HERBICIDAL PROPYNYL-PHENYL COMPOUNDS
20170183281 ยท 2017-06-29
Assignee
Inventors
Cpc classification
C07C2602/22
CHEMISTRY; METALLURGY
C07D309/32
CHEMISTRY; METALLURGY
A01N35/06
HUMAN NECESSITIES
C07C49/603
CHEMISTRY; METALLURGY
C07C321/10
CHEMISTRY; METALLURGY
A01N41/12
HUMAN NECESSITIES
C07C49/753
CHEMISTRY; METALLURGY
International classification
C07C49/603
CHEMISTRY; METALLURGY
A01N35/06
HUMAN NECESSITIES
C07C321/10
CHEMISTRY; METALLURGY
A01N41/12
HUMAN NECESSITIES
C07D309/32
CHEMISTRY; METALLURGY
Abstract
The present invention relates to a compound of formula (I) wherein: R.sup.1 is C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.2alkoxy-C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.2fluoroalkoxy, ethyl, n-propyl, n-butyl, cyclopropyl or ethynyl; R.sup.2 is hydrogen, ethyl, n-propyl, cyclopropyl, vinyl, ethynyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.2fluoroalkoxy, C.sub.1-C.sub.2alkoxy-C.sub.1-C.sub.3alkoxy-, or C.sub.1fluoroalkoxy-C.sub.1-C.sub.3alkoxy-; provided that when R.sup.1 is ethyl, n-propyl, n-butyl, cyclopropyl or ethynyl, then R.sup.2 is hydrogen, ethyl, n-propyl, cyclopropyl, vinyl or ethynyl; and Y is O, S, S(O), S(O).sub.2, N(C.sub.1-C.sub.2alkyl), N(C.sub.1-C.sub.2alkoxy), C(O), CR.sup.8R.sup.9 or CR.sup.10R.sup.11CR.sup.12R.sup.13; and G, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are as defined herein; wherein the compound of formula (I) is optionally present as an agrochemically acceptable salt thereof. These compounds are suitable for use as herbicides. The invention therefore also relates to a method of controlling weeds, especially grassy monocotyledonous weeds, in crops of useful plants, comprising applying a compound of formula (I), or a herbicidal composition comprising such a compound, to the plants or to the locus thereof.
##STR00001##
Claims
1. A compound of formula (I): ##STR00153## wherein: R.sup.1 is C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.2alkoxy-C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.2fluoroalkoxy, ethyl, n-propyl, n-butyl, cyclopropyl or ethynyl; R.sup.2 is hydrogen, ethyl, n-propyl, cyclopropyl, vinyl, ethynyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.2fluoroalkoxy, C.sub.1-C.sub.2alkoxy-C.sub.1-C.sub.3alkoxy-, or C.sub.1fluoroalkoxy-C.sub.1-C.sub.3alkoxy-; provided that when R.sup.1 is ethyl, n-propyl, n-butyl, cyclopropyl or ethynyl, then R.sup.2 is hydrogen, ethyl, n-propyl, cyclopropyl, vinyl or ethynyl; and R.sup.3, R.sup.4, R.sup.5 and R.sup.6, independently of each other, are hydrogen, C.sub.1-C.sub.5alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.1-C.sub.2fluoroalkyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3alkylthioC.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3alkylsulfinylC.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3alkylsulfonylC.sub.1-C.sub.3alkyl; C.sub.3-C.sub.4cycloalkyl; or an unsubstituted 4, 5 or 6 membered monocyclic heterocyclyl having one ring heteroatom independently selected from oxygen, sulfur and nitrogen, and attached at a ring carbon atom within the heterocyclyl; provided that no more than one of R.sup.3, R.sup.4, R.sup.5 and R.sup.6 is alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, cycloalkyl or heterocyclyl; or R.sup.3 and R.sup.4 taken together are (CH.sub.2).sub.n1 or (CH.sub.2).sub.n2X.sup.1(CH.sub.2).sub.n3 and R.sup.5 and R.sup.6 are as defined herein, or R.sup.5 and R.sup.6 taken together are (CH.sub.2).sub.n1 or (CH.sub.2).sub.n2X.sup.1(CH.sub.2).sub.n3 and R.sup.3 and R.sup.4 are as defined herein; wherein X.sup.1 is O, S, S(O), S(O).sub.2, NH, N(C.sub.1-C.sub.2alkyl), N(C.sub.1-C.sub.2alkoxy), C(H)(C.sub.1-C.sub.2alkyl), C(C.sub.1-C.sub.2alkyl).sub.2 or C(H)(C.sub.1-C.sub.2alkoxy); n1 is 2, 3, 4 or 5; and n2 and n3 are independently 1, 2 or 3 provided that n2+n3 is 2, 3 or 4; or R.sup.4 and R.sup.5 taken together are (CH.sub.2).sub.n4 or (CH.sub.2).sub.n5C(R.sup.7a)(R.sup.7b)(CH.sub.2).sub.n6 or C(R.sup.7c)C(R.sup.7d); wherein R.sup.7a is C.sub.1-C.sub.2alkyl or C.sub.1-C.sub.2alkoxy; and R.sup.7b is hydrogen or C.sub.1-C.sub.2alkyl provided that R.sup.7b is hydrogen when R.sup.7a is C.sub.1-C.sub.2alkoxy; n4 is 1, 2 or 3; and n5 and n6 are independently 0, 1 or 2 provided that n5+n6 is 0, 1 or 2; and R.sup.7c and R.sup.7d independently are hydrogen or C.sub.1-C.sub.2alkyl; and Y is O, S, S(O), S(O).sub.2, N(C.sub.1-C.sub.2alkyl), N(C.sub.1-C.sub.2alkoxy), C(O), CR.sup.8R.sup.9 or CR.sup.10R.sup.11CR.sup.12R.sup.13; and R.sup.8 and R.sup.9 are, independently of each other: hydrogen, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.4alkenyl, C.sub.2-C.sub.4alkynyl, C.sub.1-C.sub.2fluoroalkyl, C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3alkylthioC.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3alkylsulfinylC.sub.1-C.sub.3alkyl, or C.sub.1-C.sub.3alkylsulfonylC.sub.1-C.sub.3alkyl; C.sub.3-C.sub.6cycloalkyl or C.sub.3-C.sub.6cycloalkyl substituted by one or two substituents which independently are C.sub.1-C.sub.3alkyl or C.sub.1-C.sub.2fluoroalkyl; and in which one ring CH.sub.2 moiety of a C.sub.4-C.sub.6cycloalkyl is optionally replaced by an oxygen or sulfur atom or by a S(O), S(O).sub.2, NH, N(C.sub.1-C.sub.3alkyl), N(C.sub.1-C.sub.2fluoroalkyl), N[C(O)C.sub.1-C.sub.3alkyl], N[C(O)C.sub.1-C.sub.2fluoroalkyl] or N(C.sub.1-C.sub.2alkoxy) moiety; C.sub.3-C.sub.6cycloalkyl substituted by one substituent being C.sub.1-C.sub.3alkoxy and optionally further substituted by one substituent being C.sub.1-C.sub.2alkyl; C.sub.5-C.sub.6cycloalkenyl or C.sub.5-C.sub.6cycloalkenyl substituted by one or two C.sub.1-C.sub.3alkyl substituents; C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.2alkyl- or C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.2alkyl- substituted by one or two ring substituents which independently are C.sub.1-C.sub.3alkyl or C.sub.1-C.sub.2fluoroalkyl; and in which one ring CH.sub.2 moiety of a C.sub.4-C.sub.6cycloalkylC.sub.1-C.sub.2alkyl- is optionally replaced by an oxygen or sulfur atom or by a S(O), S(O).sub.2, NH, N(C.sub.1-C.sub.2alkyl), N(C.sub.1-C.sub.2fluoroalkyl), N[C(O)C.sub.1-C.sub.3alkyl], N[C(O)C.sub.1-C.sub.2fluoroalkyl] or N(C.sub.1-C.sub.2alkoxy) moiety; C.sub.3-C.sub.6cycloalkylC.sub.1-C.sub.2alkyl- substituted by one ring substituent being C.sub.1-C.sub.3alkoxy and optionally further substituted by one ring substituent being C.sub.1-C.sub.2alkyl; or Het or Het-CH.sub.2, wherein Het is a heteroaryl, attached at a ring-carbon, which is optionally substituted by 1, 2 or 3 ring-carbon substituents independently being C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.2fluoroalkyl, C.sub.1-C.sub.3alkyl-C(O), C.sub.1-C.sub.2fluoroalkyl-C(O), hydroxy (including any oxo tautomer), C.sub.2-C.sub.3alkenyl, C.sub.2-C.sub.3alkynyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.2fluoroalkoxy, halogen, cyano or nitro, provided that any non-fluorine halogen, alkoxy or fluoroalkoxy is not substituted at any ring-carbon bonded directly to a ring-nitrogen of the heteroaryl; and/or, in the case of a 5-membered heteroaryl ring containing a ring-nitrogen atom not partaking in a CN ring double bond, the heteroaryl is optionally substituted on the ring-nitrogen atom not partaking in a CN ring double bond by one C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.2fluoroalkyl, C.sub.1-C.sub.3alkyl-C(O), C.sub.1-C.sub.2fluoroalkyl-C(O) or C.sub.1-C.sub.2alkyl-S(O).sub.2 substituent; provided that no more than one of R.sup.8 and R.sup.9 is an optionally substituted cycloalkyl; an optionally substituted cycloalkyl in which one ring CH.sub.2 moiety has been replaced by an oxygen or sulfur atom or by a S(O), S(O).sub.2, NH, N(C.sub.1-C.sub.3alkyl), N(C.sub.1-C.sub.2fluoroalkyl), N[C(O)C.sub.1-C.sub.3alkyl], N[C(O)C.sub.1-C.sub.2fluoroalkyl] or N(C.sub.1-C.sub.2alkoxy) moiety; an optionally substituted cycloalkenyl; an optionally substituted cycloalkyl-alkyl-; an optionally substituted cycloalkyl-alkyl- in which one ring CH.sub.2 moiety has been replaced by an oxygen or sulfur atom or by a S(O), S(O).sub.2, NH, N(C.sub.1-C.sub.3alkyl), N(C.sub.1-C.sub.2fluoroalkyl), N[C(O)C.sub.1-C.sub.3alkyl], N[C(O)C.sub.1-C.sub.2fluoroalkyl] or N(C.sub.1-C.sub.2alkoxy) moiety; or Het or Het-CH.sub.2; or R.sup.8 is hydrogen or C.sub.1-C.sub.2alkyl, and R.sup.9 is C.sub.1-C.sub.2alkoxy; or R.sup.8 and R.sup.9 taken together are (CH.sub.2).sub.n7 or (CH.sub.2).sub.n8X.sup.2(CH.sub.2).sub.n9; wherein X.sup.2 is O, S, S(O), S(O).sub.2, NH, N(C.sub.1-C.sub.3alkyl), N(C.sub.1-C.sub.2fluoroalkyl), N[C(O)C.sub.1-C.sub.3alkyl], N[C(O)C.sub.1-C.sub.2fluoroalkyl], N(C.sub.1-C.sub.2alkoxy), C(H)(C.sub.1-C.sub.3alkyl), C(C.sub.1-C.sub.2alkyl).sub.2 or C(H)(C.sub.1-C.sub.3alkoxy); n7 is 2, 3, 4, 5 or 6; and n8 and n9 are independently 0, 1, 2 or 3 provided that n8+n9 is 2, 3, 4 or 5; and R.sup.10, R.sup.11, R.sup.12 and R.sup.13 are independently of each other hydrogen or C.sub.1-C.sub.4alkyl provided that no more than one of R.sup.10, R.sup.11, R.sup.12 and R.sup.13 is C.sub.3-C.sub.4alkyl; and and wherein: G is hydrogen; an agriculturally acceptable metal, or an agriculturally acceptable sulfonium or ammonium group; or G is C(X.sup.a)R.sup.a, C(X.sup.b)X.sup.cR.sup.b, C(X.sup.d)N(R.sup.c)R.sup.d, SO.sub.2R.sup.e, P(X.sup.e)(R.sup.f)R.sup.g, CH.sub.2X.sup.fR.sup.h; or phenyl-CH.sub.2 or phenyl-CH(C.sub.1-C.sub.2alkyl)- (in each of which the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.2alkyl, C.sub.1fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1fluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or heteroaryl-CH.sub.2 or heteroaryl-CH(C.sub.1-C.sub.2alkyl)- (in each of which the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.2alkyl, C.sub.1fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1fluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro), or phenyl-C(O)CH.sub.2 (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.2alkyl, C.sub.1fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1fluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro); or