectively controlling a harmful weed or a case of non-selectively controlling a harmful weed in culturing, for example, Zea mays, Glycine max, Gossypium spp., Triticum spp., Hordeum vulgare, Secale cereale, Avena sativa, Sorghum bicolor, Brassica napus, Helianthus annuus, Beta Vulgaris, Saccharum officinarum, Zoysia japonicaa, Arachis hypogaea, Linum usitatissmum, Nicotiana tabacum, Coffea spp. or the like, which are useful crops.
(151) The applications of the herbicides of the invention are not limited to the weeds and the crops described above as examples.
(152) If necessary, the compounds of the invention may be prepared as mixed formulations with another kind of herbicide, an insecticide, an acaricide, a nematicide, a germicide (a fungicide, a bactericide, an antiviral agent or a plant resistance inducer), a bird repellent, a plant growth regulator, a safener, a fertilizer, a soil conditioner, a synergist or the like during the formation or spraying or may be blended with such an agent in a tank mixer at spraying and applied.
(153) In particular, when the compounds are blended and applied with another kind of herbicide, the amount of the used herbicide can be reduced, and the labor can be reduced. Moreover, the range of the targets of the herbicides (weed control spectrum) broadens due to the multiplier action of the agents, and a stronger effect can be expected due to the synergistic action of the agents. At this point, more than one kind of known herbicide or safener can also be combined and blended at the same time.
(154) Of the optional components above, although representative examples of herbicides are shown below, the components are not limited to these examples only.
(155) (1) Phenoxy-based compounds such as 2,4-D, 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-dimethylammonium, 2,4-D-diolamine, 2,4-D-ethyl, 2,4-D-2-ethylhexyl, 2,4-D-isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl, 2,4-D-isopropylammonium, 2,4-D-sodium, 2,4-D-isopropanolammonium, 2,4-D-trolamine, 2,4-DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium, 2,4-DB-isoctyl, 2,4-DB-potassium, 2,4-DB-sodium 2,4-D choline salt, dichlorprop, dichlorprop-butotyl, dichlorprop-dimethylammonium, dichlorprop-isoctyl, dichlorprop-potassium, dichlorprop-P, dichlorprop-P-dimethylammonium, dichlorprop-P-potassium, dichlorprop-P-sodium, MCPA, MCPA-butotyl, MCPA-dimethylammonium, MCPA-2-ethylhexyl, MCPA-potassium, MCPA-sodium, MCPA-thioetyl, MCPB, MCPB-ethyl, MCPB-sodium, mecoprop, mecoprop-butotyl, mecoprop-sodium, mecoprop-P, mecoprop-P-butotyl, mecoprop-P-dimethyl ammonium, mecoprop-P-2-ethylhexyl, mecoprop-P-potassium, naproanilide, clomeprop and HIA-1; aromatic carboxylic acid-based compounds such as 2,3,6-TBA, dicamba, dicamba-butotyl, dicamba-diglycolamine, dicamba-dimethylammonium, dicamba-diolamine, dicamba-isopropylammonium, dicamba-potassium, dicamba-sodium, picloram, picloram-dimethylammonium, picloram-isooctyl, picloram-potassium, picloram-trii sopropanolammonium, picloram-trii sopropylammonium, picloram-trolamine, tricolopyr, tricolopyr-butotyl, tricolopyr-triethylammonium, clopyralid, clopyralid-olamine, clopyralid-potassium, clopyralid-triisopropanolammonium, aminopyralid, aminocyclopyrachlor, aminocyclopyrachlor, halauxifen, florpyrauxifen, halauxifen-methyl and DAS-534; and other compounds which are considered to exhibit a herbicidal efficacy by disturbing the hormone action of a plant, such as naptalam, naptalam-sodium, benazolin, benazolin-ethyl, quinclorac, quinmerac, diflufenzopyr, diflufenzopyr-sodium, fluroxypyr, fluroxypyr-2-butoxy-1-methylethyl, fluroxypyr-meptyl, chlorflurenol, chlorflurenol-methyl and clacyfos.
(156) (2) Urea-based compounds such as chlorotoluron, diuron, fluometuron, linuron, isoproturon, metobenzuron, tebuthiuron, dimefuron, isouron, karbutilate, methabenztiazuron, metoxuron, metoburomuron, monolinuron, neburon, siduron, terbumeton and trietazine; triazine-based compounds such as simazine, atrazine, atratone, simetryn, prometryn, dimethametryn, hexazinone, metribuzin, terbuthylazine, cyanazine, ametryn, cybutryne, terbutryn, propazine, metamitron and prometon; uracil-based compounds such as bromacil, bromacyl-lithium, lenacil and terbacil; anilide-based compounds such as propanil and cypromid; carbamate-based compounds such as swep, desmedipham and phenmedipham; hydroxybenzonitrile-based compounds such as bromoxynil, bromoxynil-octanoate, bromoxynil-heptanoate, ioxynil, ioxynil-octanoate, ioxynil-potassium and ioxynil-sodium; and other compounds which are considered to exhibit a herbicidal efficacy by inhibiting the photosynthesis of a plant, such as pyridate, bentazone, bentazone-sodium, amicarbazone, methazole, pentanochlor and phenmedipham.
(157) (3) Quaternary ammonium salt-based compounds which become free radicals in the plant and which are considered to generate active oxygen and exhibit an immediate herbicidal efficacy, such as paraquat and diquat.
(158) (4) Diphenyl ether-based compounds such as nitrofen, chlomethoxyfen, bifenox, acifluorfen, acifluorfen-sodium, fomesafen, fomesafen-sodium, oxyfluorfen, lactofen, aclonifen, ethoxyfen-ethyl, fluoroglycofen-ethyl and fluoroglycofen; cyclic imide-based compounds such as chlorphthalim, flumioxazin, flumiclorac, flumiclorac-pentyl, cinidon-ethyl, fluthiacet-methyl and EK-5385; and other compounds which are considered to exhibit a herbicidal efficacy by inhibiting chlorophyll biosynthesis of a plant and causing abnormal accumulation of a photosensitizing peroxide substance in the plant, such as oxadiargyl, oxadiazon, sulfentrazone, carfentrazone-ethyl, thidiazimin, pentoxazone, azafenidin, isopropazole, pyraflufen-ethyl, benzfendizone, butafenacil, saflufenacil, fluazolate, profluazol, flufenpyr-ethyl, bencarbazone, tiafenacil, pyrachlonil, trifludimoxazin, HNPC-B4047, IR-6396, EK-5498, SYN-523 and the compound described in WO2008/008763 (FMC).
(159) (5) Pyridazinone-based compounds such as norflurazon, chloridazon and metflurazon; pyrazole-based compounds such as pyrazolynate, pyrazoxyfen, benzofenap, topramezone, pyrasulfotole and tolpyralate; and other compounds which are considered to exhibit a herbicidal efficacy characterized by a bleaching effect by inhibiting biosynthesis of a pigment of a plant such as carotenoids, such as amitrole, fluridone, flurtamone, diflufenican, methoxyphenone, clomazone, sulcotrione, mesotrione, tembotrione, tefuryltrione, fenquinotrione, lancotrione, cyclopyrimorate, isoxaflutole, difenzoquat, difenzoquat-metilsulfate, isoxachlortole, benzobicyclon, bicyclopyron, picolinafen, beflubutamid, ketospiradox, ketospiradox-potassium and compounds described in JP2012/2571 (Sumitomo Chemical Company, Limited).
(160) (6) Compounds which are considered to inhibit biosynthesis of fatty acids and exhibit a herbicidal efficacy on a plant including aryloxyphenoxypropionic acid-based compounds such as diclofop-methyl, diclofop, pyriphenop-sodium, fluazifop-butyl, fluazifop, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-etotyl, haloxyfop-P, haloxyfop-P-methyl, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, cyhalofop-butyl, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, metamifop-propyl, metamifop, clodinafop-propargyl, propaquizafop, HNPC-A8169 and SYP-1924; cyclohexanedione-based compounds such as alloxydim-sodium, alloxydim, clethodim, sethoxydim, tralkoxydim, butroxydim, tepraloxydim, profoxydim and cycloxydim; phenylpyrazoline-based compounds such as pinoxaden; and the like.
(161) (7) Sulfonylurea compounds such as chlorimuron-ethyl, chlorimuron, sulfometuron-methyl, sulfometuron, primisulfuron-methyl, primisulfuron, bensulfuron-methyl, bensulfuron, chlorsulfuron, metsulfuron-methyl, metsulfuron, cinosulfuron, pyrazosulfuron-ethyl, pyrazosulfuron, flazasulfuron, rimsulfuron, nicosulfuron, imazosulfuron, flucetosulfuron, cyclosulfamuron, prosulfuron, flupyrsulfuron-methyl-sodium, flupyrsulfuron, triflusulfuron, flupyrsulfuron-methyl-sodium, flupyrsulfuron, triflusulfuron-methyl, triflusulfuron, halosulfuron-methyl, halosulfuron, thifensulfuron-methyl, thifensulfuron, ethoxysulfuron, oxasulfuron, ethametsulfuron, ethametsulfuron-methyl, iodosulfuron, iodosulfuron-methyl-sodium, sulfosulfuron, triasulfuron, tribenuron-methyl, tribenuron, tritosulfuron, foramsulfuron, trifloxysulfuron, trifloxysulfuron-sodium, mesosulfuron-methyl, mesosulfuron, orthosulfamuron, amidosulfuron, azimsulfuron, propyrisulfuron, metazosulfuron, methiopyrsulfuron, monosulfuron-methyl, orsosulfuron, iofensulfuron and iofensulfuron-sodium; triazolopyrimidinesulfonamide-based compounds such as flumetsulam, metosulam, diclosulam, cloransulam-methyl, florasulam, penoxsulam and pyroxsulam; imidazolinone-based compounds such as imazapyr, imazapyr-isopropylammonium, imazethapyr, imazethapyr-ammonium, imazaquin, imazaquin-ammonium, imazamox, imazamox-ammonium, imazamethabenz, imazamethabenz-methyl and imazapic; pyrimidinyl salicylic acid-based compounds such as pyrithiobac-sodium, bispyribac-sodium, pyriminobac-methyl, pyribenzoxim, pyriftalid, pyrimisulfan and triafamone; sulfonylaminocarbonyltriazolinone-based compounds such as flucarbazone, flucarbazone-sodium, propoxycarbazone-sodium, propoxycarbazone and thiencarbazone-methyl; and other compounds which are considered to exhibit a herbicidal efficacy by inhibiting amino acid biosynthesis of a plant, such as glyphosate, glyphosate-sodium, glyphosate-potassium, glyphosate-ammonium, glyphosate-isopropylammonium, glyphosate-trimesium, glyphosate-sesquisodium, glufosinate, glufosinate-ammonium, glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium, bilanafos, bilanafos-sodium and cinmethylin.
(162) (8) Dinitroaniline-based compounds such as trifluralin, oryzalin, nitralin, pendimethalin, ethalfluralin, benfluralin, prodiamine, butralin and dinitramine; amide-based compounds such as bensulide, napropamide, napropamide-M, propyzamide and pronamide; organic phosphorus-based compounds such as amiprofos-methyl, butamifos, anilofos and piperophos; phenyl carbamate-based compounds such as propham, chlorpropham, barban and carbetamide; cumylamine-based compounds such as daimuron, cumyluron, bromobutide and methyldymron; and other compounds which are considered to exhibit a herbicidal efficacy by inhibiting cell mitosis of a plant, such as asulam, asulam-sodium, dithiopyr, thiazopyr, chlorthal-dimethyl, chlorthal, diphenamid, flamprop-M-methyl, flamprop-M and flamprop-M-isopropyl.
(163) (9) Chloroacetamide-based compounds such as alachlor, metazachlor, butachlor, pretilachlor, metolachlor, S-metolachlor, thenylchlor, pethoxamid, acetochlor, propachlor, dimethenamide, dimethenamide-P, propisochlor and dimethachlor; thiocarbamate-based compounds such as molinate, dimepiperate, pyributicarb, EPTC, butylate, vernolate, cycloate, prosulfocarb, esprocarb, thiobencarb, diallate, tri-allate and orbencarb; and other compounds which are considered to exhibit a herbicidal efficacy by inhibiting protein biosynthesis or lipid biosynthesis of a plant, such as etobenzanid, mefenacet, flufenacet, tridiphane, cafenstrole, fentrazamide, ipfencarbazone, oxaziclomefone, indanofan, benfuresate, pyroxasulfone, fenoxasulfone, methiozolin, dalapon, dalapon-sodium, TCA-sodium and trichloracetic acid.
(164) (10) Compounds which are considered to exhibit a herbicidal efficacy by inhibiting cellulose biosynthesis of a plant, such as dichlobenil, triaziflam, indaziflam, flupoxam and isoxaben.
(165) (11) Other herbicides such as MSMA, DSMA, CMA, endothall, endothall-dipotassium, endothall-sodium, endothall-mono(N,N-dimethylalkylammonium), ethofumesate, sodium chlarate, pelargonic acid, nonanoic acid, fosamine, fosamine-ammonium, aclolein, ammonium sulfamate, borax, chloroacetic acid, sodium chloroacetate, cyanamide, methylarsonic acid, dimethylarsonic acid, sodium dimethylarsonate, dinoterb, dinoterb-ammonium, dinoterb-diolamine, dinoterb-acetate, DNOC, ferrous sulfate, flupropanate, flupropanate-sodium, mefluidide, mefluidide-diolamine, metam, metam-ammonium, metam-potassium, metam-sodium, methyl isothiocyanate, pentachlorophenol, sodium pentachlorophenoxide, pentachlorophenol laurate, quinoclamine, sulfuric acid, urea sulfate, zanthinosin, herbimycin, unguinol, metatyrosine, sarmentine, thaxtomin A, mevalocidin, alpha-limonene, pyribambenz-propyl, pyribambenz-isopropyl, JS-913, KHG-23844, H-9201, SIOC-0163, SIOC-0171, SIOC-0172, SIOC-0285, SIOC-0426, SIOC-H-057, ZJ-0166, ZJ-1835, ZJ-0453, ZJ-0777, ZJ-0862 and compounds described in WO2008/096398 (Kumiai Chemical Industry Co., Ltd.).
(166) (12) Those which are considered to exhibit a herbicidal efficacy by parasitizing in a plant, such as Xanthomonas campestris, Epicoccosirus nematosorus, Epicoccosirus nematosperus, Exserohilum monoseras and Drechsrela monoceras.
(167) When the compounds of the invention are used as herbicides, the compounds can be directly used but can also be used as formulations. To prepare the formulations, an appropriate carrier, an auxiliary agent, a surfactant, a binder, a stabilizer and the like described in Pesticide Formulation Guide (edited by Special Committee on Application of Pesticide Science Society of Japan, issued by Japan Plant Protection Association, 1997).
(168) The herbicides containing the compounds of the invention can be formulated into any agent forms which are generally used as agent forms. For example, although the herbicides can be used in the forms of granules, microgranules, fine granules, water dispersible powder, a granulate water dispersible (dry flowable) agent, an emulsion, water soluble powder, a sol agent (flowable agent), a liquid, powder, rough powder, DL (driftless) powder, a flow dust agent, an oil, a microcapsule, a paste, a jumbo agent and the like, the forms are not limited to these examples.
(169) As the carrier used for formulation, both solid and liquid can be used as long as the carrier is generally used for herbicide formulations. Although the carrier is not limited to a particular carrier, specific examples include the following carriers. Examples of the solid carrier include mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, quartz, calcium carbonate, apatite, white carbon, slaked lime, silica sand, Japanese acid clay, zeolite, sepiolite, expanded perlite powder, Shirasu-balloon, alumina balloon, a phenolic resin, an epoxy resin, polyacrylonitrile, microspheres of polyurethane or the like and the like), vegetable powders (soybean flour, wheat flour, wood flour, tobacco powder, starch, crystalline cellulose and the like), polymer compounds (a petroleum resin, polyvinyl chloride, a ketone resin and the like), alumina, silicate, glucose, sucrose, lactose, glycopolymers, ammonium sulfate, sodium chloride, potassium chloride, urea, highly dispersible silicic acid, waxes and the like.
