WO1991010653A1 - Herbicidal pyrimidines and triazines - Google Patents

Abstract

This invention relates to certain herbicidal sulfonylure pyrimidines and triazines useful for complete control and/or selective control of vegetation with the selectivity being important to agronomic crops.

Description

TITLE

HERBICIDAL PYRIMIDINES AND TRIAZINES

Related Applications

This is a continuation-in-part of U.S. Serial No. 07/542390 filed June 22, 1990 which is a

continuation-in-part of U.S. Serial No. 07/463,356 filed January 11, 1990.

Background of the Invention

This invention relates to certain herbicidal pyrimidines and triazines, agriculturally suitable compositions thereof and a method for their use as general or selective preemergent or postemergent herbicides or as plant 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 such as cotton, rice, corn, wheat and soybeans, to name a few. Unchecked weed growth in such crops can cause significant losses, reducing profit to the farmer and increasing costs to the consumer. In other situations, herbicides 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 purposes, but the search continues for products which are more effective, less costly and

environmentally safe.

JP Kokai Hei 1[1989]-301668 discloses mandelic acid derivatives as herbicides:

J. Chem. Res.(S) 1977, 186 discloses benzyl pyrimidines as intermediates to herbicides but includes no herbicidal test data for these

intermediates.

JP KOKAI HEI 2 [1990] -56469 (unofficial English translation) discloses as herbicides the following structures:

wherein, inter alia

Z is CH or N;

R is a formyl group or CO₂R¹; and

R¹ is H, lower alkyl, lower alkoxyalkyl or lower alkylthioalkyl.

EP-A-360,163 discloses herbicidal compounds of the formula:

SUMMARY OF THE INVENTION This invention pertains to compounds of Formula I including all geometric and stereoisomers,

agriculturally suitable salts, agricultural

compositions containing them and their method-of-use for the control of unwanted weeds both preemergence and postemergence.

wherein

Q is

A is CR², N or N-O;

X is H, F, Cl, CH₃, OH, C(O)NR¹²R¹³, CO₂R¹⁴ or CN;

R¹ is H, CHO, C(OCH₃)₂H, CO₂R⁵ or C(O)SR¹¹;

R² is H, F, Cl, C₁-C₂ alkyl, C₁-C₂-alkoxy,

C₂-C₃ alkynyl, C₂-C₃ alkenyl, S(O)_nC₁-C₂ alkyl, NO₂, phenoxy, C₂-C₄ alkylcarbonyl, C(OCH₃)₂CH₃, or C(SCH₃)₂CH₃;

R³ is C₁-C₂ alkyl, C₁-C₂ alkoxy, OCF₂H or Cl;

R⁴ is C₁-C₂ alkyl;

R⁵ is H; M; C₁-C₃ alkyl; C₂-C₃ haloalkyl;

allyl; propargyl; benzyl optionally

substituted with halogen, C₁-C₂ alkyl, C₁-C₂ alkoxy, CF₃, NO₂, SCH₃, S(O)CH₃, or

S(O)₂CH₃; C₂-C₄ alkoxyalkyl; N-CR⁷R⁸; or CHR⁹S(O)_nR¹⁰;

R⁶ is H, F, Cl, CH₃, OCH₃ or S(O)_nCH₃; R⁷ is Cl, C₁-C₂ alkyl or SCH₃;

R⁸ is C₁-C₂ alkyl, CO₂(C₁-C₂ alkyl) or

C(O)N(CH₃)₂;

R⁹ is H or CH₃;

R¹⁰ is C₁-C₃ alkyl or phenyl optionally

substituted with halogen, CH₃, OCH₃ or NO₂, R¹¹ is C₁-C₂ alkyl or benzyl;

R¹² is H or CH₃;

R¹³ is H or CH₃;

^R14 is H, C₁-C₃ alkyl, C₂-C₅ haloalkyl, C₃-C₅ alkenyl, C₃-C₅ alkynyl, C₂-C₅ alkoxyalkyl or benzyl optionally substituted with CH₃, OCH₃, SCH₃, halogen, NO₂ or CF₃;

m is 0 or 1;

n is 0, 1 or 2;

M is a alkali metal atom or an alkaline earth metal atom, an ammonium group or an alkylammonium group; and

Z is CH or N.

and their agriculturally suitable salts;

provided that:

(a) when R¹ is H, then X is CO₂R¹⁴; (b) when X is CO₂R¹⁴, then R¹ is H; and

(c) when Z is N, then R³ is C₁-C₂ alkyl or C₁-C₂ alkoxy.