C.sub.1-C.sub.6alkoxy-C(O)CH.sub.2, C.sub.1-C.sub.6alkoxy-C(O)CHCH, C.sub.2-C.sub.7alken-1-yl-CH.sub.2, C.sub.2-C.sub.7alken-1-yl-CH(C.sub.1-C.sub.2alkyl)-, C.sub.2-C.sub.4fluoroalken-1-yl-CH.sub.2, C.sub.2-C.sub.7alkyn-1-yl-CH.sub.2, or C.sub.2-C.sub.7alkyn-1-yl-CH(C.sub.1-C.sub.2alkyl)-; wherein X.sup.a, X.sup.b, X.sup.c, X.sup.d, X.sup.e and X.sup.f are independently of each other oxygen or sulfur; and wherein R.sup.a is H, C.sub.1-C.sub.21alkyl, C.sub.2-C.sub.21alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.10fluoroalkyl, C.sub.1-C.sub.10cyanoalkyl, C.sub.1-C.sub.10nitroalkyl, C.sub.1-C.sub.10aminoalkyl, C.sub.1-C.sub.5alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.7cycloalkyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkenyloxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkynyloxy (C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylthio(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfinyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8alkylideneaminoxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxycarbonyl(C.sub.1-C.sub.5)alkyl, aminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonylamino(C.sub.1-C.sub.5)alkyl, N(C.sub.1-C.sub.5)alkylcarbonyl-N(C.sub.1-C.sub.5)alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.6trialkylsilyl(C.sub.1-C.sub.5)alkyl, phenyl(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C.sub.1-C.sub.5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), C.sub.2-C.sub.5fluoroalkenyl, C.sub.3-C.sub.8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; R.sup.b is C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl, C.sub.3-C.sub.18alkynyl, C.sub.2-C.sub.10fluoroalkyl, C.sub.1-C.sub.10cyanoalkyl, C.sub.1-C.sub.10nitroalkyl, C.sub.2-C.sub.10aminoalkyl, C.sub.1-C.sub.5alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.7cycloalkyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkenyloxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkynyloxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylthio(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfinyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8alkylideneaminoxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxycarbonyl(C.sub.1-C.sub.5)alkyl, aminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonylamino(C.sub.1-C.sub.5)alkyl, N(C.sub.1-C.sub.5)alkylcarbonyl-N(C.sub.1-C.sub.5)alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.6trialkylsilyl(C.sub.1-C.sub.5)alkyl, phenyl(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), heteroarylC.sub.1-C.sub.5alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkyl-thio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), C.sub.3-C.sub.5fluoroalkenyl, C.sub.3-C.sub.8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; and R.sup.c and R.sup.d are each independently of each other hydrogen, C.sub.1-C.sub.10alkyl, C.sub.3-C.sub.10alkenyl, C.sub.3-C.sub.10alkynyl, C.sub.2-C.sub.10fluoroalkyl, C.sub.1-C.sub.10cyanoalkyl, C.sub.1-C.sub.10nitroalkyl, C.sub.1-C.sub.10aminoalkyl, C.sub.1-C.sub.5alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.7cycloalkyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkenyloxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkynyloxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylthio(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfinyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8alkylideneaminoxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxycarbonyl(C.sub.1-C.sub.5)alkyl, aminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonylamino(C.sub.1-C.sub.5)alkyl, N(C.sub.1-C.sub.5)alkylcarbonyl-N(C.sub.2-C.sub.5)alkylaminoalkyl, C.sub.3-C.sub.6trialkylsilyl(C.sub.1-C.sub.5)alkyl, phenyl(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C.sub.1-C.sub.5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), C.sub.2-C.sub.5fluoroalkenyl, C.sub.3-C.sub.8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; heteroarylamino or heteroarylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or by nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; or C.sub.3-C.sub.7cycloalkylamino, di(C.sub.3-C.sub.7cycloalkyl)amino or C.sub.3-C.sub.7cycloalkoxy; or R.sup.c and R.sup.d, together with the nitrogen to which they are bonded, to form an unsubstituted 4, 5, 6 or 7 membered ring, optionally containing one heteroatom selected from O or S; and R.sup.e is C.sub.1-C.sub.10alkyl, C.sub.2-C.sub.10alkenyl, C.sub.2-C.sub.10alkynyl, C.sub.1-C.sub.10fluoroalkyl, C.sub.1-C.sub.10cyanoalkyl, C.sub.1-C.sub.10nitroalkyl, C.sub.1-C.sub.10aminoalkyl, C.sub.1-C.sub.5alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.7cycloalkyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkenyloxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkynyloxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylthio(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfinyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8alkylideneaminoxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxycarbonyl(C.sub.1-C.sub.5)alkyl, aminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonylamino(C.sub.1-C.sub.5)alkyl, N(C.sub.1-C.sub.5)alkylcarbonyl-N(C.sub.1-C.sub.5)alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.6trialkylsilyl(C.sub.1-C.sub.5)alkyl, phenyl(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C.sub.1-C.sub.5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), C.sub.2-C.sub.5fluoroalkenyl, C.sub.3-C.sub.8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; heteroarylamino or heteroarylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; or C.sub.3-C.sub.7cycloalkylamino, di(C.sub.3-C.sub.7cycloalkyl)amino, C.sub.3-C.sub.7cycloalkoxy, C.sub.1-C.sub.10alkoxy, C.sub.1-C.sub.10fluoroalkoxy, C.sub.1-C.sub.5alkylamino or di(C.sub.1-C.sub.4alkyl)amino; R.sup.f and R.sup.g are each independently of each other C.sub.1-C.sub.10alkyl, C.sub.2-C.sub.10alkenyl, C.sub.2-C.sub.10alkynyl, C.sub.1-C.sub.10alkoxy, C.sub.1-C.sub.10fluoroalkyl, C.sub.1-C.sub.10cyanoalkyl, C.sub.1-C.sub.10nitroalkyl, C.sub.1-C.sub.10aminoalkyl, C.sub.1-C.sub.5alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.7cycloalkyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkenyloxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkynyloxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylthio(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfinyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8alkylideneaminoxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxycarbonyl(C.sub.1-C.sub.5)alkyl, aminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonylamino(C.sub.1-C.sub.5)alkyl, N(C.sub.1-C.sub.5)alkylcarbonyl-N(C.sub.2-C.sub.5)alkylaminoalkyl, C.sub.3-C.sub.6trialkylsilyl(C.sub.1-C.sub.5)alkyl, phenyl(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), heteroaryl(C.sub.1-C.sub.5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3alkylsulfonyl, halogen, cyano, or nitro), C.sub.2-C.sub.5fluoroalkenyl, C.sub.3-C.sub.8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; heteroarylamino or heteroarylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; diheteroarylamino or diheteroarylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; phenylamino or phenylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; diphenylamino or diphenylamino substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; or C.sub.3-C.sub.7cycloalkylamino, di(C.sub.3-C.sub.7cycloalkyl)amino, C.sub.3-C.sub.7cycloalkoxy, C.sub.1-C.sub.10fluoroalkoxy, C.sub.1-C.sub.5alkylamino or di(C.sub.1-C.sub.4alkyl)amino; or benzyloxy or phenoxy, wherein the benzyl and phenyl groups are in turn optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; and R.sup.h is C.sub.1-C.sub.10alkyl, C.sub.3-C.sub.10alkenyl, C.sub.3-C.sub.10alkynyl, C.sub.1-C.sub.10fluoroalkyl, C.sub.1-C.sub.10cyanoalkyl, C.sub.1-C.sub.10nitroalkyl, C.sub.2-C.sub.10aminoalkyl, C.sub.1-C.sub.5alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.7cycloalkyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkenyloxy(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.5alkynyloxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylthio(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfinyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylsulfonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8alkylideneaminoxy(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkoxycarbonyl(C.sub.1-C.sub.5)alkyl, aminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.2-C.sub.8dialkylaminocarbonyl(C.sub.1-C.sub.5)alkyl, C.sub.1-C.sub.5alkylcarbonylamino(C.sub.1-C.sub.5)alkyl, N(C.sub.1-C.sub.5)alkylcarbonyl-N(C.sub.1-C.sub.5)alkylamino(C.sub.1-C.sub.5)alkyl, C.sub.3-C.sub.6trialkylsilyl(C.sub.1-C.sub.5)alkyl, phenyl(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3 alkylsulfonyl, halogen, cyano or nitro), heteroaryl(C.sub.1-C.sub.5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3 alkylsulfonyl, halogen, cyano or nitro), phenoxy(C.sub.1-C.sub.5)alkyl (wherein the phenyl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3 alkylsulfonyl, halogen, cyano or nitro), heteroaryloxy(C.sub.1-C.sub.5)alkyl (wherein the heteroaryl is optionally substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, C.sub.1-C.sub.3alkylthio, C.sub.1-C.sub.3alkylsulfinyl, C.sub.1-C.sub.3 alkylsulfonyl, halogen, cyano or nitro), C.sub.3-C.sub.5fluoroalkenyl, C.sub.3-C.sub.8cycloalkyl; phenyl or phenyl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; or heteroaryl or heteroaryl substituted by 1, 2 or 3 of, independently, C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3fluoroalkyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.3fluoroalkoxy, halogen, cyano or nitro; C.sub.1-C.sub.6alkyl-C(O); or phenyl-C(O) wherein the phenyl is optionally substituted by 1 or 2 of, independently, C.sub.1-C.sub.2alkyl, C.sub.1fluoroalkyl, C.sub.1-C.sub.2alkoxy, C.sub.1fluoroalkoxy, fluorine, chlorine, bromine, cyano or nitro; wherein heteroaryl means an aromatic ring system containing at least one ring heteroatom and consisting either of a single ring or of two fused rings; and wherein the compound of formula (I) is optionally present (e.g. where chemically possible) as an agrochemically acceptable salt thereof.