(170) Examples of the liquid carrier include water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, butanol, ethylene glycol, benzyl alcohol and the like), aromatic hydrocarbons (toluene, benzene, xylene, ethyl benzene, methylnaphthalene and the like), ethers (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran and the like), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone and the like), esters (ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate and the like), acid amides (dimethylformamide, dimethylacetamide and the like), nitriles (acetonitrile, propionitrile, acrylonitrile and the like), sulfoxides (dimethyl sulfoxide and the like), alcoholethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane and the like), industrial gasoline (petroleum ether, solvent naphtha and the like), petroleum fractions (paraffin, kerosene, light oil and the like) and the like.
(171) When the herbicides are formulated into an emulsion, water dispersible powder, a flowable agent or the like, various kinds of surfactant are blended for the purpose of emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading or the like. Examples of such a surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyoxyethylenealkyl aryl ethers, polyoxyethylene-polyoxypropylene block polymers and polyoxyethylene styrylphenylethers, anionic surfactants such as alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates, polyoxyethylene alkyl sulfates, aryl sulfonates, alkylnaphthalene sulfonates, polyoxyethylene styrylphenylether sulfates, lignin sulfonates, naphthalene sulfonate formaldehyde condensate and polycarboxylates, cationic surfactants such as alkylamines (lauryl amine, stearyltrimethyl ammonium chloride and the like), polyoxyethylene alkyl amines, alkyl pyridinium salts, alkyltrimethyl ammonium salts and alkyldimethyl ammonium salts, ampholytic surfactants such as carboxylic acid (betaine type) and sulfate esters and the like, but the surfactant is not limited to the examples.
(172) In addition, various kinds of auxiliary agent and additive such as polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), gum arabic, polyvinyl acetate, sodium alginate, gelatin, tragacanth gum, dextrin, hydroxypropyl methylcellulose (HPMC) and methyl cellulose (MC) and the like can be used.
(173) An appropriate amount of the compound of the invention in the herbicide is around 0.01 to 90% based on the mass.
(174) Preferable methods for using the herbicides containing the compounds of the invention as active ingredients include soil treatment, water surface treatment, leave and stem treatment and the like, and the herbicides can exhibit a particularly excellent effect when applied before germination and during the plumule period of a weed to be controlled.
(175) Although the amount of the compound of the invention to be applied as an herbicide differs with the situation of the application, the time of the application, the application method, the target weed, the cultivated crop and the like, an appropriate amount of the active ingredient is generally around 0.001 to 10 Kg, and preferably around 0.01 to 1 Kg per hectare (ha).
EXAMPLES
(176) Although the invention is explained further specifically below using Synthesis Examples, Formulation Examples and Test Examples of the compounds of the invention, the invention is not limited to the examples.
Synthesis Example 1
Synthesis of 1,1,1-trifluoro-N-[2-[(2-isobutyl-3-methyl-5-oxoisoxazol-4-yl)methyl]phenyl]methanesulfonamide (1-105) and 1,1,1-trifluoro-N-[2-[(2-isobutyl-3-methyl-5-oxoisoxazol-4-yl)methyl]phenyl]-N-(trifluoromethylsulfonyl)methanesulfonamide (1-967
(177) Triethylamine (200 mg, 2.00 mmol) and trifluoromethanesulfonic acid anhydride (400 mg, 1.40 mmol) were added at 0° C. to a chloroform solution (10 ml) of 4-[(2-aminophenyl)methyl]-2-isobutyl-3-methylisoxazolin-5-one (350 mg, 1.30 mmol), and the mixture was stirred at the same temperature for an hour. Water was poured into the reaction mixture, followed by extraction with chloroform. The extraction liquid was washed with saturated brine, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/3), and 1,1,1-trifluoro-N-[2-[(2-isobutyl-3-methyl-5-oxoisoxazol-4-yl)methyl]phenyl]methanesulfonamide (amount of 230 mg, yield of 59%) as a yellow oil and 1,1,1-trifluoro-N-[2-[(2-isobutyl-3-methyl-5-oxoisoxazol-4-yl)methyl]phenyl]-N-(trifluoromethylsulfonyl)methanesulfonamide (amount of 180 mg, yield of 34%) as a yellow solid were thus obtained.
Synthesis Example 2
Synthesis of 1,1,1-trifluoro-N-[2-[(3-methyl-5-oxo-2-sec-butyl-isoxazol-4-yl)methyl]phenyl]methanesulfonamide (1-102) and 1,1,1-trifluoro-N-[2-[(3-methyl-5-oxo-2-sec-butyl-isoxazol-4-yl)methyl]phenyl]-N-(trifluoromethyl sulfonyl)methanesulfonamide (1-964
(178) Triethylamine (86.0 mg, 0.850 mmol) and trifluoromethanesulfonic anhydride (220 mg, 0.770 mmol) were added at 0° C. to a chloroform solution (3 ml) of 4-[(2-aminophenyl)methyl]-3-methyl-2-sec-butyl-isoxazolin-5-one (100 mg, 0.380 mmol), and the mixture was stirred at the same temperature for an hour. Water was poured into the reaction mixture, followed by extraction with chloroform. The extraction liquid was washed with saturated brine, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/3), and 1,1,1-trifluoro-N-[2-[(3-methyl-5-oxo-2-sec-butyl-isoxazol-4-yl)methyl]phenyl]methanesulfonamide (amount of 80.0 mg, yield of 50%) as a yellow oil and 1,1,1-trifluoro-N-[2-[(3-methyl-5-oxo-2-sec-butyl-isoxazol-4-yl)methyl]phenyl]-N-(trifluoromethylsulfonyl)methanesulfonamide (amount of 20.0 mg, yield of 10%) as a yellow gum were thus obtained.
Synthesis Example 3
Synthesis of 1,1,1-trifluoro-N-[2-[[2-(2-methoxy-1-methyl-ethyl)-3-methyl-5-oxo-isoxazol-4-yl]methyl]phenyl]methanesulfonamide (1-149) and 1,1,1-trifluoro-N-[2-[[2-(2-methoxy-1-methyl-ethyl)-3-methyl-5-oxo-isoxazol-4-yl]methyl]phenyl]-N-(trifluoromethyl sulfonyl)methanesulfonamide (1-997
(179) The same reaction and treatment as those in Synthesis Example 2 were conducted using 4-[(2-aminophenyl)methyl]-2-(2-methoxy-1-methyl-ethyl)-3-methyl-isoxazolin-5-one instead of 4-[(2-aminophenyl)methyl]-3-methyl-2-sec-butyl-isoxazolin-5-one, and 1,1,1-trifluoro-N-[2-[[2-(2-methoxy-1-methyl-ethyl)-3-methyl-5-oxo-isoxazol-4-yl]methyl]phenyl]methanesulfonamide (yield of 47%) as a white solid and 1,1,1-trifluoro-N-[2-[[2-(2-methoxy-1-methyl-ethyl)-3-methyl-5-oxo-isoxazol-4-yl]methyl]phenyl]-N-(trifluoromethylsulfonyl)methanesulfonamide (yield of 14%) as a yellow solid were thus obtained.
Synthesis Example 4
Synthesis of N-[2-[(2-isobutyl-3-methyl-5-oxoisoxazol-4-yl)methyl]phenyl]-N-(trifluoromethyl sulfonyl)acetamide (1-297
(180) Triethylamine (71.0 mg, 0.700 mmol) and acetyl chloride (51.0 mg, 0.640 mmol) were added at 0° C. to a chloroform solution (3 ml) of 1,1,1-trifluoro-N-[2-[(2-isobutyl-3-methyl-5-oxoisoxazol-4-yl)methyl]phenyl]methanesulfonamide (230 mg, 0.590 mmol), and the mixture was stirred at the same temperature for an hour. Water was poured into the reaction mixture, followed by extraction with chloroform. The extraction liquid was washed with saturated brine, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1), and the title compound (amount of 240 mg, yield of 94%) as a yellow oil was thus obtained.
Synthesis Example 5
Synthesis of methyl N-[2-[(3-methyl-5-oxo-2-sec-butyl-isoxazol-4-yl)methyl]phenyl]-N-(trifluoromethyl sulfonyl)carbamate (1-577
(181) Sodium hydrogen carbonate (161 mg, 1.91 mmol) and methyl chloroformate (181 mg, 1.91 mmol) were added to an acetonitrile solution (3 ml) of 1,1,1-trifluoro-N-[2-[(3-methyl-5-oxo-2-sec-butyl-isoxazol-4-yl)methyl]phenyl]methanesulfonamide (250 mg, 0.637 mmol), and the mixture was heated under reflux for an hour. Water was poured into the reaction mixture, followed by extraction with ethyl acetate. The extraction liquid was washed with saturated brine, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/3), and the title compound (amount of 201 mg, yield of 70%) as a yellow solid was thus obtained.
Synthesis Example 6
Synthesis of N-[2-[(2-tert-butyl-3-methyl-5-oxo-isoxazol-4-yl)]methyl]phenyl]-1,1,1-trifluoromethanesulfonamide (1-101) and N-[2-[(2-tert-butyl-3-methyl-5-oxo-isoxazol-4-yl)methyl]phenyl]-1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide (1-963
(182) Triethylamine (1.60 g, 16.0 mmol) and trifluoromethanesulfonic anhydride (4.10 g, 15.0 mmol) were added at 0° C. to a chloroform solution (100 ml) of 4-[(2-aminophenyl)methyl]-2-tert-butyl-3-methyl-isoxazolin-5-one (2.70 g, 10.0 mmol), and the mixture was stirred at the same temperature for an hour. Water was poured into the reaction mixture, followed by extraction with chloroform. The extraction liquid was washed with saturated brine, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/3), and N-[2-[(2-tert-butyl-3-methyl5-oxo-isoxazol-4-yl)]methyl]phenyl]-1,1,1-trifluoro-methanesulfonamide (amount of 1.40 g, yield of 34%) as a yellow oil and N-[2-[(2-tert-butyl-3-methyl-5-oxo-isoxazol-4-yl)methyl]phenyl]-1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide (amount of 0.95 g, yield of 17%) as a yellow amorphous material were thus obtained.
(183) The .sup.1HNMR spectrum (CDCl.sub.3) σ (ppm) values, the melting points (° C.) and the like of the compounds according to the invention produced based on the above Synthesis Examples and the above production methods are shown in Table 2. The .sup.1HNMR data were measured by JNM-ECS400 spectrometer (manufactured by JEOL Ltd.). The compound numbers in Table 2 are the same as those in Table 1 above.
