EP0652876A1

EP0652876A1 - Herbicidal triazinones

Info

Publication number: EP0652876A1
Application number: EP93916806A
Authority: EP
Inventors: Eric Deguyon Taylor
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1992-07-29
Filing date: 1993-07-01
Publication date: 1995-05-17
Also published as: WO1994003454A1; AU4653693A

Abstract

Substituted triazinones of formula (I) wherein Q is selected from the group: (Q-1, Q-2, Q-3, Q-4, Q-5 and Q-6); A is selected from alkyl, haloalkyl, alkenyl, alkynyl, OR?16, SR16¿ and halogen; B is selected from alkyl, haloalkyl, alkenyl and alkynyl; A and B can be taken together as X-Y-Z to form a fused ring such that X is connected to nitrogen and Z is connected to carbon; X is selected from the group CHR17, CH2CH2 and CR17=CR18; Y is selected from the group CHR?19, CR19=CR20, CHR19CHR20, NR21¿, O and S(O)¿n?; Z is selected from the group CHR?22, CH¿2CH2, CR?22=CR23, NR21¿, O and S(O)¿n?; n is 0, 1 or 2; R?1¿ is halogen; are useful as herbicides and/or plant growth regulants.

Description

TITLE HERBICIDAL TRIAZINONES BACKGROUND OF THE INVENTION 5 This invention relates to certain substituted fused heterocyclic compounds which are useful as herbicides and their agriculturally suitable compositions as well as methods for their use as general or selective preemergent or postemergent herbicides or as plant 0 growth regulants.

New compounds effective for controlling the growth of undesired vegetation are in constant demand. In the most common situation, such compounds are sought to selectively control the growth of weeds in useful crops 5 such as cotton, rice, corn, wheat, citrus and soybeans, to name a few. Unchecked weed growth in such crops (including plantation crops) can cause significant losses, reducing profit to the farmer and increasing costs to the consumer. In other situations, herbicides 0 are desired which will control all plant growth. Examples of areas in which complete control of all vegetation is desired are areas around railroad tracks, storage tanks and industrial storage areas. There are many products commercially available for these 5 purposes, but the search continues for products which are more effective, less costly and environmentally safe.

DE 3,340,026 discloses herbicides of the formula

wherein

R-i is H, C -Cg alkyl (optionally substituted by halogen, CN, OH and/or ^-0₄ alkoxy) , C₃-C₈ cycloalkyl (optionally substituted by alkyl, halogen and/or phenyl) , an aromatic or aromatic-aliphatic residue (optionally substituted by C-_L-C₄ alkyl, halogen, C_!-C₄ alkoxy, N0₂ and/or CF₃) , or a heterocyclic hydrocarbon residue; and R₂, ₃ and R are H, ^-Cg alkyl (optionally substituted by halogen) or aryl (optionally substituted by ^-Cg alkyl, halogen, C_3.-C₄ alkoxy, N0₂ and/or CF₃) .

SUMMARY OF THE INVENTION This invention comprises novel compounds of Formula I, agriculturally suitable compositions containing them, and their method-of-use as preemergent and/or postemergent herbicides and/or plant growth regulants. The compounds of Formula I are:

wherein

Q is selected from the group:

Q-l Q-2 Q-3

A is selected from the group ^^₄ alkyl, C₁-C haloalkyl, C₂-C alkenyl, C₂-C₄ alkynyl, OR¹⁶,

SR¹⁶ and halogen; B is selected from the group ^^₄ alkyl, C₂-C₄ haloalkyl, C3-C₄ alkenyl and C3-C₄ alkynyl; A and B can be taken together as X-Y-Z to form a fused ring such that X is connected to nitrogen and Z is connected to carbon; X is selected from the group CHR¹⁷, CH CH₂ and

CR¹⁷=CR¹⁸; Y is selected from the group CHR¹⁹, CR¹⁹=CR²⁰,

CHR¹⁹CHR²⁰, NR²¹, 0 and S(0)_n; Z is selected from the group CHR²², CH₂CH₂,

CR²²=CR²³, NR²¹, 0 and S(0)_n; R¹ is halogen; R² is selected from the group H, C^Cg alkyl, C_L-C_Q haloalkyl, halogen, OH, OR⁷, SH, S(0)_nR⁷, COR⁷, C0₂R⁷, C(0)SR⁷, C(0)NR⁹R¹⁰, CHO, CR² =NOR²⁵, CH=CR²⁸C0₂R⁷, CH₂CHR²⁸C0₂R⁷, C0₂N=CR^1:LR¹², N0₂, CN, NHS0₂R¹³, NHS0₂NHR¹³, NR⁷R²⁶, NH₂ and phenyl optionally substituted with R²⁷;

R³ is selected from the group C₁-C₂ alkyl, C₁-C₂ haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CN and

N0₂; R⁴ is selected from the group H, C^-^ alkyl and halogen; R⁵ is selected from the group H, C₁-C₃ alkyl, halogen, ^-^ haloalkyl, cyclopropyl, C₂ alkenyl, C₂ alkynyl, CN, C(0)R²⁹, C0₂R²⁹, CONR²⁹R³⁰, CR³¹R³²C(0)R²⁹, CR³¹R³²C0₂R²⁹,

_CR31_R32_CONR29_R30_/ CHR³¹OH, CHR³¹OC (0)R²⁹ and

OCHR³¹OC (0)NR²⁹R³⁰; when Q is Q-2 or Q-6, then R⁴ and R⁵ together with the carbon to which they are attached can be C=0;

R⁶ is selected from the group ^-Cg alkyl, C^Cg haloalkyl, C₂-C₆ alkoxyalkyl, C₃-C₆ alkenyl and

C₃-C₆ alkynyl; R⁷ is selected from the group ^-Cg alkyl; C₃-C₈ cycloalkyl; C₃-C₈ alkenyl; C₃-C₈ alkynyl; Ci-Cg haloalkyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkyl- thioalkyl; C₂-C₈ alkylsulfinylalkyl; C₂-C₈ alkylsulfonylalkyl; C₄-C₈ alkoxyalkoxyalkyl;

C₄-C₈ cycloalkylalkyl; C -C₈ alkenoxyalkyl; C₄-C₈ alkynoxyalkyl; C₆-C₈ cycloalkoxyalkyl;

C₄-C₈ alkenyloxyalkyl; C₄-C₈ alkynyloxyalkyl;

C₃-C₈ haloalkoxyalkyl; C₄-C₈ haloalkenoxyalkyl;

C₄-C₈ haloalkynoxyalkyl; C₆-C₈ cycloalkylthio- alkyl; C₄-C₈ alkenylthioalkyl; C₄-C₈ alkynyl- thioalkyl; ^^₄ alkyl substituted with phenoxy or benzyloxy, each ring optionally substituted with a member selected from the group halogen, ^-^ alkyl and C₁-C₃ haloalkyl; C₄-C₈ trialkylsilylalkyl; C₃-C₈ cyanoalkyl; C₃-C₈ halocycloalkyl; C₃-C₈ haloalkenyl; C₅-C₈ alkoxyalkenyl; C₅-C₈ haloalkoxyalkenyl; C₅-C₈ alkylthioalkenyl; C₃-C₈ haloalkynyl; C₅-C₈ alkoxyalkynyl; C₅-C₈ haloalkoxyalkynyl; C₅-C alkylthioalkynyl; C₂-C₈ alkyl carbonyl; benzyl optionally substituted with a member selected from the group halogen, C₂-C₃ alkyl and C₂-C₃ haloalkyl; CHR¹ COR⁸; CHR¹⁴P (0) (OR⁸) ₂; CHR¹⁴P(S) (OR⁸)₂; CHR¹ C(0)NR⁹R¹⁰; CHR¹⁴C (O)NH₂, CHR³³C0₂R³⁴; C0₂R³⁴; S0₂R³⁴; phenyl optionally substituted with R²⁷;

R⁸ is selected from the group C₁-C₆ alkyl, C₂-C₆ alkenyl and C₂-C₆ alkynyl;