2. The compound as claimed in claim 1, wherein when G is C(X.sup.a)R.sup.a or C(X.sup.b)X.sup.cR.sup.b, then X.sup.a, X.sup.b and X.sup.c are oxygen, R.sup.a is C.sub.1-C.sub.10alkyl, C.sub.2-C.sub.6alkenyl, C.sub.2-C.sub.6alkynyl, C.sub.3-C.sub.6cycloalkyl or C.sub.1-C.sub.4alkoxyC.sub.1-C.sub.4alkyl; and R.sup.b is C.sub.1-C.sub.10alkyl, C.sub.2-C.sub.5alkenyl-CH.sub.2, C.sub.2-C.sub.4alkenyl-CH(Me)-, C.sub.2-C.sub.5alkynyl-CH.sub.2, C.sub.2-C.sub.4alkynyl-CH(Me)-, C.sub.3-C.sub.6cycloalkyl or C.sub.1-C.sub.4alkoxyC.sub.1-C.sub.4alkyl.
3. The compound as claimed in claim 1, wherein R.sup.1 is selected from the group consisting of C.sub.1-C.sub.2alkoxy, C.sub.1-C.sub.2fluoroalkoxy, ethyl, n-propyl, n-butyl, cyclopropyl and ethynyl.
4. The compound as claimed in claim 1, wherein R.sup.2 is selected from the group consisting of hydrogen, ethyl, n-propyl, cyclopropyl, vinyl, ethynyl, methoxy, ethoxy and fluoromethoxy.
5. The compound as claimed in claim 1, wherein R.sup.3, R.sup.4, R.sup.5 and R.sup.6, independently of each other, are hydrogen, C.sub.1-C.sub.3alkyl or C.sub.1-C.sub.2alkoxyC.sub.1-C.sub.2alkyl; provided that no more than one of R.sup.3, R.sup.4, R.sup.5 and R.sup.6 is alkoxyalkyl; or R.sup.4 and R.sup.5 taken together are (CH.sub.2).sub.n4 or (CH.sub.2).sub.n5C(R.sup.7a)(R.sup.7b)(CH.sub.2).sub.n6; wherein R.sup.7a is C.sub.1-C.sub.2alkyl; R.sup.7b is hydrogen or C.sub.1-C.sub.2alkyl; n4 is 2 or 3; and n5 and n6 are independently 0, 1 or 2 provided that n5+n6 is 1 or 2.
6. The compound as claimed in claim 1, wherein: R.sup.8 is hydrogen or C.sub.1-C.sub.2alkyl; and R.sup.9 is: C.sub.1-C.sub.2alkoxy; C.sub.2-C.sub.3alkynyl-CH.sub.2; C.sub.1-C.sub.3alkoxyC.sub.1-C.sub.3alkyl; C.sub.1-C.sub.3alkylthioC.sub.1-C.sub.3alkyl; C.sub.1-C.sub.3alkylsulfinylC.sub.1-C.sub.3alkyl; C.sub.1-C.sub.3alkylsulfonylC.sub.1-C.sub.3alkyl; C.sub.3-C.sub.6cycloalkyl or C.sub.3-C.sub.6cycloalkyl substituted by one or two substituents which independently are C.sub.1-C.sub.3alkyl or C.sub.1-C.sub.2fluoroalkyl; and in which one ring CH.sub.2 moiety of a C.sub.4-C.sub.6cycloalkyl is optionally replaced by an oxygen or sulfur atom or by a S(O), S(O).sub.2, NH, N(C.sub.1-C.sub.3alkyl), N(C.sub.1-C.sub.2fluoroalkyl), N[C(O)C.sub.1-C.sub.3alkyl], N[C(O)C.sub.1-C.sub.2fluoroalkyl] or N(C.sub.1-C.sub.2alkoxy) moiety; C.sub.3-C.sub.6cycloalkyl substituted by one substituent being C.sub.1-C.sub.3alkoxy and optionally further substituted by one substituent being C.sub.1-C.sub.2alkyl; C.sub.3-C.sub.6cycloalkylmethyl- or C.sub.3-C.sub.6cycloalkylmethyl- substituted by one or two ring substituents which independently are C.sub.1-C.sub.3alkyl or C.sub.1-C.sub.2fluoroalkyl; and in which one ring CH.sub.2 moiety of a C.sub.4-C.sub.6cycloalkylmethyl- is optionally replaced by an oxygen or sulfur atom or by a S(O), S(O).sub.2, NH, N(C.sub.1-C.sub.2alkyl), N(C.sub.1-C.sub.2fluoroalkyl), N[C(O)C.sub.1-C.sub.3alkyl], N[C(O)C.sub.1-C.sub.2fluoroalkyl] or N(C.sub.1-C.sub.2alkoxy) moiety; C.sub.3-C.sub.6cycloalkylmethyl- substituted by one ring substituent being C.sub.1-C.sub.3alkoxy and optionally further substituted by one ring substituent being C.sub.1-C.sub.2alkyl; or Het or Het-CH.sub.2, wherein Het is a heteroaryl, attached at a ring-carbon, which is optionally substituted by 1, 2 or 3 ring-carbon substituents independently being C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.2fluoroalkyl, C.sub.1-C.sub.3alkyl-C(O), C.sub.1-C.sub.2fluoroalkyl-C(O), hydroxy (including any oxo tautomer), C.sub.2-C.sub.3alkenyl, C.sub.2-C.sub.3alkynyl, C.sub.1-C.sub.3alkoxy, C.sub.1-C.sub.2fluoroalkoxy, halogen, cyano or nitro, provided that any non-fluorine halogen, alkoxy or fluoroalkoxy is not substituted at any ring-carbon bonded directly to a ring-nitrogen of the heteroaryl; and/or, in the case of a 5-membered heteroaryl ring containing a ring-nitrogen atom not partaking in a CN ring double bond, the heteroaryl is optionally substituted on the ring-nitrogen atom not partaking in a CN ring double bond by one C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.2fluoroalkyl, C.sub.1-C.sub.3alkyl-C(O), C.sub.1-C.sub.2fluoroalkyl-C(O) or C.sub.1-C.sub.2alkyl-S(O).sub.2 substituent; or R.sup.8 and R.sup.9 taken together are (CH.sub.2).sub.n7 or (CH.sub.2).sub.n8X.sup.2(CH.sub.2).sub.n9.
7. The compound as claimed in claim 1, wherein R.sup.8 and R.sup.9 are, independently of each other, hydrogen or C.sub.1-C.sub.3alkyl.
8. The compound as claimed in claim 1, wherein Y is O, S, S(O), S(O).sub.2, C(O), CR.sup.8R.sup.9 or CR.sup.10R.sup.11CR.sup.12R.sup.13.
9. The compound as claimed in claim 1, wherein Y is CR.sup.8R.sup.9; and R.sup.4 and R.sup.5 are taken together and are (CH.sub.2).sub.n4 or (CH.sub.2).sub.n5C(R.sup.7a)(R.sup.7b)(CH.sub.2).sub.n6; wherein R.sup.7a is C.sub.1-C.sub.2alkyl; R.sup.7b is hydrogen or C.sub.1-C.sub.2alkyl; n4 is 2 or 3; and n5 and n6 are independently 0, 1 or 2 provided that n5+n6 is 1 or 2.
10. The compound as claimed in claim 9, wherein Y is CH.sub.2.
11. The compound as claimed in claim 9 or 10, wherein R.sup.3 and R.sup.6, independently of each other, are hydrogen or C.sub.1-C.sub.2alkyl; and R.sup.4 and R.sup.5 taken together are (CH.sub.2).sub.n4 wherein n4 is 2 or 3.
12. A herbicidal composition which comprises a compound of formula (I), as defined in claim 1, and an agrochemically acceptable carrier, diluent or solvent.
13. The herbicidal composition according to claim 12, which comprises one or more further herbicides or a safener.
14. A method of controlling grassy monocotyledonous weeds in crops of useful plants, comprising applying a compound of formula (I), as defined in claim 1, or a herbicidal composition comprising such a compound, to the weeds and/or to the plants and/or to the locus thereof.
15. The method as claimed in claim 14, wherein the grassy monocotyledonous weeds comprise weeds from the genus Brachiaria, Cenchrus, Digitaria, Echinochloa, Eleusine, Eriochloa, Leptochloa, Ottochloa, Panicum, Pennisetum, Phalaris, Rottboellia, Setaria and/or Sorghum, and/or volunteer corn (volunteer maize) weeds.
Description
PREPARATION EXAMPLES
[0443] Those skilled in the art will appreciate that certain compounds described below are 3-ketoenols, and as such may exist as a single tautomer or as a mixture of keto-enol and diketone tautomers, as described, for example by J. March, Advanced Organic Chemistry, third edition, John Wiley and Sons. The compounds shown below, and in Table T1 are drawn as an arbitrary single enol tautomer, but it should be inferred that this description covers both the diketone form and any possible enols which could arise through tautomerism. Where more than one tautomer is observed in proton NMR, the data shown are for the mixture of tautomers. Furthermore, some of the compounds shown below are drawn as single enantiomers for the purposes of simplicity, but unless specified as single enantiomers, these structures should be construed as representing a mixture of enantiomers. Additionally, some of the compounds can exist as diastereoisomers, and it should be inferred that these can be present as a mixture of diastereoisomers or as any possible single diastereoisomer. Within the detailed experimental section the diketone tautomer is chosen for naming purposes, even if the predominant tautomer is the enol form.
[0444] As used herein, room (ambient) temperature is typically about 15-30 C. (e.g. 15-25 C.). Herein, d4 MeOD means tetradeutero-methanol (CD.sub.3OD).
Example 1: Preparation of 3-(2-methoxy-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]octane-2,4-dione (Compound A1)
[0445] ##STR00044##
Step 1: Preparation of 3-[(4-bromo-2-methoxy-phenyl)methylene]norbornan-2-one
[0446] ##STR00045##
[0447] To a mixture of norcamphor (3.7 g) and 4-bromo-2-methoxy-benzaldehyde (9 g) in ethanol (100 mL) under nitrogen atmosphere was cautiously added potassium hydroxide (4.7 g) and the mixture heated to reflux for 18 hours. The reaction mixture was cooled to 0 C. and water (50 mL) cautiously added drop wise followed by 2M hydrochloric acid (500 mL). The mixture was partitioned with ethyl acetate and the aqueous layer extracted further with ethyl acetate (2). The combined organic extracts were washed with brine, dried with magnesium sulfate, concentrated under reduced pressure and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 3-[(4-bromo-2-methoxy-phenyl)methylene]norbornan-2-one (4.61 g) as a brown gum. The compound was used as is in the next step.