(184) TABLE-US-00002 TABLE 2 Property No. (mp.° C.) Form .sup.1HNMR spectrum σ ppm: 1-2 amorphous 9.65 (1H, brs), 7.57 (1H, d, J = 7.8 Hz), around7.24 (1H, m), 7.17-7.16 (2H, m), 4.58 (2H, s), 3.77 (1H, m), 3.66 (2H, s), 2.28 (3H, s), 1.84-1.77 (1H, m), 1.65-1.58 (1H, m), 1.19 (3H, d, J = 6.6 Hz), 0.90 (3H, t, J = 7.3 Hz) 1-3 gum 1-4 amorphous 1-5 amorphous 1-6 amorphous 1-7 gum 1-17 gum 9.20 (1H, brs), 7.35 (1H, d, J = 7.8 Hz), 7.23 (1H, t, J = 7.8 Hz), 7.17 (1H, d, J = 7.8 Hz), 7.07 (1H, t, J = 7.8 Hz), 6.12 (1H, t, J = 55.2 Hz 9, 3.82-3.76 (1H, m), 3.63 (1H, dd, J = 15.1, 3.2 Hz), 3.90 (1H, d, J = 15.1 Hz), 1.85-1.75 (1H, m), 1.67-1.56 (1H, m), 1.20 (3H, dd, J = 6.4, 1.0 Hz), 0.90 (3H, td, J = 7.3, 2.3 Hz) 1-19 amorphous 1-20 amorphous 1-28 oil 10.7 (1H, br.s), 7.46 (1H, dd, J = 8.7, 5.0 Hz), 6.96 (1H, td, J = 8.4, 2.9 Hz), 6.84 (1H, dd, J = 8.5, 3.0 Hz), 3.54 (2H, s), 3.45 (2H, d, J = 6.9 Hz), 2.32 (3H, s), 2.20-2.12 (1H, m), 0.94 (6H, d, J = 6.9 Hz). 1-29 oil 1-31 oil 1-32 65.1 solid 1-33 125 solid 1-37 gum 10.70 (1H, brs), 7.50 (1H, d, J = 2.0 Hz), 7.16 (1H, dd, J = 8.4, 2.0 Hz), 7.05 (1H, d, J = 8.4 Hz), 4.15-4.04 (1H, m), 3.31 (2H, s), 2.29 (3H, s), 1.25 (6H, d, J = 6.4 Hz). 1-41 gum 10.87 (1H, brs), 7.42 (1H, d, J = 8.8 Hz), 7.22 (1H, dd, J = 8.8, 2.4 Hz), 7.10 (1H, d, J = 2.4 Hz), 4.14-4.06 (1H, m), 3.51 (2H, s), 2.31 (3H, s), 1.27 (6H, d, J = 6.8 Hz). 1-46 gum 11.10 (1H, brs), 7.43 (1H, dd, J = 7.6, 1.2 Hz), 7.30 (1H, dd, J = 7.6, 1.2 Hz), 7.21 (1H, dd, J = 7.6, 7.6 Hz), 4.11 (1H, quint, J = 6.4 Hz), 3.71 (2H, s), 2.38 (3H, s), 1.26 (6H, d, J = 6.4 Hz). 1-47 gum 1-63 gum 10.91 (1H, brs), 7.48 (1H, d, J = 8.4 Hz), 7.28-7.22 (1H, m), 7.22-7.16 (1H, m), 7.14 (1H, dd, J = 7.2, 1.2 Hz), 4.07 (1H, quint, J = 6.8 Hz), 3.56 (2H, s), 2.67 (2H, q, J = 8.0 Hz), 1.32-1.23 (9H, m). 1-68 gum 10.93 (1H, brs), 7.48 (1H, dd, J = 7.6, 1.2 Hz), 7.28-7.22 (1H, m), 7.21-7.14 (2H, m), 4.16 (1H, quint, J = 6.4 Hz), 3.61 (2H, s), 3.27 (1H, quint, J = 7.2 Hz), 1.40 (6H, d, J = 7.2 Hz), 1.27 (6H, d, J = 6.4 Hz). 1-69 gum 1-78 gum 1-81 oil 9.92 (1H, br.s), 7.51 (1H, dd, J = 7.8, 1.4 Hz), 7.33-7.23 (3H, m), 3.79 (2H, s), 3.50 (2H, d, J = 7.3 Hz), 2.26-2.14 (1H, m), 2.17 (3H, s), 0.97 (6H, d, J = 6.9 Hz). 1-83 gum 10.79 (1H, brs), 7.52-7.48 (1H, m), 7.28-7.19 (3H, m), 4.44 (1H, quint, 6.4 Hz), 3.67 (2H, s), 1.68 (2H, m), 1.25 (6H, d, J = 6.4 Hz), 0.96-0.92 (2H, m) 1-84 105 solid 1-96 135-137 solid 10.60 (2H, brs), 7.48 (1H, dd, J = 8.4, 1.6 Hz), 7.29-7.24 (1H, m), 7.21 (1H, ddd, J = 7.4, 7.4, 1.6 Hz), 7.17 (1H, dd, J = 8.4, 2.4 Hz), 3.56 (2H, s), 2.36 (3H, s). 1-97 oil 1-98 gum 1-100 gum 1-101 oil 10.9 (1H, br.s), 7.50-7.47 (1H, m), 7.27-7.23 (1H, m), 7.22-7.18 (1H, m), 7.16-7.14 (1H, m), 3.56 (2H, s), 2.43 (3H, s), 1.42 (9H, s). 1-102 oil 7.50-7.48 (1H, d, J = 7.8 Hz), 7.28-7.15 (3H, m), 3.82 (1H, m), 3.57 (2H, s), 2.32 (3H, s), 1.85-1.74 (1H, m), 1.67-1.56 (1H, m), 1.20 (3H, d, J = 6.9 Hz), 0.89 (3H, t, J = 7.3 Hz) 1-103 oil 1-105 oil 10.9 (1H, br.s), 7.50 (1H, d, J = 8.2 Hz), 7.28-7.24 (1H, m), 7.21 (1H, td, J = 7.3, 1.4 Hz), , 7.15 (1H, dd, J = 7.8, 1.8 Hz), 3.56 (2H, s), 3.43 (2H, d, J = 6.9 Hz), 2.31 (3H, s), 2.21-2.10 (1H, m), 0.94 (6H, d, J = 6.9 Hz). 1-106 146-148 solid 1-109 gum 1-110 oil 1-112 oil 1-113 gum 1-115 68.1-72.4 solid 1-116 gum 1-120 oil 1-124 68 solid 1-130 oil 1-133 oil 1-134 oil 10.0 (1H, br.s), 7.50 (1H, d, J = 7.8 Hz), 7.31-7.27 (1H, m), 7.26-7.22 (1H, m), 7.16- 7.14 (1H, m), 4.20 (2H, d, J = 7.8 Hz), 3.61 (2H, s), 2.38 (3H, s). 1-135 oil 7.50-7.48 (1H, d, J = 6.9 Hz), 7.29-7.14 (3H, s), 5.77-5.70 (1H, m), 5.30-5.25 (2H, m), 4.24 (1H, brd, J = 6.0 Hz), 3.60 (2H, s), 2.17 (3H, s) 1-136 oil 1-137 oil 1-138 oil 10.2 (1H, br.s), 7.49 (1H, dd, J = 7.8, 1.4 Hz), 7.28 (1H, td, J = 7.3, 1.8 Hz), 7.23 (1H, td, J = 7.4, 1.5 Hz), 7.17 (1H, dd, J = 7.6, 1.6 Hz), 4.36 (2H, d, J = 2.3 Hz), 3.62 (2H, s), 2.34 (3H, s), 2.25 (1H, d, J = 2.3 Hz). 1-142 oil 10.8 (1H, br.s), 7.49 (1H, dd, J = 7.8, 0.9 Hz), 7.28-7.13 (3H, m), 3.77-3.64 (1H, m), 3.56 (2H, s), 2.36 (3H, s), 1.88-1.84 (2H, m), 1.74-1.64 (4H, m), 1.29-1.24 (2H, m). 1-143 oil 10.8 (1H, br.s), 7.50 (1H, d, J = 7.8 Hz), 7.27 (1H, td, J = 7.3, 1.4 Hz), 7.21 (1H, td, J = 7.3, 1.4 Hz), 7.16 (1H, dd, J = 7.6, 1.6 Hz), 3.58 (2H, s), 3.52 (2H, d, J = 6.9 Hz), 2.33 (3H, s), 1.05-0.95 (1H, m), 0.65-0.53 (2H, m), 0.34-0.23 (2H, m). 1-144 oil 1-145 oil 1-146 gum 1-148 109.0-112.5 solid 10.72 (1H, brs), 7.47 (1H, dd, J = 7.6, 1.2 Hz), 7.26-7.21 (1H, m), 7.19 (1H, ddd, J = 7.6, 7.6, 1.6 Hz), 7.16-7.13 (1H, m), 3.82 (2H, dd, J = 4.8, 4.8 Hz), 3.55 (2H, s), 3.48 (2H, dd, J = 4.8, 4.8 Hz), 3.15 (3H, s), 2.32 (3H, s). 1-149 107-109 solid 10.8 (1H, br.s), 7.48-7.46 (1H, m), 7.26-7.15 (3H, m), 4.17-4.08 (1H, m), 3.56 (2H, s), 3.43-3.32 (2H, m), 3.11 (3H, s), 2.33 (3H, s), 1.28-1.26 (3H, m). 1-155 oil 10.58 (1H, brs), 7.48-7.41 (1H, m), 7.37-7.31 (3H, m), 3.85 (2H, d, J = 4.8 Hz), 3.71 (2H, s), 3.59 (2H, dd, J = 4.0, 4.0 Hz), 3.53-3.44 (1H, m), 2.02 (3H, s), 1.04 (6H, d, J = 6.0 Hz). 1-156 oil 7.51-7.40 (1H, m), 7.37-7.31 (1H, m), 7.27-7.21 (1H, m), 7.19-7.11 (1H, m), 3.89- 3.85 (2H, m), 3.71 (1H, s), 3.60 (1H, dd, J = 4.0, 4.0 Hz), 3.54 (1H, s), 3.49 (1H, dd, J = 4.0, 4.0 Hz), 3.12 (1H, d, J = 6.8 Hz), 3.00 (1H, d, J = 6.8 Hz), 2.15 (3H, s), 1.64- 1.54 (1H, m), 0.81 (3H, d, J = 6.8 Hz), 0.72 (3H, d, J = 6.8 Hz). 1-162 oil 10.6 (1H, br.s), 7.49 (1H, dd, J = 8.0, 1.1 Hz), 7.27 (1H, dd, J = 7.3, 1.8 Hz), 7.21 (1H, td, J = 7.6, 1.5 Hz), 7.16 (1H, dd, J = 7.8, 1.8 Hz), 3.83 (2H, t, J = 6.6 Hz), 3.58 (2H, s), 2.75 (2H, t, J = 6.6 Hz), 2.37 (3H, s), 2.05 (3H, s). 1-166 oil 1-167 oil 1-174 oil 10.6 (1H, br.s), 7.54-7.41 (4H, m), 7.32-7.19 (5H, m), 3.67 (2H, s), 2.32 (3H, s). 1-175 oil 1-176 oil 1-177 amorphous 1-180 gum 1-181 oil 1-182 gum 1-183 gum 1-186 gum 10.4 (1H, br.s), 7.48 (1H, dd, J = 8.0, 1.1 Hz), 7.31 (2H, dt, J = 8.7, 2.2 Hz), 7.27-7.25 (1H, m), 7.21 (1H, td, J = 7.3, 1.4 Hz), 7.16 (2H, dt, J = 8.7, 2.2 Hz), 7.10 (3H, dd, J = 7.6, 1.6 Hz), 4.73 (2H, s), 3.54 (2H, s), 2.35 (3H, s). 1-187 110-115 solid 1-189 oil 1-191 88-89 solid 10.58 (1H, brs), 7.46 (1H, dd, J = 8.0, 1.2 Hz), 7.27-7.22 (1H, m), 7.18 (1H, ddd, J = 7.6, 7.6, 1.2 Hz), 7.13-7.06 (5H, m), 4.74 (2H, s), 3.51 (2H, s), 2.33 (3H, s), 2.31 (3H, s). 1-192 gum 1-193 gum 1-194 gum 10.28 (1H, brs), 7.57 (2H, d, J = 8.4 Hz), 7.45 (1H, dd, J = 8.4, 1.6 Hz), 7.33 (2H, d, J = 8.4 Hz), 7.27-7.22 (1H, m), 7.19 (1H, ddd, J = 7.6, 7.6, 1.6 Hz), 7.10 (1H, dd, J = 7.6, 1.6 Hz), 4.79 (2H, s), 3.53 (2H, s), 2.35 (3H, s). 1-195 oil 10.57 (1H, brs), 7.46 (1H, dd, J = 8.0, 1.2 Hz), 7.26-7.22 (1H, m), 7.18 (1H, ddd, J = 8.0, 8.0, 1.2 Hz), 7.12 (2H, d, J = 8.8 Hz), 7.09 (1H, dd, J = 1.6, 7.6 Hz), 6.83 (2H, d, J = 8.8 Hz), 4.71 (2H, s), 3.78 (3H, s), 3.51 (2H, s), 2.32 (3H, s). 1-198 gum 10.28 (1H, brs), 7.61 (2H, d, J = 8.0 Hz), 7.47 (1H, dd, J = 7.6, 0.8 Hz), 7.29-7.23 (3H, m), 7.19 (1H, ddd, J = 7.2, 7.2, 1.2 Hz), 7.10 (1H, dd, J = 7.2, 1.2 Hz), 4.77 (2H, s), 3.55 (2H, s), 2.36 (3H, s). 1-199 oil 1-200 gum 1-201 gum 1-202 oil 1-203 gum 10.6 (1H, br.s), 7.47-7.44 (1H, m), 7.34-7.29 (3H, m), 7.26-7.21 (3H, m), 7.18-7.14 (1H, m), 7.07-7.05 (1H, m), 5.03 (1H, q, J = 7.0 Hz), 3.50 (2H, q, J = 14.7 Hz), 2.28 (3H, s), 1.70 (3H, d, J = 6.9 Hz). 1-204 oil 10.52 (1H, brs), 7.46 (1H, dd, J = 7.6, 0.8 Hz), 7.26-7.20 (3H, m), 7.16 (1H, ddd, J = 7.2, 7.2, 1.2 Hz), 7.04 (1H, dd, J = 7.2, 1.2 Hz), 6.99 (2H, dd, J = 8.8, 8.8 Hz), 4.98 (1H, dd, J = 6.8, 6.8 Hz), 3.53 (1H, d, J = 15.2 Hz), 3.46 (1H, d, J = 15.2 Hz), 2.29 (3H, s), 1.67 (3H, d, J = 6.8 Hz). 1-205 oil 1-206 oil 1-207 oil 1-208 oil 1-209 gum 10.48 (1H, brs), 7.46 (1H, dd, J = 8.0, 0.8 Hz), 7.30-7.26 (2H, m), 7.25-7.21 (1H, m), 7.18-7.14 (3H, m), 7.05 (1H, dd, J = 7.6, 1.6 Hz), 5.01 (1H, q, J = 6.8 Hz), 3.53 (1H, d, J = 15.2 Hz), 3.47 (1H, d, J = 15.2 Hz), 2.29 (3H, s), 1.66 (3H, d, J = 6.8 Hz). 1-211 oil 10.40 (1H, brs), 7.44 (1H, dd, J = 8.0, 1.2 Hz), 7.32-7.26 (3H, m), 7.22-7.16 (3H, m), 7.12 (1H, ddd, J = 7.2, 7.2, 0.8 Hz), 7.02 (1H, dd, J = 8.0, 1.6 Hz), 4.65 (1H, dd, J = 8.0, 8.0 Hz), 3.52 (1H, d, J = 15.2 Hz), 3.41 (1H, d, J = 15.2 Hz), 2.31-2.23 (4H, m), 2.08-1.96 (1H, m), 0.95 (3H, t, J = 7.2 Hz). 1-212 gum 1-213 gum 1-214 gum 1-215 gum 1-216 oil 10.58 (1H, brs), 7.49-7.43 (1H, m), 7.37-7.31 (2H, m), 7.30-7.25 (4H, m), 7.18- 7.14 (2H, m), 3.88 (2H, dd, J = 6.8, 6.8 Hz), 3.66 (2H, s), 3.01 (2H, dd, J = 6.8, 6.8 Hz), 2.15 (3H, s). 1-218 gum 1-219 gum 1-220 oil 1-221 gum 1-222 gum 10.61 (1H, brs), 7.51-7.46 (1H, m), 7.29-7.03 (7H, m), 5.45 (1H, dd, J = 8.5, 5.3 Hz), 3.59 (2H, s), 3.16-3.08 (1H, m), 2.92-2.85 (1H, m), 2.41-2.314 (1H, m), 2.17-2.07 (1H, m), 2.03 (3H, s) 1-224 gum 10.76 (1H, brs), 7.51-7.48 (1H, m), 7.29-7.06 (7H, m), 5.14 (1H, m), 3.60 (2H, s), 2.88-2.71 (2H, m), 2.33 (3H, s), 2.02-1.87 (4H, m), 1.81-1.72 (2H, m) 1-229 oil 1-230 oil 10.66 (1H, brs), 7.42 (1H, dd, J = 8.0, 1.2 Hz), 7.27-7.22 (1H, m), 7.20-7.18 (1H, m), 7.17-7.15 (1H, m), 4.09-4.03 (1H, m), 3.80-3.66 (4H, m), 3.60 (1H, d, J = 15.2 Hz), 3.53 (1H, d, J = 15.2 Hz), 2.73 (3H, s), 2.06-1.98 (1H, m), 1.91-1.82 (2H, m), 1.61- 1.54 (1H, m). 1-231 oil 1-232 oil 10.4 (1H, br.s), 7.48-7.46 (1H, m), 7.29-7.27 (1H, m), 7.26-7.16 (3H, m), 7.10-7.08 (1H, m), 6.94-6.92 (1H, m), 4.79 (2H, s), 3.52 (2H, s), 2.33 (3H, s). 1-235 oil 1-237 oil 10.57 (1H, brs), 7.47 (1H, d, J = 6.9 Hz), 7.27-7.12 (5H, m), 6.95 (1H, t, J = 7.3 Hz), 6.68 (1H, brd, J = 7.8 Hz), 4.13-4.09 (4H, m), 3.55 (2H, s), 2.24 (3H, s) 1-238 oil 7.49 (1H, d, J = 8.2 Hz), 7.31-7.27 (3H, m), 7.22 (1H, t, J = 8.2 Hz), around7.11 (4H, m), 4.34 (2H, s), 3.87 (2H, t, J = 4.8 Hz), 3.57 (2H, t, J = 4.8 Hz), 3.55 (2H, s), 2.30 (3H, s) 1-242 oil 9.77 (1H, br.s), 7.51 (1H, d, J = 7.8 Hz), 7.31 (1H, td, J = 7.6, 1.8 Hz), 7.28-7.23 (1H, m), 7.19 (1H, dd, J = 7.8, 1.8 Hz), 3.64 (2H, s), 3.18-3.15 (1H, m), 2.75 (3H, s), 1.22 (6H, d, J = 6.9 Hz). 1-248 oil 1-249 oil 9.95 (1H, br.s), 7.50 (1H, dd, J = 8.0, 1.6 Hz), 7.35-7.26 (2H, m), 7.18 (1H, dd, J = 7.6, 1.6 Hz), 3.68 (2H, s), 3.22 (3H, s), 2.60 (3H, s). 1-251 oil 1-254 amorphous 9.98 (1H, br.s), 7.61 (2H, d, J = 8.4 Hz), 7.40 (1H, dd, J = 8.0, 1.1 Hz), 7.30-7.28 (1H, m), 7.22-7.18 (1H, m), 7.20 (1H, d, J=8.4 Hz), 6.96 (1H, dd, J = 7.6,1.6 Hz), 3.46 (2H, s), 2.60 (3H, s), 2.35 (3H, s). 1-256 gum 1-260 gum 1-263 oil 1-264 gum 7.34 (1H, dd, J = 7.3, 1.8 Hz), 7.29-7.19 (3H, m), 3.89 (2H, q, J = 7.2 Hz), 3.71 (2H, s), 3.47 (2H, d, J = 7.3 Hz), 2.09 (2H, s), 1.90-1.84 (1H, m), 1.46-1.36 (4H, m), 1.23 (3H, t, J = 7.3 Hz), 0.92 (6H, td, J = 7.3, 1.4 Hz). 