Oxa-and thia(di)azabicyclic compounds

Description

The present invention relates to novel oxa(di)azabicyclic and thia(di)azabicyclic compounds, a method for their preparation and their use as weedkillers.
As has already been reported, certain thiadiazabicyclic compounds (see EP 238 711, EP 304 920, U.S. Pat. Nos. 4,885,023, 4,684,397, US 4,801,408, WO 92/21684 and EP 600 833) can be used as weedkillers.
The present invention provides novel compounds of Formula I, ##STR1## wherein: X is selected from the group O, S, S(O), S(O).sub.2, CH.sub.2, CHF, CF.sub.2, CHCl, CHBr, CHOCH.sub.2 F, CHOCHF.sub.2, CHOCF.sub.3, CHOCH.sub.2 CF.sub.3 and NR.sup.4 ;
m and n are independently 1 or 2, where m+n=2 or 3;
p is 0 to 9;
U is N or CH;
W is independently O or S;
R.sup.A is independently selected from the group halogen, C.sub.1 -C.sub.4 alkyl, cyano, C.sub.1 -C.sub.4 haloalkyl, C.sub.3 -C.sub.4 alkenyl, C.sub.1 -C.sub.3 alkylthio, C.sub.1 -C.sub.3 haloalkylthio, C.sub.2 -C.sub.4 alkylcarbonyl, OR.sup.3, C.sub.2 -C.sub.6 alkyloxycarbonyl, C.sub.2 -C.sub.6 haloalkoxycarbonyl, and C.sub.3 -C.sub.8 alkoxycarbonylalkyl; or, two R.sup.A groups on the same carbon atom, together with this carbon, are C.dbd.O;
R.sup.3 is selected from the group hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.2 -C.sub.4 alkylcarbonyl and C.sub.2 -C.sub.4 haloalkylcarbonyl;
R.sup.4 is selected from the group hydrogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl, C.sub.2 -C.sub.4 alkylcarbonyl, C.sub.2 -C.sub.4 haloalkoxycarbonyl and C.sub.2 -C.sub.4 alkoxycarbonyl;
provided that:
i) when X is CH.sub.2 and U is N, then p is 1 to 8 and at least one R.sup.A is halogen; and
ii) when X is CHOCH.sub.2 F, CHOCHF.sub.2, CHOCF.sub.3, or CHOCH.sub.2 CF.sub.3, m and n are 1, and U is N, then p is 1 to 5 and at least one R.sup.A is other than alkyl;
Q is selected from the group ##STR2## Z is O or S; R.sup.5 is hydrogen or halogen;
R.sup.6 is selected from the group C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 haloalkyl, OCH.sub.3, SCH.sub.3, OCHF.sub.2, halogen, CN and NO.sub.2 ;
R.sup.7 is selected from the group hydrogen, C.sub.1 -C.sub.8 alkyl, C.sub.1 -C.sub.8 haloalkyl, halogen, OR.sup.11, SR.sup.11, S(O).sub.q R.sup.11, COR.sup.11, CO.sub.2 R.sup.11, C(O)SR.sup.11, C(O)NR.sup.12 R.sup.13, CHO and NHSO.sub.2 NHR.sup.16 ;
R.sup.8 is selected from the group hydrogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl and halogen;
R.sup.9 is selected from the group hydrogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl and halogen; or, when Q is Q-2 or Q-6, R.sup.8 and R.sup.9 together with the carbon to which they are bonded is additionally selected from C.dbd.O;
R.sup.10 is selected from the group C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.2 -C.sub.6 alkoxyalkyl, C.sub.3 -C.sub.6 alkenyl and C.sub.3 -C.sub.6 alkenyl;
R.sup.11 is selected from the group C.sub.1 -C.sub.8 alkyl, C.sub.3 -C.sub.8 cycloalkyl, C.sub.3 -C.sub.8 alkenyl, C.sub.3 -C.sub.8 alkenyl, C.sub.1 -C.sub.8 haloalkyl, C.sub.2 -C.sub.8 alkoxyalkyl, C.sub.2 -C.sub.8 alkylthioalkyl, C.sub.2 -C.sub.8 alkylsulphinylalkyl, C.sub.2 -C.sub.8 alkylsulphonylalkyl, C.sub.3 -C.sub.8 alkoxyalkoxyalkyl, C.sub.4 -C.sub.8 cycloalkylalkyl, C.sub.2 -C.sub.4 carboxyalkyl, C.sub.3 -C.sub.8 alkoxycarbonylalkyl, C.sub.6 -C.sub.8 alkenyloxycarbonylalkyl, C.sub.6 -C.sub.8 alkenyloxycarbonylalkyl, C.sub.5 -C.sub.8 alkoxycarbonylalkenyl, C.sub.4 -C.sub.8 alkenyloxyalkyl, C.sub.6 -C.sub.8 cycloalkoxyalkyl, C.sub.4 -C.sub.8 alkynyloxyalkyl, C.sub.3 -C.sub.8 haloalkoxyalkyl, C.sub.4 -C.sub.8 haloalkenyloxyalkyl, C.sub.4 -C.sub.8 haloalkynyloxyalkyl, C.sub.4 -C.sub.8 alkenylthioalkyl, C.sub.4 -C.sub.8 alkynylthioalkyl; C.sub.1 -C.sub.4 alkyl substituted with phenoxy or benzyloxy, each of the phenoxy and benzyloxy optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl, C.sub.4 -C.sub.8 trialkylsilylalkyl, C.sub.3 -C.sub.8 cyanoalkyl, C.sub.3 -C.sub.8 halocycloalkyl, C.sub.3 -C.sub.8 haloalkenyl, C.sub.5 -C.sub.8 alkoxyalkenyl, C.sub.5 -C.sub.8 haloalkoxyalkenyl, C.sub.5 -C.sub.8 alkylthioalkenyl, C.sub.3 -C.sub.8 haloalkynyl, C.sub.5 -C.sub.8 alkoxyalkynyl, C.sub.5 -C.sub.8 haloalkoxyalkynyl, C.sub.5 -C.sub.8 alkylthioalkynyl, C.sub.2 -C.sub.8 alkylcarbonyl; benzyl optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl; CHR.sup.17 COR.sup.18, CHR.sup.7 P(O)(ORI.sup.18).sub.2, P(O)(OR.sup.18).sub.2, CHR.sup.17 P(S)(OR.sup.18).sub.2, CHR.sup.17 C(O)NR.sup.12 R.sup.13, CHR.sup.17 C(O)NH.sub.2, phenyl and pyridyl, each of the phenyl and pyridyl optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl, C.sub.1 -C.sub.4 alkoxy and CHR.sup.17 CH.dbd.NOR.sup.18 ;
R.sup.12 and R.sup.14 are independently hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.13 and R.sup.15 are independently selected from the group C.sub.1 -C.sub.4 alkyl and phenyl optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl and C.sub.1 -C.sub.4 alkoxy; or
R.sup.12 and R.sup.13 are taken together as --(CH.sub.2).sub.5 --, --(CH.sub.2).sub.4 -- or --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --, each independently forming a ring in which one or more H atoms is optionally replaced by at least one member independently selected from the group C.sub.1 -C.sub.3 alkyl, optionally substituted phenyl and optionally substituted benzyl; or
R.sup.14 and R.sup.15 together with the carbon atom to which they are attached is C.sub.3 -C.sub.8 cycloalkyl;
R.sup.16 is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl;
R.sup.17 is hydrogen or C.sub.1 -C.sub.3 alkyl;
R.sup.18 is selected from the group C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.6 alkenyl and C.sub.3 -C.sub.6 alkynyl; and
q is 1 or2.
In the definitions given above the term `alkyl`, alone or in combined names such as `alkylthio` or `haloalkyl`, includes a straight or branched chain isomers; for example, methyl, ethyl, n-propyl, isopropyl or the various butyl isomers. Alkoxy includes methoxy, ethoxy, n-propyloxy, isopropyl oxy and the various butyl oxy isomers. Alkenyl covers straight- or branch-chain alkenes; for example, 1-propenyl, 2-propenyl, 3-propenyl and the various butenyl isomers. Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term `halogen`, alone or in combined names such as `haloalkyl`, signifies fluorine, chlorine, bromine or iodine. Furthermore, if `haloalkyl` is used in the combined name, alkyl can be partly or totally substituted with halogen atoms, which in turn can be identical or different. Examples of haloalkyl are CH.sub.2 CH.sub.2 F, CF.sub.2 CF.sub.3 and CH.sub.2 CHFC.sub.1. Brackets in the nomenclature signify an optional component; for example, thia(di)azabicyclic compounds represent the aza- or the dim-compound.
Preference is given to the following radicals,
wherein:
X is selected from the group O, CHF, CF.sub.2 and CHCl;
R.sup.A is independently selected from the group fluorine, chlorine and bromine;
R.sup.5 is selected from the group hydrogen, fluorine and chlorine;
R.sup.6 is selected from the group chlorine, bromine and cyano;
R.sup.7 is selected from the group hydrogen, OR.sup.11, CO.sub.2 R.sup.11, C.sub.1 -C.sub.2 alkyl and C.sub.1 -C.sub.2 haloalkyl;
R.sup.10 is selected from the group C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 haloalkyl, C.sub.3 -C.sub.4 alkenyl and C.sub.3 -C.sub.4 alkynyl;
R.sup.11 is selected from the group C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.6 cycloalkyl, C.sub.3 -C.sub.6 alkenyl, C.sub.3 -C.sub.6 alkynyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.2 -C.sub.4 alkoxyalkyl, C.sub.2 -C.sub.4 alkylthioalkyl, C.sub.2 -C.sub.4 alkylsulphinylalkyl, C.sub.2 -C.sub.4 alkylsulphonylalkyl, C.sub.3 -C.sub.6 alkoxyalkoxyalkyl, C.sub.4 -C.sub.8 cycloalkylalkyl, C.sub.2 -C.sub.4 carboxyalkyl, C.sub.3 -C.sub.6 alkoxycarbonylalkyl, C.sub.6 -C.sub.8 alkenyloxycarbonylalkyl, C.sub.6 -C.sub.8 alkynyloxycarbonylalkyl, C.sub.5 -C.sub.6 alkoxycarbonylalkenyl, C.sub.6 -C.sub.8 cycloalkoxyalkyl, C.sub.4 -C.sub.6 alkenyloxyalkyl, C.sub.4 -C.sub.6 alkynyloxyalkyl, C.sub.3 -C.sub.6 haloalkoxyalkyl, C.sub.4 -C.sub.8 haloalkenoxyalkyl, C.sub.4 -C.sub.6 haloalkynyloxyalkyl, C.sub.6 -C.sub.8 cycloalkylthioalkyl, C.sub.4 -C.sub.6 alkenylthioalkyl, C.sub.4 -C.sub.6 alkynylthioalkyl; C.sub.1 -C.sub.2 alkyl substituted with phenoxy or benzyloxy, each of the phenoxy and benzyloxy optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl; C.sub.4 -C.sub.8 trialkylsilylalkyl, C.sub.3 -C.sub.4 cyanoalkyl, C.sub.3 -C.sub.6 halocycloalkyl, C.sub.3 -C.sub.6 haloalkenyl, C.sub.5 -C.sub.6 alkoxyalkenyl, C.sub.5 -C.sub.6 haloalkoxyalkenyl, C.sub.5 -C.sub.6 alkylthioalkenyl, C.sub.3 -C.sub.6 haloalkynyl, C.sub.5 -C.sub.6 alkoxyalkynyl, C.sub.5 -C.sub.6 haloalkoxyalkynyl, C.sub.5 -C.sub.6 alkylthioalkynyl, C.sub.2 -C.sub.4 alkylcarbonyl, benzyl optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.2 alkyl and C.sub.1 -C.sub.2 haloalkyl; CHR.sup.17 COR.sup.18, CHR.sup.17 P(O)(OR.sup.18).sub.2, P(O)(OR.sup.18).sub.2, CHR.sup.17 P(S)(OR.sup.18).sub.2, CHR.sup.17 C(O)NR.sup.12 R.sup.13, CHR.sup.17 C(O)NH.sub.2, phenyl and pyridyl, each of the phenyl and pyridyl optionally substituted with at least one member independently selected from the group fluorine, chlorine, bromine, C.sub.1 -C.sub.2 alkylhaloalkyl and C.sub.1 1.varies.C.sub.2 alkoxy;
R.sup.12 is hydrogen or C.sub.1 -C.sub.2 alkyl;
R.sup.13 is selected from the group C.sub.1 -C.sub.2 alkyl and phenyl optionally substituted with at least one member selected from the group fluorine, chlorine, bromine, C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 haloalkyl and C.sub.1 -C.sub.2 alkoxy; or
R.sup.12 and R.sup.13 are taken together as --(CH.sub.2).sub.5 --, --(CH.sub.2).sub.4 -- or --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --, each independently forming a ring in which one or more H atoms is optionally and independently replaced by C.sub.1 -C.sub.2 alkyl;
R.sup.17 is hydrogen or C.sub.1 -C.sub.2 alkyl; and
R.sup.18 is selected from the group C.sub.1 -C.sub.2 alkyl, C.sub.3 -C.sub.4 alkenyl and C.sub.3 -C.sub.4 alkynyl.
Compounds of Formula I can exist as one or more stereoisomers. The various stereoisomers comprise enantiomers, diastereomers and geometric isomers. The skilled person knows that a stereoisomer may be more active and how the cited enantiomers, diastereomers and geometric isomers can be separated. Accordingly, the present invention covers racemic mixtures, individual stereoisomers and optically active mixtures of compounds of Formula I.
The novel oxa- or thiaazabicyclic compounds of general Formula Ia, ##STR3## wherein n, m, p, X, W, R.sup.A and Q have the meanings given above, are obtained according to the present invention by reacting an aryliso(thio)cyanate of Formula II,
Q-NCW II
wherein W and Q have the meanings given above, with a (thio)carboxylic acid or ester of Formula III, ##STR4## wherein n, m, p, X, W, and R.sup.A have the meanings given above and R represents hydroxy, C.sub.1 -C.sub.4 alkoxy, halogen or O-active esters, for example O-succinimide esters or anhydrides (see Houben-Weyl, Vol. 25/1 and 25/2 (1974)) optionally in the presence of an acid acceptor and a diluent.
The invention also provides a method for preparation of compounds of Formula I by reacting a compound of Formula IV, ##STR5## wherein n, m, p, X, R.sup.A, R.sup.5 and R.sup.6 have the meanings given above and Y=O, S, or NH, with an electrophile of Formula V, VI or VII, ##STR6## wherein Z is a chlorine, bromine or iodine atom or O--SO.sub.2 CH.sub.3, O--SO.sub.2 CF.sub.3, O--SO.sub.2 --Ph, O--SO.sub.2 -(4-methylphenyl) and R.sup.11 and R.sup.16 have the meanings given above.
The invention a/so provides a method for preparation of compounds of Formula I, wherein m, n, p, X, R.sup.A, W and Q have the meanings given above, comprising reacting a compound of Formula HI, wherein R is hydroxy, (C.sub.1 -C.sub.4) alkoxy, halogen or O-active ester, with thiophosgene or with a thiophosgene-substitute XV, wherein L.sub.1 and L.sub.2 are independently appropriate leaving groups, to produce compounds of Formula VIII, which are then reacted with compounds of Formula IX to form compounds of Formula X, ##STR7## and, finally, convening the compounds of Formula X to compounds of Formula I by cyclization.
The invention also provides a method for preparation of compounds of Formula Ib ##STR8## wherein n, W and Q have the meanings given above and R.sup.1, R.sup.19 and X have the meanings given below, by reacting a compound of Formula XI, ##STR9## wherein X is O, S, or NR.sup.4, R.sup.1 is independently R.sup.A or hydrogen, and R.sup.19 is independently selected from the group hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl or C.sub.3 -C.sub.4 alkenyl, with a compound of Formula XVb,
CWCl.sub.2 XVb
wherein W has the meaning given above, preferably in an inert organic solvent, for example in an aromatic solvent such as toluene or chlorobenzene, in a halogensted hydrocarbon such as chloroform or methylene chloride, in an ether such as diisopropylether or in acetonitrile or dimethylformamide, preferably by means of base catalysis and preferably at temperatures of 0.degree.-120.degree. C. Bases or organic bases, for example organic amines such as triethylamine, are preferably used, but pyridine may also be used, preferably in the presence of activate.sub.d charcoal.