Step 2: Preparation of 2-[(4-bromo-2-methoxy-phenyl)methylene]-3-oxabicyclo[3.2.1]octan-4-one
[0448] ##STR00046##
[0449] To a solution of 3-[(4-bromo-2-methoxy-phenyl)methylene]norbornan-2-one (400 mg) in t-butyl alcohol (1.6 mL) was added selenium dioxide (6 mg) followed by hydrogen peroxide (0.4 mL, 50% in water) in one portion. The solution was stirred at room temperature for 24 hours then partitioned between chloroform and water. The aqueous layer was extracted with further chloroform and the combined organic extracts washed with water until no more peroxide was present. The organic extract was dried with magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give (2E/Z)-2-[(4-bromo-2-methoxy-phenyl)methylene]-3-oxabicyclo[3.2.1]octan-4-one (90 mg) as a colourless gum.
[0450] LC/MS 1.06 min, MH+323 (2 min run)
Step 3: Preparation of 3-(4-bromo-2-methoxy-phenyl)bicyclo[3.2.1]octane-2,4-dione
[0451] ##STR00047##
[0452] To a solution of 2-[(4-bromo-2-methoxy-phenyl)methylene]-3-oxabicyclo[3.2.1]octan-4-one (1 g) in toluene (20 mL) at room temperature under nitrogen atmosphere was added 7.7% phosphorus pentoxide in methane sulfonic acid (Eaton's Reagent, CAS 39394-84-8, 4.1 mL) drop wise over 20 seconds. The mixture was heated to 70 C. for 140 minutes. The mixture was cooled and added to 2M sodium hydroxide (5 mL) at 0 C. and stirred for 15 minutes. Ethyl acetate (20 mL) was added followed by water (10 mL) and the phases separated. The aqueous phase was washed with further ethyl acetate (20 mL). The aqueous phase was acidified to pH1 with conc. hydrochloric acid and extracted with dichloromethane. The organic layer was concentrated to give 3-(4-bromo-2-methoxy-phenyl)bicyclo[3.2.1]octane-2,4-dione (650 mg) as a beige solid.
[0453] LC/MS 0.65 min, MH+323 (2 min run)
Step 4: Preparation of 3-(4-bromo-2-methoxy-phenyl)-2-methoxy-bicyclo[3.2.1]oct-2-en-4-one
[0454] ##STR00048##
[0455] To a solution of 3-(4-bromo-2-methoxy-phenyl)bicyclo[3.2.1]octane-2,4-dione (1 g) in acetone (30 mL) was added potassium carbonate (1 g), followed by iodomethane (0.9 mL) and water (0.2 mL). The mixture was stirred at room temperature overnight. The mixture was partitioned between dichloromethane and water and the organic layer was concentrated to give 3-(4-bromo-2-methoxy-phenyl)-2-methoxy-bicyclo[3.2.1]oct-2-en-4-one (0.93 g) as a brown gum. This was used as is in the next step.
Step 5: Preparation of 2-methoxy-3-(2-methoxy-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]oct-2-en-4-one
[0456] ##STR00049##
[0457] To a mixture of 3-(4-bromo-2-methoxy-phenyl)-2-methoxy-bicyclo[3.2.1]oct-2-en-4-one (600 mg), 2-butynoic acid (CAS 590-93-2, 180 mg), bis(triphenylphosphine)palladium(II) dichloride (CAS 13965-03-2, 63 mg) and 1,4-bis-(diphenylphosphino)butane (CAS 7688-25-7, 76 mg) in methyl sulfoxide (16 mL) under nitrogen atmosphere was added tetrabutylammonium fluoride (CAS 429-41-4, 1M in tetrahydrofuran, 5.3 mL). The reaction was heated to 110 C. for 1 hour. The reaction mixture was quenched with water and extracted twice with dichloromethane. The combined organics were concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 2-methoxy-3-(2-methoxy-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]oct-2-en-4-one (600 mg) as a white solid.
[0458] LC/MS 0.90 min, MH+297 (2 min run)
Step 6: Preparation of 3-(2-methoxy-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]octane-2,4-dione (Compound A1)
[0459] ##STR00050##
[0460] A mixture of 2-methoxy-3-(2-methoxy-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]oct-2-en-4-one (5.57 g), acetone (50 mL) and 2M hydrochloric acid (50 mL) was heated to 60 C. for 1 hour. The reaction mixture was concentrated under reduced pressure and partitioned between water and dichloromethane. The organic layer was concentrated under reduced pressure to give 3-(2-methoxy-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]octane-2,4-dione (Compound A1, 5.1 g) as a cream solid.
[0461] .sup.1H NMR (400 MHz, CD.sub.3OD) ppm 6.84-6.96 (m, 3H) 3.66-3.75 (m, 3H) 2.92-3.00 (m, 2H) 2.12-2.25 (m, 3H) 1.98-2.07 (m, 3H) 1.78-1.88 (m, 2H) 1.66 (dt, 1H)
Example 2: Preparation of 4-(2,6-Dimethoxy-4-prop-1-ynyl-phenyl)-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione (Compound A2)
[0462] ##STR00051##
Step 1: Preparation of 4-[(4-bromo-2,6-dimethoxy-phenyl)methylene]-2,2,5,5-tetramethyl-tetrahydrofuran-3-one
[0463] ##STR00052##
[0464] To a mixture of 4-bromo-2,6-dimethoxy-benzaldehyde (CAS 1354050-38-6, 5 g) and 2,2,5,5-tetramethyltetrahydrofuran-3-one (CAS 5455-94-7, 2.90 g) in ethanol (75 mL) was added a solution of potassium hydroxide (0.445 g) in ethanol (5 ml) drop wise over 5 minutes. The mixture was stirred for 3 hours then left to stand overnight. The reaction mixture was concentrated, diluted with water and acidified with 2M hydrochloric acid. The suspension was extracted twice with dichloromethane. The combined organics were washed with water, brine, dried with magnesium sulfate, concentrated, triturated with ice-cold isohexane and filtered and dried to give a mixture of isomers 4-[(4-bromo-2,6-dimethoxy-phenyl)methylene]-2,2,5,5-tetramethyl-tetrahydrofuran-3-one (6.834 g) as a pale yellow solid.
[0465] LC/MS 1.10 min, MH+369 (2 min run)
Step 2: Preparation of 1-(4-bromo-2,6-dimethoxy-phenyl)-5,5,7,7-tetramethyl-2,6-dioxaspiro[2.4]heptan-4-one
[0466] ##STR00053##
[0467] A solution of 4-[(4-bromo-2,6-dimethoxy-phenyl)methylene]-2,2,5,5-tetramethyl-tetrahydrofuran-3-one (1.5 g) in methanol (67 mL) was heated to 35 C. and hydrogen peroxide (0.35 mL, 50% in water) was added in one portion, immediately followed by lithium hydroxide hydrate (2M in water, 0.41 mL). After stirring the mixture at 35 C. for 3 hours the same amount of hydrogen peroxide and lithium hydroxide hydrate were added and the reaction stirred for a further 2 hours then allowed to cool overnight. To this was added 10% sodium metabisulfite solution until the mixture was negative to starch iodide paper. Water was added and mixture extracted with ether (3). The combined organics were washed with saturated sodium bicarbonate solution, brine, dried with magnesium sulphate and concentrated to give a pale orange gum. This can be purified by chromatography on silica eluting with ethyl acetate in iso-hexane to separate the isomers, if necessary, though the sample can be taken through the next step as a mixture.
[0468] (1 S,3S)-1-(4-bromo-2,6-dimethoxy-phenyl)-5,5,7,7-tetramethyl-2,6-dioxaspiro[2.4]heptan-4-one (0.419 g) as a pale yellow solid
[0469] LC/MS 1.12 min, MH+385 (2 min run)
[0470] (1R,3S)-1-(4-bromo-2,6-dimethoxy-phenyl)-5,5,7,7-tetramethyl-2,6-dioxaspiro[2.4]heptan-4-one (0.247 g) as a cream solid
[0471] LC/MS 1.06 min, MH+385 (2 min run)
Step 3: Preparation of 4-(4-bromo-2,6-dimethoxy-phenyl)-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione
[0472] ##STR00054##
[0473] A solution of 1-(4-bromo-2,6-dimethoxy-phenyl)-5,5,7,7-tetramethyl-2,6-dioxaspiro[2.4]heptan-4-one (2.206 g) in dichloromethane (22.06 mL) was added drop wise at 0 C. to cooled conc sulfuric acid (3.053 mL) over 0.5 hour with vigorous stirring. The emulsion was stirred vigorously at 0 C. for 1.5 hours then quenched onto iced water. The emulsion was extracted with dichloromethane (3). The combined organics were washed with brine, dried with magnesium sulfate and concentrated. Triturated the resulting solid with ice-cold iso-hexane and ether, filtered and air-dried to give 4-(4-bromo-2,6-dimethoxy-phenyl)-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione (1.913 g) as a lilac solid.
[0474] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 6.78 (s, 2H) 5.80 (brs, 1H) 3.75 (s, 6H) 1.57 (s, 6H) 1.45 (s, 6H)
Step 4: Preparation of 4-(2,6-Dimethoxy-4-prop-1-ynyl-phenyl)-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione (Compound A2)
[0475] ##STR00055##
[0476] To a mixture of 4-(4-bromo-2,6-dimethoxy-phenyl)-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione (500 mg), 2-butynoic acid (CAS 590-93-2, 130 mg), bis(triphenylphosphine)palladium(II) dichloride (CAS 13965-03-2, 46 mg) and 1,4-bis-(diphenylphosphino)butane (CAS 7688-25-7, 55 mg) in methyl sulfoxide (16 mL) under nitrogen atmosphere was added tetrabutylammonium fluoride (CAS 429-41-4, 1M in tetrahydrofuran, 3.9 mL). The reaction was heated to 110 C. for 1 hour. The reaction mixture was quenched with 2M hydrochloric acid and extracted twice with ethyl acetate. The combined organics were washed with water, brine, dried with magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 4-(2,6-dimethoxy-4-prop-1-ynyl-phenyl)-2,2,6,6-tetramethyl-tetrahydropyran-3,5-dione (354 mg) as a cream solid.
[0477] .sup.1H NMR (400 MHz, CDCl.sub.3+2 drops CD.sub.3OD) ppm 6.62-6.66 (m, 2H), 3.68-3.76 (m, 6H), 2.02-2.12 (m, 3H), 1.42-1.59 (m, 12H)
Example 3: Preparation of 3-[2-methoxy-4-prop-1-ynyl-6-(trifluoromethyl)phenyl]bicyclo[3.2.1]octane-2,4-dione (Compound A3)
[0478] ##STR00056##
Step 1: Preparation of 2-methoxy-6-(trifluoromethyl)benzaldehyde
[0479] ##STR00057##
[0480] Suspended powdered potassium hydroxide (0.482 g) and 2-fluoro-6-(trifluoromethyl)benzaldehyde (CAS 60611-24-7, 1.5 g) in methanol (10 mL) and heated to 60 C. for 2.5 hours. The mixture was cooled, diluted with water and extracted with ether (2). The combined organics were washed with water and concentrated to give 2-methoxy-6-(trifluoromethyl)benzaldehyde (1.051 g) as a colourless oil which crystallised on standing.