R⁹ and R¹¹ are independently selected from the group H and C- -C^ alkyl; R¹⁰ and R¹² are independently selected from the group C₁-C₄ alkyl and phenyl optionally substituted with a member selected from the group halogen, C^-^ alkyl and C_x-C₃ haloalkyl; R⁹ and R¹⁰ can be taken together as -(CH )₅-,

-(CH₂) - or -CH₂CH₂0CH₂CH₂-, each ring optionally and independently substituted with one or more members selected from the group

C₁-C₃ alkyl, phenyl and benzyl; R¹¹ and R¹² can be taken together with the carbon to which they are attached to form C₃-C₈ cycloalkyl; R¹³ is selected from the group C₁-C alkyl and C₁-C₄ haloalkyl; R¹⁴ is selected from the group H and C -C₄ alkyl; R¹⁶ is selected from the group C₁-C alkyl and C^-^ haloalkyl;

R¹⁷, R¹⁸, R¹⁹, R²⁰, R²² and R²³ are independently selected from the group H, halogen, C₁-C alkyl and C₁-C haloalkyl; R²¹ is selected from the group H, C₂-C₄ alkyl and ^cι~^c ₄ haloalkyl;

R²⁴ is selected from the group H and C- - .^ alkyl; R²⁵ is selected from the group H, Ci-Cg alkyl, C₃-C₆ alkenyl and C₃-Cg alkynyl; R²⁶ is selected from the group H and (^^₄ alkyl; R²⁷ is selected from the group ^-^ alkyl, C₂-C₂ haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CN and N0₂; R²⁸ is selected from the group H, ^^₄ alkyl and halogen; R²⁹, R³⁰, R³¹ and R³² are independently selected from the group H and C-_L-C3 alkyl; R³³ is selected from the group H and C__-C_ alkyl; R³⁴ is selected from the group C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ alkenyl or C₃-C₆ alkynyl; and W is selected from the group O and S; and their agriculturally suitable salts, provided that

1) the sum of atoms in the backbone of the moiety of the fused ring formed by X, Y and Z is no greater than 5 and only one of Y and Z can be other than a carbon containing link;

2) when R² is C0₂R⁷, C(0)SR⁷, CH=CR²⁸C0₂R⁷ or CH₂CHR²⁸C0₂R⁷ then R⁷ is other than C haloalkyl, and when R⁷ is CHR³³C0₂R³⁴ or C0₂R³⁴ then R³⁴ is other than C₂ haloalkyl; 3) when X is CHR¹⁷, Y is CHR¹⁹ and Z is CHR²² then at least one of R¹⁷, R¹⁹ and R²² is halogen;

4) when A and B are other than taken together as X-Y-Z and Q is Q-l then R² is OR⁷ and R⁷ is ^c3^-c ₈ alkynyl; and

5) when Z is NR²¹, 0 or S and Q is Q-l then R² is OR⁷ and R⁷ is C₃-C₈ alkynyl.

In the above definitions, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight chain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the different butyl isomers. Alkoxy includes methoxy, ethoxy, n-propyloxy, isopropyloxy, the different butoxy isomers, etc. Alkenyl and alkynyl include straight chain or branched alkenes and alkynes, e.g.,

1-propenyl, 2-propenyl, 3-propenyl and the different butenyl isomers. Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. The term "halogen", either alone or in compound words such as "haloalkyl", means fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of haloalkyl include CH₂CH₂F, CF₂CF₃ and CH₂CHFC1.

Compounds of Formula I may exist as one or more stereoisomers . The various stereoisomers include enantiomers, diastereomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be the more active. One skilled in the art knows how to separate said enantiomers, diastereomers and geometric isomers. Accordingly, the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures. Preferred for reasons including ease of synthesis and/or greater herbicidal efficacy are:

1) Compounds of Formula I wherein the compounds are of formula

wherein

X is CHR¹⁷ or CH₂CH₂;

Y is CHR¹⁹ or CHR¹⁹CHR²⁰;

Z is CHR²² or CH₂CH₂;

R² is selected from the group H, C_!-C₈ alkyl, Ci-Cs haloalkyl, halogen, OR⁷, S(0)_nR⁷, COR⁷, C0₂R⁷, C(0)SR⁷, C(0)NR⁹R¹⁰, CHO, CH=CHC0₂R⁷, C0₂N=CR^1:LR¹², N0₂, CN_r NHS0₂R¹³ and NHS0₂NHR¹³;

R⁵ is selected from the group H, C₁-C₃ alkyl and halogen;

R⁷ is selected from the group C-L-CS alkyl; C₃-C_f cycloalkyl; C₃-C₈ alkenyl; C₃-C₈ alkynyl; C-±-C_Q haloalkyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₂-C₈ alkylsulfinylalkyl; C₂-C₈ alkylsulfonylalkyl; C -C₈ alkoxy- alkoxyalkyl; C -C₈ cycloalkylalkyl; C₄-C₈ alkenoxyalkyl; C₄-C₈ alkynoxyalkyl; C₆-C₈ cycloalkoxyalkyl; C₄-C₈ alkenyloxyalkyl; C₄-C₈ alkynyloxyalkyl; C₃-C₈ haloalkoxy- alkyl; C₄-C₈ haloalkenoxyalkyl; C -C₈ haloalkynoxyalkyl; C₆-C₈ cycloalkylthio- alkyl; C -C₈ alkenylthioalkyl; C -C₈ alkynylthioalkyl; (^-0₄ alkyl substituted with phenoxy or benzyloxy, each ring optionally substituted with a member selected from the group halogen, C₂-C₃ alkyl and C₂-C₃ haloalkyl; C₄-C₈ trialkyl- silylalkyl; C₃-C₈ cyanoalkyl; C₃-C₈ halo- cycloalkyl; C₃-C₈ haloalkenyl; C₅-C₈ alkoxyalkenyl; C₅-C₈ haloalkoxyalkenyl; C₅-C₈ alkylthioalkenyl; C₃-C₈ haloalkynyl; C₅-C₈ alkoxyalkynyl; C₅-C₈ haloalkoxy- alkynyl; C₅-C₈ alkylthioalkynyl; C₂-C₈ alkyl carbonyl; benzyl optionally substituted with a member selected from the group halogen, 0 -0₃ alkyl and 0₂-0₃ haloalkyl; CHR¹ COR⁸; CHR¹⁴P (0) (OR⁸) ₂; CHR¹⁴P (S) (OR⁸)₂; CHR¹⁴C (0)NR⁹R¹⁰ and CHR¹ C(0)NH₂;

R¹⁷, R¹⁹, R²⁰ and R²² are selected from the group H, halogen and 0 -0 alkyl; provided that only one of R¹⁷, R¹⁹, R²⁰ and R²² is other than hydrogen. 2) Compounds of Formula I wherein X is CHR¹⁷; Y is CHR¹⁹CHR²⁰; Z is CHR²².

3) Compounds of Preferred 2 wherein R¹⁷, R¹⁹, R²⁰ and R²² and are independently selected from the group H, F, CH3 and CF₃.

4) Compounds of Preferred 3 wherein

R² is selected from the group H, OR⁷, SR⁷ and C0₂R⁷; R³ is selected from the group halogen and CN.

5) Compounds of Preferred 4 wherein

Q is selected from the group Q-l, Q-2, Q-4 and

Q-5; A and B are taken together as X-Y-Z; R¹⁷, R¹⁸, R¹⁹, R²⁰, R²² and R²³ are independently selected from the group H and F;

R⁷ is selected from the group 0 -0₄ alkyl, C₃-C₄ alkenyl, C3-C₄ alkynyl, C₂-C₄ alkoxyalkyl, ^C ₂-C₄ haloalkyl, C3-C₄ haloalkenyl and C₃-C₄ haloalkynyl .

6) Compounds of Formula I wherein X is CHR¹⁷;

Y is CHR¹⁹; Z is CHR²².

7) Compounds of Preferred 6 wherein

R¹⁷, R¹⁹, and R²² are independently selected from the group H, F, CH₃ and CF₃.

8) Compounds of Preferred 7 wherein R² is selected from the group H, OR⁷, SR⁷ and

C0₂R⁷; R³ is selected from the group halogen and CN.

