HERBICIDAL COMPOUNDS
20220142164 · 2022-05-12
Assignee
Inventors
Cpc classification
A01N43/80
HUMAN NECESSITIES
C07D413/04
CHEMISTRY; METALLURGY
A01N43/713
HUMAN NECESSITIES
A01N43/82
HUMAN NECESSITIES
C07D401/04
CHEMISTRY; METALLURGY
C07D417/04
CHEMISTRY; METALLURGY
International classification
A01N43/713
HUMAN NECESSITIES
A01N43/80
HUMAN NECESSITIES
A01N43/82
HUMAN NECESSITIES
Abstract
Compounds of the formula (I) wherein the substituents are as defined in claim 1, useful as a pesticides, especially as herbicides.
##STR00001##
Claims
1. Use as a herbicide of a compound of formula (I) or an agronomically acceptable salt or zwitterionic species thereof: ##STR00215## wherein T is 1, 2 or 3; R.sup.1 and R.sup.2 are independently selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, —OR.sup.7, —OR.sup.15a, —N(R.sup.6)S(O).sub.2R.sup.15, —N(R.sup.6)C(O)R.sup.15, —N(R.sup.6)C(O)OR.sup.15, —N(R.sup.6)C(O)NR.sup.16R.sup.17, —N(R.sup.6)CHO, —N(R.sup.7a).sub.2 and S(O).sub.rR.sup.15; provided that when R.sup.1 is selected from the group consisting of —OR.sup.7, —OR.sup.15a, —N(R.sup.6)S(O).sub.2R.sup.15, —N(R.sup.6)C(O)R.sup.15, —N(R.sup.6)C(O)OR.sup.15, —N(R.sup.6)C(O)NR.sup.16R.sup.17, —N(R.sup.6)CHO, —N(R.sup.7a).sub.2 and —S(O).sub.rR.sup.15, then the R.sup.2 on the same carbon atom is selected from the group consisting of hydrogen and C.sub.1-C.sub.6alkyl; or R.sup.1 and R.sup.2 together with the carbon atom to which they are attached form a C.sub.3-C.sub.6cycloalkyl ring or a 3- to 6-membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O; Y is (CR.sup.1aR.sup.2b).sub.m; m is 1, 2 or 3; each R.sup.1a is independently selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl, C.sub.1-C.sub.6haloalkyl, —OH, —OR.sup.7, —OR.sup.15a, —NH.sub.2, —NHR.sup.7, —N(R.sup.7).sub.2, —NHR.sup.15a, —NR.sup.7bR.sup.7c, —N(R.sup.6)S(O).sub.2R.sup.15, —N(R.sup.6)C(O)R.sup.15, —N(R.sup.6)C(O)OR.sup.15, —N(R.sup.6)C(O)NR.sup.16R.sup.17, —N(R.sup.6)CHO, —N(R.sup.7a).sub.2, —S(O).sub.rR.sup.15 and phenyl which is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different, —C.sub.1-C.sub.6alkylNH.sub.2, —C.sub.1-C.sub.6alkylNHR.sup.7, —C.sub.1-C.sub.6alkylN(R.sup.7).sub.2, —C.sub.1-C.sub.6alkylC(O)OR.sup.10, —C.sub.1-C.sub.6alkylOR.sup.10, —C.sub.1-C.sub.6alkylC(O)NR.sup.16R.sup.17, —C.sub.1-C.sub.6alkylSR.sup.10, —C.sub.1-C.sub.6alkylS(O)R.sup.10, —C.sub.1-C.sub.6alkylS(O).sub.2R.sup.10, —C.sub.1-C.sub.6NHC(═NH)NH.sub.2, —C.sub.1-C.sub.3alkylphenyl, wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different, and —C.sub.1-C.sub.3alkylheteroaromatic, wherein said heteroaromatic is a 5- to 10-membered cyclic or bicyclic aromatic ring which comprises 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur, optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; each R.sup.2b is independently selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, —C.sub.1-C.sub.6alkylNH.sub.2, —C.sub.1-C.sub.6alkylNHR.sup.7, —C.sub.1-C.sub.6alkylN(R.sup.7).sub.2, —C.sub.1-C.sub.6alkylC(O)OR.sup.10, —C.sub.1-C.sub.6alkylOR.sup.10, —C.sub.1-C.sub.6alkylC(O)NR.sup.16R.sup.17, —C.sub.1-C.sub.6alkyl SR.sup.10, —C.sub.1-C.sub.6alkylS(O)R.sup.10, —C.sub.1-C.sub.6alkylS(O).sub.2R.sup.10, —C.sub.1-C.sub.6NHC(═NH)NH.sub.2, —C.sub.1-C.sub.3alkylphenyl, wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different, and —C.sub.1-C.sub.3alkylheteroaromatic, wherein said heteroaromatic is a 5- to 10-membered cyclic or bicyclic aromatic ring which comprises 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur, optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; or R.sup.1a and R.sup.2b together with the carbon atom to which they are attached form a C.sub.3-C.sub.6cycloalkyl ring or a 3- to 6-membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O; R.sup.3, R.sup.3a, R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, —S(O).sub.rR.sup.15, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6fluoroalkyl, C.sub.1-C.sub.6fluoroalkoxy, C.sub.1-C.sub.6alkoxy, C.sub.3-C.sub.6cycloalkyl and —N(R.sup.6).sub.2; each R.sup.6 is independently selected from hydrogen and C.sub.1-C.sub.6alkyl; each R.sup.7 