In the above definitions, the term "alkyl", used either alone or in compound words such as

"haloalkyl" includes straight chain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the different butyl isomers. "Alkoxy", "alkenyl" and "alkynyl" analogously also includes straight chain or branched isomers. "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 include CF₃, CH₂CF₃, CH₂CH₂F, CF₂CF₃ and CH₂CHFCl.

The preferred compounds of the invention for reasons including ease of synthesis and/or greater herbicidal efficacy are:

1. Compounds of Formula I wherein

Q is Q-1 or Q-2;

2. Compounds of Preferred 1 wherein

R² is H, F, Cl, CH₃, SCH₃, OCH₃ or OCH₂CH₃;

3. Compounds of Preferred 2 wherein

R⁶ is H;

Z is CH;

R³ is OCH₃;

R⁴ is CH₃; and

X is H;

4. Compounds of Preferred 2 wherein

R⁶ is H or 3-F;

Z is CH;

R³ is OCH₃;

R⁴ is CH₃;

X is CO₂R¹⁴; and

R¹⁴ is C₁-C₃ alkyl, allyl, propargyl or benzyl; 5. Compounds of Preferred 3 wherein

Q is Q-1;

R¹ is CO₂R⁵; and

R⁵ is H or M;

6. Compounds of Preferred 3 wherein

Q is Q-2;

R¹ is CO₂R⁵; and

R⁵ is H or M;

7. The compound of Preferred 5 which is

2-[(4,6-dimethoxy-2-pyrimidinyl)methyl]- 6-methyl-benzoic acid;

8. The compound of Preferred 2 which is

2-[cyano(4,6-dimethoxy-2-pyrimidinyl)methyl]- benzoic acid;

9. The compound of Preferred 5 which is

2-[(4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl benzole acid, sodium salt; 10. The compound of Preferred 5 which is

2-[(4,6-dimethoxy-2-pyrimidinyl)methyl]- 3-pyridine carboxylic acid;

11. The compound of Preferred 4 which is ethyl 4,6-dimethoxy-alpha-phenyl-2- pyrimidineacetate.

The compounds of this invention are biologically active as herbicides both post and preemergent with selectivity to crops including barley, wheat, corn and cotton. Detailed Description of the Invention

Synthesis

The compounds of Formula I can be prepared by one or more of the following methods described in Eguations 1 to 4.

The compounds of Formula I can be prepared by the reaction of an anion, formed from intermediate II and a base, with heterocycle III as shown in

Equation 1.

Equation 1

wherein:

Q-1 to Q-6, Z, R³ and R⁴ are as previously

defined;

Y is Cl, Br, I, SO₂CH₃ and SO₂benzyl; and

within the values of Q, R¹ is C(OMe)₂H,

CH₂OH, CO₂R⁵ or C(O)N(H, alkyl) (alkyl, silylalkyl); and

X is H. The reaction wherein a benzylic anion is formed, is best carried out in a dry inert solvent such as hexane, benzene, diethyl ether or

tetrahydrofuran (THF). Appropriate bases include hindered amine bases, such as lithium

diisopropylamide (LDA) or alkyllithiums, such as methyllithium or magnesium salts, such as ethyl magnesium bromide. When R¹ contains an acidic group, a second equivalent base is required. Formation of benzylic anions is further taught by Y. Thebtaranonth et al in Synthesis, 1986, 785; in Tet. Let., 1989, 30, 3861; J. Staunton et al. in J. Chem. Soc. Perkin Trans. I, 1984, 1043-1051, and F. Hauser et al.

Synthesis, 1980, 72. The reaction can be carried out from low temperatures -78°C (dry ice/acetone) up to the reflux point of the solvent. Generally, a lower temperature is preferred for anion formation, while the coupling of the anion II and III proceeds readily at higher temperatures.