9) Compounds of Preferred 8 wherein

Q is selected from the group Q-l, Q-2, Q-4 and Q-5;

A and B are taken together as X-Y-Z;

R¹⁷, R¹⁹, and R²² are independently selected from the group H and F; R⁷ is selected from the group C₂-C alkyl, C3-C₄ alkenyl, C₃-C alkynyl, C₂-C alkoxyalkyl,

C₂-C₄ haloalkyl, C₃-C₄ haloalkenyl and C₃-C haloalkynyl. Synthesis

By using one or more of the reactions and techniques described in Schemes 1-6 of this section as well as by following the specific procedures given in Synthesis Examples 1-4, compounds of General Formula I can be prepared.

As shown in Scheme 1, compounds of Formula I can be synthesized by reacting an α-ketoacid or α-ketoacid derivative of Formula II with a compound of Formula Ilia or Formula Illb, which are amidrazones or are formally derivatives of semicarbazides or thiosemicarbazides . Compounds of Formula Ilia and Illb are generally known in the art and can either be isolated or prepared in situ, as described in Justus Liebigs Ann . Chem . 755, 101 (1972), or in a similar manner.

Q ₂

II

As shown in Scheme 2, compounds of Formula I can also be synthesized by converting an α-ketoacid of Formula II (R=H) to its hydrazono-amide IV, followed by treatment of IV with an acid anhydride, an acid halide, an orthoester, or a carboxylic acid under dehydrating conditions.

Scheme 2

.NH- i) socι_{2 N}' o II 2) B-NH₂ or

-C,

Q CON B

C0₂R 3) H₂NNH₂ H

II (R=H) IV

(~H₂0) As shown in Scheme 3, compounds of Formula I (where A is OR¹⁶, SR¹⁶ or halogen) can also be synthesized by reacting an α-ketoester (R=C₂-C₄ alkyl) or α-ketoacid (R=H) of Formula II with a semicarbazide or thiosemicarbazide of Formula V, cyclizing to form the heterocycle VI, and treating VI with an alkylating agent (R¹⁶-L, where L is a leaving group) in the presence of a base, or with a halogenating agent such as thionyl chloride, phosphorous oxychloride, or the like.

logen) VI

An alternative and more specific method for preparing compounds of Formula I which are tetrahydropyrido-[2,1-c]-as-triazinones (I; A, B is X-Y-Z; X is CHR¹⁷, Y is CHR¹⁹CHR²⁰, Z is CHR²²) , except when Q is substituted by an unsaturated group, is shown in Scheme . An α-ketoester or α-ketoacid can be condensed with a 2-hydrazinopyridine and cyclized by methods such as those described in Chem . Ber. 104, 2793 (1971) . Catalytic hydrogenation of the resultant pyridotriazinone VII in the presence of a transition metal catalyst such as platinum oxide followed by reoxidation when necessary with e.g., W-bromo- succinimide (NBS) or meta-chloroperoxybenzoic acid (MCPBA) , affords the tetrahydro derivatives. Use of 2-hydrazinothiazoles, 2-hydrazino-oxazoles, 2-hydrazinoimidazoles, 2-hydrazinopyrimidines and 2-hydrazinopyrazines in place of the 2-hydrazino- pyridine starting materials in Scheme 4 and following the same general procedures also provides compounds of Formula I, where A, B is X-Y-Z and Y or Z is a heteroatom.

Scheme 4

VII

Many of the methods for preparing triazinone derivatives such as I are also reviewed by Neunhoffer in "The Chemistry of Heterocyclic Compounds" , Volume 33, John Wiley & Sons, New York (1978), pp 189-1072. The α-ketoesters and α-ketoacids II can be prepared by various methods, including but not limited to those outlined in Scheme 5: by reaction of an organometallic species QM (M=metal, Mg(halogen), etc.) with an oxalate ester using methods such as those described in J. Org. Chem . 52, 5026 (1987), by reaction of a suitable aromatic precursor QH with an alkyl oxalyl halide using methods such as those described in J. Med. Chem. 15, 1029 (1972) and in Org. Prep. Proc. 2, 249 (1970), by oxidation of an acetophenone using methods such as those described in Monatsh . fur Chem. 83, 883 (1952) and in Liebigs Ann . Chem . 662, 147 (1963), by metal- catalyzed coupling of a halide or triflate QG (G=halogen or CF₃SO₃) , with an acetylene derivative followed by oxidation using methods such as those described in Synthesis 1980, 627, in J. Org. Chem . 46, 2280 (1981), in J. Org. Chem . 38, 3653 (1973) and in ret. Letters 27, 1947 (1986), or by metal-catalyzed coupling of a halide or triflate QG with a vinyl stannane under conditions permitting insertion of carbon monoxide followed by oxidation using methods such as those described in J. Org. Chem . 55, 3114 (1990) . Appropriate catalysts and conditions for coupling intermediates QG with alkenes and alkynes are also described by Heck in "Palladium Reagents in

Organic Syntheses", Academic Press, New York, 1985. Many of the required aryl halides QG can be synthesized via diazotization of known arylamines using conditions such as those described by Furniss, et al. in "Vogel's Textbook of Practical Organic Chemistry", Fifth Edition, Longman Scientific and Technical, Essex, England, pp 922-946. Iodine can also be incorporated into aromatic molecules by other known methods such as those described in Synthesis 1988, 923. The triflates QG can be prepared from the corresponding phenols QOH by known methods. If required, α-ketoesters and α-ketoacids II can be interconverted by methods that will be apparent to one skilled in the art.

Compounds of Formula la (R² is OCH₃, OCH₂Ph, etc.) can be dealkylated by treatment with boron tribromide or the like to afford compounds of Formula lb

(R² is OH) , which can serve as intermediates for the synthesis of compounds of Formula I containing many different R² substituents. Scheme 6 shows some, but not all of the more useful transformations. In addition to well known alkylation and acylation chemistry, compounds lb can be converted to trifluoro¬ methanesulfonates Ic (R² is OS0 CF₃) , which are substrates for metal-catalyzed coupling reactions. In the presence of a suitable palladium, nickel or other transition metal catalyst, trifluoromethanesulfonates Ic can be converted to esters, thioesters, amides, and aldehydes Id by reaction with carbon monoxide and a nucleophile (Nuc) under conditions such as those described in Chem . Comm . 1987, 904, to alkenes Ie by reaction with an alkene under conditions such as those described in Heterocycles 26, 355 (1987), to ketones If by reaction with enol ethers under conditions such as those described in J. Org. Chem . 57, 1481 (1992) , to aryl derivatives Ig by reaction with aryl (Ar) boronic acids under conditions such as those described in Tet . Letters 32, 2273 (1991) and references cited therein, and to alkyl derivatives Ih by reaction with Grignard reagents under conditions such as those described in J. Org. Chem . 57, 4066(1992) and references cited therein.

Scheme 6

Ie I ^Σ9 The following examples represent the preparation of specific compounds of the invention. The examples are for illustration and should not be regarded as limiting the invention in any way. Synthesis Example 1 3-(2_f 4-Dichlorophenyl)-6.7_f 8.9-tetrahydro-4H- pyridor2.1-cl ri.2.41triazin-4 (6H)-one Step A: Ethyl 2.4-dichloro-α-oxo-benzeneacetate A solution of l-bromo-2, -dichlorobenzene (22.6 g, 100 mmol) in dry tetrahydrofuran (THF) (10 mL) was added dropwise to a solution of 1.6 n-butyllithium (75 mL, 120 mmol) in dry THF (100 mL) maintained at -60 to -70°C. This mixture was stirred for 30 min. at -70°C, then it was added via cannula to a solution of diethyl oxalate (16.3 L, 120 mmol) in dry THF (50 mL) maintained at -60 to -70°C. The reaction mixture was allowed to warm slowly to 0°C, then it was poured into a mixture of ice (300 g) and IN aqueous hydrochloric acid (300 mL) and extracted into diethyl ether (200 mL, then 2 times with 100 mL) . The combined organic layers were washed with water (200 mL) , then brine (200 mL) , then dried over MgS0 , filtered and the solvent removed under vacuum. Flash chromatography afforded the title compound of Step A (11.04 g, 44.7%) as an oil; ¹H NMR: δ 1.40 (t,3H), 4.42 (q,2H), 7.39 (d,lH), 7.48 (s,lH), 7.73 (d,lH); IR (inter alia) : 1736, 1698 cm"¹. Step B: 2.3.4.5-Tetrahydro-6-methoxypyridine