1-270 oil 7.36-7.32 (2H, m), 7.28-7.24 (1H, m), 7.21-7.19 (1H, m), 5.20 (1H, d, J = 10.1 Hz), 4.97 (1H, d, J = 10.1 Hz), 3.71 (2H, s), 3.44 (3H, s), 3.39 (2H, d, J = 7.3 Hz), 2.22- 2.16 (1H, m), 2.09 (3H, s), 0.98 (6H, dd, J = 6.9, 1.8 Hz). 1-271 oil 1-278 oil 7.37-7.29 (2H, m), 7.28-7.24 (2H, m), 7.17-7.14 (3H, m), 7.12-7.10 (1H, m), 6.99- 6.96 (1H, m), 5.06 (1H, d, J = 14.2 Hz), 4.82 (1H, d, J = 14.2 Hz), 3.53 (1H, d, J = 16.9 Hz), 3.35 (2H, d, J = 7.3 Hz), 3.08 (1H, d, J = 16.9 Hz), 2.22-2.16 (1H, m), 1.93 (3H, s), 0.96 (6H, dd, J = 6.9 Hz). 1-279 oil 1-293 oil 1-294 92-94 solid 7.45 (1H, t, J = 7.8 Hz), 7.36 (1H, t, J = 7.8 Hz), 7.32 (1H, d, _J = 7.8 Hz), 7.21 (1H, d, J = 7.8 Hz), 3.81 (1H, m), 3.69 (1H, d, J = 18.8 Hz), 3.60 (1H, d, J = 18.8 Hz), 2.16 (3H, s), 1.92-1.82 (1H, m), 1.72-1.60 (1H, m), 1.28-1.21 (3H, m), 0.98 (3H, dt, J = 9.6, 7.3 Hz) 1-295 oil 1-297 oil 7.46-7.42 (1H, m), 7.37-7.33 (2H, m), 7.20 (1H, d, J = 8.2 Hz), 3.63 (2H, dd, J = 41.2, 16.9 Hz), 3.41 (2H, d, J = 7.3 Hz), 2.28-2.17 (1H, m), 2.15 (3H, s), 2.14 (3H, s), 0.99 (6H, dd, J = 6.6, 3.4 Hz). 1-298 oil 1-299 oil 1-300 oil 1-304 oil 7.46-7.40 (1H, m), 7.37-7.32 (1H, m), 7.31-7.28 (1H, m), 7.22-7.20 (1H, m), 4.20- 4.09 (1H, m), 3.70-3.54 (3H, m), 3.39-3.36 (1H, m), 3.32 (3H, d, J = 19.7 Hz), 2.18- 2.16 (6H, m), 1.34-1.32 (3H, m). 1-305 gum 1-306 oil 1-307 oil 1-308 oil 1-310 gum 1-315 1-316 oil 1-318 oil 1-319 122-124 solid 7.39 (1H, ddd, J = 7.2, 7.2, 0.8 Hz), 7.34-7.25 (2H, m), 7.18 (1H, d, J = 7.2 Hz), 4.18- 4.07 (1H, m), 3.65-3.50 (3H, m), 3.39-3.33 (1H, m), 3.32 (1.5H, s), 3.27 (1.5H, s), 2.50-2.30 (1H, m), 2.27-2.18 (1H, m), 2.16 (1.5H, s), 2.14 (1.5H, s), 1.31 (3H, d, J = 6.8 Hz), 1.08 (3H, t, J = 6.8 Hz). 1-320 gum 1-321 oil 1-329 1-330 oil 1-331 oil 1-333 oil 1-334 oil 1-335 oil 7.43-7.37 (1H, m), 7.35-7.30 (1H, m), 7.29-7.25 (1H, m), 7.23-7.19 (1H, m), 4.18- 4.07 (1H, m), 3.66-3.53 (3H, m), 3.38-3.34 (1H, m), 3.32 (1.5H, s), 3.27 (1.5H, s), 2.58-2.45 (1H, m), 2.12 (1.5H, s), 2.10 (1.5H, s), 1.33-1.27 (3H, m), 1.22-1.16 (3H, m), 1.08-1.03 (3H, m). 1-336 gum 1-337 oil 1-351 97-98 solid 7.43 (1H, ddd, J = 7.6, 7.6, 1.2 Hz), 7.34 (1H, ddd, J = 7.6, 7.6, 1.6 Hz), 7.21 (1H, d, J = 7.6 Hz), 7.17 (1H, d, J = 7.6 Hz), 3.64 (1H, d, J = 17.6 Hz), 3.55 (1H, d, J = 17.6 Hz), 2.31-2.24 (1H, m), 2.23 (3H, s), 2.22-2.02 (2H, m), 1.45 (9H, s), 0.91 (3H, d, J = 6.4 Hz), 0.87 (3H, d, J = 6.4 Hz). 1-352 95-97 solid 7.44 (1H, t, J = 7.6 Hz), 7.34 (1H, t, J = 7.6 Hz), 7.28 (1H, dd, J = 8.2, 5.0 Hz), 7.16 (1H, d, J = 8.2 Hz), 3.83-3.74 (1H, m), 3.65 (1H, d, J = 16.9 Hz), 3.57 (1H, d, J = 16.9 Hz), 2.28-2.02 (2H, m), 2.13 (3H, s), 1.92-1.79 (1H, m), 1.70-1.58 (2H, m), 1.29-0.85 (12H, m) 1-353 oil 1-354 oil 7.47-7.43 (1H, m), 7.37-7.32 (2H, m), 7.18 (1H, d, J=7.8 Hz), 3.62 (2H, q, J=16.5 Hz), 3.41 (2H, d, J=7.3 Hz), 2.25-2.04 (4H, m), 2.13 (3H, s), 0.99 (6H, dd, J=6.9, 2.7 Hz), 0.90 (6H, dd, J=13.7, 6.4 Hz). 1-355 oil 1-356 oil 1-357 80-82 solid 7.45-7.37 (1H, m), 7.35-7.25 (2H, m), 7.17 (1H, d, J = 8.0 Hz), 4.18-4.07 (1H, m), 3.67-3.51 (3H, m), 3.40-3.27 (4H, m), 2.34-2.24 (1H, m), 2.21-2.01 (5H, m), 1.32 (3H, d, J = 10.0 Hz), 0.93-0.90 (3H, m), 0.89-0.86 (3H, m). 1-358 gum 1-359 oil 1-403 oil 1-404 oil 7.44 (1H, t, J = 7.3 Hz), 7.39-7.33- (2H, m), around7.24 (1H, m), 3.78 (1H, d, J = 16.9 Hz), 3.78 (1H, m), 3.64 (1H, d, J = 16.9 Hz), 2.15 (3H, s), 1.90-1.78 (1H, m), 1.69-1.58 (2H, m), 1.47-1.36 (1H, m), around1.24 (1H, m), 1.21 (3H, dd, J = 6.9, 1.4 Hz), 1.11-1.03 (1H, m), 0.95 (3H, dt, J = 7.3, 1.8 Hz) 1-405 oil 1-407 oil 1-408 oil 1-412 oil 1-413 gum 1-414 oil 1-416 oil 1-431 gum 1-432 oil 7.46 (1H, t, J = 7.6 Hz), 7.36-7.29 (2H, m), 7.21 (1H, d, J = 7.6 Hz), 3.79 (1H, m), 3.58 (2H, s), 2.27-2.16 (1H, m), 2.12 (3H, s), 1.95-1.57 (8H, m), 1.46-1.37 (1H, m), 1.25 (3H, dd, J = 8.0, 6.6 Hz), around1.18 (2H, m), 0.97 (3H, dt, J = 7.3, 6.4 Hz), around0.97 (1H, m) 1-434 gum 1-444 gum 7.48 (1H, t, J = 7.8 Hz), 7.36 (1H, t, J = 7.8 Hz), 7.31 (1H, d, J = 7.8 Hz), 7.22 (1H, d, J = 7.8 Hz), 4.12 (1H, dd, J = 16.9, 3.0 Hz), 3.81 (1H, m), 3.69 (1H, d, J = 17.9 Hz), 3.57 (1H, d, J = 17.9 Hz), 3.40 (2H, s), 2.23 (3H, s), 1.92-1.81 (1H, m), 1.70-1.59 (1H, m), 1.24 (3H, dd, J = 18.5, 6.6 Hz), 0.98 (3H, dt, J = 11.0, 7.3 hz) 1-472 gum 1-473 gum 1-474 oil 7.59 (2H, d, J = 7.3 Hz), 7.45 (1H, t, J = 7.8 Hz), 7.38 (1H, t, J = 7.8 Hz), 7.38 (1H, t, J = 7.6 Hz), around7.28 (3H, m), 7.19 (1H, d, J = 7.9 Hz), 7.12 (1H, t, J = 7.6 Hz), 7.02 (1H, d, J = 7.8 Hz), 3.92-3.79 (3H, m), 2.12 (3H, s), 1.90-1.80 (1H, m), 1.67-1.64 (1H, m), around1.22 (3H, m), 0.96 (3H, dt, J = 16.9, 7.3 Hz) 1-479 gum 7.46-7.38 (1H, m), 7.35-7.25 (3H, m), 7.24-7.15 (2H, m), 7.14-7.00 (3H, m), 4.19- 4.08 (1H, m), 3.87-3.77 (1H, m), 3.74-3.51 (2H, m), 3.40-3.26 (4H, m), 2.18 (3H, d, J = 7.2 Hz), 1.33 (3H, d, J = 8.0 Hz). 1-484 amorphous 1-494 oil 1-503 gum 1-504 gum 7.44 (1H, t, J = 7.6 Hz), 7.32-7.21 (5H, m), 7.04 (2H, m), 3.82-3.54 (5H, m), 2.16 (3H, s), 1.89-1.81 (1H, m), 1.70-1.63 (1H, m), 1.22 (3H, d, J = 6.9 Hz), 0.97 (3H, dt, J = 9.2, 7.3 Hz) 1-506 gum 1-522 gum 7.50 (1H, d, J = 7.8 Hz), around7.24 (1H, m), 7.21 (1H, t, J = 7.8 Hz), 7.15 (1H, d, J = 7.8 Hz), 4.01-3.94 (1H, m), 3.84-3.74 (2H, m), 3.57 (2H, s), 2.32 (3H, s), 1.91- 1.75 (3H, m), 1.68-1.59 (2H, m), 1.20 (3H, d, J = 6.4 Hz), 0.90 (3H, t, J = 7.3 Hz) 1-528 gum 8.45 (1H, t, J = 5.7 Hz), 7.89 (1H, d, J = 7.8 Hz), around7.24 (4H, m), 7.06 (1H, t, J = 6.9 Hz), 7.01 (1H, t, J = 6.9 Hz), 7.01 (1H, t, J = 6.9 Hz), 4.30 (1H, dd, J = 17.4, 6.0 Hz), 3.88 (1H, d, J = 17.4 Hz), 3.78 (1H, m)2.12 (3H, s), 1.87 (1H, m), 1.66 (1H, m), 1.23 (3H, dd, J = 15.3, 6.6 Hz), 0.97 (3H, dt, J = 13.6, 5.4 Hz) 1-575 gum 1-576 oil 7.41-7.38 (1H, m), 7.33-7.28 (1H, m), 7.26-7.24 (1H, m), 7.19-7.14 (1H, m), 3.87 (3H, s), 3.57 (2H, s), 2.14 (3H, s), 1.44 (9H, s). 1-577 75-80 solid 7.43-7.39 (1H, m), 7.33-7.28 (2H, m), 7.18 (1H, d, J = 7.8 Hz), 3.87 (3H, d, J = 4.1 Hz), 3.79-3.73 (1H, m), 3.63 (2H, d, J = 1.8 Hz), 2.04 (3H, s), 1.90-1.81 (1H, m), 1.69-1.59 (1H, m), 1.22 (3H, d, J = 6.4 Hz), 0.96 (3H, td, J = 7.4, 2.0 Hz). 1-580 gum 1-583 oil 1-587 98-100 solid 7.41-7.36 (1H, m), 7.31-7.26 (2H, m), 7.20-7.16 (1H, m), 4.14-4.05 (1H, m), 3.88 (3H, d, J = 3.2 Hz), 3.62-3.56 (3H, m), 3.40-3.34 (1H, m), 3.30 (3H, d, J = 5.0 Hz), 2.06 (3H, d, J = 7.8 Hz), 1.31 (3H, dd, J = 7.8, 6.9 Hz). 1-592 oil 1-594 oil 1-597 gum 1-598 oil 1-604 98-100 solid 7.41-7.37 (1H, m), 7.32-7.27 (2H, m), 7.26-7.24 (1H, m), 7.18 (1H, d, J = 7.6 Hz), 4.40-4.28 (2H, m), 3.63 (2H, s), 2.13 (3H, s), 1.44 (9H, s), 1.30 (3H, t, J = 7.6 Hz). 1-605 73-75 solid 7.42-7.38 (1H, m), 7.33-7.28 (2H, m), 7.18 (1H, d, J = 7.3 Hz), 4.36-4.27 (2H, m), 3.78-3.63 (1H, m), 3.63 (2H, s), 2.03 (3H, d, J = 3.7 Hz), 1.90-1.82 (1H, m), 1.68- 1.59 (1H, m), 1.35-1.26 (3H, m), 1.23-1.16 (3H, m), 0.96 (3H, t, J = 7.3 Hz). 1-608 88 solid 1-609 oil 1-611 oil 1-615 84-88 solid 7.39-7.35 (1H, m), 7.31-7.26 (2H, m), 7.18-7.16 (1H, m), 4.37-4.30 (2H, m), 4.14- 4.07 (1H, m), 3.63-3.57 (3H, m), 3.41-3.35 (1H, m), 3.30 (3H, d, J = 5.0 Hz), 2.03 (3H, d, J = 6.4 Hz), 1.32-1.24 (6H, m). 1-620 oil 1-622 oil 1-623 oil 1-626 oil 7.38-7.27 (5H, m), 7.26-7.22 (1H, m), 7.21-7.08 (2H, m), 6.93-6.88 (0.5H, m), 6.55-6.50 (0.5H, m), 4.94 (1H, quint, J = 7.6 Hz), 4.35-4.23 (2H, m), 3.52 (2H, d, J = 5.6 Hz), 1.99 (1, 5H, s), 1.98 (1, 5H, s), 1.78 (1, 5H, d, J = 7.6 Hz), 1.75 (1, 5H, d, J = 7.6 Hz), 1.26 (3H, t, J = 6.8 Hz). 1-631 104-106 solid 1-632 84-86 solid 1-634 oil 1-641 144-146 solid 1-642 108-110 solid 7.41-7.37 (1H, m), 7.32-7.27 (2H, m), 7.17 (1H, d, J = 7.3 Hz), 5.13-5.06 (1H, m), 3.78-3.73 (1H, m), 3.63 (2H, s), 2.01 (3H, d, J = 3.7 Hz), 1.90-1.82 (1H, m), 1.68- 1.60 (1H, m), 1.34-1.27 (6H, m), 1.22 (3H, d, J = 6.4 Hz), 0.96 (3H, t, J = 7.3 Hz). 1-647 oil 7.39-7.35 (1H, m), 7.30-7.26 (2H, m), 7.18-7.14 (1H, m), 5.13-5.06 (1H, m), 4.13- 4.04 (1H, m), 3.64-3.57 (3H, m), 3.39-3.33 (1H, m), 3.30 (3H, d, J = 4.6 Hz), 2.03 (3H, d, J = 6.4 Hz), 1.34-1.28 (9H, m). 1-652 oil 1-653 oil 1-666 oil 1-667 amorphous 1-668 gum 1-669 78-80 solid 7.42-7.38 (1H, m), 7.34-7.28 (2H, m), 7.18 (1H, d, J = 7.8 Hz), 4.14-4.08 (1H, m), 4.02-3.95 (1H, m), 3.78-3.72 (1H, m), 3.64 (2H, s), 2.03 (3H, d, J = 4.1 Hz), 1.97- 1.82 (2H, m), 1.67-1.52 (1H, m), 1.24-1.20 (3H, m), 0.97-0.93 (3H, m), 0.86-0.82 (6H, m). 1-671 gum 1-674 amorphous 1-675 oil 7.40-7.35 (1H, m), 7.31-7.27 (2H, m), 7.19-7.17 (1H, m), 4.14-4.06 (2H, m), 4.03- 3.97 (1H, m), 3.64-3.56 (3H, m), 3.39-3.34 (1H, m), 3.30 (3H, d, J = 3.7 Hz), 2.04 (3H, d, J = 6.4 Hz), 1.96-1.89 (1H, m), 1.31 (3H, t, J = 6.9 Hz), 0.85 (6H, dd, J = 12.4, 6.4 Hz). 1-676 oil 1-677 amorphous 1-678 oil 1-679 oil 1-706 oil 7.42-7.38 (1H, m), 7.33-7.28 (2H, m), 7.19 (1H, d, J = 7.8 Hz), 5.91-5.80 (1H, m), 5.30-5.24 (2H, m), 4.79-4.67 (2H, m), 3.79-3.72 (1H, m), 3.63 (2H, s), 2.02 (3H, d, J = 4.1 Hz), 1.89-1.81 (1H, m), 1.69-1.59 (1H, m), 1.23-1.20 (3H, m), 0.97-0.93 (3H, m). 1-707 gum 1-708 oil 7.39-7.33 (1H, m), 7.25-7.20 (2H, m), 7.16 (1H, d, J = 8.0 Hz), 5.91-5.78 (1H, m), 5.36-5.21 (2H, m), 4.78-4.65 (2H, m), 4.13-4.03 (1H, m), 3.68-3.53 (3H, m), 3.39- 3.30 (1H, m), 3.28 (1.5H, s), 3.27 (1.5H, s), 2.02 (1.5H, s), 2.00 (1.5H, s), 1.32- 1.27 (3H, m). 1-709 oil 1-710 oil 1-731 oil 7.41-7.37 (1H, m), 7.32-7.28 (2H, m), 7.19 (1H, d, J = 7.3 Hz), 4.43-4.35 (2H, m), 3.81-3.73 (1H, m), 3.65-3.64 (2H, m), 3.60-3.52 (2H, m), 3.27 (2H, d, J = 2.7 Hz), 2.03 (3H, d, J = 2.7 Hz), 1.89-1.80 (1H, m), 1.69-1.59 (1H, m), 1.22 (3H, dd, J = 6.6, 2.5 Hz), 0.96 (3H, t, J = 7.3 Hz). 1-733 oil 1-735 oil 1-736 oil 1-762 gum 1-763 amorphous 7.45-7.18 (9H, m), 3.75 (3H, m), 2.03 (3H, brs), 1.90-1.78 (1H, m), 1.67-1.57 (1H, m), 1.20 (3H, d, J = 6.4 Hz), 0.93 (3H, brdt, J = 7.3 Hz, 1.8 Hz) 1-765 117-121 solid 7.44-7.25 (7H, m), 7.23-7.15 (2H, m), 4.14-4.02 (1H, m), 3.73 (2H, dd, J = 5.6, 5.6 Hz), 3.62-3.52 (1H, m), 3.35-3.31 (1H, m), 3.28 (1.5H, s), 3.27 (1.5H, s), 2.06 (1.5H, s), 2.02 (1.5H, s), 1.30 (1.5H, d, J = 2.8 Hz), 1.28 (1.5H, d, J = 2.8 Hz). 