When the reaction is judged complete, it is worked up in one of two manners, depending on the Regroup. If R¹ contains an acidic group such as CO₂H, then the reaction is extracted into aqueous base, and the water layer acidified. Alternately, the

carboxylate can be alkylated in situ to give an alkyl or benzyl ester. The product is either collected by filtration or extracted with an organic solvent and concentrated. The residue is further purified by trituration, crystallization or chromatography in the appropriate solvent. If the R¹ group contains no acidic group, i.e., an isopropylester, then the reaction is quenched with brine, the organic layer separated and concentrated followed by the

appropriate purification to give the desired product.

The compounds of Formula I can be prepared by the reaction of a cyanomethyl derivative IV with heterocycle III as shown in Equation 2a followed by oxidation, then reduction to give the alcohol, which can be converted to the halomethyl derivative (X is F or Cl), or further reduced to the methylene

derivative (X is H).

Equation 2

2a) T-CH₂CN + III → I

IV X=CN

2b) I + [ O]

X=CN

2C ) V → I

X=OH

2d) I → I

X=OH X=F or Cl

2e) V → I

X-H

2f ) T → I

X=CN X=CO₂H or C(O)NH₂ 2g) I → I

X-CO₂H X=CO₂R or C(O)NR¹²R¹³

R is equivalent to R⁵

2h) I → I

X=CO₂H or CO₂R X= H

2i) TCH₂CO₂R¹⁴ + III → I

X=CO₂R ¹⁴ wherein:

T is

R¹ is C(OMe)₂H, Br, CN, CH₂OSiMe₂CMe₃ or CO₂R⁵;

R⁵ is H, M, CHMe₂ or CMe₃; and

A and R⁶ are as previously defined.

The reaction of Equation 2a wherein Y is Cl or Br can be conveniently carried out under S_rnl

conditions by preparing a mixture of one equivalent or more of potassium metal, a catalytic amount of an iron compound, i.e., ferric nitrate, in liquid ammonia. The arylacetonitrile IV is added followed by the dropwise addition of the haloheterocycle III, with concomitant irradiation from a photoreactor lamp which emits maximally at 350 nm. The reaction is irradiated from 1 to 24 hours, then the reaction is quenched with solid ammonium chloride, the ammonia is allowed to slowly evaporate. The residual material is rinsed with diethylether and the filtrate is subjected to purification by recrystallization or chromatography to give the desired product.

Procedures can be adapted from J. F. Wolfe et al., J. Het. Chem., 1987, 24, 1061.

Alternatively, the reaction of Equation 2a, wherein Y is Cl, Br, I, CH₃SO₂ or PhCH₂SO₂, is carried out under basic conditions.

The starting materials can be premixed in an inert solvent such as diethylether, THF or

dimethylformamide (DMF) solvent when Y is halogen, followed by addition of a strong base, such as an alkali metal hydride, i.e., NaH, or a hindered metallated base, i.e., LDA or potassium t-butoxide. Another order of addition for any Y value can be the formation of the anion of acetonitrile IV in an inert solvent, followed by its addition to the heterocycle in an inert solvent. Yields are generally increased with the use of dry solvents and dry inert

atmospheres, with temperatures that range from -78°C to the solvent reflux point. The reaction is neutralized and the product is isolated by

chromatography or crystallization. Analogous reactions are taught by R. Y. Ning et al., J. Med. Chem., 1977, 20 , 1312 and F. Sauter et al., J. Chem. Res.(S), 1977, 186. Reactions 2a and 2b can be carried out

concurrently by allowing the reaction to be exposed to oxygen in the atmosphere. The oxidation of I (X is CN) to a diaryl ketone V can be carried out by one of several procedures. S. Murahashi et al., Syn.

Lett., 1989, 62, teach the oxidation of

alkanenitriles with ruthenium catalyzed t-butyl hydroperoxide to give intermediate

2-(t-butyldioxy)-alkanenitriles, which are further oxidized by titanium tetrachloride.