Neat 5-valerolactam (4.0 g, 40 mmol) was added to a suspension of trimethyloxonium tetrafluoroborate

(7.7 g, 52 mol) in dichloromethane (15 mL) and the mixture was stirred overnight at room temperature. The mixture was treated with a 50% aqueous solution of potassium carbonate (7.6 g) , then filtered through Celite®. The filtrate was dried over K₂C0₃, filtered, and the solvent removed under vacuum at 20°C to afford the title compound of Step B (3.97 g, 88%) as a yellow oil. Step C: 3- ( 2 _r -Dichlorophenyl1-6.7.8.9-tetrahydro-4H- pyridor2.1-cl r1.2.41 riazin-4 (6H -one The product of Step B (1.24 g, 11 mmol) was dissolved in ethanol (5 mL) , then 95% hydrazine (0.33 mL, 10 mmol) was added and the solution was stirred 2 hours at room temperature. The product of Step A (2.47 g, 10 mmol) dissolved in ethanol (1 mL) was added to the solution and the mixture was stirred overnight at room temperature. The reaction mixture was filtered and solvent removed from the filtrate under vacuum. Flash chromatography yielded a residue, which was triturated with hexanes-chlorobutane to afford the title compound of Step C (0.17 g, 5.7%) as a light yellow powder, m.p. 119-123°C; ^H NMR: δ 1.9-2.2 (m,4H), 3.10 (t,2H), 3.99 (t,2H), 7.3-7.45 ( , 2H) , 7.51 (d,lH) .

Synthesis Example 2 3-(2.4-Dichlorophenyl)-7.8_r9_r10- tetrahydrori.2. 1triazinoT4_r 3-al-azepin-4 (6H)-one Step A: 3 , 4 , 5 , 6-Tetrahydro-7-(methylthio)-2H-azepine Iodomethane (7.6 mL, 0.12 mol) was added to a mixture of ω-thiocaprolactam (12.92 g, 100 mmol) and potassium carbonate (15.36 g, 110 mmol) in dry THF (200 mL) . After stirring overnight at room temperature, the mixture was filtered and solvent removed from the filtrate under vacuum. The residue was dissolved in diethyl ether (150 L) , filtered, and the diethyl ether was removed under vacuum to afford the title compound of Step A (13.78 g, 96.3%) as a brown oil.

Step B: 3- (2 .4-Dichlorophenyl)-7.8.9.10- tetrahydror1.2.41triazino \A.3-al-azepin-4 (6H)- one The product of Step A (1.40 g, 9.8 mmol) was dissolved in ethanol (5 mL) , then 95% hydrazine (0.30 mL, 9.1 mmol) was added and the solution stirred 2 h at room temperature. The product of Step A of Synthesis Example 1 (2.47 g, 10 mmol), dissolved in ethanol (5 mL) , was added to the solution and the mixture was stirred overnight at room temperature. Solvents were removed under vacuum. Flash chromatography yielded a residue, which was triturated with hexanes-chlorobutane to afford the title compound of Step B (0.42 g, 15%), as a nearly white powder, m.p. 123-124°C; ^ NMR: δ 1.8-1.9 (m, 2H) , 1.9-2.0 (m,4H), 3.12 (m, 2H) , 4.34 (m, 2H) , 7.36 (m, IH) , 7.43 (d,lH), 7.50 (S,1H); IR (inter alia) : 1682 cm^-1.

Synthesis Example 3 3- (4-Chloro-2.5-difluorophenyl)-6.7.8.9-tetrahydro- 4H-pyridor2,1-ci r 1 , 2. 1-triazin- (6fi)-one Step A: Methyl 4-chloro-2_r 5-difluoro-α-oxo- benzeneacetate A mixture of 4-chloro-2, 5-difluoroacetophenone (11.4 g, 59.8 mmol) and selenium dioxide (11.1 g, 100 mmol) in pyridine (100 mL) was heated for 4 h at

82-95°C. The hot mixture was filtered through Celite® and volatiles were removed under vacuum. The residue was taken up in saturated aqueous NaHC0₃ (75 mL) , filtered through Celite®, acidified to pH 1 by the addition of concentrated hydrochloric acid, and extracted with dichloromethane (2 times with 100 mL) . The combined organic extracts were dried over MgS0₄, filtered and the solvent removed under vacuum. The residue was triturated with diethyl ether to afford a brown solid, 10.11 g, m.p. 104-106°C.

To a solution of this solid (9.48 g) in methanol (100 mL) was added thionyl chloride (10.0 mL, 137 mmol) dropwise with cooling. The mixture was heated at reflux for 2 h, then volatiles were removed under vacuum. The residue was taken up in diethyl ether (200 mL) , washed with water (2 times with 100 mL) , then saturated aqueous NaHC0₃ (100 mL) , then the organic layer was dried over MgS0₄, filtered and the solvent removed under vacuum. The residue was triturated with ice-cold hexanes to afford the title compound of Step A (4.73 g) as light tan crystals, m.p. 48-49°C; ¹H NMR: δ 3.97(s,3H), 7.30 (dd, IH) , 7.70 (dd,lH) .

Flash chromatography of the filtrate provided an additional quantity (1.72 g) of the title compound of Step A as light yellow crystals, m.p. 44-48°C.

Step B: 3-(4-Chloro-2.5-difluorophenyl)-6, 7.8 _r 9- tetrahydro-4H-pyrid \ , l-cl l , 2 , 4 ]-triazin- 4 (6H)-one The product of Step B of Synthesis Example 1 (1.24 g, 11 mmol) was dissolved in methanol (5 mL) , then 95% hydrazine (0.33 mL, 10 mmol) was added and the solution was stirred 2 h at room temperature. The product of Step A (2.58 g, 11 mmol) of Example 3 was added to the solution and the mixture was stirred overnight at room temperature. The reaction mixture was filtered and solvent removed from the filtrate under vacuum. Flash chromatography yielded a residue, which was triturated with hexanes-chlorobutane to afford the title compound of Step B (1.01 g, 34%) as a pale yellow powder, m.p. 127-128°C decomposed); ¹H NMR: δ 1.9-2.0 (m,2H), 2.0-2.1 (m,2H) , 3.10 (t,2H), 4.00 (t,2H), 7.26 (dd,lH), 7.46 (dd,lH) .

Synthesis Example 4 3-(4-Chloro-2-fluorophenyl)-6.7.8.9-tetrahydro-4H- pyridor2.1-cl Tl.2.41-triazin- (6H)-one

Step A: Methyl 4-chloro-2-fluoro-α-oxo-benzeneacetate

A mixture of 4-chloro-2-fluorophenyl trifluoro- methane sulfonate (prepared from 30 mmol of 4-chloro-2- fluorophenol) , butyl vinyl ether (20 L, 0.15 mol), triethylamine (5.0 mL, 36 mmol), palladium (II) acetate (0.17 g, 0.76 mmol) and 1, 3-bis (diphenylphosphino) - propane (0.34 g, 0.82 mmol) in dimethylformamide (80 mL) was heated at 60°C for 2 h, then at 80°C for 1 h. Additional quantities of palladium (II) acetate (0.08 g, 0.4 mmol) and 1, 3-bis (diphenylphosphino)- propane (0.17 g, 0.41 mmol) were added to the mixture and heating was continued at 80°C for 1 h. The mixture was cooled, poured into water (250 mL) , and extracted into diethyl ether (250 mL) . The organic layer was washed with water (3 times with 80 mL) , dried over MgS0 , filtered, and the solvent was removed under vacuum.

The residue was dissolved in THF (150 mL) , then 2N aqueous hydrochloric acid (50 mL) was added and the mixture was stirred for 3 days at room temperature. The mixture was poured into water (300 mL) and extracted into diethyl ether (3 times with 100 mL) . The combined organic layers were washed with brine (100 mL) , dried over MgS0₄, filtered, and the solvent was removed under vacuum.