[0481] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 10.52 (d, 1H) 7.60 (t, 1H) 7.37 (d, 1H) 7.22 (d, 1H) 3.95 (s, 3H)
Step 2: Preparation of 3-[2-methoxy-6-(trifluoromethyl)phenyl]spiro[norbornane-3,2-oxirane]-2-one
[0482] ##STR00058##
[0483] Potassium tert-butoxide (1M in tetrahydrofuran, 6.054 mL) was added drop wise to a solution of 2-methoxy-6-(trifluoromethyl)benzaldehyde (1.030 g) and 3-bromonorbornan-2-one (CAS 89856-55-3, 1.145 g) in anhydrous methylsulfoxide (25.23 mL) at room temperature. The reaction was stirred for 4 hours and partitioned between saturated aqueous ammonium chloride and ethyl acetate. The aqueous was extracted with further ethyl acetate and the combined organics were dried with magnesium sulfate and concentrated to give 3-[2-methoxy-6-(trifluoromethyl)phenyl]spiro[norbornane-3,2-oxirane]-2-one which was used crude in the next step.
Step 3: Preparation of 3-[2-methoxy-6-(trifluoromethyl)phenyl]bicyclo[3.2.1]octane-2,4-dione
[0484] ##STR00059##
[0485] To a solution of crude 3-[2-methoxy-6-(trifluoromethyl)phenyl]spiro[norbornane-3,2-oxirane]-2-one in toluene (25.23 mL) at room temperature and under nitrogen atmosphere was added 7.7% phosphorus pentoxide in methane sulfonic acid (Eaton's Reagent, CAS 39394-84-8, 3.532 mL) drop wise. The mixture was heated to 65 C. for 2.5 hours. The mixture was cooled and partitioned between ethyl acetate and water. The aqueous phase was extracted with further ethyl acetate and the combined organics were dried with magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 3-[2-methoxy-6-(trifluoromethyl)phenyl]bicyclo[3.2.1]octane-2,4-dione (532 mg) as a brown solid.
[0486] .sup.1H NMR (400 MHz, DMSO-d.sub.6) ppm 7.38-7.45 (m, 1H) 7.18-7.26 (m, 2H) 3.64-3.71 (m, 3H) 2.72-3.00 (m, 2H) 2.02-2.09 (m, 2H) 1.89-2.02 (m, 1H) 1.61-1.80 (m, 2H) 1.52-1.63 (m, 1H)
Step 4: Preparation of 2-methoxy-3-[2-methoxy-6-(trifluoromethyl)phenyl]bicyclo[3.2.1]oct-2-en-4-one
[0487] ##STR00060##
[0488] To a solution of 3-[2-methoxy-6-(trifluoromethyl)phenyl]bicyclo[3.2.1]octane-2,4-dione (499 mg) in acetone (20 mL) was added potassium carbonate (0.331 g), followed by iodomethane (0.497 mL) and water (0.2 mL). The mixture was stirred at room temperature for 5.5 hours. The mixture was partitioned between ethyl acetate and 2M hydrochloric acid and the organic layer was dried with magnesium sulfate and concentrated to give 2-methoxy-3-[2-methoxy-6-(trifluoromethyl)phenyl]bicyclo[3.2.1]oct-2-en-4-one (0.535 g) as a brown solid.
[0489] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 7.34-7.39 (m, 1H) 7.25-7.30 (m, 1H) 7.05 (t, 1H) 3.76 (d, 3H) 3.56-3.66 (m, 3H) 3.21 (d, 1H) 3.00-3.06 (m, 1H) 2.06-2.19 (m, 3H) 1.92 (s, 2H) 1.61-1.75 (m, 1H)
Step 5: Preparation of 2-methoxy-3-[2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-6-(trifluoromethyl)phenyl]bicyclo[3.2.1]oct-2-en-4-one
[0490] ##STR00061##
[0491] A mixture of 2-methoxy-3-[2-methoxy-6-(trifluoromethyl)phenyl]bicyclo[3.2.1]oct-2-en-4-one (532 mg), bis(pinacolato)diboron (CAS 73183-34-3, 591 mg), (1,5-cyclooctadiene)(methoxy)iridium(I) dimer (CAS 12148-71-9, 49 mg) and 4,4-di-t-butyl-2,2-bipyridine (CAS 72914-19-3, 40 mg) in 2-methoxy-2-methyl-propane (11.2 mL) under nitrogen atmosphere was heated at 80 C. for 4 hours.
[0492] The mixture was cooled and partitioned between ethyl acetate and water. The aqueous phase was extracted with further ethyl acetate and the combined organics were dried with magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 2-methoxy-3-[2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-6-(trifluoromethyl)phenyl]bicyclo[3.2.1]oct-2-en-4-one (687 mg) as a gum.
[0493] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 7.73 (s, 1H) 7.44 (s, 1H) 3.78-3.82 (m, 3H) 3.54 (s, 3H) 3.15-3.21 (m, 1H) 2.97-3.05 (m, 1H) 2.07-2.21 (m, 2H) 1.92 (s, 3H) 1.59-1.67 (m, 1H) 1.24 (s, 12H)
Step 6: Preparation of 3-[4-bromo-2-methoxy-6-(trifluoromethyl)phenyl]-2-methoxy-bicyclo[3.2.1]oct-2-en-4-one
[0494] ##STR00062##
[0495] To a solution of 2-methoxy-3-[2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-6-(trifluoromethyl)phenyl]bicyclo[3.2.1]oct-2-en-4-one (313 mg) in methanol (6.92 mL) under nitrogen atmosphere was added a solution of copper dibromide (464 mg) in water (6.92 mL). The mixture was refluxed for 2 hours. The mixture was cooled, concentrated and partitioned between ethyl acetate and water. The aqueous phase was extracted with further ethyl acetate and the combined organics were washed with brine, dried with magnesium sulfate and concentrated to give crude 3-[4-bromo-2-methoxy-6-(trifluoromethyl)phenyl]-2-methoxy-bicyclo[3.2.1]oct-2-en-4-one (285 mg) as a yellow gum which crystallised on standing.
[0496] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 7.38-7.44 (m, 1H) 7.13-7.19 (m, 1H) 3.75-3.80 (m, 3H) 3.60-3.69 (m, 3H) 3.23 (d, 1H) 2.99-3.06 (m, 1H) 2.28 (d, 1H) 2.08-2.17 (m, 2H) 1.89-2.01 (m, 1H) 1.82 (d, 1H) 1.71 (dt, 1H)
Step 7: 3-[2-methoxy-4-prop-1-ynyl-6-(trifluoromethyl)phenyl]bicyclo[3.2.1]octane-2,4-dione (Compound A3)
[0497] ##STR00063##
can be prepared using chemistry described in other examples.
Example 4: Preparation of 4-bromo-2-(2,2,2-trifluoroethoxy)benzaldehyde
[0498] ##STR00064##
[0499] To a solution of 4-bromo-2-hydroxy-benzaldehyde (CAS 22532-62-3, 1 g) in N,N-dimethylformamide (20 mL) at room temperature under nitrogen atmosphere was added sodium hydride (60% in mineral oil, 0.24 g). This mixture was stirred for 30 minutes. A solution of 2,2,2-trifluoroethyl trifluoromethanesulfonate (CAS 6226-25-1, 1.39 g) in N,N-dimethylformamide (10 mL) was added drop wise and then the reaction was heated to 65 C. for 4 hours. Iced water was added to the reaction mixture and extracted with ethyl acetate (2). The combined organics were dried with magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 4-bromo-2-(2,2,2-trifluoroethoxy)benzaldehyde (1.21 g) as a cream solid
[0500] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 10.42 (d, 1H) 7.76 (d, 1H) 7.29-7.35 (m, 1H) 7.14 (d, 1H) 4.49 (q, 2H)
Example 5: Preparation of 4-bromo-2-(difluoromethoxy)benzaldehyde
[0501] ##STR00065##
[0502] A mixture of 4-bromo-2-hydroxy-benzaldehyde (CAS 22532-62-3, 7 g) and caesium carbonate (15.884 g) in N,N-dimethylformamide (60 mL) was stirred for 5 minutes at room temperature. To this was added sodium 2-chloro-2,2-difluoro-acetic acid (CAS 1895-39-2, 12.3 g) and water (10 mL). The mixture was heated at 85-90 C. (internal temperature) for 5 hours then allowed to cool overnight. Poured the mixture onto ice-water and extracted with diethyl ether (2). The combined organics were washed with brine, dried with magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 4-bromo-2-(difluoromethoxy)benzaldehyde (4.9 g)
[0503] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 10.33 (s, 1H) 7.81 (d, 1H) 7.47-7.53 (m, 1H) 7.45 (d, 1H) 6.44-6.87 (m, 1H)
Example 6: Preparation of 3-[2-(2-methoxyethoxy)-4-prop-1-ynyl-phenyl]bicyclo[3.2.1]octane-2,4-dione (Compound A15)
[0504] ##STR00066##
Step 1: Preparation of 3-(4-bromo-2-hydroxy-phenyl)bicyclo[3.2.1]octane-2,4-dione
[0505] ##STR00067##
[0506] Potassium tert-butoxide (1M in tetrahydrofuran, 30.5 mL) was added drop wise to a solution of 4-bromo-2-(difluoromethoxy)benzaldehyde (Example 5, 6.39 g) and 3-bromonorbornan-2-one (CAS 89856-55-3, 7.2 g) in anhydrous methylsulfoxide (130 mL) at room temperature.
[0507] The reaction was stirred for 30 minutes and partitioned between saturated aqueous ammonium chloride and ethyl acetate. The aqueous was extracted with further ethyl acetate and the combined organics were dried with magnesium sulphate and concentrated to give 3-[4-bromo-2-(difluoromethoxy)phenyl]spiro[norbornane-3,2-oxirane]-2-one as a brown gum which was used crude in the next step.
[0508] The crude 3-[4-bromo-2-(difluoromethoxy)phenyl]spiro[norbornane-3,2-oxirane]-2-one was stirred in toluene (127 mL) at room temperature under nitrogen atmosphere and 7.7% phosphorus pentoxide in methane sulfonic acid (Eaton's Reagent, CAS 39394-84-8, 17.8 mL) was added drop wise. The mixture was heated to 60 C. for 3 hours. The mixture was cooled and basified to pH14 using 2M potassium hydroxide and washed twice with dichloromethane. The aqueous phase was acidified to pH1 using conc. hydrochloric acid and this was extracted with dichloromethane (2). The combined organics were concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 3-(4-bromo-2-hydroxy-phenyl)bicyclo[3.2.1]octane-2,4-dione (0.59 g) as a white solid.