is independently selected from the group consisting of C.sub.1-C.sub.6alkyl, —S(O).sub.2R.sup.15, —C(O)R.sup.15, —C(O)OR.sup.15 and —C(O)NR.sup.16R.sup.17; each R.sup.7a is independently selected from the group consisting of —S(O).sub.2R.sup.15, —C(O)R.sup.15, —C(O)OR.sup.15—C(O)NR.sup.16R.sup.17 and —C(O)NR.sup.6R.sup.15a; R.sup.7b) and R.sup.7c are independently selected from the group consisting of C.sub.1-C.sub.6alkyl, —S(O).sub.rR.sup.15, —C(O)R.sup.15, —C(O)OR.sup.15, —C(O)NR.sup.16R.sup.17 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; or R.sup.7b and R.sup.7c together with the nitrogen atom to which they are attached form a 4- to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S; A is a 5-membered heteroaryl attached to the rest of the molecule via a ring carbon atom, which comprises 1, 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S, and wherein the heteroaryl may, where feasible, be optionally substituted by 1, 2 or 3 R.sup.8 substituents, which may be the same or different, and wherein when A is substituted on one or more ring carbon atoms, each R.sup.8 is independently selected from the group consisting of halogen, nitro, cyano, —NH.sub.2, —NHR.sup.7, —N(R.sup.7).sub.2, —OH, —OR.sup.7, —S(O).sub.rR.sup.15, —NR.sup.6S(O).sub.2R.sup.15, —C(O)OR.sup.10, —C(O)R.sup.15, —C(O)NR.sup.16R.sup.17, —S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.3alkoxy C.sub.1-C.sub.3alkyl-, hydroxy C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.3alkoxy C.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.3haloalkoxy C.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6alkenyloxy, C.sub.3-C.sub.6alkynyloxy, N—C.sub.3-C.sub.6cycloalkylamino, —C(R.sup.6)═NOR.sup.6, phenyl, a 3- to 6-membered heterocyclyl, which comprises 1 or 2 heteroatoms individually selected from N and O, and a 5- or 6-membered heteroaryl, which comprises 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein said phenyl, heterocyclyl or heteroaryl are optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; and/or when A is substituted on a ring nitrogen atom, R.sup.8 is selected from the group consisting of —OR.sup.7, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.3-C.sub.6cycloalkyl, C.sub.3-C.sub.6halocycloalkyl, C.sub.3-C.sub.6cycloalkoxy, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6haloalkenyl, C.sub.2-C.sub.6alkynyl, C.sub.1-C.sub.3alkoxy C.sub.1-C.sub.3alkyl-, hydroxy C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.3alkoxy C.sub.1-C.sub.3alkoxy-, C.sub.1-C.sub.6haloalkoxy, C.sub.1-C.sub.3haloalkoxy C.sub.1-C.sub.3alkyl-, C.sub.3-C.sub.6alkenyloxy and C.sub.3-C.sub.6alkynyloxy; and each R.sup.9 is independently selected from the group consisting of OH, halogen, cyano, —N(R.sup.6).sub.2, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.4haloalkyl and C.sub.1-C.sub.4haloalkoxy; X is selected from the group consisting of —C(O)—, —C(O)O—, —C(O)N(R.sup.40)—, —C(O)N(R.sup.42)O—, —C(O)N(R.sup.40)N(R.sup.40)—, —C(O)N(R.sup.40)C(O)—, —C(O)N(R.sup.40)C(O)N(R.sup.40)—, —C(O)N(R.sup.40)C(R.sup.46).sub.2C(O)N(R.sup.40)—, —C(O)N(R.sup.40)C(R.sup.46).sub.2C(O)N(R.sup.40)C(R.sup.46).sub.2C(O)N(R.sup.40)—, —C(═NR.sup.41)—, —C(R.sup.40)═NO—, —C(═NR.sup.41)N(R.sup.40)—, —C(S)—, —C(S)N(R.sup.40)—, —N(R.sup.43)—, —N(R.sup.42)O—, —N(R.sup.43)N(R.sup.43)—, —N(R.sup.40)C(O)—, —N(R.sup.40)C(S)—, —N(R.sup.40)S(O).sub.2—, —N(R.sup.40)C(O)O—, —N(R.sup.40)P(O)(R.sup.44)—, —N(R.sup.40)P(O)(R.sup.44)O—, —N(R.sup.40)C(═NR.sup.41)—, —N(R.sup.40)S(O)(═NR.sup.40)—, —N(R.sup.40)S(O)—, —N(R.sup.40)C(O)S—, —N(R.sup.40)C(O)N(R.sup.40)—, —N(R.sup.40)S(O).sub.2N(R.sup.40)—, —N(R.sup.40)C(S)N(R.sup.40)—, —N(R.sup.40)C(═NR.sup.41)N(R.sup.40)—, —N(R.sup.40)P(O)(R.sup.44)N(R.sup.40)—, —N(R.sup.40)C(O)N(R.sup.40)C(O)—, —N(R.sup.40)N(R.sup.40)C(O)—, —O—, —OC(O)—, —OC(O)O—, —OC(O)N(R.sup.40)—, —ON(R.sup.42)—, —ON═C(R.sup.40)—, —ON(R.sup.42)C(O)—, —OP(O)(R.sup.44)—, —OP(O)(R.sup.44)O—, —OP(O)(R.sup.44)N(R.sup.40)—, —OSi(R.sup.40).sub.2—, —OSi(R.sup.40).sub.2O—, —S—, —S(O)—, —S(O).sub.2—, —S(O).sub.2N(R.sup.40)—, —SC(O)N(R.sup.40)—, —S(O)N(R.sup.40)—, —S(O)(═NR.sup.40)—, —S(═NR.sup.40).sub.2—, —S(O)(═NR.sup.40)N(R.sup.40)—, —S(═NR.sup.40)—, —P(O)(R.sup.44)—, —P(O)(R.sup.44)N(R.sup.40)—, —P(O)(R.sup.44)O—, —C(═CR.sup.45).sub.2—, —CR.sup.45═CR.sup.45-(E