The residue was dissolved in pyridine (50 mL) , selenium dioxide (5.55 g, 50 mmol) was added, and the mixture was heated for 4 h at 90-100°C. The hot mixture was filtered through Celite® and volatiles were removed under vacuum. The residue was taken up in saturated aqueous NaHC0₃ (50 mL) , filtered through Celite®, acidified to pH 1 by the addition of concentrated HC1, and extracted into dichloromethane (2 times with 50 mL) . The combined organic layers were dried over MgS0₄, filtered, and the solvent was removed under vacuum.

The residue was dissolved in methanol (50 mL) , cooled in an ice-bath, then thionyl chloride (4.2 mL, 58 mmol) was added dropwise. The mixture was heated at reflux for 2.5 h, then volatiles were removed under vacuum. The residue was taken up in diethyl ether (100 mL) , washed with water (2 times with 50 mL) , then saturated aqueous NaHC0₃ (50 mL) , then the organic layer was dried over MgS0₄, filtered, and the solvent was removed under vacuum. Flash chromatography afforded the title compound of Step A (1.47 g, 22.6% overall) as a white solid, m.p. 72-74°C; ¹H NMR: δ 3.97 (s, 3H) , 7.22 (d, IH) , 7.31 (d, IH) , 7.88 (t, IH) . Step B: 3-(4-Chloro-2-fluorophenyl)-4H-pyrido-r2.1- Cl ri.2.41-triazin-4 (6H)-one

A solution of 2-hydrazinopyridine (0.74 g, 6.8 mmol) in methanol (2 mL) was added to a mixture of the product of Step A (1.47 g, 6.8. mmol) in methanol (8 mL) . The mixture was stirred overnight at room temperature, then volatiles were removed under vacuum. The residue was taken up in diethyl ether, filtered, and the solvent was removed from the filtrate under vacuum.

The residue was dissolved in 1,2-dichlorobenzene (12 mL) and the mixture was heated at reflux overnight, then volatiles were removed under vacuum. Flash chromatography yielded a residue, which was triturated with hexanes-chlorobutane to afford the title compound of Step B (0.78 g, 42%) as a tan powder, m.p. 209-211°C; ^ NMR: δ 7.2-7.35 (m, 3H) , 7.71 (t, IH) , 7.86 (t, IH) , 7.96 (d, IH) , 8.95 (d, IH) . Step C: 3-(4-Chloro-2-fluorophenyl)-6_f7,8,9-tetrahydro- 4H-pyridor2.1-cl π.2.41-triazin-4 (6H)-one The product of Step B (0.55 g, 2.0 mmol) was dissolved in acetic acid (30 mL) , platinum oxide (25 mg, 0.11 mmol) was added and the mixture was treated with hydrogen gas (2.8 x 10⁵ - 3.4 x 10⁵ Pa) for 1.5 h. An additional quantity of platinum oxide (25 mg, 0.11 mmol) was added and the mixture was treated with hydrogen gas (2.8 x 10⁵ - 3.4 x 10⁵ Pa) overnight. The mixture was filtered, then volatiles were removed under vacuum. The residue was dissolved in dichloromethane (50 mL) , washed with saturated aqueous NaHC0₃ (25 mL) , then the organic solution was dried over MgS0 , filtered, and the solvent was removed under vacuum. The residue was triturated with chlorobutane to afford a light yellow powder, 0.26 g (46%), m.p. 159°C (decomposed) .

To a solution of this powder (0.22 g, 0.78 mmol) in chloroform (12 mL) was added -bromosuccinimide

(0.14 g, 0.79 mmol) and the mixture was stirred for 15 min. at room temperature. An additional quantity of -bromosuccinimide (0.03 g, 0.2 mmol) was added and the mixture was stirred for 1 h at room temperature. The mixture was diluted with dichloromethane (50 mL) and . shaken with 10% aqueous Na S0₃ (10 mL) . This mixture was then washed with IN NaOH (10 mL) . The organic layer was separated, dried over MgS0 , filtered, and the solvent was removed under vacuum. The residue was triturated with hexanes-chlorobutane to afford the title compound of Step C (0.16 g, 73%) as an off-white powder, m.p. 151-154°C (decomposed); ^-H NMR: δ 1.9-2.0 (m, 2H) , 2.0-2.1 (m, 2H) , 3.09 (t, 2H) , 3.98 (t, 2H) , 7.2-7.3 (m, 2H) , 7.57 (t, IH) . By the general procedures given in Schemes 1-6 and Synthesis Examples 1-4, or by obvious modifications thereof, the compounds of Tables 1-13 can be prepared.

"^■a *d "i *ι ^ "j Ω "1 Ω Ω Ω q rq Ω a __ Ω •*! "^■! *J <~i

X-

**J "I _J rq <~i "I 1 "1 "1 Ω Ω Ω Ω "i Ω Ω

co

*d •~~X "d *1

Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω x-^χ

Ω Ω Ω Ω Ω Ω Ω Ω

Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω I-" X-x

Ω Ω Ω to a to a to a Ω to a Ω to a Ω to a Ω t a Ω t a Ω o t a Ω o a Ω to a Ω t to a Ω Ω to a t a Ω t a Ω o t a Ω o a Ω t a Ω Ω t t a a Ω to t a Ω to a Ω to a Ω t a Ω o t a Ω o to a Ω a Ω to to a

Ω a Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω a a a <~i a Ω d a <*i a Ω * ad a <~i <*ι a "1 * a <~i a a a "1 a Ω Ω "d a Ω "d a "d a "d a "1 a a "d a "1 «ι a Ω a

Ω t a

Ω "d rr, ni *^~~\ <^~i "d Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω "i <--χ •n "d <~i Ω

"d O <τi tr

Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω a Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω O

"d "d "d "d ~~i "d <~~\ q HJ hq Ω Ω Ω Ω Ω

Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω x-^x x-^x

x Ω a Ω Ω to to a Ω to a to a

Ω a Ω Ω Ω to to a to a to a

a a a a a a a a in

Co O co O O O O O O O O O O O Co O O

Ω Ω Ω Ω

X

a a a ^~s. a ^~~z ^~s. a a a a ^~~ _* a a a a a m^~. Φ Φ Φ Φ Φ Ol

O O O CO O O O O O O O O O O O CO O O

X

\«

hq ti] a

CO O co co O O O °

to to to to to

"d Ω Ω "d <-. " *ι

a a if a a a a a a a a >

o o co co o o

6

A ___§. *__ ___. _≥i

Me CHF₂ F H Cl

Me CHF₂ Cl H Cl

Me CHF₂ Br H Cl

Me CHF₂ F H Br

g g g g φ φ φ φ

a a Ω " Ω •~~X Ω Ω "1 "d * Ω •*_! *d Ω 1 Ω O rτ_ H] h hq hq Ω

X-x

a a a a

Ω Ω XX> Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω

X-x X-X F- F<

Ω Ω Ω Ω 1 Ω Ω Ω *d

Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω CO Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω H X- X-x x-x x-x X-x F" F- F- H F" x-x -x X-x X-x X-x

g co cCoo O Q Ω M g g g g td g g g g g lk, ts g Ω g ^ tt Φ Φ Φ Φ rt φ φ φ φ l^ φ rt Φ ω

Φ to

Ω a φg rttd φg φg φg rttd Ω Ω Ω Ω Ω Ω Ω Ω Ω Ω |l_ω ^ro φ to

Φ Φ cn

Ω Ω Ω Ω Ω Ω Ω o o o o o o o o o o o co o o o o o

w

a a a Φ g a o o CO I* o o o o o

CO

Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent or an organic solvent. Use formulations include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up 100 weight percent.

Weight Percent

High Strength 90-99 0-10 0-2

Compositions Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents and solvents are described in arsden, Solvents Guide, 2Nd Ed., Interscience, New

York, (1950). McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, (1964), list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.

Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced be agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., (1988), pp 251-259. Suspensions are prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4,

1967, pp 147—48, Perry 's Chemical Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, (1963), pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can also be prepared as taught in DE 3,246,493.

For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10—41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, (1961), pp 81-96; and Hance et al . , Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, (1989) .