[0509] LC/MS 0.63 min, MH+309 (2 min run)
Step 2: Preparation of 3-[4-bromo-2-(2-methoxyethoxy)phenyl]-2-(2-methoxyethoxy)bicyclo[3.2.1]oct-2-en-4-one
[0510] ##STR00068##
[0511] To a mixture of 3-(4-bromo-2-hydroxy-phenyl)bicyclo[3.2.1]octane-2,4-dione (0.59 g) and potassium carbonate (290 mg) in N,N-dimethylformamide (9.5 mL) was added drop wise 1-bromo-2-methoxy-ethane (0.23 ml). The reaction mixture was stirred at room temperature for 2 hours then heated to 70 C. for 2 hours. The reaction mixture was partitioned between 2M hydrochloric acid and ethyl acetate. The organic layer was concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 3-[4-bromo-2-(2-methoxyethoxy)phenyl]-2-(2-methoxyethoxy)bicyclo[3.2.1]oct-2-en-4-one (320 mg).
[0512] LC/MS 0.91 min, MH+425 (2 min run)
Step 3: 3-[2-(2-methoxyethoxy)-4-prop-1-ynyl-phenyl]bicyclo[3.2.1]octane-2,4-dione
[0513] (Compound A15)
##STR00069##
can be prepared using chemistry described in other examples.
Example 7: Preparation of [3-(2-methoxy-4-prop-1-ynyl-phenyl)-4-oxo-2-bicyclo[3.2.1]oct-2-enyl] acetate Compound P1
[0514] ##STR00070##
[0515] To a solution of 3-(2-methoxy-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]octane-2,4-dione (Compound A1, 200 mg) in dichloromethane (7.084 mL) at room temperature was added triethylamine (108 mg) and acetyl chloride (83 mg). This mixture was stirred at room temperature overnight.
[0516] Methanol (1 mL) was added to the reaction mixture and stirred for one hour, then concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give [3-(2-methoxy-4-prop-1-ynyl-phenyl)-4-oxo-2-bicyclo[3.2.1]oct-2-enyl] acetate (175 mg) as a yellow gum.
[0517] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 6.78-7.03 (m, 3H) 3.67-3.77 (m, 3H) 2.91-3.17 (m, 2H) 2.28-2.43 (m, 1H) 1.94-2.23 (m, 9H) 1.63-1.91 (m, 2H)
Example 8: Preparation of 3-(2-methoxy-4-prop-1-ynyl-phenyl)-2-prop-2-ynoxy-bicyclo[3.2.1]oct-2-en-4-one (Compound P2)
[0518] ##STR00071##
[0519] To a solution of 3-(2-methoxy-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]octane-2,4-dione (Compound A1, 200 mg) in acetone (5 mL) was added potassium carbonate (201 mg) followed by 3-bromoprop-1-yne (80% in Toluene, 0.158 mL). The mixture was stirred at room temperature for 6 hours. The mixture was partitioned between dichloromethane and water and the organic layer concentrated to give 3-(2-methoxy-4-prop-1-ynyl-phenyl)-2-prop-2-ynoxy-bicyclo[3.2.1]oct-2-en-4-one (203 mg) as a brown gum.
[0520] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 6.82-7.03 (m, 3H) 4.20-4.52 (m, 2H) 3.68-3.75 (m, 3H) 3.23 (d, 3H) 3.17-3.30 (m, 1H) 2.94-3.07 (m, 1H) 2.45-2.56 (m, 1H) 1.55-2.28 (m, 6H)
Example 9: Preparation of 2-(2,6-dimethoxy-4-prop-1-ynyl-phenyl)cyclohexane-1,3-dione (Compound A11)
[0521] ##STR00072##
Step 1: Preparation of [diacetoxy-(2,6-dimethoxyphenyl)plumbyl] acetate
[0522] ##STR00073##
[0523] A nitrogen flushed mixture of mercury (II) acetate (0.438 g) and lead (IV) acetate (14.6 g) in chloroform (50 mL) was warmed to 40 C. with stirring. The heat source was removed and (2,6-dimethoxyphenyl)boronic acid (CAS 23112-96-1, 5 g) was added in portions over 1 minute. This mixture was heated at 40 C. for 4 hours and left to cool. Chloroform (25 mL) was added and the mixture cooled in an ice bath with stirring. Potassium carbonate (34 g) was added gradually and the mixture stirred for 10 minutes under nitrogen. The resulting dark orange suspension was filtered through chloroform-washed Celite and washed through with further chloroform (40 ml). The filtrate was concentrated to leave a yellow solid which was triturated with iso-Hexane and chloroform and filtered, washed with a little cold iso-Hexane and air-dried to give
[0524] [diacetoxy-(2,6-dimethoxyphenyl)plumbyl] acetate (10.9 g) as a yellow solid.
[0525] Used as is in the next step.
Step 2: Preparation of 2-(2,6-dimethoxyphenyl)cyclohexane-1,3-dione
[0526] ##STR00074##
[0527] To a mixture of cyclohexane-1,3-dione (0.66 g) and 4-(dimethylamino)pyridine (3.6 g) in chloroform (32 mL) under nitrogen atmosphere was added toluene (8 mL) followed by [diacetoxy-(2,6-dimethoxyphenyl)plumbyl] acetate (3.7 g). This mixture was heated at 80 C. for 3 hours. Diluted the reaction with chloroform (50 mL) and cooled with an ice-water-bath. Gradually acidified the mixture with aqueous 2M hydrochloric acid (20 mL) then stirred the mixture vigorously for 10 minutes. Filtered the mixture through water-washed Celite then washed through with chloroform. The organic layer was separated, concentrated under reduced pressure and purified by chromatography on silica eluting with methanol in dichloromethane to give 2-(2,6-dimethoxyphenyl)cyclohexane-1,3-dione (1.4 g) as a yellow gum.
[0528] LC/MS 0.28 min, MH+249 (2 min run)
Step 3: 2-(2,6-dimethoxy-4-prop-1-ynyl-phenyl)cyclohexane-1,3-dione (Compound A11)
[0529] ##STR00075##
can be prepared using chemistry described in other examples.
Example 10: Preparation of 2-(2,6-dimethoxy-4-prop-1-ynyl-phenyl)-5-(2-methylsulfanylethyl)cyclohexane-1,3-dione (Compound A13)
[0530] ##STR00076##
Step 1: Preparation of 5-bromo-2-iodo-1,3-dimethoxy-benzene
[0531] ##STR00077##
[0532] Methanol (338 mL) was cooled to 5 C. and potassium hydroxide (29.3 g) was added portion wise over 15 minutes maintaining the temperature below 10 C. This solution was added over 15 minutes to a solution of 5-bromo-1,3-difluoro-2-iodo-benzene (CAS 160976-02-3, 15 g) in methanol (9 mL) at 60 C. under nitrogen atmosphere. The mixture was heated at 60 C. for 168 hours. The reaction was concentrated and partitioned between ethyl acetate and water. The aqueous phase was extracted with further ethyl acetate and the combined organic phases were washed with brine, dried over magnesium sulfate and concentrated to give 5-bromo-2-iodo-1,3-dimethoxy-benzene (10.83 g) as a white solid.
[0533] .sup.1H NMR (500 MHz, CDCl.sub.3) ppm 6.65 (s, 2H), 3.88 (s, 6H)
Step 2: Preparation of (4-bromo-2,6-dimethoxy-phenyl)boronic acid
[0534] ##STR00078##
[0535] A solution of 5-bromo-2-iodo-1,3-dimethoxy-benzene (8.5 g) in tetrahydrofuran (99 mL) was cooled to 78 C. under nitrogen atmosphere. A solution of i-propyl magnesium chloride (25 mL) was added drop wise over 1 hour, maintaining the temperature below 65 C. The reaction mixture was stirred at 78 C. for 25 minutes and then allowed to warm to room temperature and stirred for 1.25 hours.
[0536] After this time, the solution was cooled back to 78 C. and trimethyl borate (8.8 mL) was added drop wise over 5 minutes, maintaining the temperature below 65 C. On completion of the addition the cooling was removed and the solution was stirred for 2.5 hours. The reaction mixture was diluted with water and acidified with 2M hydrochloric acid and stirred for 2 hours. Ethyl acetate was added and the layers separated. The aqueous was extracted with further ethyl acetate (2) and the combined organic phases were washed with brine, dried over magnesium sulfate and concentrated. The residue was triturated with iso-hexane and air dried to give (4-bromo-2,6-dimethoxy-phenyl)boronic acid (5.85 g) as an off-white solid.
[0537] .sup.1H NMR (500 MHz, CDCl.sub.3) ppm 7.00-7.05 (m, 2H), 6.78-6.82 (m, 2H), 3.91 (s, 6H)
Step 3: Preparation of (E)-6-Methylsulfanylhex-3-en-2-one
[0538] ##STR00079##
[0539] To a solution of 3-methylsulfanylpropanal (CAS 3268-49-3, 5.6 g) in dichloromethane (120 mL) was added 1-(triphenylphosphoranylidene)-2-propanone (CAS 1439-36-7, 17 g) in a single portion. The reaction mixture was heated and stirred at reflux for 5 hours. The cooled reaction mixture was concentrated to leave a pale yellow solid which was triturated with a 1:1 mixture of ether:iso-hexane (100 mL). The resulting solid was collected by filtration and washed with further 1:1 ether:iso-hexane (50 mL). The filtrate was concentrated to a yellow oil and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give (E)-6-methylsulfanylhex-3-en-2-one (5.890 g) as a colourless liquid.
[0540] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.81 (dt, 1H), 6.08-6.15 (m, 1H), 2.61-2.67 (m, 2H), 2.49-2.58 (m, 2H), 2.24-2.27 (m, 3H), 2.10-2.15 (m, 3H)
Step 4: Preparation of Ethyl 2-(2-methylsulfanylethyl)-4,6-dioxo-cyclohexanecarboxylate
[0541] ##STR00080##
[0542] To ice cooled ethanol (50 mL) was added sodium metal (1.249 g) in small portions under nitrogen and the resulting solution was stirred for 15 minutes. Diethyl propanedioate (7.901 g) in ethanol (25 mL) was added drop wise to this cooled solution over 20 minutes. The reaction was allowed to warm to ambient temperature and stirred for a further 2 hours. The mixture was cooled in an ice bath and a solution of (E)-6-methylsulfanylhex-3-en-2-one (5.890 g) in ethanol (25 mL) was added drop wise. The reaction was allowed to warm to ambient temperature, stirred for 4 hours and then left to stand overnight. The reaction was concentrated to a yellow slurry which was poured into a cooled solution of 2M hydrochloric acid and stirred for 5 minutes. This was extracted with dichloromethane (2) and the combined organic layers dried over anhydrous magnesium sulfate and concentrated to give ethyl 2-(2-methylsulfanylethyl)-4,6-dioxo-cyclohexanecarboxylate (11.446 g) as a yellow oil.