Compounds of Formula XI can be obtained by reacting compounds of Formula XIII, ##STR10## wherein X is 0, S, or NR.sup.4, and n, R.sup.1, R.sup.4, W and Q have the meanings given above, with ketones or aldehydes of Formula XII ##STR11## or with phosgene or a phosgene substitute. In Formula XII, R.sup.19 has the meaning given above. C.dbd.O is obtained in the ring upon reaction with phosgene or phosgene substitute. The reaction is preferably carried out in an inert organic solvent, for example in an aromatic solvent such as toluene or chlorobenzene, a halogenated hydrocarbon such as chloroform or methylene chloride, an ether such as diisopropylether or in acetonitrile or dimethylformamide, preferably by means of acid catalysis and preferably at temperatures of 20.degree.-120.degree. C. Preferred acids are organic acids, for example organic sulfonic acids such as p-toluenesulfonic acid.
Compounds of Formula XII are obtained by reacting 2-mercapto-, 2-hydroxyalkylhydrazines or 2-aminoalkylhydrazines of Formula XIV, ##STR12## wherein X is O, S, or NR.sup.4 and R.sup.1 and R.sup.4 have the meanings given above, with aryliso(thio)cyanates of Formula II, wherein Q has the meaning given above, preferably in an inert organic solvent, for example in an aromatic solvent such as toluene or chlorobenzene, in a halogensted hydrocarbon such as chloroform or methylene chloride, in an ether such as diisopropylether or in acetonitrile or dimethylformamide or alcohols, such as methanol or ethanol, preferably by means of base catalysis and preferably at temperatures of 20.degree.-120.degree. C. Bases or organic bases, for example organic amines such as triethylamine, but also pyridine, are preferably used.
In the reaction of a compound of Formula II with a compound of Formula III when R=alkyl, the reaction is carried out in an inert organic solvent, for example in an aromatic solvent such as toluene or chlorobenzene, in a halogenated hydrocarbon such as chloroform or methylene chloride, in an ether such as diisopropylether or tetrahydrofuran or in acetonitrile or dimethylformamide, optionally with base catalysis at temperatures between -20.degree. C. and 125.degree. C. Organic bases, for example organic amines such as triethylamine or even pyridine or also for example inorganic bases such as potassium carbonate (see EP-A10 272 594) are preferably used as bases. Variants of the general method A are described in EP-A2 0 070 389.
In the case where R=hydroxy, the reaction is carded out in water or methanol as solvent or, preferably, in a biphasic water/organic solvent system. Particular preference is given to the method in which a compound of Formula III, optionally salts of III, is added in water together with an inorganic base, for example an alkali- or alkaline earth metal hydroxide, carbonate or bicarbonate such as sodium hydrolide or potassium carbonate, or together with an organic base, for example, an organic amine such as triethylamine, followed by addition of compounds of Formula II dissolved in an inert solvent, for example, toluene, chlorobenzene or chloroform. Compounds II can, if necessary, also be added directly to the aqueous or alcoholic solution. The reaction mixture is then kept for several days, preferably for between 3 and 50 hours, at temperatures of between -40.degree. C. and +50.degree. C., preferably between -10.degree. C. and +30.degree. C.
The aqueous phase is then adjusted to a pH between 1 and 3 with acid, preferably an inorganic acid such as aqueous hydrochloric or sulphuric acid. The thiourea derivatives (see compounds X) thus produced are then cyclized at temperatures of between 0.degree. C. and 100.degree. C., optionally in the presence of an acid such as hydrochloric acid and/or formic acid, or with the aid of a dehydrating substance, for example, dicyclohexylcarbodiimide (DCC), in a solvent known to the skilled person (for example, acetonitrile), or optionally by conversion into an ester (R=alkyl or active ester) by known methods (see Houben-Weyl, Methoden der organischen Chemie, Vol. XV (1974)).
The compounds of Formula II are known or can be prepared by known methods; for these see EP 304 920, EP 238 711, EP 409 025, EP 373 461, EP 311 135 and DE 37 24 096.
Amines of Formula III are known and can be prepared by the known methods; for these see for example M. Sekiya et al., Chem. Pharm. Bull. (1983), 31(1), p 94; J. M. Cassal, A. Furst, W. Meier. Helv. Chim. Acta (1976), 59(6), p 1917; S. -K. Tsui, J. D. Wood, Can. J. Chem. (1979), 57(15), p 1977; M. Sekiya et al., Chem. Lett. (1982), (2), p 231.

EXAMPLE 1
N-Amino-N-(2-hydroxyethyl)-N'-(2 4-dichlorophenyl)thiourea
7.61 g (0.10 mol) 2-hydroxyethylhydrazine was dissolved in 100 mL methylene chloride at 0.degree.-5.degree. C. After dropwise addition of 10.2 g (0.10 tool) triethylamine, 20.4 g (0.10 mol) 2,4-dichlorophenylisothiocyanate dissolved in 70 mL methylene chloride was added over a period of 4 h. The reaction mixture was left to warm up to room temperature, stirred for a further 2 h, the precipitate filtered off, washed with methylene chloride and the desired compound isolated.
EXAMPLE 2
N-(2,4-Dichlorophenyl)tetrahydro-4H-1,3,4-oxadiazine-4-carbothioamide ##STR13##
1.72 g (6.20 mmol) N-amino-N-(2-hydroxyethyl)-N'-(2,4-dichlorophenyl)thiourea was suspended in 40 mL methylene chloride. 0.52 g (37% aqueous, 6.4 mmol) formaldehyde and a small quantity of p-toluenesulfonic acid were added before the reaction mixture was heated for 17 h in a Dean-Stark apparatus. The solvent was then removed and the desired product isolated.
EXAMPLE 3
1-�(2,4-Dichlorophenyl)imino!dihydro-1H,3H,5H-�1,3,4!thiadiazolo�3,4-c!-�1,3,4!oxadiazin-3-one ##STR14##
1.8 g (6.2 mmol) N-(2,4-dichlorophenyl)tetrahydro-4H-1,3,4-oxadiazine-4-carbothioamide was dissolved in 30 mL toluene and 1 mL triethylamine in the presence of a small quantity of activated charcoal at 0.degree.-5.degree. C. 3.49 g (6.81 mmol) phosgene as 20% solution in 30 mL toluene was added dropwise over 1.5 h. The reaction mixture was then left to warm up to room temperature and stirred overnight. The activated charcoal was removed by filtration and the solvent evaporated in vacuo. The desired product was isolated after chromatography on silica gel.
EXAMPLE 4
3-��4-Chloro-2-fluoro-5-(1-methylethoxy)phenyl!imino!-6-fluorotetrahydro-1H,3H-pyrrolo �1,2-c!thiazol-1-one ##STR15##
A mixture of 1.31 g (0.01 mol) 4-fluoroproline, 30 mL 2N KOH in methanol and 10 mL water is prepared before 2.46 g (0.01 mol) 4-chloro-2-fluoro-5-isopropoxy-phenylisothiocyanate dissolved in 250 mL methanol is added dropwise. The reaction mixture is stirred overnight at room temperature, the aqueous phase adjusted to pH 2 and the resultant product (3.77 g, See Formula X) is filtered. The compound thus obtained is dissolved in 50 mL acetonitrile before 2.59 g (0.01 mol) dicyclohexylcarbodiimide is added at room temperature. The reaction mixture is stirred for 3 h and the crude product is purified by silica gel chromatography to give 3.24 g (85% yield) of the desired product.
EXAMPLE 5
3-��4-Chloro-2-fluoro-5-(propynyloxy)phenyl!imino!-6-fluorotetrahydro-1H,3H-pyrrolo�1,2c!thiazol-1-one ##STR16##
A mixture of 3.18 g (0.01 tool) 3-��4-chloro-2-fluoro-5-(1 -methylethoxy)phenyl!-imino!-6-fluorotetrahydro-1H,3H-pyrrolo�l,2-c!thiazol-l-one, 6.95 g (0.05 tool) potassium carbonate, 1.78 g (12.0 mmol) propargyl bromide and 60 mL acetonitrile is stirred for 20 h at room temperature. The reaction mixture is adjusted to pH 2 with 5% aqueous hydrochloric acid and extracted with diethylether (3.times.15 mL). The organic phase is then dried, the solvent distilled off in vacuo and the crude product purified on a silica gel column.
TABLE 1______________________________________ ##STR17##R.sup.1 R.sup.1 R.sup.5 R.sup.6 R.sup.7 X______________________________________H H F Cl H OH H F Cl CO.sub.2 CH(CH.sub.3).sub.2 OH H F Cl CO.sub.2 CH.sub.3 OH H F Cl CO.sub.2 C.sub.2 H.sub.5 OH H F Cl CO.sub.2 CH(CH.sub.3)CF.sub.3 OH H F Cl CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 OH H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 OH H F Cl CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 OH H F Cl CO.sub.2 CH.sub.2 CCH OH H F Cl CO.sub.2 CH(CH.sub.3)CCH OH H F Cl CO.sub.2 CH.sub.2 CF.sub.3 OH H F Cl CON(CH.sub.3).sub.2 OH H F Cl CO.sub.2 CH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5 OH H F Cl OCH.sub.3 OH H F Cl OCH(CH.sub.3).sub.2 OH H F Cl OCH.sub.2 CCH OH H F Cl OCH(CH.sub.3)CCH OH H F Cl OCH.sub.2 C(O)N(CH.sub.3).sub.2 OH H F Cl OCH.sub.2 P(O)(OC.sub.2 H.sub.5).sub.2 OH H F Cl OCH.sub.2 P(S)(OC.sub.2 H.sub.5).sub.2 OH H F Cl OCF.sub.2 CHFCl OH H F Cl OCHF.sub.2 OH H F Cl OCH.sub.2 CHCH.sub.2 OH H F Cl OCH.sub.2 CHCHCl OH H F Cl OCH.sub.2 C(Cl)CH.sub.2 OH H F Cl SCH.sub.2 CO.sub.2 H OH H F Cl SCH.sub.2 CO.sub.2 CH.sub.3 OH H F Cl NHSO.sub.2 CH.sub.3 OH H F Cl NHSO.sub.2 CF.sub.3 OH H F Cl NHSO.sub.2 CH(CH.sub.3).sub.2 OH H F Cl NHSO.sub.2 NHCH.sub.3 OH H H Cl H CHFH H F Cl H CHFH H F Cl CO.sub.2 CH(CH.sub.3).sub.2 CHFH H F Cl CO.sub.2 CH.sub.3 CHFH H F Cl CO.sub.2 C.sub.2 H.sub.5 CHFH H F Cl CO.sub.2 CH(CH.sub.3)CF.sub.3 CHFH H F Cl CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 CHFH H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 CHFH H F Cl CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 CHFH H F Cl CO.sub.2 CH.sub.2 CCH CHFH H F Cl CO.sub.2 CH(CH.sub.3)CCH CHFH H F Cl CO.sub.2 CH.sub.2 CF.sub.3 CHFH H F Cl CON(CH.sub.3).sub.2 CHFH H F Cl CO.sub.2 CH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5 CHFH H F Cl OCH.sub.3 CHFH H F Cl OCH(CH.sub.3).sub.2 CHFH H F Cl OCH.sub.2 CCH CHFH H F Cl OCH(CH.sub.3)CCH CHFH H F Cl OCH.sub.2 C(O)N(CH.sub.3).sub.2 CHFH H F Cl OCH.sub.2 P(O)(OC.sub.2 H.sub.5).sub.2 CHFH H F Cl OCH.sub.2 P(S)(OC.sub.2 H.sub.5).sub.2 CHFH H F Cl OCF.sub.2 CHFCl CHFH H F Cl OCHF.sub.2 CHFH H F Cl OCH.sub.2 CHCH.sub.2 CHFH H F Cl OCH.sub.2 CHCHCl CHFH H F Cl OCH.sub.2 C(Cl)CH.sub.2 CHFH H F Cl CN CHFH H F Cl SCH.sub.2 CO.sub.2 H CHFH H F Cl SCH(CH.sub.3).sub.2 CHFH H F Cl SCH.sub.2 CO.sub.2 CH.sub.3 CHFH H F Cl SCH.sub.2 CCH CHFH H F Cl NHSO.sub.2 CH.sub.3 CHFH H F Cl NHSO.sub.2 CF.sub.3 CHFH H F Cl NHSO.sub.2 CH(CH.sub.3).sub.2 CHFH H F Cl NHSO.sub.2 NHCH.sub.3 CHFH H F Cl OCH.sub.2 CO.sub.2 C.sub.5 H.sub.11 CHFH H F Cl OCH.sub.2 CHNOCH.sub.3 CHFH H F Cl OCH.sub.2 CHNOCH.sub.2 CHCH.sub.2 CHFH H F Cl OCH.sub.2 Si(CH.sub.3).sub.3 CHFH H F Cl ##STR18## CHFH H Cl Cl CO.sub.2 CH(CH.sub.3).sub.2 CHFH H Cl Cl OCH.sub.2 CCH CHFH H Cl Cl CO.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5 CHFH H Cl CN CO.sub.2 CH(CH.sub.3).sub.2 CHFH H Cl CN CO.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5 CHFF H F Cl CO.sub.2 CH(CH.sub.3).sub.2 CH.sub.2F H F Cl CO.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5 CH.sub.2F H F Cl CO.sub.2 CH.sub.2 CH.sub.2 CCl.sub.3 CH.sub.2F H F Cl OCH.sub.2 CCH CH.sub.2F H F Cl OCH(CH.sub.3)CCH CH.sub.2F H F Cl OCH(CH.sub.3).sub.2 CH.sub.2F H F Cl CO.sub.2 CH.sub.3 CH.sub.2F H F Cl SCH.sub.2 CO.sub.2 H CH.sub.2H H Cl Cl H CH.sub.2H H Cl Cl H CH.sub.2H H Cl Cl Cl CH.sub.2F H F Cl CO.sub.2 C.sub.2 H.sub.5 CH.sub.2F H F Cl SCH.sub.2 CO.sub.2 Me CH.sub.2F H F Cl NHSO.sub.2 CH.sub.3 CH.sub.2F H F Cl NHSO.sub.2 C.sub.2 H.sub.5 CH.sub.2H H F Cl CO.sub.2 CH.sub.3 CHClH H F Cl CO.sub.2 C.sub.2 H.sub.5 CHClH H F Cl CO.sub.2 CH(CH.sub.3).sub.2 CHClH H F Cl CO.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5 CHClH H F Cl CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 CHClH H F Cl CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 CHClH H F Cl SCH.sub.2 CO.sub.2 Me CHClH H F Cl OCH(CH.sub.3).sub.2 CHClH H F Cl SCH.sub.2 CO.sub.2 H CHClH H F Cl OCH.sub.2 CCH CHClH H F Cl OCH(CH.sub.3)CCH CHClH H F Cl NHSO.sub.2 CH.sub.3 CHClH H F Cl NHSO.sub.2 C.sub.2 H.sub.5 CHClH H F Cl CO.sub.2 CH(CH.sub.3).sub.2 CHBrH H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 CHBrH H F Cl OCH.sub.3 CHBrH H F Cl OCH(CH.sub.3).sub.2 CHBrH H F Cl OCH.sub.2 CCH CHBrH H F Cl OCH(CH.sub.3)CCH CHBrH H F Cl OCH.sub.2 CHCH.sub.2 CHBrH H F Cl SCH.sub.2 CO.sub.2 Me CHBrH H F Cl CO.sub.2 CH(CH.sub.3).sub.2 CHOCHF.sub.2H H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 CHOCHF.sub.2H H F Cl OCH.sub.3 CHOCHF.sub.2H H F Cl OCH(CH.sub.3).sub.2 CHOCHF.sub.2H H F Cl OCH.sub.2 CCH CHOCHF.sub.2H H F Cl OCH(CH.sub.3)CCH CHOCHF.sub.2H H F Cl OCH.sub.2 CHCH.sub.2 CHOCHF.sub.2H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 CHOCF.sub.3H H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 CHOCF.sub.3H H F Cl OCH.sub.3 CHOCF.sub.3H H F Cl OCH(CH.sub.3).sub.2 CHOCF.sub.3H H F Cl OCH.sub.2 CCH CHOCF.sub.3H H F Cl OCH(CH.sub.3)CCH CHOCF.sub.3H H F Cl OCH.sub.2 CHCH.sub.2 CHOCF.sub.3H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 CHOCH.sub.2 CF.sub.3H H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 CHOCH.sub.2 CF.sub.3H H F Cl OCH.sub.3 CHOCH.sub.2 CF.sub.3H H F Cl OCH(CH.sub.3).sub.2 CHOCH.sub.2 CF.sub.3H H F Cl OCH.sub.2 CCH CHOCH.sub.2 CF.sub.3H H F Cl OCH(CH.sub.3 (CCH CHOCH.sub.2 CF.sub.3H H F Cl OCH.sub.2 CHCH.sub.2 CHOCH.sub.2 CF.sub.3______________________________________