In the following Examples, all percentages are by weight and all formulations are worked up in conventional ways. Compound numbers refer to Table 13.

Example A High Strength Concentrate

Compound 1 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.

Example B Wettable Powder

Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.

Example C Granule Compound 1 10.0% attapulgite granules (low volative matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.

Example D Extruded Pellet

Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%. Utility

The compounds of the present invention are active postemergence and preemergence herbicides. Several compounds of this invention are useful for the control of selected grass and broadleaf weeds with tolerance to important agronomic crops such as, but not limited to, corn ( Zea mays) , cotton ( Gossypium hirsutu ) , rice ( Oryza sativa) , soybean ( Glycine max) , wheat { Tritium aestivum) , barley (Hordeum vulgare) and plantation crops.

Alternatively, compounds of this invention can be used in areas where complete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, oil well sites, drive-in theaters, around billboards, highways and railroad structures and in fence rows.

In general, effective application rates for the compounds of this invention are 0.001 to 20 kg/ha with a preferred rate range of 0.004 to 0.25 kg/ha. Effective rates of application for this invention are determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. One skilled in the art can select the effective rates for a given situation.

The compounds of this invention may be used alone or in combination with other commercial herbicides, insecticides or fungicides. The following list exemplifies some of the herbicides suitable for use in mixtures. A combination of a compound from this invention with one or more of the following herbicides may be particularly useful for weed control in plantation crops.

Compounds of this invention can be used alone or in combination with other commercial herbicides, insecticides or fungicides. A mixture of one or more of the following herbicides with a compound of this invention can be particularly useful for weed control: acetochlor, acifluorfen, acrolein, 2-propenal, alachlor, ametryn, amidosulfuron, ammonium sulfamate, amitrole, anilofos, asulam, atrazine, barban, benefin, bensulfuron methyl, bensulide, bentazon, benzofluor, benzoylprop, bifenox, bromacil, bromoxynil, bromoxynil heptanoate, bromoxynil octanoate, butachlor, buthidazole, butralin, butylate, cacodylic acid,

2-chloro-N,W-di-2-propenylacetamide, 2-chloroally1 diethyldithiocarbamate, chloramben, chlorbromuron, chloridazon, chlorimuron ethyl, chlormethoxynil, chlornitrofen, chloroxuron, chlorpropham, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodi , clomazone, cloproxydim, clopyralid, calcium salt of methylarsonic acid, cyanazine, cycloate, cycluron, cyperquat, cyprazine, cyprazole, cypromid, dalapon, dazomet, dimethyl 2,3,5, 6-tetrachloro-l,4- benzenedicarboxylate, desmedipham, desmetryn, dicamba, dichlobenil, dichlorprop, diclofop, diethatyl, difenzoquat, diflufenican, dimepiperate, dinitramine, dinoseb, diphenamid, dipropetryn, diquat, diuron, 2-methyl-4, 6-dinitrophenol, disodium salt of methylarsonic acid, dymron, endothall, S-ethyl dipropylcarbamothioate, esprocarb, ethalfluralin, ethametsulfuron methyl, ethofumesate, fenac, fenoxaprop, fenuron, salt of fenuron and trichloro- acetic acid, flamprop, fluazifop, fluazifop-P, fluchloralin, flumesulam, flumipropyn, fluometuron, fluorochloridone, fluorodifen, fluoroglycofen, flupoxam, fluridone, fluroxypyr, fluzasulfuron, fomesafen, fosamine, glyphosate, haloxyfop, hexaflurate, hexazinone, imazamethabenz, imazapyr, imazaquin, imazamethabenz methyl, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, karbutilate, lactofen, lenacil, linuron, metobenzuron, metsulfuron methyl, methyl¬ arsonic acid, monoammonium salt of methylarsonic acid, (4-chloro-2-methylphenoxy) acetic acid, S, S^X-dimethyl-2- (difluoromethyl) -4-(2-methylpropyl)-6-(trifluoro- methyl)-3, 5-pyridinedicarbothioate, mecoprop, mefenacet, mefluidide, methalpropalin, methabenz- thiazuron, metham, methazole, methoxuron, metolachlor, metribuzin, 1, 2-dihydropyridazine-3, 6-dione, molinate, monolinuron, monuron, monuron salt and trichloroacetic acid, monosodium salt of methylarsonic acid, napropamide, naptalam, neburon, nicosulfuron, nitralin, nitrofen, nitrofluorfen, norea, norflurazon, oryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pendimethalin, perfluidone, phenmedipham, picloram, 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitro- acetophenone oxime-O-acetic acid methyl ester, pretilachlor, primisulfuron, procyazine, profluralin, prometon, prometryn, pronamide, propachlor, propanil, propazine, propham, prosulfalin, prynachlor, pyrazolate, pyrazon, pyrazosulfuron ethyl, quinchlorac, quizalofop ethyl, rimsulfuron, secbumeton, sethoxydim, siduron, simazine, 1-(a,a-dimethylbenzyl)-3-(4- methylphenyl)urea, sulfometuron methyl, trichloroacetic acid, tebuthiuron, terbacil, terbuchlor, terbuthylazine, terbutol, terbutryn, thifensulfuron methyl, thiobencarb, tri-allate, trialkoxydi , triasulfuron, tribenuron methyl, triclopyr, tridiphane, trifluralin, trimeturon, (2, 4-dichlorophenoxy) acetic acid, 4-(2, 4-dichlorophenoxy)butanoic acid, vernolate, and xylachlor.

Selective herbicidal properties of the subject compounds were discovered in greenhouse tests as described below. TABLE 13

^ddecomposed during melting

TEST A

Seeds of barley {Hordeum vulgare) , barnyardgrass (Echinochloa crus-galli) , bedstraw { Galium aparine) , blackgrass {Alopecurus myosuroides) , cheatgrass {Bromus secalinus) , chickweed {Stellaria media) , cocklebur {Xanthium pensylvanicum) , corn { Zea mays) , cotton

{ Gossypium hirsutum) , crabgrass {Digitaria spp.), giant foxtail {Setaria faberii) , lambsquarters ( Chenopodium album) , morningglory {Ipomoea hederacea) , rape {Brassica napus) , rice {Oryza sativa) , sorghum {Sorghum bicolor) , soybean {Glycine max) , sugar beet {Beta vulgaris) , velvetleaf {Abutilon theophrasti) , wheat { Triticum aestivum) , wild buckwheat {Polygonum 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.

Seeds of barnyardgrass {Echinochloa crus-galli) , cheatgrass {Bromus secalinus) , cocklebur {Xanthium pensylvanicum) , crabgrass {Digitaria spp.), giant foxtail {Setaria faberii) , morningglory {Ipomoea spp.), sorghum {Sorghum bicolor) , velvetleaf {Abutilon theophrasti) , and wild oat {Avena fatua) were planted into a sandy loam soil and treated preemergence with test chemicals dissolved in a non-phytotoxic solvent.

At the same time, these crop and weed species were also treated postemergence 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.

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 cm 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 barley {Hordeum vulgare) , bedstraw { Galium aparine) , blackgrass {Alopecurus myosuroides) , chickweed {Stellaria media) , corn {Zea mays) , cotton { Gossypium hirsutum) , crabgrass {Digitaria sanguinalis) , downy brome {Bromus tectorum) , giant foxtail {Setaria faberii) , lambsquarters { Chenopodium album) , morningglory {Ipomoea hederacea) , pigweed {Amaranthusretroflexus) , rape {Brassica napus) , ryegrass {Lolium multiflorum) , sorghum {Sorghum bicolor) , soybean {Glycine max) , speedwell {Veronica persica) , sugar beet (Beta vulgaris) , velvetleaf (Abutilon theophrasti) , wheat ( Triticum aestivum) , wild buckwheat (Polygonum 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 post-emergence portion of the test. Plant species in the flood test consisted of rice (Oryza sativa) , umbrella sedge ( Cyperus difformis) , duck salad (Heteranthera limosa) and barnyardgrass (Echinochloa crus-galli ) 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.