and Z isomers), —C≡C—, —Si(R.sup.40).sub.2— and —Si(R.sup.40).sub.2O—; R.sup.40 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.3alkoxy C.sub.1-C.sub.3alkyl; R.sup.41 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6alkylamino, di-C.sub.1-C.sub.6alkylamino, cyano; R.sup.42 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.6 alkylcarbonyl, C.sub.1-C.sub.6alkoxycarbonyl, C.sub.1-C.sub.6alkylsulfonyl; R.sup.43 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.3alkoxy C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.6alkylcarbonyl, C.sub.1-C.sub.6alkoxycarbonyl, and C.sub.1-C.sub.6alkylsulfonyl; R.sup.44 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, OH, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6alkoxy C.sub.1-C.sub.3alkyl, NH.sub.2, and C.sub.1-C.sub.6alkylamino, di-C.sub.1-C.sub.6alkylamino, R.sup.45 is selected from the group consisting of hydrogen, halogen, and C.sub.1-C.sub.6alkyl; R.sup.46 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6alkoxy C.sub.1-C.sub.3alkyl, —C.sub.1-C.sub.6alkylNH.sub.2, —C.sub.1-C.sub.6alkylNHR.sup.7, —C.sub.1-C.sub.6alkylN(R.sup.7).sub.2, —C.sub.1-C.sub.6alkylC(O)OR.sup.10, —C.sub.1-C.sub.6alkylOR.sup.10, —C.sub.1-C.sub.6alkylC(O)NR.sup.16R.sup.17, —C.sub.1-C.sub.6alkyl SR.sup.10, —C.sub.1-C.sub.6alkyl S(O)R.sup.10, —C.sub.1-C.sub.6alkyl S(O).sub.2R.sup.10, —C.sub.1-C.sub.6NHC(═NH)NH.sub.2, —C.sub.1-C.sub.3alkyl C.sub.1-C.sub.3alkoxy, —C.sub.1-C.sub.3alkylphenyl, wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different, and —C.sub.1-C.sub.3alkylheteroaromatic, wherein said heteroaromatic is a 5- to 10-membered cyclic or bicyclic aromatic ring which comprises 1, 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur, optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; Z is selected from the group consisting of —C(O)OR.sup.10, —OH, —CH.sub.2OH, —CHO, —C(O)NHOR.sup.11, —C(O)NHCN, —OC(O)NHOR.sup.11, —OC(O)NHCN, —NR.sup.6C(O)NHOR.sup.11, —NR.sup.6C(O)NHCN, —C(O)NHS(O).sub.2R.sup.12, —OC(O)NHS(O).sub.2R.sup.12, —NR.sup.6C(O)NHS(O).sub.2R.sup.12, —S(O).sub.2OR.sup.10, —OS(O).sub.2OR.sup.10, —NR.sup.6S(O).sub.2OR.sup.10, —NR.sup.6S(O)OR.sup.10, —NHS(O).sub.2R.sup.14, —S(O)OR.sup.10, —OS(O)OR.sup.10, —S(O).sub.2NHCN, —S(O).sub.2NHC(O)R.sup.18, —S(O).sub.2NHS(O).sub.2R.sup.12, —OS(O).sub.2NHCN, —S(O).sub.2NHS(O).sub.2R.sup.12, —OS(O).sub.2NHC(O)R.sup.18, —NR.sup.6S(O).sub.2NHCN, —NR.sup.6S(O).sub.2NHC(O)R.sup.18, —N(OH)C(O)R.sup.15, —ONHC(O)R.sup.15, —NR.sup.6S(O).sub.2NHS(O).sub.2R.sup.12, —P(O)(R.sup.13)(OR.sup.10), —P(O)H(OR.sup.10), —OP(O)(R.sup.13)(OR.sup.10), —NR.sup.6P(O)(R.sup.13)(OR.sup.10) and tetrazole; R.sup.10 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, phenyl and benzyl, and wherein said phenyl or benzyl are optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.11 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.12 is selected from the group consisting of C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, —OH, —N(R.sup.6).sub.2 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.13 is selected from the group consisting of —OH, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy and phenyl; R.sup.14 is C.sub.1-C.sub.6haloalkyl; R.sup.15 is selected from the group consisting of C.sub.1-C.sub.6alkyl and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.15a is phenyl, wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; R.sup.16 and R.sup.17 are independently selected from the group consisting of hydrogen and C.sub.1-C.sub.6alkyl; or R.sup.16 and R.sup.17 together with the nitrogen atom to which they are attached form a 4- to 6-membered heterocyclyl ring which optionally comprises one additional heteroatom individually selected from N, O and S; R.sup.18 is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, —N(R.sup.6).sub.2 and phenyl, and wherein said phenyl is optionally substituted by 1, 2 or 3 R.sup.9 substituents, which may be the same or different; and r is 0, 1 or 2.