TABLE 2______________________________________ ##STR19##R.sup.1 R.sup.1 R.sup.5 R.sup.6 R.sup.8 R.sup.9 X W______________________________________H H F Cl H CH.sub.3 O OH H F Cl H CH.sub.3 CHF OH H F Cl CH.sub.3 CH.sub.3 CHF OH H F Cl H CH.sub.2 F CHF OH H F Cl H CH.sub.2 Cl CHF OH H F Cl H CH.sub.2 Br CHF OH H F Cl H CH(CH.sub.3).sub.2 CHF OH H F Cl H CH.sub.2 CH.sub.3 CHF OH H F Br H CH.sub.3 CHF OH H F OCH.sub.3 H CH.sub.3 CHF OH H F CH.sub.3 H CH.sub.3 CHF OH H F CN H CH.sub.3 CHF OH H F CF.sub.3 H CH.sub.3 CHF OH H F OCHF.sub.2 H CH.sub.3 CHF OH H F Cl H CH.sub.3 CHF SH H F Cl H CH.sub.3 O SF H F Cl H CH.sub.3 CH.sub.2 OH H F Cl H CH.sub.3 CHCl OF H F Cl H CH.sub.3 CH.sub.2 SH H F Cl H CH.sub.3 CHCl SH H F Cl H CH.sub.3 CHBr OH H F Cl H CH.sub.3 CHOCHF.sub.2 OH H F Cl H CH.sub.3 CHOCF.sub.3 OH H F Cl H CH.sub.3 CHOCH.sub.2 CF.sub.3 O______________________________________
TABLE 3______________________________________ ##STR20##R.sup.1 R.sup.1 R.sup.5 R.sup.6 R.sup.8 R.sup.9 X W______________________________________H H F Cl H Cl O SH H F Cl H CH.sub.3 O SH H F Cl H H CHF SH H F Cl H Cl CHF SH H F Cl H CH.sub.3 CHF SH H F Cl CH.sub.3 CH.sub.3 CHF SH H H SCH.sub.3 H H CHF SH H F Cl H Cl CHCl SF H F Cl H Cl CH.sub.2 SH H F Cl H CH.sub.3 CHCl SF H F Cl H CH.sub.3 CH.sub.2 SH H F Cl H Cl CHF OH H F Cl H H CHF OH H F Cl H CH.sub.3 CHF OH H F Cl H C.sub.2 H.sub.5 CHF SH H F Cl H Cl CHBr SH H F Cl H CH.sub.3 CHBr SH H F Cl H Cl CHOCHF.sub.2 SH H F Cl H CH.sub.3 CHOCHF.sub.2 SH H F Cl H Cl CHOCF.sub.3 SH H F Cl H CH.sub.3 CHOCF.sub.3 SH H F Cl H Cl CHOCH.sub.2 CF.sub.3 S______________________________________
TABLE 4______________________________________ ##STR21##R.sup.1 R.sup.1 R.sup.5 R.sup.10 X W______________________________________H H F CH.sub.2 CCH O SH H F CH.sub.2 CHCH.sub.2 O SH H F H CHF SH H F CH.sub.3 CHF SH H F CH.sub.2 CCH CHF SH H F CH(CH.sub.3)CCH CHF SH H F CH.sub.2 CHCH.sub.2 CHF SH H F CH.sub.2 OCH.sub.3 CHF SH H F CH(CH.sub.3).sub.2 CHF SH H F CHF.sub.2 CHF SH H F CF.sub.2 CHF.sub.2 CHF SH H F CH.sub.2 CHCHCH.sub.3 CHF SH H F CH.sub.2 CH.sub.2 CH.sub.3 CHF SH H F CH.sub.2 CCH CHF OH H F CH.sub.2 CHCH.sub.2 CHF OH H Cl CH.sub.2 CCH CHF SF H F CH.sub.2 CCH CHF SF H F CH.sub.2 CHCH.sub.2 CHF SH H F CH.sub.2 CCH CHCl SH H F CH.sub.2 CHCH.sub.2 CHCl SH H F CH.sub.3 CHCl SH H F CH.sub.2 CCH CHBr SH H F CH.sub.2 CHCH.sub.2 CHBr SH H F CH.sub.2 CCH CHBr OH H F CH.sub.2 CCH CHOCHF.sub.2 SH H F CH.sub.2 CCH CHOCF.sub.3 SH H F CH.sub.2 CCH CHOCH.sub.2 CF.sub.3 S______________________________________
TABLE 5______________________________________ ##STR22## ##STR23##R.sup.1 R.sup.1 R.sup.5 R.sup.8 R.sup.9 R.sup.10 X W______________________________________H H F H H CH.sub.2 C CH O OH H F H H CH.sub.2 CHCH.sub.2 O OH H F H H CH.sub.3 O OH H H H H CH.sub.3 CHF OH H H H H CH.sub.2 C CH CHF OH H F H H CH.sub.3 CHF OH H F H H C.sub.2 H.sub.5 CHF OH H F H H CH(CH.sub.3).sub.2 CHF OH H F H H CH.sub.2 CH.sub.2 CH.sub.3 CHF OH H F H H CH.sub.2 CHCH.sub.2 CHF OH H F H H CH.sub.2 C CH CHF OH H F H H CH(CH.sub.3)C CH CHF OH H H H H CH.sub.2 C CH CHF SH H F H H CH.sub.2 C CH CHF SH H Cl H H CH.sub.2 C CH CHF OH H F H CH.sub.3 CH.sub.2 C CH CHF OF H H H H CH.sub.2 C CH CH.sub.2 OF H F H H CH.sub.3 CH.sub.2 OF H F H H CH.sub.2 C CH CH.sub.2 OF H F H H CH.sub.2 CHCH.sub.2 CH.sub.2 OH H H H H CH.sub.2 C CH CHCl OH H F H H CH.sub.3 CHCl OH H F H H CH.sub.2 C CH CHCl OH H F H H CH.sub.2 CHCH.sub.2 CHCl OH H F H H CH.sub.2 CHCH.sub.2 CHCl SH H F H H CH.sub.2 C CH CHBr OH H F H H CH.sub.2 C CH CHBr SH H F H H CH.sub.2 CHCH.sub.2 CHBr OH H F H H CH.sub.2 C CH CHOCHF.sub.2 OH H F H H CH.sub.2 C CH CHOCF.sub.3 OH H F H H CH.sub.2 C CH CHOCH.sub.2 CF.sub.3 O______________________________________
TABLE 6______________________________________ ##STR24## ##STR25##R.sup.1 R.sup.1 R.sup.5 R.sup.8 R.sup.9 X______________________________________H H H F F OH H F F F OH H F H H OH H H F F CHFH H F F F CHFH H F H H CHFF H H F F CH.sub.2F H F F F CH.sub.2F H F H H CH.sub.2H H H F F CHClH H F F F CHClH H F H H CHClH H H F F CHBrH H F F F CHBrH H F H H CHBrH H F F F CHOCHF.sub.2H H F F F CHOCF.sub.3H H F F F CHOCH.sub.2 CF.sub.3______________________________________
TABLE 7______________________________________ ##STR26## ##STR27##R.sup.1 R.sup.1 R.sup.5 R.sup.6 R.sup.7 R.sup.8 X______________________________________H H H H CO.sub.2 CH.sub.3 H OH H H H CO.sub.2 CH.sub.3 CH.sub.3 OH H H H CO.sub.2 CH.sub.3 CH.sub.3 CHFH H H H CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CHFH H H H CO.sub.2 C.sub.2 H.sub.5 H CHFH H H H CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 CHFH H H H CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 H CHFH H H H CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 CHFH H H H CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 H CHFH H H H CO.sub.2 CH.sub.2 C CH CH.sub.3 CHFH H H Cl CO.sub.2 CH.sub.3 CH.sub.3 CHFH H H Cl CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CHFH H H Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 CHFH H H Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 CHFH H H Cl CO.sub.2 CH.sub.2 C CH CH.sub.3 CHFH H F Cl CO.sub.2 CH.sub.3 CH.sub.3 CHFH H F Cl CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CHFH H F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 CHFH H F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 H CHFH H F Cl CO.sub.2 CH.sub.2 CH CH CH.sub.3 CHFH H F Cl CO.sub.2 CH(CH.sub.3)C CH CH.sub.3 CHFH H F Cl CO.sub.2 CH.sub.2 CHCH.sub.2 CH.sub.3 CHFF H F Cl CO.sub.2 CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.2F H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 CH.sub.2F H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.2F H F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 CH.sub.2F H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 CH.sub.2H H F Cl CO.sub.2 CH(CH.sub.3).sub.2 CH.sub.3 CHClH H F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 CHClH H F Cl CO.sub.2 CH.sub.3 CH.sub.3 CHClH H F Cl CO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 CHClH H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 CHBrH H F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3 CHBrH H F Cl CO.sub.2 CH.sub.3 CH.sub.3 CHBrH H F Cl CO.sub.2 CH.sub.3 CH.sub.3 CHOCHF.sub.2H H F Cl CO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 CHOCHF.sub.2H H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 CHOCHF.sub.2H H F Cl CO.sub.2 CH.sub.3 CH.sub.3 CHOCF.sub.3H H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 CHOCF.sub.3H H F Cl CO.sub.2 CH.sub.3 CH.sub.3 CHOCH.sub.2 CF.sub.3H H F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3 CHOCH.sub.2 CF.sub.3F H H H CO.sub.2 CH.sub.2 C CH CH.sub.3 CH.sub.2F H H Cl CO.sub.2 CH.sub.2 C CH CH.sub.3 CH.sub.2F H F Cl CO.sub.2 CH.sub.2 C CH CH.sub.3 CH.sub.2F H F Cl CO.sub.2 CH(CH.sub.3)C CH CH.sub.3 CH.sub.2H H F Cl CO.sub.2 CH.sub.2 CHCH.sub.2 CH.sub.3 CHFH H H H CO.sub.2 CH.sub.2 C CH CH.sub.3 CHClH H H Cl CO.sub.2 CH.sub.2 C CH CH.sub.3 CHClH H F Cl CO.sub.2 CH.sub.2 C CH CH.sub.3 CHClH H F Cl CO.sub.2 CH(CH.sub.3)C CH CH.sub.3 CHClH H F Cl CO.sub.2 CH.sub.2 CHCH.sub.2 CH.sub.3 CHCl______________________________________
TABLE 8______________________________________ ##STR28## ##STR29##R.sup.5 R.sup.6 R.sup.7______________________________________H Cl HH Br HH CH.sub.3 HF Cl HCl Cl HF Cl OCH(CH.sub.3).sub.2F Cl OCH.sub.2 C CHF Cl OCH(CH.sub.3)C CHF Cl OCH.sub.3F Cl OCH.sub.2 CH.sub.2 CH.sub.3F Cl OCH.sub.2 CHCH.sub.2F Cl OCH.sub.2 CO.sub.2 CH.sub.3F Cl OCH.sub.2 CO.sub.2 CH.sub.2 C CHF Cl OCH.sub.2 CO.sub.2 C.sub.5 H.sub.11F Cl CNF Cl SCH.sub.3F Cl OCH.sub.2 CHCHCO.sub.2 CH.sub.3F Cl OCH.sub.2 C.sub.6 H.sub.5F Cl ##STR30##F Cl SCH(CH.sub.3).sub.2F Cl SCH.sub.2 CHCH.sub.2F Cl SCH.sub.2 C CHF Cl SCH.sub.2 CO.sub.2 HF Cl SCH.sub.2 CO.sub.2 CH.sub.3F Cl ##STR31##F Cl OCH(CH.sub.3)CHNOCH.sub.3F Cl SCH.sub.2 CO.sub.2 CH.sub.2 C CHF Cl OCHF.sub.2F Cl OCH.sub.2 C(Cl)CH.sub.2F Cl OCF.sub.2 CHFClF Cl NHSO.sub.2 CH.sub.3F Cl NHSO.sub.2 CH(CH.sub.3).sub.2F Cl NHSO.sub.2 NHCH.sub.3F Cl NHSO.sub.2 NHCH.sub.2 CH.sub.3F Cl CO.sub.2 CH(CH.sub.3).sub.2F Cl CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3F Cl CO.sub.2 CH.sub.2 CF.sub.3F Cl CON(CH.sub.3).sub.2F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3F Cl CO.sub.2 CH(CH.sub.3)CF.sub.3F Cl ##STR32##F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 SCH.sub.3Cl Cl HCl Cl OCHF.sub.2Cl Cl OCH(CH.sub.3).sub.2Cl Cl OCF.sub.2 CHFClCl Cl OCH.sub.2 C CHF Cl OCH.sub.2 P(O)(OC.sub.2 H.sub.5).sub.2Cl Cl OCH(CH.sub.3)C CHF Cl OCH.sub.2 C(O)N(CH.sub.3).sub.2F Cl O(CH.sub.2).sub.2 OCH.sub.2 CH.sub.3Cl Cl SCH.sub.2 C CHCl Cl SCH.sub.2 CO.sub.2 HCl Cl SCH.sub.2 CO.sub.2 CH.sub.2 C CHCl Cl NHSO.sub.2 CH.sub.3F Cl NHSO.sub.2 CF.sub.3Cl Cl CO.sub.2 CH(CH.sub.3).sub.2Cl Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 SCH.sub.3Cl Cl CO.sub.2 CH(CH.sub.3)CF.sub.3Cl Cl CON(CH.sub.3).sub.2F Cl CO.sub.2 CH.sub.2 C CHF Cl CO.sub.2 CH(CH.sub.3)C CHCl Cl CO.sub.2 CH.sub.2 CF.sub.3Cl Cl ClF Cl CO.sub.2 CH(CH.sub.3).sub.2F Cl CO.sub.2 CH.sub.3F Cl CO.sub.2 CH.sub.2 CH.sub.3F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3F Cl OCHF.sub.2F Cl SCH.sub.2 CO.sub.2 HF Cl SCH.sub.2 CO.sub.2 CH.sub.3F Cl NHSO.sub.2 CH.sub.2 CH.sub.3F Cl NHSO.sub.2 CH(CH.sub.3).sub.2Cl Cl ##STR33##Cl Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3F Cl CHCHCO.sub.2 CH.sub.2 CH.sub.3F CN CO.sub.2 CH(CH.sub.3).sub.2Cl CN CO.sub.2 CH(CH.sub.3).sub.2F CN OCH.sub.2 C CHF CN OCH(CH.sub.3).sub.2Cl CN OCH(CH.sub.3).sub.2F CN CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3Cl CN OCH.sub.2 C CHF CN OCH(CH.sub.3)C CHF CN CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3F CN OCHF.sub.2F CN OCH(CH.sub.3).sub.2F CN OCF.sub.2 CHF.sub.2F CN SCH.sub.2 CO.sub.2 HF CN NHSO.sub.2 CH.sub.3F CN NHSO.sub.2 CF.sub.3______________________________________
TABLE 9______________________________________ ##STR34## ##STR35##R.sup.5 R.sup.6 R.sup.8 R.sup.9 W______________________________________F Cl H CH.sub.3 OF Cl H H OF Cl CH.sub.3 CH.sub.3 OF Cl CH.sub.3 CH.sub.2 F OF CN CH.sub.3 CH.sub.2 F OF Cl H CH.sub.2 CH.sub.3 OF Cl H CH.sub.2 F OF Cl H CH.sub.2 Cl OF Cl H CH.sub.2 Br OF Br H CH.sub.3 OF CH.sub.3 H CH.sub.3 OF OCH.sub.3 H CH.sub.3 OF CN H CH.sub.3 OF CF.sub.3 H CH.sub.3 OF OCF.sub.2 H H CH.sub.3 OCl Cl H CH.sub.3 OCl CN H CH.sub.3 OF CN CH.sub.3 CH.sub.3 OF CN H CH.sub.2 F OF CN H CH.sub.2 Cl OF CN H CH.sub.2 Br OF CN H CH(CH.sub.3).sub.2 OF CN H CH.sub.2 CH.sub.2 Cl OF CN H CH.sub.2 CH.sub.3 OF CN H CH.sub.2 (CH.sub.2).sub.2 F OCl Br H CH.sub.3 OCl CH.sub.3 H CH.sub.3 OCl OCH.sub.3 H CH.sub.3 OCl CN H CH.sub.3 OCl CF.sub.3 H CH.sub.3 OCl OCF.sub.2 H H CH.sub.3 OCl Cl H CH.sub.2 F OCl Cl CH.sub.3 CH.sub.2 F OCl Cl H CH.sub.2 Cl OCl Cl H CH.sub.2 Br OCl Cl H CH.sub.2 CH.sub.3 OCl Cl CH.sub.3 CH.sub.3 O______________________________________
TABLE 10______________________________________ ##STR36## ##STR37##R.sup.5 R.sup.6 R.sup.8 R.sup.9 W______________________________________H H H Cl SF Cl H Cl SCl Cl H Cl SF Cl H CH.sub.3 SF Cl H CH.sub.2 CH.sub.3 SH SCH.sub.3 H H SF Cl H Cl OF Cl H CH.sub.3 OCl CN H Cl SCl Cl H CH.sub.3 SCl Cl H CH.sub.2 CH.sub.3 SCl Cl H Cl OF CN H CH.sub.3 OF CN H CH.sub.3 SCl Cl H CH.sub.3 O______________________________________
TABLE 11______________________________________ ##STR38## ##STR39##R.sup.5 R.sup.5 W______________________________________F H SF CH.sub.3 SF CH.sub.2 CH.sub.3 SF CH.sub.2 C CH SCl CH.sub.2 C CH SF CH(CH.sub.3)C CH SF CH.sub.2 C CH OCl H SCl CH.sub.3 SCl CH.sub.2 CH.sub.3 SCl CH.sub.2 C CH SF CH.sub.2 OCH.sub.3 SF CH.sub.2 CH.sub.2 CH.sub.3 SCl CH(CH.sub.3)C CH SF CH(CH.sub.3).sub.2 SF CH.sub.2 CHCH.sub.2 SCl CH.sub.2 CHCH.sub.2 SF CF.sub.2 CHF.sub.2 SCl CH.sub.2 C CH OCl CH(CH.sub.3).sub.2 SCl CH.sub.2 CH.sub.2 CH.sub.3 SCl CF.sub.2 CHF.sub.2 SF CH.sub.2 CHCHCH.sub.3 S______________________________________
TABLE 12______________________________________ ##STR40## ##STR41##R.sup.5 R.sup.8 R.sup.9 R.sup.10 W______________________________________H H H H OF H H CH.sub.3 OF H H CH.sub.2 C CH OF H H CH(CH.sub.3)C CH OCl H H CH.sub.2 C CH OF CH.sub.3 H CH.sub.2 C CH OF H H CH.sub.2 C CH SCl H H CH.sub.3 OF H H CH.sub.2 CH.sub.3 OF H H CH.sub.2 CH.sub.2 CH.sub.3 OF H H CH(CH.sub.3).sub.2 OF H H CH.sub.2 CHCH OCl H H CH(CH.sub.3)C CH OCl H H CH.sub.2 C CH SF CH.sub.3 CH.sub.3 CH.sub.2 C CH OF H H H OCl H H CH.sub.2 CH.sub.3 OCl H H CH(CH.sub.3).sub.2 OCl CH.sub.3 H CH.sub.2 CHCH.sub.2 OF CH.sub.3 H CH.sub.2 C CH OCl CH.sub.3 CH.sub.3 CH.sub.2 C CH OCl CH.sub.3 CH.sub.3 CH.sub.2 CHCH.sub.2 OCl H H CH.sub.2 CH.sub.2 CH.sub.3 OCl CH.sub.3 H CH.sub.2 C CH O______________________________________
TABLE 13______________________________________ ##STR42## ##STR43##R.sup.5 R.sup.8 R.sup.9______________________________________H F FF F FF H H______________________________________