1-766 gum 1-781 oil 1-782 oil (TLC top) 1-783 oil (TLC bottom) 1-785 gum 1-788 oil (TLC top) 1-789 oil (TLC bottom) 1-790 oil 7.39-7.32 (4H, m), 7.30-7.25 (4H, m), 7.15-7.13 (1H, m), 5.33-5.23 (2H, m), 4.14- 4.03 (1H, m), 3.69-3.52 (3H, m), 3.38-3.32 (1H, m), 3.29 (3H, d, J = 5.0 Hz), 2.02 (3H,d, J = 6.4 Hz), 1.31-1.25 (3H, m). 1-791 oil 1-793 oil 1-794 oil 1-796 oil 1-829 oil 7.40 (1H, t, J = 6.9 Hz), 7.35-7.28 (2H, m), 7.20 (1H, d, J = 7.8 Hz), 4.34-4.28 (1H, m), 4.23-4.01 (2H, m), around3.74 (1H, m), 3.65 (2H, s), 2.04 (3H, m), 2.00-1.46 (8H, m), around1.23 (3H, m), 0.96 (3H, t, J = 7.3 Hz) 1-874 oil 1-886 oil 1-888 158-160 solid 7.42 (1H, m), 7.37-7.30 (2H, m), 7.16 (1H .Math. m), 4.06 (1H, m), 3.69 (2H, m), 3.66 (3H, s), 2.03 (3H, s), around1.25 (6H, m) 1-889 oil 1-890 oil 7.45-7.41 (1H, m), 7.37-7.29 (2H, m), 7.22-7.19 (1H, m), 3.84-3.75 (1H, m), 3.71 (2H, d, J = 6.4 Hz), 3.63 (3H, s), 2.12 (3H, s), 1.91-1.82 (1H, m), 1.70-1.62 (1H, m), 1.27-1.22 (3H, m), 1.00-0.95 (3Hm). 1-892 oil 1-893 oil 1-894 oil 1-895 oil 1-899 oil 1-900 oil 1-901 oil 1-903 oil 1-904 oil 1-906 gum 1-907 oil 1-913 oil 1-915 oil 7.49-7.33 (2H, m), 7.32-7.26 (1H, m), 7.22-7.14 (1H, m), 4.19-4.07 (1H, m), 3.89- 3.76 (1H, m), 3.73-3.62 (3H, m), 3.61-3.53 (1H, m), 3.41-3.32 (1H, m), 3.31-3.28 (3H, m), 2.17-2.08 (3H, m), 1.60 (3H, t, J = 7.2 Hz), 1.35-1.29 (3H, m). 1-916 oil 1-917 oil 1-960 135-137 solid 1-962 144-146 solid 1-963 amorphous 7.52-7.45 (1H, m), 7.38-7.34 (2H, m), 7.30-7.26 (1H, m), 3.71 (2H, s), 2.11 (3H, s), 1.46 (9H, s). 1-964 gum 7.52-7.48 (1H, m), 7.36-7.35 (3H, m), 3.79 (1H, m), 3.75 (2H, s), 2.01 (3H, s), 1.89 (1H, m), 1.67 (1H, m), 1.25 (3H, dJ = 6.9 Hz), 0.97 (3H, t, J = 7.3 Hz) 1-965 oil 1-967 120-122 solid 7.52-7.46 (1H, m), 7.39-7.34 (3H, m), 3.73 (2H, s), 3.43 (2H, d, J = 6.9 Hz), 2.31- 2.16 (1H, m), 2.00 (3H, s), 0.99 (6H, d, J = 6.9 Hz). 1-968 113-115 solid 1-969 amorphous 1-970 gum 1-971 oil 1-972 amorphous 1-973 gum 1-974 oil 1-975 gum 1-977 oil 1-978 gum 1-980 oil 1-981 oil 1-982 60-62 solid 1-983 93.8-97.0 solid 1-985 oil 1-986 amorphous 1-988 106-112 solid 1-990 134-136 solid 1-991 96-97 solid 1-992 oil 1-993 oil 1-994 105 solid 1-996 amorphous 1-997 116-118 solid 7.48-7.42 (1H, m), 7.35-7.28 (3H, m), 4.15-4.07 (1H, m), 3.72 (2H, d, J = 2.0 Hz), 3.61 (1H, dd, J = 9.6, 9.6 Hz), 3.37 (1H, dd, J = 9.6, 4.0 Hz), 3.30 (3H, s), 1.99 (3H, s), 1.32 (3H, d, J = 7.2 Hz). 1-1000 oil 1-1002 oil 1-1003 oil 1-1005 oil 1-1006 oil 1-1008 oil 1-1009 105-107 solid 1-1010 oil 1-1011 amorphous 1-1012 90-94 solid 1-1013 gum 1-1014 gum 1-1015 gum 1-1016 112-117 solid 1-1017 119.6 solid 1-1018 108 solid 1-1019 gum 1-1020 118 solid 1-1021 gum 1-1022 oil 1-1023 oil 1-1026 oil 1-1027 gum 1-1028 gum 1-1029 124-126 solid 1-1030 107-112 solid 1-1031 oil 1-1032 172-175 solid 1-1033 108.7-113.4 solid 1-1034 oil 1-1036 gum 1-1037 oil 1-1038 gum 1-1039 gum 1-1040 gum 1-1041 gum 1-1042 gum 1-1043 oil 1-1044 oil 1-1045 gum 1-1046 gum 1-1047 amorphous 1-1048 gum 1-1049 gum 1-1050 gum 1-1051 oil 1-1054 oil 1-1055 oil 1-1057 oil 1-1058 oil 1-1059 88-92 solid 1-1061 oil 1-1063 151-153 solid 1-1064 oil 1-1066 oil 1-1093 oil 1-1127 gum 7.80 (2H, d, J = 8.2 Hz), 7.39 (2H, d, J = 8.2 Hz), around7.39 (1H, m), around7.24 (1H, m), 7.20 (1H, d, J = 7.8 Hz), 7.12 (1H, dJ = 7.8 Hz), 4.02 (1H, m), 3.46 (1H, d, J = 17.4 Hz), 3.12 (1H, d, J = 17.4 Hz), 2.49 (3H, s), 2.05 (3H, s), 1.29-1.26 (6H, m)
(185) Although the Reference Examples below show Synthesis Examples for synthesizing the starting substances of the syntheses above from commercial products, the syntheses are not limited to the examples.
Reference Example 1
Synthesis of 3-methyl-4-[(2-nitrophenyl)methyl]-2H-isoxazol-5-one
(186) Ethyl acetoacetate (834 g, 641 mmol) was added at 0° C. to a dimethoxyethane solution (1000 ml) of 60% sodium hydride (25.6 g, 641 mmol), and the mixture was stirred at room temperature for 30 minutes. To the mixture solution, 2-Nitrobenzyl chloride (100 g, 583 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at 0° C., and the mixture solution was stirred at 80° C. for three hours. The reaction mixture was poured into an aqueous dilute hydrochloric acid solution, followed by extraction with ethyl acetate. The extraction liquid was washed with saturated brine, dried over anhydrous sodium sulfate and then concentrated under reduced pressure, and ethyl 2-[(2-nitrophenyl)methyl]-3-oxo-butanoate (amount of 155 g, yield of 100%) as a yellow oil was thus obtained. Hydroxylamine chloride (60.7 g, 873 mmol) was added to a methanol solution (500 ml) of the obtained oil, and the mixture was stirred at 80° C. for an hour. Water was poured into the reaction mixture, followed by extraction with ethyl acetate. The extraction liquid was washed with saturated brine, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was washed with a mixed solvent (ethyl acetate/n-hexane=1/2), and the title compound (amount of 100 g, yield of 73%) as a white solid was thus obtained.
(187) Melting point: 148 to 150° C.
(188) .sup.1HNMR spectrum (DMSO-d6) σ: 12.1 (1H, br.s), 7.89 (1H, d, J=7.6 Hz), 7.60 (1H, t, J=7.6 Hz), 7.44 (1H, t, J=7.6 Hz), 7.36 (1H, d, J=7.6 Hz), 2.00 (3H, s).
Reference Example 2
Synthesis of 2-isobutyl-3-methyl-4-[(2-nitrophenyl)methyl]isoxazol-5-one
(189) Potassium carbonate (5.50 g, 40.0 mmol) and 1-iodo-2-methylpropane (5.80 g, 32.0 mmol) were added to a N,N-dimethylformamide solution (15 ml) of 3-methyl-4-[(2-nitrophenyl)methyl]-2H-isoxazol-5-one (6.20 g, 26.0 mmol), and the mixture was stirred at 80° C. for five hours. Water was poured into the reaction mixture, followed by extraction with ethyl acetate. The extraction liquid was washed with saturated brine, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/5), and the title compound (amount of 3.50 g, yield of 46%) as a yellow gum was thus obtained. .sup.1HNMR spectrum (CDCl.sub.3) σ: 7.89 (1H, d, J=7.8 Hz), 7.55-7.51 (2H, m), 7.38-7.34 (1H, m), 3.89 (2H, s), 3.37 (2H, d, J=6.4 Hz), 2.22-2.14 (1H, m), 2.13 (3H, s), 0.96 (6H, d, J=6.4 Hz).
Reference Example 3
Synthesis of 3-methyl-4-[(2-nitrophenyl)methyl]-2-sec-butyl-isoxazol-5-one
(190) The same reaction and treatment as those in Reference Example 2 were conducted using 2-iodobutane instead of 1-iodo-2-methylpropane, and the title compound (yield of 47%) as a yellow gum was thus obtained. .sup.1HNMR spectrum (CDCl.sub.3) σ: 7.89 (1H, d, J=7.8 Hz), 7.54-7.51 (2H, m), 7.38-7.34 (1H, m), 3.90 (2H, d, J=2.3 Hz), 3.88-3.72 (1H, m), 2.13 (3H, s), 1.86-1.79 (1H, m), 1.65-1.58 (1H, m), 1.19 (3H, d, J=7.0 Hz), 0.94 (3H, t, J=7.0 Hz).
Reference Example 4
Synthesis of 2-(2-methoxy-1-methyl-ethyl)-3-methyl-4-[(2-nitrophenyl)methyl]-isoxazol-5-one
(191) The same reaction and treatment as those in Reference Example 2 were conducted using (2-methoxy-1-methyl-ethyl) 4-methylbenzenesulfonate instead of 1-iodo-2-methylpropane, and the title compound (yield of 40%) as a light red solid was thus obtained.
(192) Melting point: 89 to 91° C.
(193) .sup.1HNMR spectrum (CDCl.sub.3) σ: 7.91 (1H, d, J=8.0 Hz), 7.54-7.47 (2H, m), 7.38-7.34 (1H, m), 4.13-4.05 (1H, m), 3.92 (2H, m), 3.56 (1H, t, J=10.0 Hz), 3.36 (1H, dd, J=10.0, 4.0 Hz), 3.27 (3H, s), 2.14 (3H, s), 1.28 (3H, d, J=6.8 Hz).
Reference Example 5
Synthesis of 4-[(2-aminophenyl)methyl]-2-isobutyl-3-methylisoxazol-5-one
(194) Reduced iron (3.00 g), ammonium chloride (1.81 g, 33.9 mmol) and water (10 ml) were added to an ethanol solution (30 ml) of 2-isobutyl-3-methyl-4-[(2-nitrophenyl)methyl]isoxazol-5-one (1.97 g, 6.79 mmol), and the mixture was stirred at 90° C. for an hour. The reaction mixture was filtered through Celite, and an aqueous saturated sodium hydrogen carbonate solution was poured, followed by extraction with ethyl acetate. The extraction liquid was washed with saturated brine, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/3), and the title compound (amount of 1.73 g, yield of 98%) as a yellow oil was thus obtained.
(195) .sup.1HNMR spectrum (CDCl.sub.3) σ: 7.05-6.98 (2H, m), 6.67-6.63 (2H, m), 4.32 (2H, br.s), 3.43 (2H, s), 3.31 (2H, d, J=7.0 Hz), 2.22-2.12 (1H, m), 2.13 (3H, s), 0.94 (6H, d, J=7.0 Hz).
Reference Example 6
Synthesis of 4-[(2-aminophenyl)methyl]-3-methyl-2-sec-butylisoxazol-5-one
(196) The same reaction and treatment as those in Reference Example 5 were conducted using 3-methyl-4-[(2-nitrophenyl)methyl]-2-sec-butyl-isoxazol-5-one instead of 2-isobutyl-3-methyl-4-[(2-nitrophenyl)methyl]isoxazol-5-one, and the title compound (yield of 97%) as a yellow oil was thus obtained.
(197) .sup.1HNMR spectrum (CDCl.sub.3) σ: 7.05-6.99 (2H, m), 6.67-6.63 (2H, m), 4.28 (2H, br.s), 3.74-3.67 (1H, m), 3.40 (2H, s), 2.12 (3H, s), 1.86-1.75 (1H, m), 1.65-1.57 (1H, m), 1.17 (3H, d, J=7.0 Hz), 0.92 (3H, d, J=7.0 Hz).
Reference Example 7
Synthesis of 4-[(2-aminophenyl)methyl]-2-(2-methoxy-1-methyl-ethyl)-3-methyl-isoxazolin-5-one
(198) The same reaction and treatment as those in Reference Example 5 were conducted using 2-(2-methoxy-1-methyl-ethyl)-3-methyl-4-[(2-nitrophenyl)methyl]-isoxazol-5-one instead of 2-isobutyl-3-methyl-4-[(2-nitrophenyl)methyl]isoxazol-5-one, and the title compound (yield of 99%) as a yellow oil was thus obtained.
(199) .sup.1HNMR spectrum (CDCl.sub.3) σ: 7.03-6.99 (2H, m), 6.67-6.62 (2H, m), 4.22 (2H, br.s), 4.08-4.00 (1H, m), 3.48 (1H, t, J=10.0 Hz), 3.43 (2H, s), 3.35 (1H, dd, J=10.0, 4.0 Hz), 2.12 (3H, s), 3.18 (3H, s), 2.15 (3H, s), 1.25 (3H, d, J=6.8 Hz).
Reference Example 8
Synthesis of [2-ethoxy-1-[(2-nitrophenyl)methyl]2-oxo-ethyl]triphenyl-phosphonium bromide
(200) Ethyl (triphenylphosphoranylidene)acetate (25.0 g, 71.8 mmol) was added at room temperature to a chloroform (500 ml) solution of 2-nitrobenzyl bromide (15.5 g, 71.8 mol), and the mixture was heated under reflux for five hours. The reaction mixture was concentrated under reduced pressure, and the obtained concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=9/1). The title compound (amount of 29.0 g, yield of 72%) as a brown gum was thus obtained.
(201) .sup.1HNMR spectrum (CDCl.sub.3) σ: 8.00-7.38 (19H, m), 3.80 (2H, q, J=7.2 Hz), 3.69-3.55 (3H, m), 0.51 (3H, t, J=7.2 Hz).