2. The compound of formula (I) as defined in claim 1 with the proviso that the compound is not 1-[2-(3-carboxy-1-oxopropoxy)ethyl]-4-[5-(4-methoxyphenyl)-2-oxazolyl]pyridinium.
3. The compound according to claim 2 wherein T is 1.
4. The compound according to claim 2, wherein R.sup.1 and R.sup.2 are independently selected from the group consisting of hydrogen and C.sub.1-C.sub.6alkyl.
5. The compound according to claim 2, wherein m is 1 or 2.
6. The compound according to claim 2, wherein R.sup.3, R.sup.3a, R.sup.4 and R.sup.5 are independently selected from the group consisting of hydrogen and methyl.
7. The compound of formula (I) according to claim 2, wherein A is selected from the group consisting of formula A-I to A-XXXII below ##STR00216## ##STR00217## ##STR00218## ##STR00219## wherein the jagged line defines the point of attachment to a compound of formula (I); R.sup.8a is selected from the group consisting of hydrogen, C.sub.1-C.sub.6alkyl and C.sub.1-C.sub.6haloalkyl; each R.sup.8b, R.sup.8c and R.sup.8d are independently selected from the group consisting of hydrogen, halogen, nitro, cyano, —NH.sub.2, —S(O).sub.rR.sup.15, —C(O)OR.sup.10, —C(O)R.sup.15, —C(O)NR.sup.16R.sup.17, S(O).sub.2NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl and C.sub.1-C.sub.6haloalkyl; and R.sup.10, R.sup.15, R.sup.16, R.sup.17 and r are as defined in claim 1.
8. The compound of formula (I) according to claim 2, wherein A is selected from the group consisting of formula A-Ia to A-VIIIa below ##STR00220##
9. The compound according to claim 2, wherein A is selected from the group consisting of formula A-I to A-III below ##STR00221## wherein the jagged line defines the point of attachment to a compound of formula (I); R.sup.8b is hydrogen, halogen, cyano, —NH.sub.2, —C(O)NR.sup.16R.sup.17, C.sub.1-C.sub.6alkyl and C.sub.1-C.sub.6haloalkyl or C.sub.1-C.sub.6haloalkyl; and R.sup.16 and R.sup.17 are as defined in claim 1.
10. The compound according to claim 2, wherein A is substituted with 1 or 2 R.sup.8 and each R.sup.8 is independently selected from the group consisting of chloro, fluoro, cyano, —NH.sub.2, —NMe.sub.2, —OMe, —S(O).sub.2Me, —C(O)NHMe, —C(O)NMe.sub.2, methyl and trifluoromethyl.
11. The compound according to claim 2, wherein A is substituted with 3 or 4 R.sup.8 and each R.sup.8 is independently selected from the group consisting of C.sub.1-C.sub.6alkyl and C.sub.1-C.sub.6haloalkyl.
12. The compound according to claim 2 wherein X is selected from the group consisting of —C(O)N(R.sup.40)—, —S(O)—, —S(O).sub.2— and —S(O).sub.2N(R.sup.40)— and R.sup.40 is selected from hydrogen and C.sub.1-C.sub.6alkyl.
13. The compound according to claim 2, wherein Z is selected from the group consisting of —C(O)OR.sup.10, —C(O)NHS(O).sub.2R.sup.12, —S(O).sub.2OR.sup.10, and —P(O)(R.sup.13)(OR.sup.10).
14. The compound according to claim 13, wherein Z is —C(O)OH or —S(O).sub.2OH.
15. Use of a compound as defined in claim 1 as a herbicide.
16. An agrochemical composition comprising a herbicidally effective amount of a compound of formula (I) as defined in claim 2.
17. The composition according to claim 16, further comprising at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.
18. A method of controlling unwanted plant growth, comprising applying a compound of formula (I) as defined in claim 2, or a herbicidal composition according to claim 16, to the unwanted plants or to the locus thereof.
Description
EXAMPLES
[0239] The Examples which follow serve to illustrate, but do not limit, the invention.
FORMULATION EXAMPLES
[0240]
TABLE-US-00082 Wettable powders a) b) c) active ingredients 25% 50% 75% sodium lignosulfonate 5% 5% — sodium lauryl sulfate 3% — 5% sodium diisobutylnaphthalenesulfonate — 6% 10% phenol polyethylene glycol ether — 2% — (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27% —
[0241] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
TABLE-US-00083 Emulsifiable concentrate active ingredients 10% octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether 4% (35 mol of ethylene oxide) Cyclohexanone 30% xylene mixture 50%
[0242] Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
TABLE-US-00084 Dusts a) b) c) Active ingredients 5% 6% 4% Talcum 95% — — Kaolin — 94% mineral filler — — 96%
[0243] Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill.
TABLE-US-00085 Extruder granules Active ingredients 15% sodium lignosulfonate 2% carboxymethylcellulose 1% Kaolin 82%
[0244] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
TABLE-US-00086 Coated granules Active ingredients 8% polyethylene glycol (mol. wt. 200) 3% Kaolin 89%
[0245] The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
TABLE-US-00087 Suspension concentrate active ingredients 40% propylene glycol 10% nonylphenol polyethylene glycol ether 6% (15 mol of ethylene oxide) Sodium lignosulfonate 10% carboxymethylcellulose 1% silicone oil (in the form of a 75% 1% emulsion in water) Water 32%
[0246] The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
Slow Release Capsule Suspension
[0247] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.