TABLE 14______________________________________ ##STR44## ##STR45##R.sup.5 R.sup.6 R.sup.7 R.sup.8______________________________________H H CO.sub.2 CH.sub.3 HH H CO.sub.2 CH.sub.3 CH.sub.3H H CO.sub.2 C.sub.2 H.sub.5 CH.sub.3H H CO.sub.2 C.sub.2 H.sub.5 HH H CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3H H CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 HH H CO.sub.2 CH.sub.2 C CH CH.sub.3H Cl CO.sub.2 CH.sub.3 CH.sub.3H Cl CO.sub.2 C.sub.2 H.sub.5 CH.sub.3H Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3H Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3H Cl CO.sub.2 CH.sub.2 C CH CH.sub.3F Cl CO.sub.2 CH.sub.3 CH.sub.3F Cl CO.sub.2 C.sub.2 H.sub.5 CH.sub.3F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 HF Cl CO.sub.2 CH.sub.2 C CH CH.sub.3F Cl CO.sub.2 CH(CH.sub.3)C CH CH.sub.3F Cl CO.sub.2 CH.sub.2 CHCH.sub.2 CH.sub.3F Cl CO.sub.2 CH(CH.sub.3).sub.2 CH.sub.3F Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 CH.sub.3Cl Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH.sub.3Cl Cl CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3Cl Cl CO.sub.2 CH(CH.sub.3).sub.2 CH.sub.3Cl Cl CO.sub.2 CH.sub.3 CH.sub.3Cl Cl CO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3F CN CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3Cl Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3 HF CN CO.sub.2 CH.sub.3 CH.sub.3F CN CO.sub.2 CH.sub.2 CH.sub.3 CH.sub.3Cl CN CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CH.sub.3Cl Cl CO.sub.2 CH.sub.2 C CH CH.sub.3Cl CN CO.sub.2 CH.sub.2 C CH CH.sub.3Cl CN CO.sub.2 CH(CH.sub.3)C CH CH.sub.3Cl Cl CO.sub.2 CH.sub.2 CHCH.sub.2 CH.sub.3Cl Cl CO.sub.2 CH(CH.sub.3)C CH CH.sub.3______________________________________
Formulations
Practical formulations of compounds of Formula I can be manufactured in a conventional manner, namely as powders, granules, pellets, solutions, suspensions, emulsions, wettable powders and emulsifiable concentrates, etc. Many of these formulations can be used directly. Sprayable preparations can be diluted with suitable media and sprayed in quantifies of a few to several hundred liters per hectare. Highly concentrated preparations are mainly used as intermediate products for further formulations. The formulations contain roughly between 0.1 and 99% by weight of active substance(s) and at least one carrier from the group a) 0.1 to 20% surfactant substances and b) about 1 to 99.9% solid or liquid diluents. More precisely, they contain these constituents in approximately the quantities stated below, where the formulations can be mixed with further active substances or additives.
______________________________________ Weight-%* Active substance Diluent Surfactant______________________________________Wettable powders 20-90 0-74 1-10Suspensions in oil, 3-50 40-95 0-15emulsions, solutions(includingemulsifiableconcentrates)Aqueous suspensions 10-50 40-84 1-20Dry powders 1-25 70-99 0-5Granules and pellets 0.1-95 5-99.9 0-15Highly concentrated 90-99 0-10 0-2preparations______________________________________ *Active substance plus a carrier comprising at least one surfactant and/o diluent = 100 weight%.
Lower or higher active substance contents can of course be present, depending on the anticipated use and the physical properties of the compound. Higher quantity ratios of surfactant component to active substance are sometimes desirable and are attained by incorporation into the formulation or by mixing in the container.
Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey, though other mined or industrially prepared solid substances can also be used. The more absorbant diluents are preferred for wettable powders whilst the denser diluents are preferred for dry powders. Typical liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, (1950) and are preferred for concentrated suspensions under 0.1%. Concentrated solutions are preferably resistant to phase separation at 0.degree. C. Lists of surfactant substances and applications recommended for these are contained in McCutchen's Detergents and Emulsifiers Annual, MC Publishing. Corp., Ridgewood, N. J. and in Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publishing Co. Inc., New York, (1964). All formulations may contain small quantities of additives for reducing frothing, agglomeration, corrosion and growth of microorganisms etc.
The methods for preparation of such products are well known. Solutions are prepared by simply mixing the ingredients. Finely powdered solid preparations are obtained by mixing and, usually, by grinding, for example in a hammer mill or jet mill. Suspensions axe obtained by wet grinding (see for example Littler, U.S. Pat. No. 3,060,084). Granules and pellets can be prepared by spraying the active substance onto preformed granular carriers or by agglomerating them. For these see J. E Browning, Agglomeration, Chemical Engineering, Dec. 4, (1967), p 147 ff. and Perry's Chemical Engineer's Handbook, 5th Ed., McGraw-Hill, New York, (1973), pp 8-57 ff.
For further information on formulation technology see for example:
H. M. Loux, U.S. Pat. No. 3,235,361, 15 Feb. 1966, column 6, line 16 to column 7, line 19 and Examples 10 to 41;
R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, 14 Mar. 1967, column 5, line 43 to column 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;
H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, 23 Jun. 1959, column 3, line 66 to column 5, line 17 and Examples 1-4;
G. C. Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, (1961), pp 81-96 and
J. D. Fryer and S. A. Evans, Weed Control Handbook, 5th Ed., Blackwell
Scientific Publications, Oxford, (1968), pp 101-103.
Unless stated otherwise, ihe figures given in the following Examples are parts by weight.
EXAMPLE A
______________________________________Wettable powder______________________________________1-�(2,4-Dichlorophenyl)imino!dihydro-1H,3H,5H- 80%�1,3,4!thiadiazolo�3,4-c!-�1,3,4!oxadiazin-3-oneSodium alkylnaphthalenesulfonate 2%Sodium ligninsulfonate 2%Synthetic amorphous silicic acid 3%Kaolinite 13%______________________________________
The ingredients are mixed together and ground in a hammer mill until all the solids essentially have a particle size of less than 50 .mu.m, after which they are mixed again and packed.
EXAMPLE B
______________________________________Wettable powder______________________________________1-�(2,4-Dichlorophenyl)imino!dihydro-1H,3H,5H- 50%�1,3,4!thiadiazolo�3,4-c!-�1,3,4!oxadiazin-3-oneSodium alkylnaphthalenesulfonate 2%Low-viscosity methylcellulose 2%Diatomic earth 46%______________________________________
The ingredients are mixed, coarsely ground in a hammer mill and then ground in a jet mill so that practically all particles have a diameter of less than 10 .mu.m. The product is then mixed again before packing.
EXAMPLE C
______________________________________Granulate______________________________________Wettable powder of Example B 5%Attapulgite granulate 95%(USS 20-40 mesh; 0.84-0.42 mm)______________________________________
A slurry of wettable powder with 25 % solid substances is sprayed into a double cone mixer and the granules are then dried and packed.
EXAMPLE D
______________________________________Extrusion-pressed pellets______________________________________1-�(2,4-Dichlorophenyl)imino!dihydro-1H,3H,5H- 25%�1,3,4!thiadiazolo�3,4-c!-�1,3,4!oxadiazin-3-oneAnhydrous sodium sulfate 10%Crude calcium ligninsulfonate 5%Sodium alkylnaphthalenesulfonate 1%Calcium/magnesium bentonite 59%______________________________________
The ingredients are mixed together, ground in a hammer mill and then moistened with about 12% water. The mixture is extrusion-pressed into cylinders with a diameter of about 3 mm which are then cut up into pellets of a length of about 3 mm. These can be used directly after drying; however, the dried pellets can be ground up so that the ground particles pass through a USS No. 20 sieve (mesh diameter 0.84 mm). The granules remaining on a sieve of USS No. 40 (mesh diameter 0.42 mm) can be packed for use, whilst the fine particles are recycled.
EXAMPLE E
______________________________________Granulate of low tensile strength______________________________________1-�(2,4-Dichlorophenyl)imino!dihydro-1H,3H,5H- 1%�1,3,4!thiadiazolo�3,4-c!-�1,3,4!oxadiazin-3-oneN,N-Dimethylformamide 9%Attapulgite granulate (USS sieves 20 to 40) 90%______________________________________
The active substance is dissolved in the solvent and the solution is sprayed on to dust-free granules in a double-cone mixer. After spraying of the solution the mixer is left running for a further short time, after which the granules are packed.
EXAMPLE F
______________________________________Granulate______________________________________1-�(2,4-Dichlorophenyl)imino!dihydro-1H,3H,5H- 80%�1,3,4!thiadiazolo�3,4-c!-�1,3,4!oxadiazin-3-oneWetting agent 1%Crude ligninsulfonate (with 5-20% of the natural sugars) 10%Attapulgite clay 9%______________________________________
The ingredients are mixed and ground until they pass through a 100-mesh sieve. This material is then put in a fluid bed granulator, where the airflow is adusted so that the material is easily whirled up and a free water jet is sprayed on to the whirled up material. Fluidisation and spraying are continued until granules of the desired size are obtained. Spraying is then stopped, but fluidisation is continued, optionally with heating, until the water content has fallen to the desired level, which is generally below 1%. The material is then drawn off and the desired granule size range (usually 1410 to 149 .mu.m) is obtained by sieving on 14- to 100-mesh sieves, after which the granules are packed for use.
EXAMPLE G
______________________________________Aqueous suspension______________________________________1-�(2,4-Dichlorophenyl)imino!dihydro-1H,3H,5H- 40.0%�1,3,4!thiadiazolo�3,4-c!-�1,3,4!oxadiazin-3-onePolyacrylic acid-based thickener 0.3%Dodecylphenol polyethylene glycol ether 0.5%Disodium phosphate 1.0%Monosodium phosphate 0.5%Polyvinyl alcohol 1.0%Water 56.7%______________________________________
The ingredients are mixed and ground together in a sand mill to obtain particles essentially of a size of less than 5 .mu.m.
EXAMPLE H
______________________________________Strong concentrate______________________________________1-�(2,4-Dichlorophenyl)imino!dihydro-1H,3H,5H- 99.0%�1,3,4!thiadiazolo�3,4-c!-�1,3,4!oxadiazin-3-oneSilicic acid-Aerogel 0.5%Synthetic amorphous silicic acid 0.5%______________________________________
The ingredients are mixed and ground in a hammer mill to obtain material that passes through a USS sieve No. 50 (0.3 mm aperture). The concentrate may if necessary also contain further ingredients.
EXAMPLE I
______________________________________Wettable powder______________________________________1-�(2,4-Dichlorophenyl)imino!dihydro-1H,3H,5H- 90.0%�1,3,4!thiadiazolo�3,4-c!-�1,3,4!oxadiazin-3-oneDioctylsodium sulphosuccinate 0.1%Synthetic fine silicic acid 9.9%______________________________________
The ingredients are mixed and ground in a hammer mill to obtain particles essentially of a size of less than 100 .mu.m. The material is sieved through a USS No. 50 sieve and then packed.
EXAMPLE J
______________________________________Wettable powder______________________________________1-�(2,4-Dichlorophenyl)imino!dihydro-1H,3H,5H- 40%�1,3,4!thiadiazolo�3,4-c!-�1,3,4!oxadiazin-3-oneSodium ligninsulfonate 20%Montmorillonite clay 40%______________________________________
The ingredients are thoroughly mixed, coarsely ground in a hammer mill, then ground in an air-jet mill to obtain particles essentially of a size of less than 10 .mu.m and then mixed again and packed.
EXAMPLE K
______________________________________Suspension in oil______________________________________1-�(2,4-Dichlorophenyl)imino!dihydro-1H,3H,5H- 35%�1,3,4!thiadiazolo�3,4-c!-�1,3,4!oxadiazin-3-oneMixture of polyalcohol carboxylic acid esters 6%and oil-soluble petroleum sulfonatesXylene 59%______________________________________
The ingredients are mixed and ground in a sand mill to obtain particles essentially of a size of less than 5 .mu.m. The product can be used as it is or diluted with off or emulsified in water.
EXAMPLE L
______________________________________Fine powder______________________________________1-�(2,4-Dichlorophenyl)imino!dihydro-1H,3H,5H- 10%�1,3,4!thiadiazolo�3,4-c!-�1,3,4!oxadiazin-3-oneAttapulgite 10%Pyrophyllite 80%______________________________________
The active substance is mixed with attapulgite and then passed through a hammer mill to obtain particles of essentially less than 200 .mu.m in diameter. The ground concentrate is then mixed with the powdered pyrophyllite until a homogeneous mixture is obtained.
EXAMPLE M
______________________________________Suspension in oil______________________________________1-�(2,4-Dichlorophenyl)imino!dihydro-1H,3H,5H- 25%�1,3,4!thiadiazolo�3,4-c!-�1,3,4!oxadiazin-3-onePolyoxyethylene sorbitol hexaoleate 5%High molecular weight aliphatic hydrocarbon oil 70%______________________________________
The ingredients are ground together in a sand mill until the .size of the solid particles is below about 5 .mu.m. The resultant thick suspension can be used as it is, though it is preferably used after dilution with oils or after emulsification in water.
Application
The compounds of the invention are active weedkillers. They are used for wide-range weed control in the pre- and/or post-germination period in areas in which complete control of all vegetation is desirable, such as, for example, around industrial plants, warehouses, car parks, reclaimed land, fenced areas, roads and railway lines. Some of these compounds are used for selective weed control in crops such as rice, wheat, oats, maize, soybeans, sugar-beet, cotton and groundnuts. The compounds of the invention are active weedkillers for selective and/or general weed control of dicotyledonous weeds and grasses in all plantation crops, including coffee, cocoa, sugar cane, oil palms, robber, citrus fruits, grapes, fruit trees, nut trees, bananas, plantain, pineapples and conifers such as Scots and other pines and spruces.