Reference Example 9
Synthesis of ethyl 2-[(2-nitrophenyl)methyl]buta-2,3-dienoate
(202) Diisopropylethylamine (2.98 g, 23.0 mmol) was added at room temperature to a chloroform (80 ml) solution of [2-ethoxy-1-[(2-nitrophenyl)methyl]2-oxo-ethyl]triphenyl-phosphonium bromide (13.0 g, 23.0 mmol), and the mixture was stirred at the same temperature for 30 minutes. Then, acetyl chloride (1.81 g, 23.0 mmol) was dropped using a dropping funnel, and the mixture was stirred at the same temperature for an hour. The reaction mixture was concentrated under reduced pressure, and the obtained concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1). The title compound (amount of 5.69 g, yield of 100%) as a light-yellow oil was thus obtained.
(203) .sup.1HNMR spectrum (CDCl.sub.3) σ: 7.92-7.90 (1H, m), 7.51 (1H, m), 7.39-7.34 (2H, m), 5.02 (2H, t, J=3.2 Hz), 4.18 (2H, q, J=7.0 Hz), 3.92 (2H, t, J=3.2 Hz), 1.25 (3H, t, J=7.0 Hz).
Reference Example 10
Synthesis of 2-tert-butyl-3-methyl-[(2-nitrophenyl)methyl]isoxazol-5-one
(204) N-(Tert-butyl)hydroxylamine hydrochloride (1.68 g, 13.4 mmol) and triethylamine (1.35 g, 13.4 mmol) were added to a toluene (15 ml) solution of ethyl 2-[(2-nitrophenyl)methyl]buta-2,3-dienoate (3.00 g, 12.1 mmol), and the mixture was stirred at 100° C. for 10 minutes. The reaction mixture was concentrated under reduced pressure, and the obtained concentrate was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane=1/1). The title compound (amount of 3.5 g, yield of 100%) as a white solid was thus obtained.
(205) Melting point: 86 to 88° C.
(206) .sup.1HNMR spectrum (CDCl.sub.3) σ: 7.89 (1H, m), 7.53 (1H, m), 7.46 (1H, m), 7.37 (1H, m), 3.91 (2H, s), 2.23 (3H, s), 1.42 (9H, s).
Reference Example 11
Synthesis of 4-[(2-aminophenyl)methyl]-2-tert-butyl-isoxazol-5-one
(207) The same reaction and treatment as those in Reference Example 5 were conducted using 2-tert-butyl-3-methyl-[(2-nitrophenyl)methyl]isoxazol-5-one instead of 2-isobutyl-3-methyl-4-[(2-nitrophenyl)methyl]isoxazol-5-one, and the title compound (yield of 86%) as a light-yellow solid was thus obtained.
(208) Melting point: 98 to 100° C.
(209) .sup.1HNMR spectrum (CDCl.sub.3) σ: 7.01 (2H, m), 6.65 (2H, m), 4.27 (2H, brs), 3.44 (2H, s), 2.25 (3H, s), 1.40 (9H, s)
(210) Next, the methods for formulating the compounds of the invention as herbicides are explained specifically by the Formulation Examples below. In this regard, however, the herbicides are not limited to these Formulation Examples only and can be blended with various other additives at any ratios and formulated.
Formulation Example 1 (Granules
(211) Fifteen parts of water was added to 1 part of the compound of Synthesis Example 1, 1 part of calcium lignin sulfonate, 1 part of lauryl sulfate, 30 parts of bentonite and 67 parts of talc, and the mixture was kneaded with a kneader and then granulated with an extrusion granulator. By drying the granules with a fluidized-bed dryer, granules containing 1% active herbicide ingredient can be obtained. Furthermore, granules can be obtained by the same method except that each compound in Table 1 is used instead of the compound of Synthesis Example 1.
Formulation Example 2 (Flowable Agent
(212) By evenly mixing and pulverizing 20.0 parts of the compound of Synthesis Example 1, 2.0 parts of di-2-ethylhexyl sulfosuccinate sodium salt, 2.0 parts of polyoxyethylene nonylphenyl ether, 5.0 parts of propylene glycol, 0.5 parts of a defoaming agent and 70.5 parts of water in a wet type ball mill, a flowable agent containing 20% active herbicide ingredient can be obtained. Furthermore, a flowable agent can be obtained by the same method except that each compound in Table 1 is used instead of the compound of Synthesis Example 1.
Formulation Example 3 (Dry Flowable Agent
(213) By evenly mixing and finely pulverizing 75 parts of the compound of Synthesis Example 1, 10 parts of naphthalene sulfonate formaldehyde condensate, 5 parts of sodium lauryl sulfate, 5 parts of white carbon and 5 parts of clay, a dry flowable (granulate water dispersible) agent containing 75% active herbicide ingredient can be obtained. Furthermore, a dry flowable (granulate water dispersible) agent can be obtained by the same method except that each compound in Table 1 is used instead of the compound of Synthesis Example 1.
Formulation Example 4 (Water Dispersible Powder
(214) By evenly mixing 15 parts of the compound of Synthesis Example 1, 15 parts of white carbon, 3 parts of calcium lignin sulfonate, 2 parts of polyoxyethylene alkyl ether, 5 parts of diatomaceous earth and 60 parts of clay with a pulverizing mixer, water dispersible powder containing 15% active herbicide ingredient can be obtained. Furthermore, water dispersible powder can be obtained by the same method except that each compound in Table 1 is used instead of the compound of Synthesis Example 1.
Formulation Example 5 (Emulsion
(215) By mixing 20 parts of the compound of Synthesis Example 1, 18 parts of polyoxyethylene styrylphenylether, 2 parts of calcium dodecylbenzene sulfonate and 60 parts of xylene, an emulsion containing 20% active herbicide ingredient can be obtained. Furthermore, an emulsion can be obtained by the same method except that each compound in Table 1 is used instead of the compound of Synthesis Example 1.
Formulation Example 6 (Powder
(216) By evenly mixing and pulverizing 0.5 parts of the compound of Synthesis Example 1, 0.5 parts of white carbon, 0.5 parts of calcium stearate, 50.0 parts of clay and 48.5 parts of talc, powder containing 0.5% active herbicide ingredient can be obtained. Furthermore, powder can be obtained by the same method except that each compound in Table 1 is used instead of the compound of Synthesis Example 1.
Formulation Example 7 (Jumbo Agent
(217) After mixing 15 parts of the compound of Synthesis Example 1, 2 parts of sodium lauryl sulfate, 5 parts of di-2-ethylhexyl sulfosuccinate sodium salt, 5 parts of carboxymethyl cellulose sodium salt, 35 parts of Shirasu-balloon, 10 parts of lactose and 28 parts of expanded perlite, 35 parts of water was added, and the mixture was kneaded with a kneader and then granulated with an extrusion granulator. By drying the granules with a fluidized-bed dryer, a jumbo agent containing 15% active herbicide ingredient can be obtained. Furthermore, a jumbo agent can be obtained by the same method except that each compound in Table 1 is used instead of the compound of Synthesis Example 1.
(218) Next, Test Examples are shown in order to demonstrate the herbicidal effect of the isoxazolin-5-one derivatives of the invention.
Test Example 1
(219) Herbicidal Effect Test by Treatment of Rice Paddy Soil
(220) Wagner pots with an area of 1/10000 ares were filled with a paddy soil, and after adding water, a compound fertilizer (N:P:K=17:17:17) was added, followed by soil puddling. Then, Echinochloa crus-galli, broad leaf weeds (Lindernia pyxidaria and Monochoria vaginalis) and Scirpus juncoides, 30 seeds each, were sown in a depth of 0 to 1 cm. Water was poured immediately after seeding, and the water depth was kept at about 3 cm. The subsequent management was conducted in a glass greenhouse. Immediately after that, emulsions prepared using the compounds in Table 3 below according to Formulation Example 5 were diluted with water, and a certain amount of the water-diluted agent solutions were dropped. The converted amount of the applied active ingredient corresponded to 120 g per 10 ares.
(221) This test was conducted in a double system per one agent solution concentration area, and the herbicidal rates (%) were determined by the following equation (Math. 1) on 14 days after the treatment with the agents.
Herbicidal Rate (%)={1-(Average Dry Weight (g) of Plant of Treated Area)/(Average Dry Weight (g) of Plant of Untreated Area)}×100 [Math. 1]
(222) The results are shown in Table 3 below. In this regard, a herbicidal rate of 80% or more is the maximum effect, and it has been confirmed that the effect is exhibited also in a test at a low concentration. The compound numbers in Table 3 are the same as those in Table 1 and Table 2 above.
(223) TABLE-US-00003 TABLE 3 Concen- tration Echinochloa Monochoria Lindernia Scirpus No. (g/10a) crus-galli vaginalis pyxidaria juncoides 1-28 120 100 100 90 90 1-29 120 100 90 90 90 1-31 120 90 80 90 90 1-32 120 80 90 80 90 1-33 120 80 90 90 100 1-37 120 60 40 80 90 1-41 120 100 100 100 100 1-46 120 60 80 80 90 1-47 120 40 70 70 80 1-63 120 90 100 100 100 1-68 120 80 80 90 90 1-69 120 80 70 70 90 1-78 120 40 50 50 70 1-81 120 90 80 80 90 1-83 120 90 70 100 90 1-84 120 80 70 70 80 1-97 120 100 100 100 100 1-98 120 100 100 100 90 1-100 120 90 100 100 90 1-101 120 90 90 90 90 1-102 120 100 100 100 100 1-103 120 100 100 80 90 1-105 120 90 100 100 90 1-106 120 90 90 90 90 1-109 120 100 100 100 100 1-110 120 100 100 100 100 1-112 120 100 90 90 90 1-113 120 100 100 100 100 1-115 120 100 90 90 90 1-116 120 90 80 90 90 1-120 120 100 100 100 100 1-124 120 100 90 90 90 1-130 120 100 100 100 100 1-133 120 80 100 100 100 1-134 120 80 80 60 80 1-135 120 90 60 90 90 1-136 120 100 70 80 90 1-137 120 90 70 90 90 1-138 120 90 100 100 90 1-142 120 100 90 100 90 1-143 120 90 100 100 90 1-144 120 100 100 90 90 1-145 120 100 100 100 100 1-146 120 100 100 100 100 1-148 120 90 90 100 100 1-149 120 90 90 90 90 1-155 120 90 60 60 80 1-156 120 100 80 100 100 1-162 120 100 100 100 100 1-166 120 100 90 90 90 1-167 120 100 80 90 90 1-180 120 90 90 90 90 1-181 120 90 90 100 90 1-182 120 90 90 100 100 1-183 120 100 100 100 100 1-186 120 90 100 100 90 1-187 120 90 90 90 80 1-189 120 90 90 100 90 1-191 120 90 90 100 90 1-192 120 90 100 100 40 1-193 120 90 100 100 90 1-194 120 80 80 100 80 1-195 120 90 60 70 90 1-198 120 80 100 100 80 1-199 120 100 100 100 90 1-200 120 90 100 100 90 1-201 120 90 80 90 100 1-202 120 100 90 100 80 1-203 120 90 100 100 90 1-204 120 100 90 90 90 1-205 120 100 100 100 90 1-206 120 90 100 100 90 1-207 120 100 100 100 90 1-208 120 90 90 80 90 1-209 120 90 60 60 70 1-211 120 90 90 90 90 1-212 120 90 80 90 90 1-213 120 100 90 90 90 1-214 120 100 90 100 90 1-215 120 100 80 100 90 1-216 120 90 100 100 100 1-218 120 100 90 90 90 1-219 120 100 80 90 90 1-220 120 90 100 100 90 1-221 120 90 60 70 80 1-222 120 100 90 90 90 1-224 120 100 100 100 90 1-229 120 70 100 80 90 1-230 120 100 80 100 90 1-231 120 90 90 80 80 1-232 120 90 90 80 90 1-235 120 90 80 60 80 1-237 120 90 80 90 80 1-238 120 100 80 80 80 1-248 120 60 80 90 50 1-251 120 100 100 90 80 1-263 120 50 50 80 60 1-264 120 90 90 80 100 1-293 120 90 90 90 90 1-294 120 90 90 90 90 1-295 120 90 90 90 90 1-297 120 100 100 100 100 1-298 120 90 90 90 90 1-299 120 100 80 100 90 1-300 120 100 70 80 90 1-304 120 90 90 90 90 1-305 120 90 90 90 90 1-310 120 90 90 90 90 1-315 120 90 90 90 90 1-316 120 90 90 90 90 1-318 120 90 90 90 90 1-319 120 90 90 90 90 1-320 120 90 90 90 90 1-321 120 90 90 90 90 1-329 120 90 90 90 90 1-330 120 90 90 90 90 1-331 120 90 90 90 90 1-333 120 90 90 90 90 1-334 120 100 80 70 90 1-335 120 90 90 90 90 1-336 120 90 90 90 90 1-337 120 90 90 90 90 1-351 120 90 90 90 90 1-352 120 90 90 90 90 1-353 120 90 90 90 90 1-354 120 100 90 90 90 1-355 120 90 90 90 90 1-356 120 100 60 90 90 1-357 120 90 90 90 90 1-358 120 90 90 90 90 1-359 120 90 90 90 90 1-403 120 90 90 90 90 1-404 120 90 90 90 90 1-405 120 90 90 90 90 1-407 120 90 90 90 90 1-408 120 100 80 80 90 1-412 120 90 90 90 90 1-413 120 90 90 90 90 1-416 120 90 90 90 90 1-431 120 90 90 90 90 1-432 120 90 90 90 90 1-434 120 90 90 90 90 1-444 120 90 90 90 90 1-472 120 90 60 90 90 1-473 120 90 90 90 90 1-474 120 90 90 90 90 1-479 120 90 90 90 90 1-484 120 90 90 90 90 1-494 120 90 90 90 90 1-503 120 90 90 90 90 1-504 120 90 90 90 90 1-506 120 90 90 90 90 1-522 120 90 90 90 90 1-528 120 90 90 90 90 1-575 120 90 100 100 100 1-576 120 90 90 90 90 1-577 120 90 90 90 90 1-580 120 90 90 90 90 1-583 120 100 90 90 90 1-587 120 90 90 90 90 1-592 120 90 90 90 90 1-597 120 90 100 90 90 1-598 120 90 90 90 90 1-604 120 90 90 90 90 1-605 120 90 90 90 90 1-608 120 70 80 70 90 1-609 120 90 90 90 90 1-611 120 100 80 90 90 1-615 120 90 90 90 90 1-620 120 90 90 90 90 1-626 120 90 90 90 90 1-631 120 90 90 90 90 1-632 120 90 90 90 90 1-634 120 90 90 90 90 1-641 120 90 90 90 90 1-642 120 90 90 90 90 1-647 120 90 90 90 90 1-652 120 90 90 90 90 1-653 120 90 90 90 90 1-666 120 100 100 80 90 1-667 120 90 90 90 90 1-668 120 90 90 90 90 1-669 120 90 90 90 90 1-671 120 90 90 90 90 1-674 120 100 90 90 90 1-675 120 90 90 90 90 1-676 120 90 90 90 90 1-677 120 90 100 100 90 1-678 120 90 90 90 90 1-679 120 60 50 50 50 1-706 120 90 90 90 90 1-707 120 90 90 90 90 1-708 120 90 90 90 90 1-709 120 90 90 90 90 1-710 120 90 90 90 90 1-731 120 90 90 90 90 1-733 120 100 90 90 100 1-735 120 90 90 90 90 1-736 120 90 90 90 90 1-762 120 90 90 90 90 1-763 120 90 90 90 90 1-765 120 90 90 90 90 1-766 120 90 90 90 90 1-781 120 90 90 90 90 1-783 120 90 90 90 90 (TLC bottom) 1-785 120 90 90 90 90 1-788 120 80 50 60 80 (TLC top) 1-789 120 100 90 90 90 (TLC bottom) 1-790 120 90 90 90 90 1-796 120 90 90 90 90 1-829 120 90 90 90 90 1-874 120 90 90 90 90 1-886 120 90 90 90 90 1-888 120 100 90 100 90 1-889 120 90 90 90 90 1-890 120 90 90 90 90 1-892 120 100 90 90 90 1-893 120 90 90 90 90 1-894 120 100 60 80 100 1-895 120 100 80 90 90 1-899 120 90 90 90 90 1-900 120 90 90 90 90 1-906 120 100 100 100 100 1-907 120 90 90 90 90 1-913 120 90 90 90 90 1-915 120 90 90 90 90 1-916 120 90 90 90 90 1-917 120 90 90 90 90 1-960 120 80 70 70 80 1-962 120 100 100 100 90 1-963 120 90 90 90 90 1-964 120 90 100 100 90 1-965 120 100 100 80 80 1-967 120 90 100 90 90 1-968 120 90 90 90 90 1-969 120 100 80 100 90 1-970 120 100 100 100 100 1-971 120 100 100 100 100 1-972 120 100 100 100 100 1-973 120 100 80 100 100 1-974 120 100 80 90 90 1-975 120 100 80 90 90 1-977 120 100 100 100 90 1-978 120 100 80 90 90 1-980 120 100 80 100 90 1-981 120 80 50 60 70 1-983 120 70 90 90 90 1-985 120 90 70 100 90 1-986 120 90 80 90 90 1-988 120 90 100 100 90 1-990 120 90 80 90 80 1-991 120 90 100 100 90 1-992 120 100 100 90 100 1-993 120 100 100 100 100 1-994 120 90 60 100 90 1-996 120 90 80 80 90 1-997 120 90 80 90 90 1-1000 120 100 90 80 100 1-1002 120 100 100 100 100 1-1003 120 100 90 90 90 1-1005 120 90 70 60 90 1-1006 120 70 60 70 90 1-1011 120 90 90 90 90 1-1012 120 90 100 100 100 1-1013 120 40 90 90 90 1-1014 120 90 100 90 90 1-1015 120 90 90 100 90 1-1016 120 90 60 90 80 1-1017 120 40 90 60 90 1-1018 120 90 90 100 90 1-1019 120 40 60 60 40 1-1020 120 50 40 80 40 1-1021 120 40 40 40 60 1-1022 120 90 100 100 90 1-1023 120 50 50 40 50 1-1026 120 100 100 100 90 1-1027 120 90 100 100 80 1-1028 120 80 90 80 40 1-1029 120 60 60 60 60 1-1030 120 90 100 100 90 1-1031 120 100 100 100 100 1-1032 120 80 90 90 90 1-1033 120 90 100 100 90 1-1034 120 100 100 100 90 1-1036 120 70 60 60 70 1-1037 120 90 60 70 90 1-1038 120 90 90 90 90 1-1039 120 90 80 90 90 1-1040 120 100 90 100 90 1-1041 120 100 90 90 90 1-1042 120 90 80 90 90 1-1043 120 100 100 100 90 1-1044 120 90 40 60 40 1-1045 120 100 80 90 90 1-1046 120 100 80 70 90 1-1047 120 90 80 100 90 1-1048 120 90 60 80 80 1-1049 120 90 80 90 90 1-1050 120 100 100 100 90 1-1051 120 80 80 60 100 1-1054 120 90 100 100 90 1-1055 120 60 100 100 90 1-1057 120 90 80 80 90 1-1058 120 90 70 80 90 1-1059 120 100 90 80 80 1-1064 120 90 90 90 90 1-1127 120 100 100 100 90
Test Example 2
(224) Herbicidal Effect Test by Treatment During Growing Period in Paddy Rice Cultivation
(225) Wagner pots with an area of 1/10000 ares were filled with a paddy soil, and after adding water, a compound fertilizer (N:P:K=17:17:17) was mixed, followed by soil puddling. Then, Echinochloa crus-galli, broad leaf weeds (Lindernia pyxidaria and Monochoria vaginalis) and Scirpus juncoides, 30 seeds each, were sown in a depth of 0 to 1 cm. Water was poured immediately after seeding, and the water depth was kept at about 3 cm. The subsequent management was conducted in a glass greenhouse. Emulsions prepared using the compounds in Table 4 below according to Formulation Example 5 were diluted with water seven days after seeding, and a certain amount of the water-diluted agent solutions were dropped. The converted amount of the applied active ingredient corresponded to 120 g per 10 ares. The test was conducted in a double system per one agent solution concentration area, and the herbicidal rates (%) were determined by the equation (Math. 1) on 14 days after the treatment with the agents. The results are shown in Table 4. In this regard, a herbicidal rate of 80% or more is the maximum effect, and it has been confirmed that the effect is exhibited also in a test at a low concentration. The compound numbers in Table 4 are the same as those in Table 1 and Table 2 above.