[0543] .sup.1H NMR (400 MHz, CDCl.sub.3) 5.48-5.56 (m, 1H), 4.13-4.33 (m, 2H), 3.38-3.48 (m, 1H), 3.11-3.21 (m, 1H), 2.44-2.75 (m, 3H), 2.17-2.26 (m, 1H), 2.09 (s, 3H), 1.63-1.86 (m, 2H), 1.30 (t, 3H)
Step 5: Preparation of 5-(2-Methylsulfanylethyl)cyclohexane-1,3-dione
[0544] ##STR00081##
[0545] A solution of ethyl 2-(2-methylsulfanylethyl)-4,6-dioxo-cyclohexanecarboxylate (11.446 g) in propan-2-ol (32 mL) was stirred with 2M sodium hydroxide solution (115.2 mL) for 4 hours. The reaction was concentrated to remove the propan-2-ol and the remaining aqueous solution was taken to pH 1 by the addition of conc. hydrochloric acid. This solution was heated to 70 C. for 1.5 hours, then left to cool overnight. The resulting solid was collected by filtration and washed with water then iso-hexane and air dried to leave a pale yellow powder. The powder was washed further with water (4) and air dried to give 5-(2-methylsulfanylethyl)cyclohexane-1,3-dione (6.583 g) as a yellow solid
[0546] 1H NMR (400 MHz, CDCl.sub.3) 5.48 (s, 1H), 3.41 (d, 1H), 2.77 (dd, 3H), 2.45-2.61 (m, 2H), 2.25-2.43 (m, 2H), 2.08-2.18 (m, 3H), 1.63-1.74 (m, 2H)
Step 6: 2-(2,6-dimethoxy-4-prop-1-ynyl-phenyl)-5-(2-methylsulfanylethyl)cyclohexane-1,3-dione
[0547] (Compound A13)
##STR00082##
can be prepared using chemistry described in other examples.
LC-MS Analysis
[0548] Note: Compounds characterised by HPLC-MS were analysed using an Agilent 1100 Series HPLC equipped with a Waters Atlantis dC18 column (column length 20 mm, internal diameter of column 3 mm, particle size 3 micron, temperature 40 C.), Waters photodiode array and Micromass ZQ2000. The analysis was conducted using either a two or five minute run time, using a solvent gradient between Solvent A: H.sub.2O with 0.1% HCOOH and Solvent B: 0.1% HCOOH in CH.sub.3CN. The characteristic values obtained for each compound were the retention time (RT, recorded in minutes) and the molecular ion, typically the cation MH+.
Example 11: Preparation of 3-(2-butyl-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]octane-2,4-dione (Compound A18)
[0549] ##STR00083##
Step 1: Preparation of 4-bromo-2-butyl-aniline
[0550] ##STR00084##
[0551] A solution of 2-butylaniline (CAS 2696-85-7, 5 g) in acetonitrile (100 mL) was cooled to 0 C. To this was added N-bromosuccinimde (6 g) portion wise over 25 minutes. The reaction was stirred for 1 hour at 0 C. The reaction was partitioned between water (200 mL) and ethyl acetate (200 mL) and extracted with further ethyl acetate. The combined organic layers were washed with aqueous sodium thiosulfate solution, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 4-bromo-2-butyl-aniline as a pale brown liquid (1.37 g)
[0552] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 7.14 (d, 1H) 7.10 (dd, 1H) 6.54 (d, 1H) 3.60 (brs, 2H) 2.40-2.47 (m, 2H) 1.53-1.62 (m, 2H) 1.40 (dq, 2H) 0.95 (t, 3H)
Step 2: Preparation of 4-bromo-2-butyl-1-iodo-benzene
[0553] ##STR00085##
[0554] To a solution of 4-methylbenzenesulfonic acid (3.10 g) in acetonitrile (41.1 mL) was added 4-bromo-2-butyl-aniline (1.37 g). This mixture was stirred for 10 minutes at room temperature and then cooled to 5-10 C. To this suspension was added, portion wise over 10 minutes, a solution of sodium nitrite (0.829 g) and potassium iodide (2.49 g) in water (4.80 mL). On completion of addition, the reaction mixture was stirred at 5 C. for 20 minutes and then the cooling removed and the mixture stirred at room temperature for 1 hour. The reaction mixture was adjusted to pH 9/10 by addition of aqueous sodium hydrogen carbonate solution. The mixture was partitioned between 10% aqueous sodium metabisulfite solution (100 mL) was then added followed by ethyl acetate (100 mL). The layers were separated and the aqueous extracted with further ethyl acetate (2100 mL). The combined organic phases were washed with 10% aqueous sodium metabisulfite solution (100 mL), water (100 mL) and brine (100 mL), then dried with magnesium sulfate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 4-bromo-2-butyl-1-iodo-benzene as a colourless gum (0.99 g).
[0555] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 7.64 (d, 1H) 7.33 (d, 1H) 7.00 (dd, 1H) 2.62-2.69 (m, 2H) 1.50-1.60 (m, 2H) 1.41 (dq, 2H) 0.92-0.99 (m, 3H)
Step 3: Preparation of 4-bromo-2-butyl-benzaldehyde
[0556] ##STR00086##
[0557] A solution of 4-bromo-2-butyl-1-iodo-benzene (0.99 g) in anhydrous tetrahydrofuran (8 mL) was cooled to 78 C. under nitrogen atmosphere. A solution of i-propyl magnesium chloride (2M in tetrahydrofuran, 2.9 mL) was added drop wise over 5 minutes. The reaction mixture was stirred at 78 C. for 25 minutes and then allowed to warm to room temperature and stirred for 45 minutes. After this time, the reaction mixture was cooled to 78 C. and a solution of 4-formyl morpholine (1.2 g) in anhydrous tetrahydrofuran (4 mL) was added drop wise. On completion of addition the cooling was removed and solution was stirred at room temperature for 18 hours. To the reaction mixture was added 2M hydrochloric acid (20 mL) and the mixture stirred for 30 minutes. Ethyl acetate (20 mL) and water (20 mL) were added and the phases separated. The aqueous phase was extracted with further ethyl acetate (2) and the combined organics were washed with brine, dried over magnesium sulphate, concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 4-bromo-2-butyl-benzaldehyde as a yellow oil (0.42 g).
[0558] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 10.23 (s, 1H) 7.69 (d, 1H) 7.49 (dd, 1H) 7.44 (d, 1H) 2.96-3.02 (m, 2H) 1.55-1.68 (m, 2H) 1.36-1.46 (m, 2H) 0.92-0.98 (m, 3H)
Step 4: Preparation of 3-(4-bromo-2-butyl-phenyl)spiro[norbornane-3,2-oxirane]-2-one
[0559] ##STR00087##
[0560] Potassium tert-butoxide (1M in tetrahydrofuran, 29 ml) was added drop wise to a solution of 3-bromonorbornan-2-one (CAS 89856-55-3, 5.42 g) and 4-bromo-2-butyl-benzaldehyde (5.77 g) in anhydrous methyl sulfoxide (120 mL) at room temperature. The reaction was stirred for 1 hour, quenched with saturated aqueous ammonium chloride and extracted twice with ethyl acetate. The combined organics were washed with water, brine, dried over magnesium sulfate and concentrated to give 3-(4-bromo-2-butyl-phenyl)spiro[norbornane-3,2-oxirane]-2-one as a brown gum which solidified on standing.
[0561] This compound was used crude in the next step.
Step 5: Preparation of 3-(4-bromo-2-butyl-phenyl)bicyclo[3.2.1]octane-2,4-dione
[0562] ##STR00088##
[0563] Crude 3-(4-bromo-2-butyl-phenyl)spiro[norbornane-3,2-oxirane]-2-one (0.32 g) was dissolved in acetonitrile (3 mL) and dry Amberlyst 15 resin (CAS 39389-20-3, 320 mg) was added. This mixture was stirred and heated at 75 C. overnight. The resin is removed by filtration and the filtrate concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 3-(4-bromo-2-butyl-phenyl)bicyclo[3.2.1]octane-2,4-dione (120 mg) as a brown gum.
[0564] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 7.39-7.46 (m, 1H) 7.31-7.38 (m, 1H) 6.78-6.92 (m, 1H) 3.03 (brs, 2H) 2.33-2.52 (m, 1H) 2.02-2.30 (m, 4H) 1.83-2.00 (m, 1H) 1.61-1.83 (m, 2H) 1.24-1.52 (m, 4H) 0.82-0.97 (m, 3H)
Step 6: Preparation of 3-(2-butyl-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]octane-2,4-dione Compound A3
[0565] ##STR00089##
[0566] To a mixture of 3-(4-bromo-2-butyl-phenyl)bicyclo[3.2.1]octane-2,4-dione (500 mg), 2-butynoic acid (CAS 590-93-2, 144 mg), bis(triphenylphosphine)palladium(II) dichloride (CAS 13965-03-2, 51 mg) and 1,4-bis-(diphenylphosphino)butane (CAS 7688-25-7, 61 mg) in methyl sulfoxide (10 mL) under nitrogen atmosphere was added tetrabutylammonium fluoride (CAS 429-41-4, 1M in tetrahydrofuran, 4.3 mL). The reaction was heated to 110 C. for 3 hours. The reaction contents were transferred to a microwave vial and subjected to microwave heating at 160 C. for 1 hr. The reaction mixture was quenched with 2M hydrochloric acid and extracted twice with dichloromethane. The combined organics were concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give a yellow gum. The gum was partitioned between 0.5M potassium carbonate solution and dichloromethane. The aqueous phase was acidified with conc. hydrochloric acid and extracted with dichloromethane (2). The combined organics were concentrated to give 3-(2-butyl-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]octane-2,4-dione as a colourless gum
[0567] .sup.1H NMR (400 MHz, CDCl.sub.3) =7.34-7.28 (m, 1H), 7.23 (dd, 1H), 6.9-6.81 (m, 1H), 5.92 (brs, 1H), 3.12-2.83 (m, 2H), 2.43-2.09 (m, 5H), 2.07-2.01 (m, 3H), 1.98-1.58 (m, 3H), 1.49-1.14 (m, 4H), 0.94-0.78 (m, 3H)
Example 12: Preparation of 3-(2-propyl-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]octane-2,4-dione (Compound A16)
[0568] ##STR00090##
Step 1: Preparation of 3-(4-bromo-2-propyl-phenyl)-2-methoxy-bicyclo[3.2.1]oct-2-en-4-one
[0569] ##STR00091##
[0570] To a solution of 3-(4-bromo-2-propyl-phenyl)bicyclo[3.2.1]octane-2,4-dione (0.96 g) in acetone (30 mL) was added potassium carbonate (0.93 g) followed by iodomethane (0.89 mL). The reaction was stirred at room temperature overnight. The mixture was partitioned between dichloromethane and water and the organics were concentrated to give 3-(4-bromo-2-propyl-phenyl)-2-methoxy-bicyclo[3.2.1]oct-2-en-4-one (0.97 g) as a brown gum.