[0248] The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.
[0249] The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
LIST OF ABBREVIATIONS
[0250] Boc=tert-butyloxycarbonyl [0251] br=broad [0252] CDCl.sub.3=chloroform-d [0253] CD.sub.3OD=methanol-d [0254] ° C.=degrees Celsius [0255] D.sub.2O=water-d [0256] DCM=dichloromethane [0257] d=doublet [0258] dd=double doublet [0259] dt=double triplet [0260] DMSO=dimethylsulfoxide [0261] EtOAc=ethyl acetate [0262] h=hour(s) [0263] HCl=hydrochloric acid [0264] m=multiplet [0265] M=molar [0266] min=minutes [0267] MHz=mega hertz [0268] mL=millilitre [0269] mp=melting point [0270] ppm=parts per million [0271] q=quartet [0272] quin=quintet [0273] rt=room temperature [0274] s=singlet [0275] t=triplet [0276] THF=tetrahydrofuran [0277] LC/MS=Liquid Chromatography Mass Spectrometry
PREPARATION EXAMPLES
Example 1: Preparation of 2-[[2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]acetic Acid Chloride A3
[0278] ##STR00178##
Step 1: Preparation of (NE)-N-(dimethylaminomethylene)pyridine-4-carbothioamide
[0279] ##STR00179##
[0280] A mixture of pyridine-4-carbothioamide (5 g) and 1,1-dimethoxy-N,N-dimethyl-methanamine (4.82 mL) were stirred together at room temperature for one hour. The reaction mixture was concentrated and purified by silica gel chromatography eluting with 0-50% methanol in acetonitrile to give (NE)-N-(dimethylaminomethylene)pyridine-4-carbothioamide as a red gum
[0281] .sup.1H NMR (400 MHz, CD.sub.3OD) 8.81 (s, 1H), 8.58-8.52 (m, 2H), 8.23-8.20 (m, 2H), 3.36-3.32 (m, 3H), 3.30-3.26 (m, 3H)
Step 2: Preparation of 5-(4-pyridyl)-1,2,4-thiadiazole
[0282] ##STR00180##
[0283] To a stirred mixture of (NE)-N-(dimethylaminomethylene)pyridine-4-carbothioamide (3.08 g), pyridine (2.58 mL) and ethanol (80 mL) at room temperature was added a solution of amino hydrogen sulfate (1.89 g) in methanol (32 mL) rapidly. The reaction mixture was stirred at room temperature for one hour then quenched with saturated aqueous sodium bicarbonate and extracted with dichloromethane. The organic phase was concentrated, triturated with hexane then dried to give 5-(4-pyridyl)-1,2,4-thiadiazole.
[0284] .sup.1H NMR (400 MHz, CD.sub.3OD) 8.90 (s, 1H), 8.80-8.74 (m, 2H), 8.06-8.02 (m, 2H)
Step 3: Preparation of Methyl 2-[[2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]acetate Bromide A5
[0285] ##STR00181##
[0286] To a stirred solution of 5-(4-pyridyl)-1,2,4-thiadiazole (0.5 g) in acetonitrile (10 mL) was added methyl 2-[(2-bromoacetyl)amino]acetate (0.917 g) at room temperature. The resulting reaction mixture was heated at 80° C. for 16 hours. The reaction mixture was cooled to room temperature and concentrated. The resulting residue was dissolved in water (20 mL) and washed with dichloromethane (2×50 mL). The aqueous layer was concentrated and purified by reverse phase chromatography eluting with 50% water in acetonitrile to afford methyl 2-[[2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]acetate bromide as an off-white solid.
[0287] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.32 (s, 1H), 9.25-9.15 (m, 3H), 8.82 (d, 2H), 5.63 (s, 2H), 4.02 (d, 2H), 3.66 (s, 3H)
Step 4: Preparation of 2-[[2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]acetic Acid Chloride A3
[0288] A mixture of methyl 2-[[2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]acetate bromide (150 mg) and conc. hydrochloric acid (5 mL) was stirred at room temperature for 16 hours. The reaction mixture was concentrated and purified by reverse phase chromatography eluting with 50% water in acetonitrile to afford 2-[[2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]acetic acid chloride as a dark brown solid.
[0289] .sup.1H NMR (400 MHz, D.sub.2O) 9.00-8.89 (m, 3H), 8.59 (d, 2H), 5.53 (s, 2H), 3.77 (s, 2H)(NH and CO.sub.2H protons missing)
Example 2: Preparation of 2-[[2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]ethanesulfonate A9
[0290] ##STR00182##
Step 1: Preparation of 2,2-dimethylpropyl 2-aminoethanesulfonate
[0291] ##STR00183##
[0292] A mixture of ammonium hydroxide (13 mL) and tetrahydrofuran (20 mL) was cooled to ˜0° C. and a solution of 2,2-dimethylpropyl ethanesulfonate (4 g) in tetrahydrofuran (20 mL) was added drop wise. The mixture was stirred at ˜0° C. for 1 hour and then at room temperature for 16 hours. The mixture was partitioned between water (50 mL) and ethyl acetate (100 mL). The aqueous layer was extracted with further ethyl acetate (2×100 mL). The combined organic layers were dried over sodium sulfate, concentrated and purified by chromatography on silica eluting with a mixture of ethyl acetate in cyclohexane to give 2,2-dimethylpropyl 2-aminoethanesulfonate as a pale-yellow liquid.