(226) TABLE-US-00004 TABLE 4 Concen- tration Echinochloa Monochoria Lindernia Scirpus No. (g/10a) crus-galli vaginalis pyxidaria juncoides 1-28 120 100 100 80 90 1-29 120 100 90 80 90 1-31 120 50 80 60 70 1-32 120 90 90 80 90 1-33 120 60 60 60 80 1-37 120 40 40 40 0 1-41 120 90 80 90 60 1-46 120 40 40 40 60 1-47 120 40 40 40 70 1-63 120 80 90 80 90 1-68 120 40 80 70 80 1-69 120 60 60 40 60 1-78 120 40 60 40 80 1-81 120 80 80 60 90 1-83 120 40 40 40 60 1-84 120 40 40 40 70 1-97 120 90 60 80 90 1-98 120 80 60 60 90 1-100 120 90 100 90 90 1-101 120 90 90 90 90 1-102 120 90 90 60 90 1-103 120 90 80 60 80 1-105 120 90 90 90 90 1-106 120 90 90 90 90 1-109 120 90 90 70 90 1-110 120 100 100 80 80 1-112 120 90 80 80 90 1-113 120 90 80 60 90 1-115 120 90 80 80 90 1-116 120 90 80 60 90 1-120 120 90 80 80 90 1-124 120 90 70 60 80 1-130 120 100 90 90 80 1-133 120 60 80 60 80 1-134 120 80 80 40 80 1-135 120 80 60 40 90 1-136 120 90 70 60 90 1-137 120 90 60 40 80 1-138 120 90 80 80 80 1-142 120 100 100 90 90 1-143 120 90 80 70 90 1-144 120 90 80 50 90 1-145 120 90 80 60 80 1-146 120 100 90 70 90 1-148 120 90 80 60 90 1-149 120 100 90 90 90 1-155 120 100 60 60 80 1-156 120 80 100 100 90 1-162 120 90 80 70 80 1-166 120 100 90 90 90 1-167 120 90 90 90 90 1-180 120 70 90 80 90 1-181 120 50 90 80 90 1-182 120 40 60 60 70 1-183 120 80 100 100 100 1-186 120 50 80 80 80 1-187 120 40 80 70 70 1-189 120 60 80 80 80 1-191 120 90 80 80 90 1-192 120 40 80 80 60 1-193 120 60 80 80 70 1-194 120 40 60 60 60 1-195 120 80 40 40 80 1-198 120 40 90 90 40 1-199 120 90 80 80 80 1-200 120 60 90 90 80 1-201 120 40 70 70 40 1-202 120 40 60 60 40 1-203 120 90 90 90 90 1-204 120 80 80 80 80 1-205 120 50 90 90 80 1-206 120 60 90 80 80 1-207 120 60 70 60 70 1-208 120 90 90 60 80 1-209 120 40 80 60 90 1-211 120 90 80 60 90 1-212 120 90 90 70 90 1-213 120 90 80 70 80 1-214 120 90 80 70 80 1-215 120 90 80 90 90 1-216 120 90 100 100 90 1-218 120 90 80 40 90 1-219 120 90 70 40 90 1-220 120 40 90 100 90 1-221 120 60 40 40 40 1-222 120 90 90 90 90 1-224 120 90 80 60 80 1-229 120 70 90 60 90 1-230 120 90 90 70 90 1-231 120 60 40 40 60 1-232 120 70 40 40 60 1-235 120 50 60 40 60 1-237 120 90 90 60 90 1-238 120 80 80 40 80 1-248 120 40 90 90 90 1-251 120 50 80 50 90 1-263 120 90 60 40 90 1-264 120 80 80 50 90 1-293 120 90 90 90 90 1-294 120 90 90 90 90 1-295 120 90 90 90 90 1-297 120 100 90 100 90 1-298 120 90 90 90 90 1-299 120 100 70 60 90 1-300 120 100 90 70 80 1-304 120 90 90 90 90 1-305 120 90 90 90 90 1-310 120 90 90 90 90 1-315 120 90 90 90 90 1-316 120 90 90 90 90 1-318 120 90 90 90 90 1-319 120 90 90 90 90 1-320 120 90 90 90 90 1-321 120 90 90 90 90 1-329 120 90 90 90 90 1-330 120 90 90 90 90 1-331 120 90 90 90 90 1-333 120 90 90 90 90 1-334 120 100 70 70 90 1-335 120 90 90 90 90 1-336 120 90 90 90 90 1-337 120 90 90 90 90 1-351 120 90 90 90 90 1-352 120 90 90 90 90 1-353 120 90 90 90 90 1-354 120 100 90 70 90 1-355 120 90 90 90 90 1-356 120 100 70 60 90 1-357 120 90 90 90 90 1-358 120 90 90 90 90 1-359 120 90 90 90 90 1-403 120 90 90 90 90 1-404 120 90 90 90 90 1-405 120 90 90 90 90 1-407 120 90 90 90 90 1-408 120 90 60 70 90 1-412 120 90 90 90 90 1-413 120 90 90 90 90 1-416 120 90 90 90 90 1-431 120 90 90 90 90 1-432 120 90 90 90 90 1-434 120 90 90 90 90 1-444 120 90 90 90 90 1-472 120 90 90 80 90 1-473 120 90 90 90 90 1-474 120 90 90 90 90 1-479 120 90 90 90 90 1-484 120 90 90 90 90 1-494 120 90 90 90 90 1-503 120 90 90 90 90 1-504 120 90 90 90 90 1-506 120 90 90 90 90 1-522 120 90 90 90 90 1-528 120 90 90 90 90 1-575 120 90 100 100 100 1-576 120 90 90 90 90 1-577 120 90 90 90 90 1-580 120 90 90 90 90 1-583 120 100 90 80 90 1-587 120 90 90 90 90 1-592 120 90 90 90 90 1-597 120 90 100 80 90 1-598 120 90 90 90 90 1-604 120 90 90 90 90 1-605 120 90 90 90 90 1-608 120 90 80 60 80 1-609 120 90 90 90 90 1-611 120 100 80 70 90 1-615 120 90 90 90 90 1-620 120 90 90 90 90 1-626 120 90 90 90 90 1-631 120 90 90 90 90 1-632 120 90 90 90 90 1-634 120 90 90 90 90 1-641 120 90 90 90 90 1-642 120 90 90 90 90 1-647 120 90 90 90 90 1-652 120 90 90 90 90 1-653 120 90 90 90 90 1-666 120 100 90 90 90 1-667 120 90 90 90 90 1-668 120 90 90 90 90 1-669 120 90 90 90 90 1-671 120 90 90 60 90 1-674 120 100 90 70 90 1-675 120 90 90 90 90 1-676 120 90 90 90 90 1-677 120 70 80 80 90 1-678 120 90 90 90 90 1-679 120 50 40 40 40 1-706 120 90 90 90 90 1-707 120 90 90 90 90 1-708 120 90 90 90 90 1-709 120 90 90 90 90 1-710 120 90 90 90 90 1-731 120 90 90 90 90 1-733 120 100 90 70 90 1-735 120 90 90 90 90 1-736 120 90 90 90 90 1-762 120 90 90 90 90 1-763 120 90 90 90 90 1-765 120 90 90 90 90 1-766 120 90 90 90 90 1-781 120 90 90 90 90 1-783 120 90 90 90 90 (TLC bottom) 1-785 120 90 90 90 90 1-788 120 40 40 40 50 (TLC top) 1-789 120 100 90 60 90 (TLC bottom) 1-790 120 90 90 90 90 1-796 120 90 90 90 90 1-829 120 90 90 90 90 1-874 120 90 90 90 90 1-886 120 90 90 90 90 1-888 120 90 100 80 90 1-889 120 90 90 90 90 1-890 120 90 90 90 90 1-892 120 90 80 80 90 1-893 120 90 90 90 90 1-894 120 90 70 70 80 1-895 120 90 80 70 90 1-899 120 90 90 90 90 1-900 120 90 90 90 90 1-906 120 90 100 100 100 1-907 120 90 90 90 90 1-913 120 90 90 90 90 1-915 120 90 90 90 90 1-916 120 90 90 90 90 1-917 120 90 90 90 90 1-960 120 70 70 70 70 1-962 120 90 80 60 80 1-963 120 90 90 90 90 1-964 120 90 90 90 90 1-965 120 100 80 50 80 1-967 120 90 90 100 80 1-968 120 90 90 90 90 1-969 120 100 90 60 90 1-970 120 100 90 70 90 1-971 120 100 90 80 90 1-972 120 100 100 80 90 1-973 120 100 90 60 90 1-974 120 100 90 90 90 1-975 120 100 80 70 80 1-977 120 100 90 80 90 1-978 120 100 60 50 60 1-980 120 100 80 80 80 1-981 120 90 40 50 40 1-983 120 40 80 80 80 1-985 120 90 60 60 60 1-986 120 90 70 40 90 1-988 120 90 100 100 90 1-990 120 100 80 100 80 1-991 120 90 80 70 90 1-992 120 90 90 50 80 1-993 120 90 60 50 90 1-994 120 90 80 60 80 1-996 120 70 80 70 90 1-997 120 90 90 70 90 1-1000 120 90 70 40 90 1-1002 120 90 80 60 80 1-1003 120 100 70 70 90 1-1005 120 90 90 70 90 1-1006 120 80 80 60 90 1-1011 120 40 90 90 90 1-1012 120 60 80 80 90 1-1014 120 90 80 80 90 1-1015 120 70 90 90 90 1-1016 120 40 80 70 60 1-1017 120 0 80 80 80 1-1018 120 40 80 80 80 1-1019 120 0 40 40 0 1-1020 120 60 40 40 40 1-1022 120 70 100 100 90 1-1023 120 40 40 40 40 1-1026 120 60 90 100 80 1-1027 120 40 40 40 40 1-1028 120 0 40 40 0 1-1030 120 90 90 90 90 1-1031 120 90 100 100 100 1-1032 120 40 40 40 40 1-1033 120 70 80 80 80 1-1034 120 90 80 80 90 1-1036 120 40 60 60 60 1-1037 120 90 50 60 60 1-1038 120 90 80 60 90 1-1039 120 100 80 70 80 1-1040 120 100 60 60 70 1-1041 120 90 70 70 70 1-1042 120 60 60 60 70 1-1043 120 90 100 100 90 1-1044 120 70 40 40 70 1-1045 120 90 90 60 90 1-1046 120 90 90 60 90 1-1047 120 80 80 90 80 1-1048 120 90 60 60 40 1-1049 120 80 70 60 70 1-1050 120 90 90 100 90 1-1051 120 90 80 40 90 1-1054 120 90 100 100 90 1-1055 120 80 60 40 80 1-1057 120 80 80 60 80 1-1058 120 90 90 80 80 1-1059 120 90 70 40 70 1-1064 120 70 80 50 90 1-1127 120 100 100 100 90
Test Example 3
(227) Herbicidal Effect Test by Treatment of Dry Field Farming Soil
(228) Pots with a size of 36 cm.sup.2 were filled with a dry field farming soil (alluvium). The soil of the top layer of 1 cm and seeds of weeds, namely southern crabgrass, Echinochloa crus-galli, Chenopodium album and Amaranthus viridis, 20 seeds each, were evenly mixed, and the top layer was gently pressed. Emulsions prepared using the compounds in Table 5 below according to Formulation Example 5 were diluted with water one day after seeding, and the water-diluted agent solutions were sprayed to the soil surfaces at a ratio of 100 liters per 10 ares. The converted amount of the applied active ingredient corresponded to 120 g per 10 ares. The herbicidal effects were evaluated by the same standard as that in Test Example 1 on 14 days after the treatment with the agents. The results are shown in Table 5. In this regard, a herbicidal rate of 80% or more is the maximum effect, and it has been confirmed that the effect is exhibited also in a test at a low concentration. The compound numbers in Table 5 are the same as those in Table 1 and Table 2 above.