The compounds can be used in the pre- and/or post-germination period using techniques such as `banding`, direct spraying or broadcast sowing. The applied quantities are determined by a number of factors, including whether they are used as general herbicides, the environment in which they are used, the crop being treated, the types of weeds to be controlled, the weather at the time and the climate in general, the choice of formulation, the method of application, foliage stage, and the like. The quantity of the compounds of the invention that appears optimum to the expert can thus be selected for use in areas where complete control of the entire vegetation is desirable, such as, for example, around storage tanks, industrial plants, advertising areas, roads; railway lines, and fencing. Alternatively, when the correct quantities have been selected for application, the compounds of the invention can be used for selective weed control in plantations for groundnuts, citrus fruits, sugar cane, coffee, oil palms, robber, cocoa, grapes, fruit trees, nut trees, pineapples and bananas. The compounds in question are generally applied in quantities of between 0.001 to 20 kg/hectare, the preferred application quantity being 0.01 to 2 kg/hectare.
The compounds of the invention can be used in combination with other herbicides which are listed below. They are particularly useful in combination with triazines, triazoles, uracils, ureas, amides, carbamates, bipyridyl and phenoxy compounds, sulphone ureas and imidazoles for total control of vegetation in plantation and other crops. The compounds can also be used in combination with mefluidide, glyphosate or gluphosinate.
A mixture of one or more of the following herbicides with a compound of the invention can be particularly useful for weed control. Examples of other herbicides with which the compounds of the invention can be formulated are: .
Acetochlor, acifluorfen, acrolein, 2-propenal, alachior, ametryn, amidosulfuron, ammonium sulfamate, amitroles, Anilofos, asulam, atrazines, Barban, Benefin, bensulfuron methyl, bensulides, bentazone, benzofluorine, Benzoylprop, Bifenox, bromacil, bromoxynil, bromoxynil heptanoate and octanoate, butachlor, buthidazoles, butraline, butylates, cacodylic acid, 2-chloro-N,N-di-2-propenyl-acetamide, 2-chloroallyldiethyldithiocarbamate, Chloramben, chlorbromuron, chloridazon, chlorimuron ethyl, chlormethoxynil, chlomitrofen, chloroxuron, chlorpropham, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, Clethodium, clomazone, cloproxydim, clopyralid, methylarsonic acid or the corresponding calcium salt, cyanazines, cycloates, cyluron, Cyperquat, cyprazines, cyprazoles, cypromid, Delapon, dazomate, dimethyl 2,3,5,6-tetrachloro-1,4-dibenzenedicarboxylate, Desmedipham, Desmetryn, Dicamba, dichlobenil, dichlorprop, Diclofop, diethatyl, Difenzoquat, diflufenican, dimepiperates, dinitramines, Dinoseb, diphenamid, Dipropetryn, Diquat, diuron, 2-methyl-4,6-dinitrophenol, methylarsonic acid disodium salt, Dymron, Endothall, S-ethyldipropylcarbamothioate, Esprocarb, ethalfluralin, ethametsulfuron methyl, ethofumesate, Fenac, Fenoxaprop, fenuron, fenuron trichloroacetate, Flameprop, Fluazifop, Fluazifop-P, fluchloralin, Flumesulam, Flumipropyn, fluometuron, fluorochloridone, fluorodifen, fluoroglycofen, flupoxam, fluridones, Fluroxypyr, fluzasulfuron, Fomasafen, fosamines, glyphosates, Haloxyfop, hexaflurates, hexazinones, imazamethabenz, Imazethapyr, imazosulfuron, Ioxynil, isopropalin, isoproturon, isottron, isoxaben, karbutilate, lactofen, Lenacil, linuron, metobenzuron, metsulfuron methyl, methylarsonic acid, monoammonium methylarsonate, (4-chloro-2-methylphenoxy)acetic acid, S,S'-dimethyl-2-(difluoromethyl))-4-(2-methylpropyl)-6-(trifluoromethyl)-3,5-pyridinedicarbothioate, Mecoprop, Mefenacet, mefluidides, methalpropalin, methabenzthiazttron, Metham, methazoles, methoxuron, Metolachlor, Metribuzin, 1,2-dihydropyridazine-3,6-dione, molinates, monolinuron, monuron, monuron trichloroacetate, monososodium methylarsonate, napropamides, naptalam, neburon, nicosulfuron, nitralin, nitrofen, nitrofluorofen, Norea, norflurazon, oryzalin, oxadiazon, oxyflorofen, Paraquat, pebulates, pendimethalin, perfluidone, phenmedipham, picloram, 5-�2-chloro-4-(trifluoromethyl)phenoxy!-2-nitroacetophenone oxime-O-acetic acid methyl ester, pretilachlor, primisulfuron, procyazines, profluralin, prometon, Prometryn, pronamides, propachlor, propanil, propazines, Propham, prosulfalin, Prynachlor, pyrazolates, pyrazon, pyrazosulfuron ethyl, Quinchlorac, Quizalofop ethyl, rimsulfuron, secbumeton, sethoxydim, siduron, simazines, 1-(.alpha.,.alpha.-dimethylbenzyl)-3-(4-methylphenyl)urea, sulfometuron methyl, trichloroacetic acid, tebuthiuron, terbacil, terbuchlor, terbuthylazines, terbutol, Terbutryn, thifensulfuron methyl, thiobencarb, triallates, trialkoxydim, triasulfuron, tribenuron methyl, triclopyr, tridiphans, trifluralin, trimeturon, (2,4-dichlorophenoxy)acetic acid, 4-(2,4-dichlorophenoxy)butyric acid, vemolates and xylachlor. Results for Tests A-D are given in Tables A-D.
INDEX TABLE A______________________________________ ##STR46##Cmpd # R.sup.5 R.sup.7 mp.sup.a______________________________________1 H H oil2 Cl H oil3 Cl Cl oil9 F CO.sub.2 CH(CH.sub.3).sub.2 118-119.degree. C.10 f OCH2CHCH2 119.degree. C.11 F OCH.sub.2 C CH 194.degree. C.12 F OCH.sub.2 -cyclopropyl 104.degree. C.13 F OCH(CH.sub.3)C CH 108.degree. C.14 F OCH(CH.sub.3).sub.2 129.degree. C.15 F OCH.sub.2 Ph 126.degree. F.16 F OCH.sub.2 CHCHCO.sub.2 CH.sub.3 119-121.degree. C.______________________________________ ##STR47## ##STR48## ##STR49## ##STR50## .sup.a1 H NMR data for oils are given in Index Table B.
______________________________________INDEX TABLE BCmpd No. .sup.1 H NMR Data.sup.a______________________________________1 Me.sub.2 SO-d.sub.6 4.11(t,2H), 4.50(t,2H), 5.18(s,2H), 6.98 (d,2H), 7.37(d,2H).2 Me.sub.2 SO-d.sub.6 Two isomers: 3.82 and 4.01(2t,2H), 4.12 and 4.53(2t,2H), 5.17 and 5.22(2s,2H), 7.10(2d,1H), 7.30-7.35(m,1H), 7.50 and 7.56(2d,1H).3 CDCl.sub.3 3.85(t,2H), 4.05(t,2H), 5.16(s,2H), 7.07 (s,1H), 7.53(s,1H).5 CDCl.sub.3 1.85-1.98(m,1H), 2.08-2.22(m,1h), 2.22-2.37(m,2H), 3.55-3.65(m,1H), 4.00-4.11(m,1H), 4.54(dd,1H), 6.84 (d,1H), 7.17(d,1H), 7.40(s,1H).6 CDCl.sub.3 1.85-1.95(m,1H), 2.08-2.19(m,1H), 2.20-2.35(m,2H), 3.51-3.61(m,1H), 3.95-4.08(m,1H), 4.52(dd,1H), 7.01 (s,1H), 7.43(s,1H).7 CDCl.sub.3 1.85-1.98(m,1H), 2.08-2.22(m,1h), 2.22-2.37(m,2H), 3.55-3.65(m,1H), 4.00-4.11(m,1H), 4.54(dd,1H), 6.84 (d,1H), 7.17(d,1H), 7.40(s,1H).______________________________________ .sup.a 1 H NMR data are in ppm downfield from tetramethylsilane and were measured at 500 MHz. Couplings are designated by ssinglet, ddoublet, ttriplet, mmultiplet, dddoublet of doublets.
TEST A
Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloa crus-galli), bedstraw (Galium aparine ), blackgrass (Alopecurus myosur oides ), cheatgrass (Bromus secalinus), chickweed (Stellaria media), cocklebur (Xanthium pensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria spp.), downy brome (Bromus tectorum), giant foxtail (Setaria faberii), morningglory (Ipomoea hederacea), rape (Brassica napus), rice (Oryza saliva), sorghum (Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonurn convolvulus), wild oat (Avena fatua) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species were also treated with postemergence applications of test chemicals. Plants ranged in height from two to eighteen cm (one to four leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table A, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.
TABLE A__________________________________________________________________________ COMPOUND COMPOUNDRate 1000 g/ha 2 3 5 6 7 Rate 1000 g/ha 2 3 5 6 7__________________________________________________________________________Postemergence PreemergenceBarley 3 2 2 2 3 Barley 0 0 0 0 0Barnyardgrass 8 4 4 4 5 Barnyardgrass 7 0 0 0 0Bedstraw 7 5 5 6 3 Bedstraw 7 0 2 0 --Blackgrass 2 2 2 1 2 Blackgrass 1 0 0 0 0Cheatgrass -- -- -- -- -- Cheatgrass -- -- -- -- --Chickweed 2 2 1 0 0 Chickweed 0 0 2 0 0Cocklebur 7 4 5 6 6 Cocklebur 0 0 0 0 0Corn 3 3 2 2 3 Corn 3 0 0 0 0Cotton 10 9 10 9 9 Cotton 2 2 0 0 0Crabgrass 5 3 3 3 4 Crabgrass 8 3 0 0 0Downy brome 3 0 3 1 1 Downy brome 1 0 0 0 0Giant foxtail 5 2 3 4 3 Giant foxtail 7 3 0 0 0Morningglory 8 7 6 9 8 Morningglory 0 0 0 0 0Nutsedge 7 -- 0 0 6 Nutsedge 0 8 0 0 0Rape 8 5 9 5 3 Rape 10 8 0 0 0Rice 3 3 3 0 2 Rice 0 0 0 0 0Sorghum 4 3 4 3 4 Sorghum 2 0 0 0 0Soybean 8 3 4 3 6 Soybean 0 0 0 0 0Sugarbeet 9 6 8 10 9 Sugarbeet 4 2 0 0 0Velvetleaf 10 9 8 9 10 Velvetleaf 10 10 0 0 0Wheat 3 1 2 1 2 Wheat 0 0 0 0 0Wild buckwheat 9 8 10 10 9 Wild buckwheat 9 2 0 0 0Wild oat 2 0 2 2 2 Wild oat 3 0 0 0 0__________________________________________________________________________ COMPOUNDRate 200 g/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16__________________________________________________________________________PostemergenceBarley 3 3 0 5 2 2 2 5 8 7 9 7 8 8 3 9Barnyardgrass 5 5 3 9 2 2 3 7 10 9 9 9 10 10 5 9Bedstraw 5 6 5 10 3 3 3 10 10 10 10 9 10 10 9 10Blackgrass 2 1 0 7 2 1 1 4 9 8 9 8 9 8 4 4Cheatgrass -- -- -- -- -- -- -- -- -- -- -- -- 9 8 3 4Chickweed 2 1 0 10 0 0 0 10 10 10 10 8 10 8 7 6Cocklebur 6 6 5 10 6 5 5 10 10 10 10 10 10 10 10 10Corn 3 3 2 7 2 2 2 2 8 8 9 8 8 9 2 4Cotton 9 10 9 10 9 8 9 10 10 10 10 10 10 10 10 10Crabgrass 5 2 3 -- 2 3 2 7 8 9 9 9 9 9 7 4Downy brome 3 3 1 5 1 0 0 4 6 8 8 6 -- -- -- --Giant foxtail 4 4 3 9 2 1 2 6 8 9 9 9 9 9 6 6Morningglory 8 7 6 10 5 6 7 10 10 10 10 10 10 10 10 9Nutsedge 2 -- 6 5 0 4 0 0 4 6 7 3 4 7 1 1Rape 2 7 4 10 4 2 1 10 10 10 10 10 10 10 10 10Rice 3 2 2 9 1 0 0 4 10 9 9 9 10 9 4 4Sorghum 4 3 2 8 3 3 3 6 9 9 9 9 9 9 4 7Soybean 5 3 3 10 3 3 3 10 9 9 10 9 10 10 8 9Sugarbeet 3 4 3 10 5 6 7 10 10 10 10 10 10 10 10 10Velvetleaf 9 9 9 10 8 7 6 10 10 10 10 10 10 10 10 10Wheat 1 1 0 7 0 0 1 5 6 8 9 8 9 9 4 9Wild buckwheat 6 8 9 10 7 8 7 10 10 10 10 10 10 10 10 10Wild oat 2 2 0 7 1 0 1 5 7 8 9 7 9 8 3 8PreemergenceBarley 0 0 0 6 0 0 0 0 6 5 6 2 6 2 0 1Barnyardgrass 0 0 0 8 0 0 0 0 9 9 9 9 9 10 3 6Bedstraw 0 2 0 10 -- -- 0 3 10 10 10 10 10 10 10 10Blackgrass 0 0 0 6 0 0 0 7 7 4 6 4 7 8 3 1Cheatgrass -- -- -- -- -- -- -- -- -- -- -- -- 6 8 3 1Chickweed 0 0 0 10 0 0 0 10 10 10 10 10 10 9 6 0Cocklebur 0 0 0 10 0 0 0 3 10 10 10 9 10 9 8 8Corn 0 0 0 4 0 0 0 0 6 7 8 2 6 6 2 1Cotton 0 0 0 8 0 0 0 0 9 10 10 10 10 10 7 10Crabgrass 4 3 2 9 0 0 0 0 9 10 10 9 10 10 8 4Downy brome 0 0 0 3 0 0 0 0 5 6 7 6 -- -- -- --Giant foxtail 0 2 0 9 0 0 0 0 10 10 10 8 9 10 5 3Morningglory 0 0 0 10 0 0 0 10 10 10 10 10 10 10 10 7Nutsedge -- 0 0 0 0 -- 0 -- -- 10 7 9 4 7 9 8Rape 0 2 0 10 0 0 0 9 10 10 10 10 10 10 8 10Rice 0 0 0 3 0 0 0 0 6 7 8 3 9 9 0 3Sorghum 0 0 0 3 0 0 0 0 4 6 7 5 9 9 0 2Soybean 0 0 0 10 0 0 0 0 8 10 10 10 10 10 2 2Sugarbeet 0 0 0 10 0 0 0 9 10 10 10 10 10 10 10 10Velvetleaf 10 8 7 10 0 0 0 10 10 10 10 10 10 10 10 10Wheat 0 0 0 7 0 0 0 2 6 3 7 3 7 6 1 2Wild buckwheat 0 0 1 10 0 0 0 2 10 10 10 10 10 10 7 6Wild oat 0 0 0 8 0 0 0 4 7 7 9 6 9 8 3 0__________________________________________________________________________ COMPOUNDRate 50 g/ha 1 4 8 9 10 11 12 13 14 15 16__________________________________________________________________________PostemergenceBarley 2 4 4 5 6 7 4 6 4 5 5Barnyardgrass 3 6 6 8 9 9 9 9 9 4 9Bedstraw 3 10 10 10 10 10 9 10 10 8 9Blackgrass 1 3 4 6 6 8 4 7 6 3 3Cheatgrass -- -- -- -- -- -- -- 7 4 3 3Chickweed 2 10 10 9 8 10 7 9 4 4 6Cocklebur 6 10 10 10 10 10 10 10 9 9 10Corn 3 5 3 5 6 8 5 5 5 2 3Cotton 9 10 10 10 10 10 10 10 10 10 10Crabgrass 3 5 6 6 8 9 8 8 8 7 6Downy brome 3 4 4 5 4 6 4 -- -- -- --Giant foxtail 3 6 6 6 7 9 8 7 8 5 8Morningglory 7 10 10 10 10 10 10 10 10 9 9Nutsedge 0 5 3 3 3 6 6 3 7 1 1Rape 2 10 10 10 10 10 10 10 10 10 10Rice 2 6 3 8 9 9 7 9 9 4 4Sorghum 3 6 4 6 8 9 7 8 9 3 5Soybean 4 8 9 9 9 9 9 10 9 8 8Sugarbeet 2 10 9 10 10 10 10 10 10 10 10Velvetleaf 7 10 10 10 10 10 10 10 10 10 10Wheat 1 7 5 5 6 7 5 6 6 3 6Wild buckwheat 6 10 10 10 10 10 10 10 10 10 10Wild oat 1 5 4 6 6 8 4 7 5 2 8PreemergenceBarley 0 1 0 1 2 2 2 2 2 0 0Barnyardgrass 0 3 0 6 7 8 6 8 8 0 3Bedstraw 0 6 0 10 10 10 9 10 9 2 0Blackgrass 0 4 0 4 1 5 1 5 3 0 0Cheatgrass -- -- -- -- -- -- -- 3 2 2 0Chickweed -- 10 9 8 8 10 4 10 6 2 0Cocklebur 0 9 0 6 8 10 8 7 9 3 5Corn 0 3 0 2 3 3 1 3 3 1 0Cotton 0 2 0 0 10 9 2 7 6 0 0Crabgrass 0 5 0 9 9 10 8 9 9 2 2Downy brome 0 3 0 3 3 8 3 -- -- -- --Giant foxtail 0 5 0 7 8 8 5 6 9 0 3Morningglory 0 10 7 10 9 10 9 10 10 4 5Nutsedge -- 0 -- -- 7 3 4 3 8 3 3Rape 0 10 2 9 10 10 7 9 10 3 3Rice 0 0 0 2 3 5 2 3 5 0 0Sorghum 0 2 0 2 5 4 2 3 5 0 0Soybean 0 6 0 0 8 6 4 5 10 0 0Sugarbeet 0 9 8 10 10 10 10 10 10 8 8Velvetleaf 0 10 3 9 10 10 10 10 10 10 8Wheat 0 5 0 3 3 5 2 4 5 0 0Wild buckwheat 0 0 0 9 10 10 5 10 9 3 3Wild oat 0 7 0 5 6 7 3 6 6 2 0__________________________________________________________________________
TEST B
Seeds of barnyardgrass (Echinochloa crus-galli), cocklebur (Xanthium pensylvanicum), crabgrass (Digitaria spp.), downy brome (Bromus rectorurn), giant foxtail (Setaria faberii), morningglory (Ipomoea spp.), sorghum (Sorghum bicolor), velvetleaf (Abutlion theophrasti), and wild oat (Avenafatua) were planted into a sandy loam soil and treated preemergence, or with a soil drench (PDRN), with test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species were also treated postemergence, or sprayed to runoff (STRO), with test chemicals. Plants ranged in height from two to eighteen cm and were in the two to three leaf stage for the postemergence treatment. Treated plants and untreated controls were maintained in a greenhouse for approximately eleven days, after which all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table B, are based on a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test results.