[0293] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 3.86 (s, 2H), 3.34-3.38 (m, 2H), 2.91 (t, 2H), 0.93 ppm (s, 9H)
Step 2: Preparation of 2,2-dimethylpropyl 2-[(2-bromoacetyl)amino]ethanesulfonate
[0294] ##STR00184##
[0295] A mixture of 2,2-dimethylpropyl 2-aminoethanesulfonate (1 g) in dichloromethane (10 mL), under nitrogen atmosphere, was cooled to −10° C. and triethylamine (1.02 mL) was added, followed by a solution of 2-bromoacetyl bromide (0.468 mL) in dichloromethane (5 mL). The resulting reaction mixture was stirred at −10° C. for 30 minutes then allowed to warm to room temperature and stirred for 4 hours. Water (50 mL) was added to reaction mixture and this was extracted with dichloromethane (2×75 mL). The combined organic layers were washed with brine (200 mL), dried over sodium sulfate, concentrated and purified by silica gel chromatography eluting with a mixture of ethyl acetate in hexanes to give 2,2-dimethylpropyl 2-[(2-bromoacetyl)amino]ethanesulfonate as a brown liquid.
[0296] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.12 (br s, 1H), 3.92 (s, 2H), 3.88 (s, 2H), 3.84-3.77 (m, 2H), 3.36-3.31 (m, 2H), 1.00 (s, 9H)
Step 3: Preparation of 2,2-dimethylpropyl 2-[[2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]ethanesulfonate Bromide A12
[0297] ##STR00185##
[0298] To a mixture of 5-(4-pyridyl)-1,2,4-thiadiazole (0.2 g) in acetonitrile (5 mL) was added 2,2-dimethylpropyl 2-[(2-bromoacetyl)amino]ethanesulfonate (0.42 g) at room temperature. The resulting reaction mixture was heated at 80° C. for 16 hours. The reaction mixture was cooled, concentrated and the resulting residue was dissolved in water (10 mL) and washed with dichloromethane (2×30 mL). The aqueous layer was concentrated and purified by reverse phase chromatography (50% water in acetonitrile) to give 2,2-dimethylpropyl 2-[[2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]ethanesulfonate bromide as a white solid.
[0299] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.33 (s, 1H), 9.16 (d, 2H), 8.99-8.93 (m, 1H), 8.83 (d, 2H), 5.51 (s, 2H), 3.91 (s, 2H), 3.59-3.49 (m, 4H), 0.94 (s, 9H)
Step 4: Preparation of 2-[[2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]ethanesulfonate A9
[0300] A mixture of 2,2-dimethylpropyl 2-[[2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]ethanesulfonate bromide (0.2 g) and 6M aqueous hydrochloric acid (5 mL) was heated at 70° C. for 4 hours. The reaction mixture was concentrated and purified by reverse phase chromatography to give 2-[[2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]ethanesulfonate as an off-white solid.
[0301] .sup.1H NMR (400 MHz, D.sub.2O) 9.01 (s, 1H), 8.98 (d, 2H), 8.63 (d, 2H), 5.51 (s, 2H), 3.64 (t, 2H), 3.09 (t, 2H) (NH proton missing)
Example 3: Preparation of 3-[[2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]propanoic Acid Chloride A4
[0302] ##STR00186##
Step 1: Preparation of methyl 3-[(2-bromoacetyl)amino]propanoate
[0303] ##STR00187##
[0304] A mixture of methyl 3-aminopropanoate hydrochloride (2 g) in dichloromethane (20 mL) was cooled to ˜0° C. and triethylamine (3.99 mL) followed by 2-bromoacetyl bromide (1.59 g) were added. The resulting reaction mixture was stirred at ˜0° C. for 30 minutes and then at room temperature for 16 hours. Water (50 mL) was added and the mixture extracted with dichloromethane (2×50 mL). The combined organic layers were washed with brine (50 mL), dried over sodium sulfate and concentrated. The obtained residue was purified by silica gel chromatography eluting with a mixture of ethyl acetate in hexanes to give methyl 3-[(2-bromoacetyl)amino]propanoate as an orange sticky liquid.
Step 2: Preparation of methyl 3-[[-2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]propanoate Bromide A2
[0305] ##STR00188##
[0306] To a stirred solution of 5-(4-pyridyl)-1,2,4-thiadiazole (0.5 g) in acetonitrile (10 mL) was added methyl 3-[(2-bromoacetyl)amino]propanoate (0.97 g) at room temperature. The resulting reaction mixture was heated at 80° C. for 16 hours. The reaction mixture was cooled and concentrated. The resulting residue was dissolved in water (20 mL) and washed with dichloromethane (2×50 mL). The aqueous layer was concentrated and purified by reverse phase chromatography eluting with 50% water in acetonitrile to give methyl 3-[[-2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]propanoate bromide as an orange solid.
[0307] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 9.32 (s, 1H), 9.20 (d, 2H), 8.88-8.76 (m, 3H), 5.52 (s, 2H), 3.64 (s, 3H), 3.43-3.36 (m, 2H), 2.59-2.53 (m, 2H)
Step 3: Preparation of 3-[[-2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]propanoic Acid Chloride A4
[0308] A mixture of methyl 3-[[-2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]propanoate bromide (0.15 g) and conc. hydrochloric acid (5 mL) was stirred at room temperature for 16 hours. The reaction mixture was concentrated and purified by reverse phase chromatography eluting with a mixture of water and acetonitrile to give 3-[[-2-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]acetyl]amino]propanoic acid chloride as an off-white solid.