TEST D

Seeds, tubers, or plant parts of alfalfa (Medicago sativa) , annual bluegrass (Poa annua) , bermudagrass

( Cynodon dactylon) , broadleaf signalgrass (Brachiaria plantaginea) , dallisgrass (Paspalum Dilatatum) , goosegrass (Eleusine indica) , guineagrass (Panicum maximum) , itchgrass (_RottjboelIia exaltata) , johnsongrass ( Sorghum halepense) , large crabgrass

(Digitaria sanguinalis) , peanuts (Arachis hypogaea) , pitted morningglory ( Ipomoea lacunosa) , purple nutsedge

( Cyperus rotundus) , purslane (Portulaca oleracea) , ragweed (Ambrosia elatior) , sandbur ( Cenchrus echinatus) , and smooth crabgrass (Digitaria ischaemum) were planted into greenhouse pots of flats containing greenhouse planting medium. Plant species were grown grown in separate pots or individual compartments. Preemergence applications were made within one day of planting the seed or plant part. Postemergence applications were applied when the plants were in the two to four leaf stage (three to twenty cm) . Test chemicals were dissolved in a non-phytotoxic solvent and applied preemergence and postemergence to the plants. Untreated control plants and treated plants were placed in the greenhouse and visually evaluated for injury 13 to 21 days after herbicide application. Plant response ratings, summarized in Table D, are based on a 0 to 100 scale where 0 is no injury and 100 is complete control. A dash (-) response means no test result.

Pit Morninglory 0 Pit Morninglory 0

Purple Nutsedge 0 Purple Nutsedge 0

S. Sandbur 0 S. Sandbur 0

Smooth Crabgras 0 Smooth Crabgras 0

TEST E

Compounds evaluated in this test were formulated in a non-phytoxic solvent and applied to the soil surface before plant seedlings emerged (preemergence application) and to plants that were in the one-to-four leaf stage (postemergence application) . A sandy loam soil was used for the preemergence test while a mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test. Test compounds were applied within approximately one day after planting seeds for the preemergence test.

Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include winter barley (Hordeum vulgare cv. 'Igri¹), blackgrass (Alopecurus myosuroides) , chickweed (Stellaria media) , downy brome (Bromus tectorum) , field violet (Viola arvensis) , galium (Galium aparine) , green foxtail (Setaria viridis) , kochia (Kochia scoparia) , lambsquarters (Chenopodium album) , speedwell (Veronica persica) , rape (Brassica napus) , ryegrass (Lolium multiflorum) , sugar beet (Beta vulgaris cv. 'US1'), sunflower (Helianthus annuus cv. 'Russian Giant'), spring wheat ( Triticum aestivum cv. 'ERA'), winter wheat ( Triticum aestivum cv. 'Talent'), wild buckwheat (Polygonum convolvulus) , wild mustard (Sinapis arvensis) , wild oat (Avena fatua) , and wild radish (Raphanus raphanistrum) . Blackgrass, galium and wild oat were treated at two growth stages. The first stage (1) was when the plants had two to three leaves. The second stage (2) was when the plants had approximately four leaves or in the initial stages of tillering. Treated plants and untreated controls were maintained in a greenhouse for approximately 21 to 28 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table E, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash response (-) means no test result.

Claims

A compound of the formula

wherein

Q is selected from the group:

, , ,

, . and ;

A is selected from the group C₁-C₄ alkyl, C₁-C₄

haloalkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, OR¹⁶, SR¹⁶ and halogen;

B is selected from the group C₁-C₄ alkyl, C₁-C₄

haloalkyl, C₃-C₄ alkenyl and C₃-C₄ alkynyl; A and B can be taken together as X-Y-Z to form a fused ring such that X is connected to nitrogen and Z is connected to carbon;

X is selected from the group CHR¹⁷, CH₂CH₂ and

CR¹⁷=CR¹⁸;

Y is selected from the group CHR¹⁹, CR¹⁹=CR²⁰,

CHR¹⁹CHR²⁰, NR²¹, O and S(O)_n;

Z is selected from the group CHR²², CH₂CH₂,

CR²²=CR²³, NR²¹, O and S(O)_n;

n is 0, 1 or 2;

R¹ is halogen;

R² is selected from the group H, C₁-C₈ alkyl, C₁-C₈ haloalkyl, halogen, OH, OR⁷, SH, S(O)_nR⁷, COR⁷,

CO₂R⁷, C(O)SR⁷, C(O)NR⁹R¹⁰, CHO, CR²⁴=NOR²⁵, CH=CR²⁸CO₂R⁷, CH₂CHR²⁸CO₂R⁷, CO₂N=CR¹¹R¹², NO₂,

CN, NHSO₂R¹³, NHSO₂NHR¹³, NR⁷R²⁶, NH₂ and phenyl optionally substituted with R²⁷;

R³ is selected from the group C₁-C₂ alkyl, C₁-C₂ haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CN and NO₂;

R⁴ is selected from the group H, C₁-C₃ alkyl and halogen;

R⁵ is selected from the group H, C₁-C₃ alkyl,

halogen, C₁-C₃ haloalkyl, cyclopropyl, C₂ alkenyl, C₂ alkynyl, CN, C(O)R²⁹, CO₂R²⁹,

CONR²⁹R³⁰, CR³¹R³²C(O)R²⁹, CR³¹R³²CO₂R²⁹,

CR³¹R³²CONR²⁹R³⁰, CHR³¹OH, CHR³¹OC (O) R²⁹ and

OCHR³¹OC (O) NR²⁹R³⁰;

when Q is Q-2 or Q-6, R⁴ and R⁵ together with the carbon to which they are attached can be C=0;

R⁶ is selected from the group C₁-C₆ alkyl, C^_^-Cg haloalkyl, C₂-Cg alkoxyalkyl, C₃-Cg alkenyl and

C₃-C₆ alkynyl;

R⁷ is selected from the group C₁-C₈ alkyl; C₃-C₈ cycloalkyl; C₃-C₈ alkenyl; C₃-C₈ alkynyl; C₁-C₈ haloalkyl; C₂-C₈ alkoxyalkyl; C₂-C₈

alkylthioalkyl; C₂-C₈ alkylsulfirtylalkyl; C₂-C₈ alkylsulfonylalkyl; C₄-C₈ alkoxyalkoxyalkyl; C₄-C₈ cycloalkylalkyl; C₄-C₈ alkenoxyalkyl;

C₄-C₈ alkynoxyalkyl; C₆-C₈ cycloalkoxyalkyl; C₄-C₈ alkenyloxyalkyl; C₄-C₈ alkynyloxyalkyl; C₃-C₈ haloalkoxyalkyl; C₄-C₈ haloalkenoxyalkyl; C₄-C₈ haloalkynoxyalkyl; C₆-C₈ cycloalkylthioalkyl; C₄-C₈ alkenylthioalkyl; C₄-C₈ alkynylthioalkyl; C₁-C₄ alkyl substituted with phenoxy or benzyloxy, each ring optionally substituted with a member selected from the group halogen, C₁-C₃ alkyl and C₁-C₃ haloalkyl; C₄-C₈ trialkylsilylalkyl; C₃-C₈ cyanoalkyl;

C₃-C₈ halocycloalkyl; C₃-C₈ haloalkenyl; C₅-C₈ alkoxyalkenyl; C₅-C₈ haloalkoxyalkenyl; C₅-C₈ alkylthioalkenyl; C₃-C₈ haloalkynyl; C₅-C₈ alkoxyalkynyl; C₅-C₈ haloalkoxyalkynyl; C₅-C₈ alkylthioalkynyl; C₂-C₈ alkyl carbonyl; benzyl optionally substituted with a member selected from the group halogen, C₁-C₃ alkyl and C₁-C₃ haloalkyl; CHR¹⁴COR⁸; CHR¹⁴P(O)(OR⁸)₂;

CHR¹⁴P(S)(OR⁸)₂; CHR¹⁴C(O)NR⁹R¹⁰; CHR¹⁴C(O)NH₂, CHR³³CO₂R³⁴; CO₂R³⁴; SO₂R³⁴; phenyl optionally substituted with R²⁷; and ;

R⁹ and R¹¹ are independently selected from the

group H and C₁-C₄ alkyl;