(229) TABLE-US-00005 TABLE 5 Concentration southern Echinochloa Chenopodium Amaranthus No. (g/10a) crabgrass crus-galli album viridis 1-28 120 80 90 100 100 1-29 120 70 70 40 40 1-33 120 70 90 40 0 1-37 120 40 70 40 0 1-41 120 90 90 50 0 1-63 120 90 90 40 40 1-83 120 40 50 40 40 1-97 120 90 90 0 0 1-98 120 90 90 0 0 1-100 120 100 100 100 100 1-101 120 90 90 90 90 1-102 120 90 90 80 80 1-103 120 100 100 100 100 1-105 120 90 60 50 70 1-106 120 90 90 90 90 1-109 120 90 90 60 60 1-110 120 90 90 80 80 1-112 120 90 90 80 60 1-113 120 90 90 100 80 1-115 120 90 90 100 100 1-116 120 90 90 50 80 1-120 120 90 90 50 50 1-124 120 80 100 50 40 1-130 120 70 90 50 40 1-136 120 100 100 60 100 1-137 120 50 70 40 40 1-138 120 90 90 0 0 1-142 120 90 100 90 70 1-143 120 40 50 0 60 1-144 120 80 70 0 0 1-145 120 80 90 40 40 1-146 120 100 100 90 90 1-148 120 100 100 80 80 1-149 120 90 90 40 40 1-156 120 80 80 60 60 1-166 120 90 90 60 60 1-180 120 80 80 30 30 1-183 120 90 90 60 50 1-203 120 90 60 40 40 1-208 120 50 100 40 40 1-211 120 90 90 0 0 1-212 120 90 90 0 0 1-213 120 100 100 100 100 1-214 120 70 80 90 90 1-215 120 50 50 40 40 1-216 120 70 60 0 40 1-218 120 40 80 40 40 1-219 120 80 90 40 90 1-221 120 50 70 40 50 1-222 120 100 100 100 100 1-224 120 100 100 90 100 1-229 120 60 40 40 60 1-230 120 100 100 60 60 1-237 120 50 50 40 80 1-248 120 80 70 60 50 1-251 120 80 100 80 80 1-293 120 90 90 90 90 1-294 120 90 90 90 90 1-295 120 90 90 90 90 1-297 120 90 100 90 90 1-298 120 90 90 90 90 1-299 120 80 90 40 70 1-300 120 100 90 60 80 1-304 120 90 90 90 90 1-305 120 90 90 90 90 1-310 120 90 90 90 90 1-315 120 90 90 90 90 1-316 120 90 90 90 90 1-318 120 90 90 90 90 1-319 120 90 90 90 90 1-320 120 90 90 90 90 1-321 120 90 90 90 90 1-329 120 90 90 90 90 1-330 120 90 90 90 90 1-331 120 90 90 90 90 1-333 120 90 90 90 90 1-334 120 70 90 40 50 1-335 120 90 90 90 90 1-336 120 90 90 90 90 1-337 120 90 90 90 90 1-351 120 90 90 90 90 1-352 120 90 90 90 90 1-353 120 90 90 90 90 1-354 120 80 90 90 90 1-355 120 90 90 90 90 1-356 120 90 90 60 90 1-357 120 90 90 90 90 1-358 120 90 90 90 90 1-359 120 90 90 90 90 1-403 120 90 90 90 90 1-404 120 90 90 90 90 1-405 120 90 90 90 90 1-407 120 90 90 90 90 1-408 120 100 100 60 80 1-412 120 90 90 90 90 1-413 120 90 90 90 90 1-416 120 90 90 90 90 1-431 120 90 90 90 90 1-432 120 90 90 90 90 1-434 120 90 90 90 90 1-444 120 90 90 90 90 1-472 120 70 90 50 0 1-473 120 90 90 90 90 1-474 120 90 90 90 90 1-479 120 90 90 90 90 1-484 120 90 90 90 90 1-494 120 90 90 90 90 1-503 120 90 90 90 90 1-504 120 90 90 90 90 1-506 120 90 90 90 90 1-522 120 90 90 90 90 1-528 120 90 90 90 90 1-575 120 90 90 40 40 1-576 120 90 90 90 90 1-577 120 90 90 90 90 1-580 120 90 90 90 90 1-583 120 90 100 50 60 1-587 120 90 90 90 90 1-592 120 90 90 90 90 1-597 120 90 90 0 0 1-598 120 90 90 90 90 1-604 120 90 90 90 90 1-605 120 90 90 90 90 1-609 120 90 90 90 90 1-611 120 70 70 40 40 1-615 120 90 90 90 90 1-620 120 90 90 90 90 1-626 120 90 90 90 90 1-631 120 90 90 90 90 1-641 120 90 90 90 90 1-642 120 90 90 90 90 1-647 120 90 90 90 90 1-652 120 90 90 90 90 1-653 120 90 90 90 90 1-666 120 100 90 40 0 1-667 120 80 90 90 80 1-668 120 90 90 90 90 1-669 120 90 90 90 90 1-674 120 50 80 40 40 1-675 120 90 90 90 90 1-676 120 90 90 90 90 1-678 120 90 90 90 90 1-706 120 90 90 90 90 1-707 120 90 90 90 90 1-708 120 90 90 90 90 1-709 120 90 90 90 90 1-710 120 90 90 90 90 1-731 120 90 90 90 90 1-733 120 100 100 60 80 1-735 120 90 90 90 90 1-736 120 90 90 90 90 1-762 120 90 90 90 90 1-763 120 90 90 90 90 1-765 120 90 90 90 90 1-766 120 90 90 90 90 1-781 120 90 90 90 90 1-783 120 90 90 90 90 (TLC bottom) 1-785 120 90 90 90 90 1-789 120 60 90 80 70 (TLC bottom) 1-790 120 90 90 90 90 1-796 120 90 90 90 90 1-829 120 90 90 90 90 1-874 120 90 90 90 90 1-886 120 90 90 90 90 1-888 120 70 90 60 40 1-889 120 90 90 90 90 1-890 120 90 90 90 90 1-892 120 90 90 80 90 1-893 120 90 90 90 90 1-894 120 90 90 60 70 1-895 120 100 100 50 80 1-899 120 90 90 90 90 1-900 120 90 90 90 90 1-906 120 90 100 70 50 1-907 120 90 90 90 90 1-913 120 90 90 90 90 1-915 120 90 90 90 90 1-916 120 90 90 90 90 1-917 120 90 90 90 90 1-960 120 80 100 0 0 1-962 120 90 90 70 80 1-963 120 90 90 90 90 1-964 120 90 90 90 90 1-965 120 100 100 100 100 1-967 120 90 50 40 80 1-968 120 90 90 90 90 1-969 120 80 90 40 40 1-970 120 90 90 40 60 1-971 120 80 90 60 80 1-972 120 90 90 100 100 1-973 120 100 100 90 90 1-974 120 90 90 100 100 1-975 120 90 80 90 90 1-977 120 80 80 50 70 1-978 120 90 80 90 90 1-980 120 60 40 40 40 1-985 120 70 70 80 80 1-986 120 80 100 60 60 1-990 120 50 50 50 0 1-992 120 90 90 40 40 1-993 120 80 90 40 40 1-997 120 90 90 50 50 1-1000 120 80 60 40 40 1-1005 120 40 60 40 40 1-1006 120 60 80 60 60 1-1011 120 80 90 40 40 1-1014 120 70 90 40 40 1-1038 120 90 90 0 0 1-1039 120 90 90 0 0 1-1040 120 100 100 80 100 1-1041 120 80 70 50 50 1-1045 120 50 90 40 40 1-1048 120 0 40 40 40 1-1049 120 80 90 50 50 1-1050 120 90 100 90 90 1-1051 120 80 80 60 80 1-1064 120 60 100 80 80 1-1127 120 70 90 60 40
Test Example 4
(230) Herbicidal Effect Test by Treatment of Leave and Stem in Dry Field Farming
(231) Pots with a size of 36 cm.sup.2 were filled with a dry field farming soil (alluvium). The soil of the top layer of 1 cm and seeds of weeds, namely southern crabgrass, Echinochloa crus-galli, Chenopodium album and Amaranthus viridis, 20 seeds each, were evenly mixed, and the top layer was gently pressed. Emulsions prepared using the compounds in Table 6 below according to Formulation Example 5 were diluted with water seven days after seeding, and the water-diluted agent solutions were sprayed to the soil surfaces at a ratio of 100 liters per 10 ares. The converted amount of the applied active ingredient corresponded to 120 g per 10 ares. The herbicidal effects were evaluated by the same standard as that in Test Example 1 on 14 days after the treatment with the agents. The results are shown in Table 6. In this regard, a herbicidal rate of 80% or more is the maximum effect, and it has been confirmed that the effect is exhibited also in a test at a low concentration. The compound numbers in Table 6 are the same as those in Table 1 and Table 2 above.
(232) TABLE-US-00006 TABLE 6 Concentration southern Echinochloa Chenopodium Amaranthus No. (g/10a) crabgrass crus-galli album viridis 1-28 120 50 90 40 80 1-29 120 40 60 0 60 1-32 120 40 0 60 40 1-33 120 40 90 40 0 1-37 120 40 90 80 40 1-41 120 90 90 90 60 1-63 120 60 90 60 40 1-81 120 80 90 0 0 1-97 120 90 90 40 40 1-100 120 90 90 90 30 1-101 120 90 90 40 40 1-102 120 80 90 0 40 1-103 120 90 90 40 90 1-105 120 50 90 40 50 1-106 120 90 90 40 40 1-109 120 80 90 50 70 1-110 120 90 90 50 60 1-112 120 50 90 0 40 1-113 120 60 80 40 60 1-115 120 40 60 40 40 1-116 120 40 80 50 60 1-120 120 80 90 50 60 1-124 120 60 70 40 40 1-130 120 60 60 40 50 1-133 120 40 90 40 0 1-134 120 60 90 40 50 1-136 120 70 70 60 60 1-137 120 0 80 0 80 1-138 120 80 80 0 40 1-142 120 80 90 40 60 1-144 120 90 90 0 50 1-145 120 50 90 40 0 1-146 120 40 80 40 50 1-148 120 80 90 40 40 1-149 120 90 90 40 40 1-162 120 60 90 60 50 1-180 120 50 50 40 0 1-183 120 50 90 50 40 1-191 120 40 90 40 80 1-208 120 0 90 40 40 1-211 120 60 90 50 40 1-212 120 90 90 60 80 1-213 120 90 90 50 40 1-214 120 50 60 50 40 1-215 120 50 40 40 50 1-218 120 40 90 40 60 1-219 120 60 90 0 40 1-222 120 80 70 50 40 1-230 120 80 80 40 40 1-248 120 40 80 0 40 1-293 120 90 90 40 40 1-294 120 90 90 40 40 1-295 120 90 90 40 40 1-297 120 60 80 40 40 1-298 120 90 90 40 40 1-299 120 80 90 90 40 1-300 120 90 90 60 70 1-304 120 90 90 40 40 1-305 120 90 90 40 40 1-310 120 90 90 40 40 1-315 120 90 90 40 40 1-316 120 90 90 40 40 1-318 120 90 90 40 40 1-319 120 90 90 40 40 1-320 120 90 90 40 40 1-321 120 90 90 40 40 1-329 120 90 90 40 40 1-330 120 90 90 40 40 1-331 120 90 90 40 40 1-333 120 90 90 40 40 1-334 120 90 90 60 60 1-335 120 90 90 40 40 1-336 120 90 90 40 40 1-337 120 90 90 40 40 1-351 120 90 90 40 40 1-352 120 90 90 40 40 1-353 120 90 90 40 40 1-354 120 60 80 40 40 1-355 120 90 90 40 40 1-356 120 80 90 60 60 1-357 120 90 90 40 40 1-358 120 90 90 40 40 1-359 120 90 90 40 40 1-403 120 90 90 40 40 1-404 120 90 90 40 40 1-405 120 90 90 40 40 1-407 120 90 90 40 40 1-408 120 90 90 70 40 1-412 120 90 90 40 40 1-413 120 90 90 40 40 1-416 120 90 90 40 40 1-431 120 90 90 40 40 1-432 120 90 90 40 40 1-434 120 90 90 40 40 1-444 120 90 90 40 40 1-473 120 90 90 40 40 1-474 120 90 90 40 40 1-479 120 90 90 40 40 1-484 120 90 90 40 40 1-494 120 90 90 40 40 1-503 120 90 90 40 40 1-504 120 90 90 40 40 1-506 120 90 90 40 40 1-522 120 90 90 40 40 1-528 120 90 90 40 40 1-575 120 90 90 90 30 1-576 120 90 90 40 40 1-577 120 90 90 40 40 1-580 120 90 90 40 40 1-583 120 60 80 50 50 1-587 120 90 90 40 40 1-592 120 90 90 40 40 1-597 120 50 40 40 40 1-598 120 90 90 40 40 1-604 120 90 90 40 40 1-605 120 90 90 40 40 1-609 120 90 90 40 40 1-611 120 70 80 50 60 1-615 120 90 90 40 40 1-620 120 90 90 40 40 1-626 120 90 90 40 40 1-632 120 90 90 40 40 1-642 120 90 90 40 40 1-647 120 90 90 40 40 1-652 120 90 90 40 40 1-653 120 90 90 40 40 1-666 120 70 90 50 40 1-668 120 90 90 40 40 1-669 120 90 90 40 40 1-674 120 80 70 50 60 1-675 120 90 90 40 40 1-676 120 90 90 40 40 1-678 120 90 90 40 40 1-706 120 90 90 40 40 1-707 120 90 90 40 40 1-708 120 90 90 40 40 1-709 120 90 90 40 40 1-710 120 90 90 40 40 1-731 120 90 90 40 40 1-733 120 80 90 60 60 1-735 120 90 90 40 40 1-736 120 90 90 40 40 1-762 120 90 90 40 40 1-763 120 90 90 40 40 1-765 120 90 90 40 40 1-766 120 90 90 40 40 1-781 120 90 90 40 40 1-783 120 90 90 40 40 (TLC bottom) 1-785 120 90 90 40 40 1-789 120 50 50 40 60 (TLC bottom) 1-790 120 90 90 40 40 1-796 120 90 90 40 40 1-829 120 90 90 40 40 1-874 120 90 90 40 40 1-886 120 90 90 40 40 1-888 120 40 80 40 40 1-889 120 90 90 40 40 1-890 120 90 90 40 40 1-892 120 40 50 40 40 1-893 120 90 90 40 40 1-894 120 90 90 60 60 1-895 120 80 80 60 50 1-899 120 90 90 40 40 1-900 120 90 90 40 40 1-906 120 50 90 50 100 1-907 120 90 90 40 40 1-913 120 90 90 40 40 1-915 120 90 90 40 40 1-916 120 90 90 40 40 1-917 120 90 90 40 40 1-962 120 60 90 50 40 1-963 120 90 90 40 40 1-964 120 60 90 0 40 1-965 120 90 90 40 90 1-967 120 0 60 40 40 1-968 120 90 90 40 40 1-970 120 70 90 40 60 1-971 120 90 90 50 40 1-973 120 80 90 0 40 1-974 120 50 90 40 40 1-975 120 0 50 40 50 1-977 120 80 90 80 60 1-978 120 50 60 40 40 1-980 120 40 60 40 40 1-983 120 40 60 0 40 1-985 120 60 90 60 60 1-986 120 90 90 40 60 1-990 120 0 60 40 50 1-992 120 50 90 40 40 1-993 120 40 60 40 40 1-997 120 40 70 0 40 1-1000 120 40 60 0 40 1-1002 120 60 90 70 50 1-1003 120 40 60 0 40 1-1005 120 40 60 40 40 1-1006 120 40 40 40 40 1-1014 120 40 70 50 40 1-1030 120 40 90 40 40 1-1038 120 60 90 40 40 1-1039 120 90 90 40 40 1-1040 120 90 90 40 50 1-1041 120 50 40 40 60 1-1042 120 50 0 40 40 1-1045 120 40 90 0 60 1-1046 120 60 90 0 90 1-1050 120 40 50 50 40 1-1127 120 40 90 40 40
INDUSTRIAL APPLICABILITY
(233) According to the invention, novel isoxazolin-5-one derivatives having an excellent herbicidal activity and herbicides containing the isoxazolin-5-one derivatives can be provided.
(234) Although the invention has been explained in detail referring to specific embodiments, it is obvious to one skilled in the art that various changes and modifications can be made without departing from the spirit and the scope of the invention.
(235) The application is based on a Japanese patent application filed on Jan. 20, 2017 (patent application No. 2017-008553), which is hereby incorporated by reference.