TABLE B__________________________________________________________________________ COMPOUND COMPOUNDRate 2000 g/ha 1 2 3 4 5 6 7 8 Rate 1000 g/ha 1 2 3 4 5 6 7 8__________________________________________________________________________Preemergence PostemergenceBarnyardgrass 8 9 0 9 0 4 0 9 Barnyardgrass 8 5 4 10 3 2 3 9Cocklebur 5 4 3 10 0 0 0 10 Cocklebur 7 7 2 10 4 4 1 10Crabgrass 8 9 7 10 1 0 0 9 Crabgrass 8 6 4 10 3 2 2 10Downy brome 2 0 0 10 0 0 0 0 Downy brome 3 2 1 6 1 0 0 4Giant foxtail 9 9 4 10 3 0 0 9 Giant foxtail 9 7 3 10 4 3 3 10Morningglory 3 4 2 10 0 0 0 10 Morningglory 8 9 9 10 8 9 8 10Sorghum 4 8 0 10 0 0 0 8 Sorghum 3 4 3 9 2 3 3 6Velvetleaf 10 10 7 10 0 0 0 10 Velvetleaf 10 10 10 10 10 10 10 10Wild oats 0 0 0 10 0 0 0 7 Wild oats 2 3 1 9 3 2 2 7__________________________________________________________________________
TEST C
The compounds evaluated in this test were formulated in a non-phytoxic solvent and applied to the soil surface before plant seedlings emerged (preemergence application), to water that covered the soil surface (flood application), and to plants that were in the one-to-four leaf stage (postemergence application). A sandy loam soil was used for the preemergence and postemergence tests, while a silt loam soil was used in the flood test. Water depth was approximately 2.5 era for the flood test and was maintained at this level for the duration of the test. Plant species in the preemergence and postemergence tests consisted of barnyardgrass (Echinochloa crus-galli), barley (Hordeurn vulgare), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium pensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinaIis), downy brome (Bromus rectorurn), giant foxtail (Setaria faberii), johnsongrass (Sorghum halpense), morningglory (Ipomoea hederacea), pigweed (Amaranthus retroflexus), rape (Brassica napus), ryegrass (Lollurn multiflorum), soybean (Glycine max), speedwell (Veronica persica), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonurn convolvulus), and wild oat (Avena fatua). All plant species were planted One day before application of the compound for the preemergence portion of this test. Plantings of these species were adjusted to produce plants of appropriate size for the postemergence portion of the test. Plant species in the flood test consisted of rice (Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa), barnyardgrass (Echinochloa crus-galli) and Late watergrass (Echinocloa oryzicola) grown to the 1 and 2 leaf stage for testing. All plant species were grown using normal greenhouse practices. Visual evaluations of injury expressed on treated plants, when compared to untreated controls, were recorded approximately fourteen to twenty one days after application of the test compound. Plant response ratings, summarized in Table C, were recorded on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
TABLE C__________________________________________________________________________ Compound CompoundRate 125 g/ha 9 Rate 125 g/ha 9__________________________________________________________________________Postemergence PreemergenceBarley 30 Barley 50Barnyardgrass 95 Barnyardgrass 100Blackgrass 80 Blackgrass 80Chickweed 100 Chickweed 100Cocklebur 100 Cocklebur 95Corn 50 Corn 25Cotton 100 Cotton 50Crabgrass 65 Crabgrass 95Downy brome 35 Downy brome 0Duck salad 20 Galium 55Galium 100 Giant foxtail 100Giant foxtail 95 It. Ryegrass 85It. Ryegrass 80 Johnsongrass 95Johnsongrass 95 Morningglory 100Morningglory 100 Rape 50Rape 100 Redroot pigweed 100Redroot pigweed 100 Soybean 100Rice japonica 100 Speedwell 100Soybean 100 Sugar beet 100Speedwell 100 Velvetleaf 100Sugar beet 100 Wheat 0Umbrella sedge 90 Wild buckwheat 100Velvetleaf 100 Wild oat 80Watergrass-2 100Wheat 60Wild buckwheat 100Wild oat 40Barnyardgrass-2 100__________________________________________________________________________ CompoundRate 62 g/ha 4 8 9 10 11 12 13 14 15 16__________________________________________________________________________PostemergenceBarley 35 30 30 40 65 35 60 50 20 30Barnyardgrass 40 40 90 90 95 95 95 95 10 80Blackgrass 50 40 70 45 80 50 95 75 40 20Chickweed 95 95 100 100 100 90 100 85 75 25Cocklebur 100 100 100 100 100 100 100 100 100 100Corn 25 30 45 35 60 25 55 50 20 30Cotton 100 100 100 100 100 100 100 100 100 100Crabgrass 40 20 55 65 80 45 90 85 25 20Downy brome 50 40 35 35 35 25 50 35 20 0Duck salad 0 0 20 90 30 50 25 -- 40 0Galium 100 100 100 95 100 90 100 90 90 35Giant foxtail 70 50 85 80 95 90 95 95 35 60It. ryegrass 50 30 60 70 95 60 95 75 25 0Johnsongrass 90 50 90 90 95 90 95 90 45 80Morningglory 100 100 100 100 100 100 100 100 95 100Rape 100 100 100 100 100 100 100 100 100 100Redroot pigweed 100 95 100 100 100 100 100 100 100 100Rice japonica 95 10 100 90 95 75 65 -- 40 10Soybean 90 95 95 75 100 85 100 90 100 70Speedwell 100 100 100 -- 100 100 100 100 -- 95Sugar beet 100 100 100 100 100 100 100 100 100 100Umbrella sedge 0 0 90 100 85 100 80 -- 65 0Velvetleaf 100 100 100 100 100 100 100 100 100 100Watergrass-2 70 10 100 95 100 90 95 -- 50 10Wheat 35 30 -- 35 75 40 75 35 40 20Wild buckwheat 100 95 100 100 100 100 100 100 100 --Wild oat 50 40 40 70 90 40 90 75 25 25Barnyardgrass-2 10 0 100 95 100 85 75 -- 75 10PreemergenceBarley 0 0 30 30 75 35 60 80 0 0Barnyardgrass 60 10 100 95 100 85 100 95 20 0Blackgrass 30 0 55 50 90 85 90 85 20 0Chickweed 100 100 90 65 100 60 100 30 10 0Cocklebur 50 0 85 40 85 80 65 85 10 15Corn 20 10 25 35 60 25 40 30 0 0Cotton 75 10 -- 60 100 35 90 90 0 10Crabgrass 55 40 90 90 100 100 100 95 20 0Downy brome 0 0 0 10 35 10 40 30 10 20Galium 100 35 40 30 100 35 100 70 60 20Giant foxtail 80 0 100 95 100 80 100 95 10 20It. ryegrass 55 0 10 70 95 10 95 90 10 20Johnsongrass 40 0 85 90 90 90 95 95 35 10Morningglory 100 90 50 100 100 70 100 95 50 0Rape 100 30 20 90 100 20 100 100 20 10Redroot pigweed 100 85 100 100 100 100 100 100 100 60Soybean 0 40 100 40 100 15 60 85 10 15Speedwell 100 100 100 100 100 100 100 100 100 50Sugar beet 95 100 100 100 100 100 100 100 50 0Velvetleaf 100 40 100 100 100 100 100 100 30 0Wheat 0 0 0 30 45 20 50 55 10 0Wild buckwheat 90 90 100 100 100 100 100 100 95 0Wild oat 55 0 60 60 90 40 90 80 10 0__________________________________________________________________________ CompoundRate 31 g/ha 4 8 9 10 11 12 13 14 15 16__________________________________________________________________________PostemergenceBarley 35 30 30 40 50 30 50 40 20 20Barnyardgrass 35 30 40 90 85 85 95 95 10 80Blackgrass 40 30 35 40 80 35 80 65 35 20Chickweed 80 80 100 100 100 70 100 70 60 25Cocklebur 95 100 100 100 100 100 100 100 100 80Corn 25 25 30 30 35 20 35 35 15 25Cotton 100 100 100 100 100 100 100 100 100 100Crabgrass 30 20 55 50 65 40 45 50 20 0Downy brome 40 30 10 35 30 20 35 35 20 0Duck salad 0 0 15 85 30 0 0 45 25 0Galium 100 100 100 -- 100 80 100 90 85 0Giant foxtail 50 45 85 70 80 40 90 90 25 40It. ryegrass 40 25 30 60 90 30 80 70 20 0Johnsongrass 90 40 45 80 95 50 90 90 30 70Morningglory 100 100 100 100 100 100 100 100 90 85Rape 100 100 100 100 100 100 100 100 100 50Redroot pigweed 100 -- 100 100 100 100 100 100 100 85Rice japonica 85 10 90 70 70 45 40 65 35 10Soybean 90 95 95 65 95 85 100 90 55 60Speedwell 100 100 100 -- 100 100 -- 100 -- 95Sugar beet 100 100 100 100 100 100 100 100 100 100Umbrella sedge 0 0 70 100 85 85 40 80 0 0Velvetleaf 100 100 100 100 100 100 100 100 100 100Watergrass-2 55 0 90 95 100 60 70 85 45 10Wheat 30 30 30 35 50 35 60 35 35 20Wild buckwheat 100 95 100 100 100 100 100 100 100 100Wild oat 35 30 30 65 90 30 80 70 20 10Barnyardgrass-2 0 0 100 90 95 80 60 90 65 10PreemergenceBarley 0 0 20 20 70 35 40 60 0 0Barnyardgrass 20 0 95 50 100 80 95 95 15 0Blackgrass 20 0 35 35 60 30 70 70 0 0Chickweed 20 80 80 50 100 30 75 0 0 0Cocklebur 20 0 60 35 65 30 35 50 0 10Corn 0 0 20 25 55 25 30 20 -- 0Cotton 40 10 30 50 100 20 50 60 0 0Crabgrass 70 20 80 60 100 55 90 70 10 0Downy brome 0 0 0 0 10 0 30 10 0 10Galium 70 -- 20 30 100 10 100 70 10 0Giant foxtail 70 0 95 85 100 60 95 90 0 0It. ryegrass 0 0 0 30 75 -- 70 20 0 10Johnsongrass 30 0 50 75 90 40 95 70 15 0Morningglory 20 20 50 75 100 50 50 75 20 0Rape 0 0 0 45 100 -- 90 100 0 0Redroot pigweed 100 50 100 100 100 100 100 100 90 30Soybean 0 20 100 10 15 10 60 75 0 0Speedwell 100 95 100 60 100 100 100 100 90 --Sugar beet 95 0 100 100 100 60 100 100 10 0Velvetleaf 100 0 100 100 100 100 100 100 20 0Wheat 0 0 0 20 25 10 30 10 0 0Wild buckwheat 55 90 100 100 100 90 100 100 30 0Wild oat 25 0 30 30 85 40 50 65 0 0__________________________________________________________________________ CompoundRate 16 g/ha 4 8 9 10 11 12 13 14 15 16__________________________________________________________________________PostemergenceBarley 30 25 30 35 35 25 40 30 -- 10Barnyardgrass 30 25 30 30 85 35 70 70 10 65Blackgrass 40 -- 30 40 55 35 75 60 30 20Chickweed 70 70 80 90 95 65 90 70 55 25Cocklebur 90 95 100 85 100 95 100 100 95 --Corn 20 20 20 25 25 15 20 20 10 25Cotton 100 100 100 100 100 100 100 100 100 100Crabgrass 25 15 30 30 45 25 35 45 20 0Downy brome 30 25 10 30 25 10 30 25 15 0Duck salad 0 0 10 50 0 0 0 35 0 0Galium 90 95 100 90 85 80 85 90 65 0Giant foxtail 45 35 60 55 80 20 80 55 25 40It. ryegrass 25 20 20 30 35 20 40 35 20 0Johnsongrass 85 30 40 65 70 35 60 50 25 70Morningglory 100 100 100 100 100 100 100 100 -- 85Rape 100 100 100 -- 100 100 100 100 90 40Redroot pigweed 100 90 100 100 100 100 100 100 100 80Rice japonica 55 0 50 25 30 30 35 60 20 10Soybean 85 95 85 65 85 75 85 80 55 45Speedwell 100 90 100 -- -- 100 -- 100 70 90Sugar beet 100 100 100 100 100 100 100 100 100 65Umbrella sedge 0 0 10 90 35 20 0 50 0 0Velvetleaf 100 100 100 100 100 100 100 100 100 100Watergrass-2 0 0 55 35 70 30 70 35 25 0Wheat 25 25 20 25 40 35 40 30 35 10Wild buckwheat 90 80 100 100 100 100 100 100 100 85Wild oat 30 30 20 40 55 30 45 40 20 10Barnyardgrass-2 0 0 95 40 65 20 25 60 50 0PreemergenceBarley 0 0 0 0 40 20 30 30 0 0Barnyardgrass 20 0 85 30 65 35 90 50 10 0Blackgrass 20 0 10 25 40 10 50 50 0 0Chickweed 20 10 70 35 70 0 -- 0 -- 0Cocklebur 0 0 35 10 60 20 20 35 0 0Corn 0 0 10 0 25 10 20 0 0 0Cotton -- 0 25 20 60 15 45 10 0 0Crabgrass 20 10 30 30 75 35 70 70 10 0Downy brome 0 0 0 0 0 0 20 0 0 0Galium 0 0 0 10 30 0 100 30 0 0Giant foxtail 50 0 90 65 50 50 90 35 0 0It. ryegrass 0 0 0 10 20 0 50 10 0 0Johnsongrass 10 0 20 20 65 20 55 35 0 0Morningglory 0 10 20 30 100 40 50 30 10 0Rape 0 0 0 10 20 10 85 85 0 0Redroot pigweed 100 30 100 100 100 90 100 100 -- 30Soybean 0 -- 35 0 10 0 35 0 0 0Speedwell 100 0 100 40 100 100 100 100 50 0Sugar beet 35 0 100 60 75 0 100 100 0 0Velvetleaf 70 0 55 100 100 100 100 100 0 0Wheat 0 0 0 0 20 0 20 10 0 0Wild buckwheat 0 0 50 100 100 90 100 100 -- 0Wild oat 0 0 10 20 60 35 30 30 0 0__________________________________________________________________________ CompoundRate 8 g/ha 4 8 10 11 12 13 14 15 16__________________________________________________________________________PostemergenceBarley 25 20 35 25 25 35 25 20 0Barnyardgrass 30 20 15 40 35 40 50 10 50Blackgrass 35 25 35 40 35 70 35 25 20Chickweed 40 60 80 90 55 85 45 50 25Cocklebur 90 90 85 90 90 95 90 90 65Corn 15 15 25 25 15 20 15 10 10Cotton 100 100 100 100 100 100 100 100 100Crabgrass 20 10 20 10 25 30 30 15 0Downy brome 30 20 25 25 10 30 20 10 0Duck salad 0 0 40 0 0 0 0 0 0Galium 60 60 75 75 75 70 35 55 0Giant foxtail 30 35 20 35 20 35 40 25 20It. ryegrass 20 20 0 30 20 20 20 20 0Johnsongrass 40 25 65 45 30 25 25 20 60Morningglory 95 100 80 100 90 95 95 90 75Rape 95 100 100 100 100 100 100 90 20Redroot pigweed 95 90 100 100 100 100 90 100 80Rice japonica 40 0 15 20 20 30 30 0 0Soybean 50 90 65 80 50 85 80 55 35Speedwell 100 90 -- -- 100 70 -- 50 80Sugar beet 100 100 100 100 100 100 90 100 50Umbrella sedge 0 0 80 20 20 0 40 0 0Velvetleaf 100 100 100 100 100 100 100 100 100Watergrass-2 0 0 30 25 25 45 25 10 0Wheat 20 20 25 25 30 40 20 20 0Wild buckwheat 75 80 100 100 100 100 100 100 80Wild oat 30 20 25 45 30 40 30 20 10Barnyardgrass-2 0 0 25 25 0 20 30 0 0PreemergenceBarley 0 0 0 20 20 0 0 0 0Barnyardgrass 10 0 0 35 10 40 30 10 0Blackgrass 0 0 25 20 10 10 0 0 0Chickweed 20 0 20 -- 0 30 0 0 0Cocklebur 0 0 0 25 0 0 15 0 0Corn 0 0 0 25 10 10 0 0 0Cotton -- 0 10 30 10 30 0 0 0Crabgrass 0 0 10 25 10 40 45 0 0Downy brome 0 0 0 0 0 0 0 0 0Galium 0 0 10 0 0 0 0 0 0Giant foxtail 0 0 30 50 50 40 20 0 0It. ryegrass 0 0 0 0 0 10 0 0 0Johnsongrass 0 0 0 30 10 20 25 0 0Morningglory 0 10 10 60 30 20 20 10 0Rape 0 0 0 0 0 10 20 0 0Redroot pigweed 30 20 80 100 70 100 90 65 0Soybean 0 10 0 10 0 10 0 0 0Speedwell 100 -- -- 100 95 100 100 -- 0Sugar beet 35 0 30 55 0 20 0 0 0Velvetleaf 45 0 20 100 30 100 100 0 0Wheat 0 0 0 0 0 0 0 0 0Wild buckwheat 0 0 100 95 35 90 100 0 0Wild oat 0 0 10 10 35 20 20 0 0__________________________________________________________________________ Compound CompoundRate 4 g/ha 13 14 Rate 4 g/ha 13 14__________________________________________________________________________Postemergence PreemergenceBarley 35 20 Barley 0 0Barnyardgrass 30 15 Barnyardgrass 30 20Blackgrass 60 20 Blackgrass -- 0Chickweed 85 35 Chickweed -- 0Cocklebur 90 90 Cocklebur 0 0Corn 20 10 Corn 10 0Cotton 100 100 Cotton 10 0Crabgrass 20 20 Crabgrass 0 20Downy brome 20 10 Downy brome 0 0Duck salad -- 0 Galium 9 0Galium 50 30 Giant foxtail 35 0Giant foxtail 25 35 It. ryegrass 10 0It. ryegrass 20 10 Johnsongrass 10 0Johnsongrass 25 20 Morningglory 10 0Morningglory 90 90 Rape 0 0Rape 100 95 Redroot pigweed 95 30Redroot pigweed 100 90 Soybean 0 0Rice japonica -- 0 Speedwell 100 95Soybean 55 75 Sugar beet 20 0Speedwell 60 -- Velvetleaf 40 0sugar beet 90 65 Wheat 0 0Umbrella sedge -- 25 Wild buckwheat 40 30Velvetleaf 100 100 Wild oat 0 20Watergrass-2 -- 0Wheat 40 15Wild buckwheat 95 100Wild oat 40 20Barnyardgrass-2 -- 10__________________________________________________________________________