[0309] .sup.1H NMR (400 MHz, D.sub.2O) 9.00-8.90 (m, 3H), 8.59 (d, 2H), 5.46 (s, 2H), 3.43 (t, 2H), 2.42 (t, 2H)(NH and CO.sub.2H protons missing)
Example 4: Preparation of 3-[[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]methylsulfonyl]propanoic acid 2,2,2-trifluoroacetate A18
[0310] ##STR00189##
Step 1: Preparation of methyl 3-(chloromethylsulfonyl)propanoate
[0311] ##STR00190##
[0312] Sodium hydride (60% in mineral oil, 0.36 g) was washed with cyclohexane (x2) then was suspended in dry tetrahydrofuran (5 mL), under nitrogen atmosphere. To this was added a solution of methyl 3-mercaptopropionate (1 mL) in dry tetrahydrofuran (1.3 mL) drop wise over 40 minutes at room temperature. After stirring for 30 minutes this suspension was added drop wise to cooled (˜0° C.) bromochloromethane (2.92 mL) over 40 minutes. The mixture was stirred at ˜0° C. for 18 hours. The mixture was diluted with tert-butyl methyl ether (5 mL) and filtered through celite, washing through with further tert-butyl methyl ether (5 mL). The filtrate was cautiously concentrated to give crude methyl 3-(chloromethylsulfonyl)propanoate, which was used without further purification.
[0313] .sup.1H NMR (400 MHz, CDCl.sub.3) 4.75 (s, 2H), 3.72 (s, 3H), 3.03 (t, 2H), 2.73 (t, 2H)
Step 2: Preparation of methyl 3-[[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]methylsulfanyl]propanoate Chloride
[0314] ##STR00191##
[0315] To a stirred solution of 5-(4-pyridyl)-1,2,4-thiadiazole (0.3 g) in acetonitrile (10 mL) was added methyl 3-(chloromethylsulfonyl)propanoate (0.465 g) at room temperature. The resulting reaction mixture was heated at 80° C. for 16 hours. The reaction mixture was cooled and concentrated. The resulting residue was dissolved in water (20 mL) and washed with dichloromethane (2×20 mL). The aqueous layer was concentrated and purified by reverse phase chromatography to give still crude methyl 3-[[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]methylsulfanyl]propanoate chloride, which was used without further purification.
Step 3: Preparation of 3-[[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]methylsulfanyl]propanoic Acid Chloride A15
[0316] ##STR00192##
[0317] A mixture of methyl 3-[[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]methylsulfanyl]propanoate chloride (0.35 g), methanol (0.5 mL) and concentrated hydrochloric acid (10 mL) was stirred at room temperature for 16 hours. The reaction mixture was purified by preparative reverse phase HPLC to give 3-[[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]methylsulfanyl]propanoic acid chloride as a yellow solid.
[0318] .sup.1H NMR (400 MHz, D.sub.2O) 9.19 (d, 2H), 8.95 (s, 1H), 8.57 (d, 2H), 5.75 (s, 2H), 2.83 (t, 2H), 2.60 (t, 2H) (CO.sub.2H proton missing)
Step 4: Preparation of 3-[[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]methylsulfonyl]propanoic acid 2,2,2-trifluoroacetate A18
[0319] To a mixture of 3-[[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]methylsulfanyl]propanoic acid chloride (0.05 g), trifluoroacetic acid (1 mL) and water (1 mL), cooled to 0° C., was added hydrogen peroxide (30% aqueous, 0.136 g). After 15 minutes the reaction was warmed to room temperature and the mixture was stirred for 16 hours. The mixture was filtered, washing through with water and the filtrate was freeze-dried. The residue was purified by preparative reverse phase HPLC (trifluoroacetic acid was present in the eluent) to give 3-[[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]methylsulfonyl]propanoic acid 2,2,2-trifluoroacetate as a grey solid.
[0320] .sup.1H NMR (400 MHz, D.sub.2O) 9.09 (d, 2H), 8.99 (d, 2H), 8.92 (d, 2H), 7.64 (t, 1H), 6.27 (s, 2H), 3.77 (t, 2H), 2.93 (t, 2H)(CO.sub.2H proton missing)
Example 5: Preparation of ethyl 2-(chloromethylsulfanyl)acetate
[0321] ##STR00193##
[0322] Sodium hydride (60% in mineral oil, 0.72 g) was washed with cyclohexane (x2) then was suspended in dry tetrahydrofuran (10 mL), under nitrogen atmosphere. To this was added a solution of ethyl thioglycolate (2.163 g) in dry tetrahydrofuran (2.6 mL) drop wise over 40 minutes at room temperature. After stirring for 30 minutes this suspension was added drop wise to cooled (˜0° C.) bromochloromethane (5.9 mL) over 40 minutes. The mixture was stirred at ˜0° C. for 18 hours. The mixture was diluted with pentane (5 mL) and filtered through celite, washing through with further pentane (5 mL). The filtrate was cautiously concentrated to give crude ethyl 2-(chloromethylsulfanyl)acetate, which was used without further purification.