R¹⁰ and R¹² are independently selected from the

group C₁-C₄ alkyl and phenyl optionally substituted with a member selected from the group halogen, C₁-C₃ alkyl and C₁-C₃ haloalkyl; R⁹ and R¹⁰ can be taken together as -(CH₂)₅-,

-(CH₂)₄- or -CH₂CH₂OCH₂CH₂-, each ring

optionally and independently substituted with one or more members selected from the group C₁-C₃ alkyl, phenyl and benzyl;

R¹¹ and R¹² can be taken together with the carbon to which they are attached to form C₃-C₈ cycloalkyl;

R¹³ is selected from the group C₁-C₄ alkyl and C₁-C₄ haloalkyl;

R¹⁴ is selected from the group H and C₁-C₄ alkyl; R¹⁶ is selected from the group C₁-C₄ alkyl and C₁-C₄ haloalkyl;

R¹⁷, R¹⁸, R¹⁹, R²⁰, R²² and R²³ are independently

selected from the group H, halogen, C₁-C₄ alkyl and C₂-C₄ haloalkyl;

R²¹ is selected from the group H, C₁-C₄ alkyl and C₁-C₄ haloalkyl;

R²⁴ is selected from the group H and C₁-C₄ alkyl; R²⁵ is selected from the group H, C₁-C₆ alkyl, C₃-C₆ alkenyl and C₃-C₆ alkynyl;

R²⁶ is selected from the group H and C₁-C₄ alkyl; R²⁷ is selected from the group C₁-C₂ alkyl, C₁-C₂ haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CN and

NO₂;

R²⁸ is selected from the group H, C₁-C₄ alkyl and halogen;

R²⁹, R³⁰, R³¹ and R³² are independently selected

from the group H and C₁-C₃ alkyl;

R³³ is selected from the group H and C₁-C₄ alkyl; R³⁴ is selected from the group C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ alkenyl or C₃-C₆ alkynyl; and W is selected from the group O and S; and their agriculturally suitable salts,

provided that

1) the sum of X, Y and Z is no greater than 5

atoms in length and only one of Y and Z can be other than a carbon containing link;

2) when R² is CO₂R⁷, C(O)SR⁷, CH=CR²⁸CO₂R⁷ or

CH₂CHR²⁸CO₂R⁷ then R⁷ is other than C_x haloalkyl, and when R⁷ is CHR³³CO₂R³⁴ or CO₂R³⁴ then R³⁴ is other than C₁ haloalkyl;

3) when X is CHR¹⁷, Y is CHR¹⁹ and Z is CHR²² then at least one of R¹⁷, R¹⁹ and R²² is halogen; 4) when A and B are other than taken together as X-Y-Z and Q is Q-l then R² is OR⁷ and R⁷ is C₃-C₈ alkynyl; and

5) when Z is NR²¹, O or S and Q is Q-l then R² is OR⁷ and R⁷ is C₃-C₈ alkynyl.

2. A compound of Claim 1 wherein the compounds are of the formula

wherein

X is CHR¹⁷ or CH₂CH₂;

Y is CHR¹⁹ or CHR¹⁹CHR²⁰;

Z is CHR²² or CH₂CH₂;

R² is selected from the group H, C₁-C₈ alkyl, C₁-C₈ haloalkyl, halogen, OR⁷, S(O)_nR⁷, COR⁷, CO₂R⁷, C(O)SR⁷, C(O)NR⁹R¹⁰, CHO, CH=CHCO₂R⁷,

CO₂N=CR¹¹R¹², NO₂, CN, NHSO₂R¹³ and NHSO₂NHR¹³; R⁵ is selected from the group H, C₁-C₃ alkyl and halogen; R⁷ is selected from the group C₁-C₈ alkyl; C₃-C₈ cycloalkyl; C₃-C₈ alkenyl; C₃-C₈ alkynyl; C₁-C₈ haloalkyl; C₂-C₈ alkoxyalkyl; C₂-C₈

alkylthioalkyl; C₂-C₈ alkylsulfinylalkyl; C₂-C₈ alkylsulfonylalkyl; C₄-C₈ alkoxyalkoxyalkyl;

C₄-C₈ cycloalkylalkyl; C₄-C₈ alkenoxyalkyl;

C₄-C₈ alkynoxyalkyl; C₆-C₈ cycloalkoxyalkyl; C₄-C₈ alkenyloxyalkyl; C₄-C₈ alkynyloxyalkyl; C₃-C₈ haloalkoxyalkyl; C₄-C₈ haloalkenoxyalkyl; C₄-C₈ haloalkynoxyalkyl; C₆-C₈ cycloalkylthioalkyl; C₄-C₈ alkenylthioalkyl; C₄-C₈ alkynylthioalkyl; C₁-C₄ alkyl substituted with phenoxy or benzyloxy, each ring optionally substituted with a member selected from the group halogen, C₁-C₃ alkyl and C₁-C₃ haloalkyl;

C₄-C₈ trialkylsilylalkyl; C₃-C₈ cyanoalkyl;

C₃-C₈ halocycloalkyl; C₃-C₈ haloalkenyl; C₅-C₈ alkoxyalkenyl; C₅-C₈ haloalkoxyalkenyl; C₅-C₈ alkylthioalkenyl; C₃-C₈ haloalkynyl; C₅-C₈ alkoxyalkynyl; C₅-C₈ haloalkoxyalkynyl; C₅-C₈ alkylthioalkynyl; C₂-C₈ alkyl carbonyl; benzyl optionally substituted with a member selected from the group halogen, C_!-C₃ alkyl and C^Cs haloalkyl; CHR¹⁴COR⁸; CHR¹⁴P(O)(OR⁸)₂;

CHR¹⁴P(S)(OR⁸)₂; CHR¹⁴C(O)NR⁹R¹⁰ and

CHR¹⁴C(O)NH₂;

R¹⁷, R¹⁹, R²⁰ and R²² are selected from the group H, halogen and C₂-C₄ alkyl;

provided that only one of R¹⁷, R¹⁹, R²⁰ and R²² is other than hydrogen.

3. A compound of Claim 1 wherein

X is CHR¹⁷;

Y is CHR¹⁹CHR²⁰;

Z is CHR²².

4. A compound of Claim 3 wherein R² is selected from the group H, OR⁷, SR⁷ and

CO₂R⁷;

R³ is selected from the group halogen and CN; R¹⁷, R¹⁹, R²⁰ and R²² are independently selected from the group H, F, CH₃ and CF₃.

5. A compound of Claim 4 wherein

Q is selected from the group Q-1, Q-2, Q-4 and

Q-5;

A and B are taken together as X-Y-Z;

R¹⁷, R¹⁸, R¹⁹, R²⁰, R²² and R²³ are independently selected from the group H and F;

R⁷ is selected from the group C₁-C₄ alkyl, C₃-C₄ alkenyl, C₃-C₄ alkynyl, C₂-C₄ alkoxyalkyl, C₁-C₄ haloalkyl, C₃-C₄ haloalkenyl and C₃-C₄ haloalkynyl.

6. A compound of Claim 1 wherein

X is CHR¹⁷;

Y is CHR¹⁹;

Z is CHR²².

7. A compound of Claim 6 wherein

R² is selected from the group H, OR⁷, SR⁷ and

CO₂R⁷;

R³ is selected from the group halogen and CN; R¹⁷, R¹⁹, and R²² are independently selected

from the group H, F, CH₃ and CF₃.

8. A compound of Claim 7 wherein

Q is selected from the group Q-1, Q-2, Q-4 and

Q-5;

A and B are taken together as X-Y-Z;

R¹⁷, R¹⁹, and R²² are independently selected

from the group H and F;

R⁷ is selected from the group C₁-C₄ alkyl, C₃-C₄ alkenyl, C₃-C₄ alkynyl, C₂-C₄ alkoxyalkyl, C₂-C₄ haloalkyl, C₃-C₄ haloalkenyl and C₃-C₄ haloalkynyl.

9. A composition for controlling growth of

undesired vegetation comprising an effective amount of a compound of Claim 1 and a carrier therefor.

10. A method for controlling growth of undesired vegetation comprising applying to the locus to be protected an effective amount of a compound of Claim 1.