TEST D
Seeds of barnyardgrass (Echinochloa crus-galli), bindweed (Convolvulus althaeoides), black nightshade (Solanum ptycanthum dunal), cassia (Cassia obtusifolia ), cocklebur (Xanthium pensylvanicum), common ragweed (Ambrosia artemisiifolia), tom (Zea mays), cotton (Gossypium hirsutam), crabgrass (Digitaria spp.), fall panicum (Panicum dichotomiflorum), giant foxtail (Setaria faberii), green foxtail (Setaria viridis), jimsonweed (Datura stramonium), johnson grass (Sorghum halepense), morningglory (Ipomoea spp.), pigweed (Amaranthus retroflexus), prickly sida (Sida spinosa), shattercane (Sorghum vulgare), signalgrass (Brachiaria platyphylla), smartweed (Polygonurn pensylvanicum), soybean (Glycine max), sunflower (Helianthus annuus), velvetleaf (Abutilon theophrasti), wild proso (Pancium miliaceum), wooly cupgrass (Eriochloa villosa), yellow foxtail (Setaria lutescens), and purple nutsedge (Cyperus rotundus) tubers were planted into a matapeake sandy loam soil. These crops and weeds were grown in the greenhouse until the plants ranged in height from two to eighteen em (one to four leaf stage), then treated postemergence with the test chemicals dissolved in a non-phytotoxic solvent. Pots receiving these postemergence treatments were placed in the greenhouse and maintained according to routine greenhouse procedures. Treated plants and untreated controls were maintained in the greenhouse approximately 14-21 days after application of the test compound. Visual evaluations of plant injury responses were then recorded. Plant response ratings, summarized in Table D, are reported on a 0 to 100 scale where 0 is no effect and 100 is complete control.
TABLE D______________________________________Rate 140 g/ha Compound Rate 70 g/ha CompoundPreemergence 9 Postemergence 9______________________________________Barnyardgrass 95 Barnyardgrass 45Bindweed 100 Bindweed 100Blk nightshade 100 Blk nightshade 70Cassia 20 Cassia 100Cocklebur 55 Cocklebur 90Corn 65 Corn 35Cotton 20 Cotton 100Crabgrass 100 Crabgrass 25Fall panicum 95 Fall panicum 35Giant foxtail 100 Giant foxtail 40Green foxtail 100 Green foxtail 40Jimsonweed 100 Jimsonweed 100Johnson grass 90 Johnson grass 40Morningglory 85 Morningglory 100Nutsedge 40 Nutsedge 20Pigweed 100 Pigweed 100Prickly sida 100 Prickly sida 95Ragweed 90 Ragweed 75Shattercane 45 Shattercane 45Signalgrass 100 Signalgrass 55Smartweed 100 Smartweed 75Soybean 20 Soybean 90Sunflower 65 Sunflower 100Velvetleaf 100 Velvetleaf 100Wild proso 100 Wild proso 40Yellow foxtail 100 Wooly cup grass 35 Yellow foxtail 45______________________________________Rate 70 g/ha Compound Rate 35 g/ha CompoundPreemergence 9 Postemergence 4 8 9______________________________________Barnyardgrass 75 Barnyardgrass 0 10 35Bindweed 100 Bindweed 100 100 60Blk nightshade 100 Blk nightshade 100 85 35Cassia 0 Cassia 100 100 65Cocklebur 45 Cocklebur 100 100 65Corn 20 Corn 25 35 30Cotton 0 Cotton 100 100 100Crabgrass 85 Crabgrass 0 10 25Fall panicum 95 Fall panicum 0 0 30Giant foxtail 100 Giant foxtail 0 15 30Green foxtail 100 Green foxtail 0 15 30Jimsonweed 65 Jimsonweed 100 100 75Johnson grass 60 Johnson grass 0 15 35Morningglory 20 Morningglory 100 100 65Nutsedge 20 Nutsedge 0 0 15Pigweed 100 Pigweed 100 85 90Prickly sida 100 Prickly sida 65 75 35Ragweed 55 Ragweed 100 90 20Shattercane 25 Shattercane 15 10 30Signalgrass 85 Signalgrass 0 0 35Smartweed 100 Smartweed 100 100 25Soybean 0 Soybean 80 80 50Sunflower 30 Sunflower 70 100 60Velvetleaf 100 Velvetleaf 100 100 75Wild proso 85 Wild proso 15 0 35Yellow foxtail 95 Wooly cup grass 15 0 30 Yellow foxtail 0 15 30______________________________________Rate 35 g/ha Compound Rate 17 g/ha CompoundPreemergence 9 Postemergence 4 8 9______________________________________Barnyardgrass 55 Barnyardgrass 0 5 35Bindweed 20 Bindweed 85 100 40Blk nightshade 100 Blk nightshade 95 75 30Cassia 0 Cassia 80 75 55Cocklebur 30 Cocklebur 85 100 60Corn 0 Corn 20 30 25Cotton 0 Cotton 100 100 100Crabgrass 55 crabgrass 0 5 15Fall panicum 95 Fall panicum 0 0 25Giant foxtail 50 Giant foxtail 0 15 25Green foxtail 50 Green foxtail 0 15 25Jimsonweed 10 Jimsonweed 100 95 70Johnson grass 15 Johnson grass 0 10 30Morningglory 0 Morningglory 100 100 40Nutsedge 0 Nutsedge 0 0 15Pigweed 100 Pigweed 90 75 90Prickly sida 100 Prickly sida 55 65 25Ragweed 45 Ragweed 100 75 15Shattercane 15 Shattercane 10 5 25Signalgrass 0 Signalgrass 0 0 30Smartweed 100 Smartweed 100 90 25Soybean 0 Soybean 70 75 35Sunflower 0 Sunflower 65 85 55Velvetleaf 65 Velvetleaf 100 100 55Wild proso 25 Wild proso 10 0 30Yellow foxtail 40 Wooly cup grass 10 0 25 Yellow foxtail 0 10 25______________________________________Rate 17 g/ha Compound Rate 8 g/ha CompoundPreemergence 9 Postemergence 4 8 9______________________________________Barnyardgrass 15 Barnyardgrass 0 0 30Bindweed 0 Bindweed 70 80 35Blk nightshade 100 Blk nightshade 60 70 25Cassia 0 Cassia 60 65 50Cocklebur 15 Cocklebur 55 80 20Corn 0 Corn 20 20 25Cotton 0 Cotton 100 100 100Crabgrass 15 Crabgrass 0 0 10Fall panicum 35 Fall panicum 0 0 20Giant foxtail 10 Giant foxtail 0 10 25Green foxtail 10 Green foxtail 0 10 20Jimsonweed 0 Jimsonweed 100 80 65Johnson grass 0 Johnson grass 0 0 25Morningglory 0 Morningglory 100 65 35Nutsedge 0 Nutsedge 0 0 0Pigweed 100 Pigweed 65 70 85Prickly sida 65 Prickly sida 45 45 20Ragweed 15 Ragweed 65 65 10Shattercane 10 Shattercane 0 0 20Signalgrass 0 Signalgrass 0 0 25Smartweed 100 Smartweed 55 80 20Soybean 0 Soybean 65 70 20Sunflower 0 Sunflower 60 55 50Velvetleaf 40 Velvetleaf 100 65 45Wild proso 15 Wild proso 0 0 25Yellow foxtail 10 Wooly cup grass 5 0 20 Yellow foxtail 0 5 20______________________________________Rate 8 g/ha Compound Rate 4 g/ha CompoundPreemergence 9 Postemergence 4 8 9______________________________________Barnyardgrass 0 Barnyardgrass 0 0 15Bindweed 0 Bindweed 25 65 15Blk nightshade 100 Blk nightshade 40 60 20Cassia 0 Cassia 20 35 10Cocklebur 0 Cocklebur 45 65 15Corn 0 Corn 15 15 20Cotton 0 Cotton 75 100 100Crabgrass 0 Crabgrass 0 0 0Fall panicum 0 Fall panicum 0 0 10Giant foxtail 0 Giant foxtail 0 0 10Green foxtail 0 Green foxtail 0 0 10Jimsonweed 0 Jimsonweed 100 65 10Johnson grass 0 Johnson grass 0 0 15Morningglory 0 Morningglory 95 60 10Nutsedge 0 Nutsedge 0 0 0Pigweed 90 Pigweed 55 55 10Prickly sida 20 Prickly sida 25 15 0Ragweed 0 Ragweed 35 40 0Shattercane 0 Shattercane 0 0 10Signalgrass 0 Signalgrass 0 0 15Smartweed 55 Smartweed 0 60 15Soybean 0 Soybean 40 60 15Sunflower 0 Sunflower 55 45 40Velvetleaf 15 Velvetleaf 55 45 15Wild proso 0 Wild proso 0 0 20Yellow foxtail 0 Wooly cup grass 0 0 15 Yellow foxtail 0 0 10______________________________________Rate 2 g/ha CompoundPostemergence 4 8______________________________________Barnyardgrass 0 0Bindweed 0 45Blk nightshade 0 40Cassia 10 10Cocklebur 30 50Corn 10 10Cotton -- 100Crabgrass 0 0Fall panicum 0 0Giant foxtail 0 0Green foxtail 0 0Jimsonweed 100 55Johnson grass 0 0Morningglory 35 40Nutsedge 0 0Pigweed 45 35Prickly sida 0 0Ragweed 30 25Shattercane 0 0Signalgrass 0 0Smartweed 0 35Soybean 10 15Sunflower 35 20Velvetleaf 45 20Wild proso 0 0Wooly cup grass 0 0Yellow foxtail 0 0______________________________________

Claims

1. A compound of the formula ##STR51## wherein: X is selected from the group O, S, S(O), S(O).sub.2, CHOCH.sub.2 F, CHOCHF.sub.2, CHOCF.sub.3, CHOCH.sub.2 CF.sub.3 and NR.sup.4 ;
m and n are independently 1 or 2, where m+n=2 or 3;
p is 0 to 9;
U is N or CH;
W is independently O or S;
R.sup.A is independently selected from the group halogen, C.sub.1 -C.sub.4 alkyl, cyano, C.sub.1 -C.sub.4 haloalkyl, C.sub.3 -C.sub.4 alkenyl, C.sub.1 -C.sub.3 alkylthio, C.sub.1 -C.sub.3 haloalkylthio, C.sub.2 -C.sub.4 alkylcarbonyl, OR.sup.3, C.sub.2 -C.sub.6 alkyloxycarbonyl, C.sub.2 -C.sub.6 haloalkoxycarbonyl, and C.sub.3 -C.sub.8 alkoxycarbonylalkyl; or, two R.sup.A groups on the same carbon atom, together with this carbon, are C.dbd.O;
R.sup.3 is selected from the group hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.2 -C.sub.4 alkylcarbonyl and C.sub.2 -C.sub.4 haloalkylcarbonyl;
R.sup.4 is selected from the group hydrogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl, C.sub.2 -C.sub.4 alkylcarbonyl, C.sub.2 -C.sub.4 haloalkoxycarbonyl and C.sub.2 -C.sub.4 alkoxycarbonyl;
provided that when X is CHOCH.sub.2 F, CHOCHF.sub.2, CHOCF.sub.3, or CHOCH.sub.2 CF.sub.3, m and n are 1, and U is N, then p is 1 to 5 and at least one R.sup.A is other than alkyl;
Q is selected from the group ##STR52## Z is O or S; R.sup.5 is hydrogen or halogen;
R.sup.6 is selected from the group C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 haloalkyl, OCH.sub.3, SCH.sub.3, OCHF.sub.2, halogen, CN and NO.sub.2 ;
R.sup.7 is selected from the group hydrogen, C.sub.1 -C.sub.8 alkyl, C.sub.1 -C.sub.8 haloalkyl, halogen, OR.sup.11, SR.sup.11, S(O).sub.q R.sup.11, COR.sup.11, CO.sub.2 R.sup.11, C(O)SR.sup.11, C(O)NR.sup.12 R.sup.13, CHO and NHSO.sub.2 NHR.sup.16 ;
R.sup.8 is selected from the group hydrogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl and halogen;
R.sup.9 is selected from the group hydrogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl and halogen; or, when Q is Q-2 or Q-6, R.sup.8 and R.sup.9 together with the carbon to which they are bonded is additionally selected from C.dbd.O;
R.sup.10 is selected from the group C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.2 -C.sub.6 alkoxyalkyl, C.sub.3 -C.sub.6 alkenyl and C.sub.3 -C.sub.6 alkynyl;
R.sup.11 is selected from the group C.sub.1 -C.sub.8 alkyl, C.sub.3 -C.sub.8 cycloalkyl, C.sub.3 -C.sub.8 alkenyl, C.sub.3 -C.sub.8 alkynyl, C.sub.1 -C.sub.8 haloalkyl, C.sub.2 -C.sub.8 alkoxyalkyl, C.sub.2 -C.sub.8 alkylthioalkyl, C.sub.2 -C.sub.8 alkylsulphinylalkyl, C.sub.2 -C.sub.8 alkylsulphonylalkyl, C.sub.3 -C.sub.8 alkoxyalkoxyalkyl, C.sub.4 -C.sub.8 cycloalkylalkyl, C.sub.2 -C.sub.4 carboxyalkyl, C.sub.3 -C.sub.8 alkoxycarbonylalkyl, C.sub.6 -C.sub.8 alkenyloxycarbonylalkyl, C.sub.6 -C.sub.8 alkynyloxycarbonylalkyl, C.sub.5 -C.sub.8 alkoxycarbonylalkenyl, C.sub.4 -C.sub.8 alkenyloxyalkyl, C.sub.6 -C.sub.8 cycloalkoxyalkyl, C.sub.4 -C.sub.8 alkynyloxyalkyl, C.sub.3 -C.sub.8 haloalkoxyalkyl, C.sub.4 -C.sub.8 haloalkenyloxyalkyl, C.sub.4 -C.sub.8 haloalkynyloxyalkyl, C.sub.4 -C.sub.8 alkenylthioalkyl, C.sub.4 -C.sub.8 alkynylthioalkyl; C.sub.1 -C.sub.4 alkyl substituted with phenoxy or benzyloxy, each of the phenoxy and benzyloxy optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl, C.sub.4 -C.sub.8 trialkylsilylalkyl, C.sub.3 -C.sub.8 cyanoalkyl, C.sub.3 -C.sub.8 halocycloalkyl, C.sub.3 -C.sub.8 haloalkenyl, C.sub.5 -C.sub.8 alkoxyalkenyl, C.sub.5 -C.sub.8 haloalkoxyalkenyl, C.sub.5 -C.sub.8 alkylthioalkenyl, C.sub.3 -C.sub.8 haloalkynyl, C.sub.5 -C.sub.8 alkoxyalkynyl, C.sub.5 -C.sub.8 haloalkoxyalkynyl, C.sub.5 -C.sub.8 alkylthioalkynyl, C.sub.2 -C.sub.8 alkylcarbonyl; benzyl optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl; CHR.sup.17 COR.sup.18, CHR.sup.7 P(O)(ORI.sup.18).sub.2, P(O)(OR.sup.18).sub.2, CHR.sup.17 P(S)(OR.sup.18).sub.2, CHR.sup.17 C(O)NR.sup.12 R.sup.13, CHR.sup.17 C(O)NH.sub.2, phenyl and pyridyl, each of the phenyl and pyridyl optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl, C.sub.1 -C.sub.4 alkoxy and CHR.sup.17 CH.dbd.NOR.sup.18 ;
R.sup.12 and R.sup.14 are independently hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.13 and R.sup.15 are independently selected from the group C.sub.1 -C.sub.4 alkyl and phenyl optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl and C.sub.1 -C.sub.4 alkoxy; or
R.sup.12 and R.sup.13 are taken together as --(CH.sub.2).sub.5 --, --(CH.sub.2).sub.4 -- or --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --, each independently forming a ring in which one or more H atoms is optionally replaced by at least one member independently selected from the group C.sub.1 -C.sub.3 alkyl, optionally substituted phenyl and optionally substituted benzyl; or
R.sup.14 and R.sup.15 together with the carbon atom to which they are attached is C.sub.3 -C.sub.8 cycloalkyl;
R.sup.16 is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl;
R.sup.17 is hydrogen or C.sub.1 -C.sub.3 alkyl;
R.sup.18 is selected from the group C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.6 alkenyl and C.sub.3 -C.sub.6 alkynyl; and
q is 1 or2.