[0571] LC-MS (2 min run) 1.08 min MH+349
Step 2: Preparation of 2-methoxy-3-(2-propyl-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]oct-2-en-4-one
[0572] ##STR00092##
[0573] To a mixture of 3-(4-bromo-2-propyl-phenyl)-2-methoxy-bicyclo[3.2.1]oct-2-en-4-one (300 mg), 2-butynoic acid (CAS 590-93-2, 87 mg), bis(triphenylphosphine)palladium(II) dichloride (CAS 13965-03-2, 30 mg) and 1,4-bis-(diphenylphosphino)butane (CAS 7688-25-7, 37 mg) in methyl sulfoxide (8 mL) under nitrogen atmosphere was added tetrabutylammonium fluoride (CAS 429-41-4, 1M in tetrahydrofuran, 2.4 mL). The reaction was heated to 110 C. for 1 hour. The reaction mixture was quenched with water and extracted twice with dichloromethane. The combined organics were concentrated and purified by chromatography on silica eluting with ethyl acetate in iso-hexane to give 2-methoxy-3-(2-propyl-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]oct-2-en-4-one (100 mg) as a yellow gum.
[0574] LC-MS (2 min run) 1.08 min MH+309
Step 3: Preparation of 3-(2-propyl-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]octane-2,4-dione Compound A1
[0575] ##STR00093##
[0576] To a solution of 2-methoxy-3-(2-propyl-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]oct-2-en-4-one (100 mg) in acetone (1 mL) was added 2M hydrochloric acid (1 mL) and the mixture heated to 60 C. for 1 hour. The reaction mixture was concentrated and partitioned between water and dichloromethane. The organic layer was concentrated to give 3-(2-propyl-4-prop-1-ynyl-phenyl)bicyclo[3.2.1]octane-2,4-dione (100 mg) as a gum.
[0577] .sup.1H NMR (400 MHz, CDCl.sub.3) ppm 7.30-7.36 (m, 1H) 7.21-7.27 (m, 1H) 6.85-6.99 (m, 1H) 2.99-3.09 (m, 2H) 2.32-2.42 (m, 1H) 2.09-2.30 (m, 4H) 1.99-2.07 (m, 3H) 1.87 (brs, 2H) 1.30-1.73 (m, 3H) 0.88 (q, 3H)
LC-MS Analysis
[0578] Note: Compounds characterised by HPLC-MS were analysed using an Agilent 1100 Series HPLC equipped with a Waters Atlantis dC18 column (column length 20 mm, internal diameter of column 3 mm, particle size 3 micron, temperature 40 C.), Waters photodiode array and Micromass ZQ2000. The analysis was conducted using either a two or five minute run time, using a solvent gradient between Solvent A: H.sub.2O with 0.1% HCOOH and Solvent B: 0.1% HCOOH in CH.sub.3CN. The characteristic values obtained for each compound were the retention time (RT, recorded in minutes) and the molecular ion, typically the cation MH+. Additional compounds in Tables T1 and P1 below illustrate the present invention, and are particular embodiments of the compounds of formula (I) according to the present invention. For the most part, these compounds can generally be prepared by methods similar to those shown in the Examples and/or shown in the process section hereinabove using appropriate starting materials.
TABLE-US-00010 TABLE T1 Compound .sup.1H NMR 400 MHz (CDCl.sub.3 solvent Number Structure unless stated otherwise) (delta) A1
TABLE-US-00011 TABLE P1 Compound .sup.1H NMR 400 MHz (delta) CDCl.sub.3 Number Structure (unless stated) P1
Compounds of Tables 1 to 22
[0579] The compounds of the following Tables 1 to 22 also illustrate the present invention, and are also particular embodiments of the compounds of formula (I) according to the present invention. For the most part, these compounds can generally be prepared by methods similar or analogous to those shown in the Examples and/or in the process section hereinabove using appropriate starting materials.
[0580] Table 1 covers 22 compounds of the following type
##STR00131##
[0581] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
TABLE-US-00012 TABLE 1 Compound Number R.sup.1 R.sup.2 1.01 methoxy hydrogen 1.02 methoxy methoxy 1.03 methoxy n-propyl 1.04 methoxy trifluoromethoxy 1.05 methoxy difluoromethoxy 1.06 methoxy ethyl 1.07 trifluoromethoxy hydrogen 1.08 trifluoromethoxy trifluoromethoxy 1.09 trifluoromethoxy difluoromethoxy 1.10 trifluoromethoxy ethyl 1.11 trifluoromethoxy n-propyl 1.12 difluoromethoxy n-propyl 1.13 difluoromethoxy hydrogen 1.14 difluoromethoxy difluoromethoxy 1.15 difluoromethoxy ethyl 1.16 ethoxy ethoxy 1.17 ethoxy methoxy 1.18 ethoxy n-propyl 1.19 ethoxy ethyl 1.20 ethoxy trifluoromethoxy 1.21 ethoxy hydrogen 1.22 ethoxy difluoromethoxy 1.23 ethyl hydrogen 1.24 ethyl ethyl 1.25 ethyl n-propyl 1.26 n-propyl hydrogen 1.27 n-propyl n-propyl
[0582] Table 2 covers 27 compounds of the following type
##STR00132##
[0583] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0584] Table 3 covers 27 compounds of the following type
##STR00133##
[0585] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0586] Table 4 covers 27 compounds of the following type
##STR00134##
[0587] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0588] Table 5 covers 27 compounds of the following type
##STR00135##
[0589] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0590] Table 6 covers 27 compounds of the following type
##STR00136##
[0591] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0592] Table 7 covers 27 compounds of the following type
##STR00137##
[0593] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0594] Table 8 covers 27 compounds of the following type
##STR00138##
[0595] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0596] Table 9 covers 27 compounds of the following type
##STR00139##
[0597] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0598] Table 10 covers 27 compounds of the following type
##STR00140##
[0599] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0600] Table 11 covers 27 compounds of the following type
##STR00141##
[0601] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0602] Table 12 covers 27 compounds of the following type
##STR00142##
[0603] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0604] Table 13 covers 27 compounds of the following type
##STR00143##
[0605] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0606] Table 14 covers 27 compounds of the following type
##STR00144##
[0607] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0608] Table 15 covers 27 compounds of the following type
##STR00145##
[0609] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0610] Table 16 covers 27 compounds of the following type
##STR00146##
[0611] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0612] Table 17 covers 27 compounds of the following type
##STR00147##
[0613] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0614] Table 18 covers 27 compounds of the following type
##STR00148##
[0615] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0616] Table 19 covers 27 compounds of the following type
##STR00149##
[0617] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0618] Table 20 covers 27 compounds of the following type
##STR00150##
[0619] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0620] Table 21 covers 27 compounds of the following type
##STR00151##
[0621] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
[0622] Table 22 covers 27 compounds of the following type
##STR00152##
[0623] wherein R.sup.1 and R.sup.2 are as defined in Table 1.
BIOLOGICAL EXAMPLES
Biological Example 1Glasshouse Assay for Herbicidal Activity
[0624] Seeds of a variety of test plant species were sown in standard soil ** in pots. After cultivation for one day (pre-emergence) or after 8 days cultivation (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 formulation of the technical active ingredient (the test herbicide) in acetone/water (50:50) solution containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate, CAS Reg. No. 9005-64-5). The test plants were then grown on under controlled conditions in a glasshouse (at 24/16 C., day/night; 14 hours light; 65% humidity) and watered twice daily. 13 Days after application of the test herbicide, for pre- and post-emergence, the test was evaluated visually for percentage phytotoxicity to each plant (where 100%=total damage to plant; 0%=no damage to plant). Generally, each test herbicide is only tested on 1 plant per plant species for each application rate tested and for each application timing.
[0625] The standard soil in Biological Example 1 is usually a sand or sandy loam type of soil.
Biological Example 1Pre-Emergence ApplicationHerbicidal Activity Results (Percentage Phytotoxicity)
[0626] Test Plants:
[0627] Dicotyledonous weeds: ABUTH=Abutilon theophrasti; AMARE=Amaranthus retroflexus. Grassy monocotyledonous weeds: SETFA=Setaria faberi; ALOMY=Alopecurus myosuroides; ECHCG=Echinochloa crus-galli; ZEAMX=Zea mays (corn, maize, e.g. volunteer corn).
Biological Example 1Post-Emergence ApplicationHerbicidal Activity Results (Percentage Phytotoxicity)
[0628] Test Plants:
[0629] Dicotyledonous weeds: ABUTH=Abutilon theophrasti; AMARE=Amaranthus retroflexus. Grassy monocotyledonous weeds: SETFA=Setaria faberi; ALOMY=Alopecurus myosuroides; ECHCG=Echinochloa crus-galli; ZEAMX=Zea mays (corn, maize, e.g. volunteer corn).
TABLE-US-00013 Appli- cation Compound Rate Number g/ha ABUTH AMARE SETFA ALOMY ECHCG ZEAMX A1 250 20 50 100 100 100 100 A1 30 10 30 90 100 100 100 A2 250 10 0 90 90 70 70 A3 250 0 0 90 70 100 90 A3 30 0 0 70 40 70 90 A4 250 0 0 70 30 40 60 A4 30 0 0 40 10 20 30 A5 250 0 0 90 80 100 100 A5 30 0 0 60 50 90 100 A6 250 0 0 50 - 70 80 A6 30 0 0 10 - 40 40 A7 250 10 0 100 100 100 100 A7 30 0 0 100 90 100 100 A8 250 80 10 100 100 100 100 A9 250 40 20 90 90 90 100 A9 30 20 0 80 30 80 90 A10 250 10 20 70 70 30 90 A10 30 0 10 60 0 20 90 A11 250 0 30 100 90 100 100 A11 30 0 10 100 70 100 100 A12 250 20 30 100 100 100 100 A12 30 0 0 100 90 100 100 A14 250 0 0 90 - 100 90 A14 30 0 0 50 - 70 70 A15 250 0 0 80 20 40 80 A15 30 0 0 50 10 10 40 A16 250 0 0 100 100 100 100 A17 250 50 0 90 100 100 100 P1 250 10 20 90 100 100 100 P2 250 0 0 80 70 90 100 P3 250 0 10 90 70 100 100 P4 250 10 0 100 100 100 100 P5 250 50 30 90 90 100 100 P6 250 60 40 90 90 100 100 P7 250 40 30 90 90 100 100 P8 250 60 20 90 90 100 100 P10 250 70 40 90 90 100 100 P11 250 70 20 100 90 100 100 P12 250 70 20 90 100 100 100 P13 250 40 60 100 90 100 100 P14 250 70 20 100 90 100 100 P15 250 70 10 100 90 100 100 P16 250 40 40 70 80 90 100 P17 250 70 0 80 90 90 100 P18 250 70 30 90 90 100 100 Note: a hyphen (-) in the table above indicates that no measurement was made.