[0323] .sup.1H NMR (400 MHz, CDCl.sub.3) 4.84 (s, 2H), 4.22 (q, 2H), 3.47 (s, 2H), 1.30 (t, 3H)
Example 6: Preparation of [3-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]propanoylamino]methanesulfonate A14
[0324] ##STR00194##
Step 1: Preparation of (prop-2-enoylamino)methanesulfonic Acid
[0325] ##STR00195##
[0326] A mixture of acetonitrile (40 mL), aminomethanesulfonic acid (2 g) and triethylamine (12.6 mL) was stirred at room temperature for 1 hour. The reaction was cooled to 0° C. and 3-bromopropionyl chloride (2 mL) was added drop wise. After stirring at 0° C. for 30 minutes the reaction was allowed to warm to room temperature and stirred overnight. The reaction was partitioned between water and ethyl acetate. The aqueous layer was concentrated to give (prop-2-enoylamino)methanesulfonic acid, which was used without further purification.
[0327] .sup.1H NMR (400 MHz, D.sub.2O) 6.43-6.53 (m, 1H), 6.30-6.39 (m, 1H), 5.91-6.01 (m, 1H), 4.48-4.56 (m, 2H)
Step 2: Preparation of [3-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]propanoylamino]methanesulfonate A14
[0328] A suspension of 5-(4-pyridyl)-1,2,4-thiadiazole (0.05 g) and (prop-2-enoylamino)methanesulfonic acid (0.107 g) in water (2 mL) was heated at 100° C. for 16 hours. The reaction mixture was cooled and concentrated. The resulting residue was dissolved in water (10 mL) and washed with dichloromethane (2×20 mL). The aqueous layer was concentrated and purified by reverse phase chromatography to give [3-[4-(1,2,4-thiadiazol-5-yl)pyridin-1-ium-1-yl]propanoylamino]methanesulfonate as an off-white solid.
[0329] .sup.1H NMR (400 MHz, D.sub.2O) 8.99 (br d, 2H), 8.93 (s, 1H), 8.51 (br d, 2H), 4.90 (t, 2H), 4.23 (s, 2H), 3.07 (t, 2H)(NH proton missing)
[0330] Additional compounds in Table A (below) were prepared by analogous procedures, from appropriate starting materials. The skilled person would understand that the compounds of formula (I) may exist as an agronomically acceptable salt, a zwitterion or an agronomically acceptable salt of a zwitterion as described hereinbefore. Where mentioned the specific counterion is not considered to be limiting, and the compound of formula (I) may be formed with any suitable counter ion.
[0331] NMR spectra contained herein were recorded on either a 400 MHz Bruker AVANCE III HD equipped with a Bruker SMART probe unless otherwise stated. Chemical shifts are expressed as ppm downfield from TMS, with an internal reference of either TMS or the residual solvent signals. The following multiplicities are used to describe the peaks: s=singlet, d=doublet, t=triplet, dd=double doublet, dt=double triplet, q=quartet, quin=quintet, m=multiplet. Additionally br. is used to describe a broad signal and app. is used to describe and apparent multiplicity.
TABLE-US-00088 TABLE A Physical Data for Compounds of the Invention Com- pound Number Structure .sup.1H NMR A1
BIOLOGICAL EXAMPLES
Post-Emergence Efficacy
[0332] Seeds of a variety of test species were sown in standard soil in pots. After cultivation for 14 days (post-emergence) under controlled conditions in a glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from the dissolution of the technical active ingredient formula (I) in a small amount of acetone and a special solvent and emulsifier mixture referred to as IF50 (11.12% Emulsogen EL360 TM+44.44% N-methylpyrrolidone+44.44% Dowanol DPM glycol ether), to create a 50 g/I solution which was then diluted to required concentration using 0.25% or 1% Empicol ESC70 (Sodium lauryl ether sulphate)+1% ammonium sulphate as diluent.
[0333] The test plants were then grown in a glasshouse under controlled conditions (at 24/16° C., day/night; 14 hours light; 65% humidity) and watered twice daily. After 13 days the test was evaluated (100=total damage to plant; 0=no damage to plant).
[0334] Test Plants:
Ipomoea hederacea (IPOHE), Euphorbia heterophylla (EPHHL), Chenopodium album (CHEAL), Amaranthus palmeri (AMAPA), Lolium perenne (LOLPE), Digitaria sanguinalis (DIGSA), Eleusine indica (ELEIN), Echinochloa crus-galli (ECHCG), Setaria faberi (SETFA)
TABLE-US-00089 Compound Application Number Rate g/Ha AMAPA CHEAL EPHHL IPOHE ELEIN LOLPE DIGSA SETFA ECHCG A1 500 0 10 10 10 10 10 0 0 0 A2 500 80 90 40 50 30 10 40 50 20 A3 500 90 90 100 100 100 70 100 100 100 A4 500 90 90 90 90 100 90 100 70 70 A5 500 90 90 80 80 100 30 100 60 90 A6 500 100 90 90 40 20 40 90 40 60 A7 500 100 90 100 100 100 80 100 100 100 A8 500 100 90 100 100 100 60 100 100 100 A9 500 90 70 90 60 50 30 30 60 30 A10 500 90 20 80 50 40 20 40 50 30 A13 500 100 30 60 20 70 40 70 80 50 A14 500 100 90 20 30 60 10 100 70 70 A15 500 100 90 40 40 90 50 100 100 100 A16 500 100 90 90 50 40 50 80 100 90 A17 500 100 50 70 40 60 30 80 80 60 A18 500 100 90 60 70 100 40 100 100 90 A19 500 40 50 30 10 30 20 30 20 30