2. A compound according to claim 1, wherein:
X is group O;
R.sup.A is independently selected from the group fluorine, chlorine and bromine;
R.sup.5 is selected from the group hydrogen, fluorine and chlorine;
R.sup.6 is selected from the group chlorine, bromine and cyano;
R.sup.7 is selected from the group hydrogen, OR.sup.11, CO.sub.2 R.sup.11, C.sub.1 -C.sub.2 alkyl and C.sub.1 -C.sub.2 haloalkyl;
R.sup.10 is selected from the group C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 haloalkyl, C.sub.3 -C.sub.4 alkenyl and C.sub.3 -C.sub.4 alkynyl;
R.sup.11 is selected from the group C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.6 cycloalkyl, C.sub.3 -C.sub.6 alkenyl, C.sub.3 -C.sub.6 alkynyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.2 -C.sub.4 alkoxyalkyl, C.sub.2 -C.sub.4 alkylthioalkyl, C.sub.2 -C.sub.4 alkylsulphinylalkyl, C.sub.2 -C.sub.4 alkylsulphonylalkyl, C.sub.3 -C.sub.6 alkoxyalkoxyalkyl, C.sub.4 -C.sub.8 cycloalkylalkyl, C.sub.2 -C.sub.4 carboxyalkyl, C.sub.3 -C.sub.6 alkoxycarbonylalkyl, C.sub.6 -C.sub.8 alkenyloxycarbonylalkyl, C.sub.6 -C.sub.8 alkynyloxycarbonylalkyl, C.sub.5 -C.sub.6 alkoxycarbonylalkenyl, C.sub.6 -C.sub.8 cycloalkoxyalkyl, C.sub.4 -C.sub.6 alkenyloxyalkyl, C.sub.4 -C.sub.6 alkynyloxyalkyl, C.sub.3 -C.sub.6 haloalkoxyalkyl, C.sub.4 -C.sub.8 haloalkenoxyalkyl, C.sub.4 -C.sub.6 haloalkynyloxyalkyl, C.sub.6 -C.sub.8 cycloalkylthioalkyl, C.sub.4 -C.sub.6 alkenylthioalkyl, C.sub.4 -C.sub.6 alkynylthioalkyl; C.sub.1 -C.sub.2 alkyl substituted with phenoxy or benzyloxy, each of the phenoxy and benzyloxy optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl; C.sub.4 -C.sub.8 trialkylsilylalkyl, C.sub.3 -C.sub.4 cyanoalkyl, C.sub.3 -C.sub.6 halocycloalkyl, C.sub.3 -C.sub.6 haloalkenyl, C.sub.5 -C.sub.6 alkoxyalkenyl, C.sub.5 -C.sub.6 haloalkoxyalkenyl, C.sub.5 -C.sub.6 alkylthioalkenyl, C.sub.3 -C.sub.6 haloalkynyl, C.sub.5 -C.sub.6 alkoxyalkynyl, C.sub.5 -C.sub.6 haloalkoxyalkynyl, C.sub.5 -C.sub.6 alkylthioalkynyl, C.sub.2 -C.sub.4 alkylcarbonyl, benzyl optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.2 alkyl and C.sub.1 -C.sub.2 haloalkyl; CHR.sup.17 COR.sup.18, CHR.sup.17 P(O)(OR.sup.18).sub.2, P(O)(OR.sup.18).sub.2, CHR.sup.17 P(S)(OR.sup.18).sub.2, CHR.sup.17 C(O)NR.sup.12 R.sup.13, CHR.sup.17 C(O)NH.sub.2, phenyl and pyridyl, each of the phenyl and pyridyl optionally substituted with at least one member independently selected from the group fluorine, chlorine, bromine, C.sub.1 -C.sub.2 alkylhaloalkyl and C.sub.1 1.varies.C.sub.2 alkoxy;
R.sup.12 is hydrogen or C.sub.1 -C.sub.2 alkyl;
R.sup.13 is selected from the group C.sub.1 -C.sub.2 alkyl and phenyl optionally substituted with at least one member selected from the group fluorine, chlorine, bromine, C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 haloalkyl and C.sub.1 -C.sub.2 alkoxy; or
R.sup.12 and R.sup.13 are taken together as --(CH.sub.2).sub.5 --, --(CH.sub.2).sub.4 -- or --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --, each independently forming a ring in which one or more H atoms is optionally and independently replaced by C.sub.1 -C.sub.2 alkyl;
R.sup.17 is hydrogen or C.sub.1 -C.sub.2 alkyl; and
R.sup.18 is selected from the group C.sub.1 -C.sub.2 alkyl, C.sub.3 -C.sub.4 alkenyl and C.sub.3 -C.sub.4 alkynyl.
3. A process for making a compound of Formula I ##STR53## wherein: X is selected from the group O, S, S(O), S(O).sub.2, CH.sub.2, CHF, CF.sub.2, CHCl, CHBr, CHOCH.sub.2 F, CHOCHF.sub.2, CHOCF.sub.3, CHOCH.sub.2 CF.sub.3 and NR.sup.4 ;
m and n are independently 1 or 2, where m+n=2 or 3;
p is 0 to 9;
U is N or CH;
W is independently O or S;
R.sup.A is independently selected from the group halogen, C.sub.1 -C.sub.4 alkyl, cyano, C.sub.1 -C.sub.4 haloalkyl, C.sub.3 -C.sub.4 alkenyl, C.sub.1 -C.sub.3 alkylthio, C.sub.1 -C.sub.3 haloalkylthio, C.sub.2 -C.sub.4 alkylcarbonyl, OR.sup.3, C.sub.2 -C.sub.6 alkyloxycarbonyl, C.sub.2 -C.sub.6 haloalkoxycarbonyl, and C.sub.3 -C.sub.8 alkoxycarbonylalkyl; or, two R.sup.A groups on the same carbon atom, together with this carbon, are C.dbd.O;
R.sup.3 is selected from the group hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.2 -C.sub.4 alkylcarbonyl and C.sub.2 -C.sub.4 haloalkylcarbonyl;
R.sup.4 is selected from the group hydrogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl, C.sub.2 -C.sub.4 alkylcarbonyl, C.sub.2 -C.sub.4 haloalkoxycarbonyl and C.sub.2 -C.sub.4 alkoxycarbonyl;
Q is selected from the group ##STR54## Z is O or S; R.sup.5 is hydrogen or halogen;
R.sup.6 is selected from the group C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 haloalkyl, OCH.sub.3, SCH.sub.3, OCHF.sub.2, halogen, CN and NO.sub.2 ;
R.sup.7 is selected from the group hydrogen, C.sub.1 -C.sub.8 alkyl, C.sub.1 -C.sub.8 haloalkyl, halogen, OR.sup.11, SR.sup.11, S(O).sub.q R.sup.11, COR.sup.11, CO.sub.2 R.sup.11, C(O)SR.sup.11, C(O)NR.sup.12 R.sup.13, CHO and NHSO.sub.2 NHR.sup.16 ;
R.sup.8 is selected from the group hydrogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl and halogen;
R.sup.9 is selected from the group hydrogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl and halogen; or, when Q is Q-2 or Q-6, R.sup.8 and R.sup.9 together with the carbon to which they are bonded is additionally selected from C.dbd.O;
R.sup.10 is selected from the group C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.2 -C.sub.6 alkoxyalkyl, C.sub.3 -C.sub.6 alkenyl and C.sub.3 -C.sub.6 alkynyl;
R.sup.11 is selected from the group C.sub.1 -C.sub.8 alkyl, C.sub.3 -C.sub.8 cycloalkyl, C.sub.3 -C.sub.8 alkenyl, C.sub.3 -C.sub.8 alkynyl, C.sub.1 -C.sub.8 haloalkyl, C.sub.2 -C.sub.8 alkoxyalkyl, C.sub.2 -C.sub.8 alkylthioalkyl, C.sub.2 -C.sub.8 alkylsulphinylalkyl, C.sub.2 -C.sub.8 alkylsulphonylalkyl, C.sub.3 -C.sub.8 alkoxyalkoxyalkyl, C.sub.4 -C.sub.8 cycloalkylalkyl, C.sub.2 -C.sub.4 carboxyalkyl, C.sub.3 -C.sub.8 alkoxycarbonylalkyl, C.sub.6 -C.sub.8 alkenyloxycarbonylalkyl, C.sub.6 -C.sub.8 alkynyloxycarbonylalkyl, C.sub.5 -C.sub.8 alkoxycarbonylalkenyl, C.sub.4 -C.sub.8 alkenyloxyalkyl, C.sub.6 -C.sub.8 cycloalkoxyalkyl, C.sub.4 -C.sub.8 alkynyloxyalkyl, C.sub.3 -C.sub.8 haloalkoxyalkyl, C.sub.4 -C.sub.8 haloalkenyloxyalkyl, C.sub.4 -C.sub.8 haloalkynyloxyalkyl, C.sub.4 -C.sub.8 alkenylthioalkyl, C.sub.4 -C.sub.8 alkynylthioalkyl; C.sub.1 -C.sub.4 alkyl substituted with phenoxy or benzyloxy, each of the phenoxy and benzyloxy optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl, C.sub.4 -C.sub.8 trialkylsilylalkyl, C.sub.3 -C.sub.8 cyanoalkyl, C.sub.3 -C.sub.8 halocycloalkyl, C.sub.3 -C.sub.8 haloalkenyl, C.sub.5 -C.sub.8 alkoxyalkenyl, C.sub.5 -C.sub.8 haloalkoxyalkenyl, C.sub.5 -C.sub.8 alkylthioalkenyl, C.sub.3 -C.sub.8 haloalkynyl, C.sub.5 -C.sub.8 alkoxyalkynyl, C.sub.5 -C.sub.8 haloalkoxyalkynyl, C.sub.5 -C.sub.8 alkylthioalkynyl, C.sub.2 -C.sub.8 alkylcarbonyl; benzyl optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl; CHR.sup.17 COR.sup.18, CHR.sup.7 P(O)(ORI.sup.18).sub.2, P(O)(OR.sup.18).sub.2, CHR.sup.17 P(S)(OR.sup.18).sub.2, CHR.sup.17 C(O)NR.sup.12 R.sup.13, CHR.sup.17 C(O)NH.sub.2, phenyl and pyridyl, each of the phenyl and pyridyl optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl, C.sub.1 -C.sub.4 alkoxy and CHR.sup.17 CH.dbd.NOR.sup.18 ;
R.sup.12 and R.sup.14 are independently hydrogen or C.sub.1 -C.sub.4 alkyl;
R.sup.13 and R.sup.15 are independently selected from the group C.sub.1 -C.sub.4 alkyl and phenyl optionally substituted with at least one member independently selected from the group halogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 haloalkyl and C.sub.1 -C.sub.4 alkoxy; or
R.sup.12 and R.sup.13 are taken together as --(CH.sub.2).sub.5 --, --(CH.sub.2).sub.4 -- or --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --, each independently forming a ring in which one or more H atoms is optionally replaced by at least one member independently selected from the group C.sub.1 -C.sub.3 alkyl, optionally substituted phenyl and optionally substituted benzyl; or
R.sup.14 and R.sup.15 together with the carbon atom to which they are attached is C.sub.3 -C.sub.8 cycloalkyl;
R.sup.16 is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl;
R.sup.17 is hydrogen or C.sub.1 -C.sub.3 alkyl;
R.sup.18 is selected from the group C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.6 alkenyl and C.sub.3 -C.sub.6 alkynyl; and
q is 1 or 2
comprising one of the following steps:
a) reacting a compound of Formula II with a compound of Formula III, ##STR55## wherein R=hydroxy, C.sub.1 -C.sub.4 alkoxy, halogen or O-active ester, optionally in the presence of a solvent;
b) reacting a compound of Formula IV, ##STR56## wherein Y is selected from the group O, S and NH, with a compound of Formula V, VI or VII, ##STR57## wherein Z is selected from the group chlorine, bromine, iodine, O--SO.sub.2 CH.sub.3, O--SO.sub.2 CF.sub.3, O--SO.sub.2 --Ph, and ##STR58## c) reacting a compound of Formula HI first with a compound of Formula XV, wherein L.sup.1 and L.sup.2 are independently selected leaving groups, to form a compound of Formula VIII, then, with a compound of Formula IX to form a compound of Formula X, ##STR59## and cyclizing the compound of Formula X; and d) reacting a compound of Formula XI with a compound of Formula XVb optionally in the presence of a diluent and optionally in the presence of an acid-acceptor, ##STR60## wherein R.sup.1 is independently H or R.sup.A; and
R.sup.19 is independently selected from the group H, C.sub.1-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, and C.sub.3 -C.sub.4 alkenyl.
4. A herbicidal composition comprising an herbicidally effective mount of a compound according to claim 1 and a carrier therefor.
5. A method of controlling unwanted vegetation comprising applying to the unwanted vegetation or the environment in which it is grown an herbicidally effective amount of a compound according to claim 1.

PCT Information

Filing Document	Filing Date	Country	Kind	102e Date	371c Date
PCT/US94/09522	8/30/1994			2/28/1996	2/28/1996

Publishing Document	Publishing Date	Country	Kind
WO95/06643	3/9/1995

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Oxa-and thia(di)azabicyclic compounds

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