Diarylketones V can be reduced directly to the diarylmethanes via Equation 2e by Wolff-Kishner conditions as taught by Cram et al., J. Am. Chem.

Soc., 1962, 84, 1734; Clemmensen conditions as taught by Yamamura and Hirata, J. Chem. Soc. C. 1968, 2887; or hydrogenation with a catalyst such as CuCr₂O₄.

The diarylketones V can also be reduced

stepwise to the alcohol, I (X=OH), with lithium aluminum hydride or sodium borohydride. The alcohol can be converted to the chloride with thionyl

chloride or methanesulfonyl chloride and

triethylamine and to the fluoride with "DAST"

(diethylaminosulfur trifluoride), see Synthesis,

1973, 787 and J. Org. Chem., 1975, 40, 574, as shown in Equations 2c and 2d.

Cyanomethanes of Formula I (X=CN) can be converted to carboxylic acids and amides by

hydrolysis with either base or acid, as shown in

Equation 2f.

Carboxylic acids I (X=CO₂H) can be esterified or converted to amides by methods well known to a chemist skilled in the art.

Equation 2h shows that compounds of Formula I

(X=CO₂R) can be decarboxylated to the methylene bridged compounds. Such decarboxylations are well known in the art and generally are accomplished by heating the compound with or without solvent and with or without a catalyst.

Equation 2i is carried out in a similar fashion to 2a wherein an appropriate base is reacted with the aryl acetate followed by addition of heterocycle III.

The cyanomethanes and arylacetates of Formula IV are either known in the art or prepared by simple modifications thereof. Cyanomethanes are most conveniently prepared by nucleophilic reaction of a metal cyanide, i.e., NaCN, with a benzyl halide in a suitable solvent, such as dimethylformamide,

dimethylsulfoxide or THF. The benzyl halides are also well known, and easily prepared from II by methods adapted from T. Eicher, Synthesis, 1988, 1, 525 and Clarke et al., J. Chem. Perkin Trans. I, 1984, 1501.

The compounds of Formula I can be prepared by a cross-coupling reaction between an aryl boronic acid and a bromomethyl heterocycle with a catalyst as shown in Equation 3.

Equation 3

wherein:

T, Z, R³ and R⁴ are as previously defined;

R¹ is C(OMe₂)H, CH₂OH, CO₂R⁵ or CON(H,CH₃)- (alkyl, alkylsilyl); and

R⁵ is H, M, isopropyl or t-butyl.

The reaction is carried out by mixing the bromide (VII) with a transition metal catalyst, such as Ni(O) or Pd(O), preferably Pd(PPh₃)₄ in a suitable solvent, such as toluene or glyme, followed by the addition of boronic acid VI and the base, such as an alkoxide, hydroxide or carbonate, for example NaOEt, NaOH or Na₂CO₃ in a suitable solvent such as water or ethanol. The reaction mixture is stirred from 1 to 24 hours at room temperature to reflux. At

completion, the reaction is filtered, and the

filtrate is concentrated. The residue is partitioned between brine and an organic solvent (EtOAc, CH₂Cl₂), separated, dried (Na₂SO₄, MgSO₄), and concentrated, whereupon the product is isolated and purified, if necessary, by flash chromatography, recrystallization or distillation. Similar procedures and

modifications can be found in Snieckus et al.,

Tet. Let., 1987, 28, 5093; ibid., 1985, 26 , 5997;

Yamamoto et al., Synthesis, 1986, 564; Suzuki et al. Synth. Comm., 1981, 11, 513 and references

incorporated therein.

Formation of aryl boronic acids, VI , is well known in the art. They can be prepared by contacting an aryl organo metallic compound with B(OMe)₃

followed by acidic workup, as in J. Org. Chem., 1984, 49, 5237 and Tetrahedron, 1983, 39, 1955; or by reaction of an arylsilane with BBr₃, followed by addition of methanol, then dilute acid, as described in Tet. Let., 1987, 28, 5093.

Bromomethanes VII can be prepared by well known methods for conversion from alcohols and from methyl groups. A representative example is described in

J. Het. Chem. , 1989 , 26, 913 .

Compounds of Formula I, wherein Z is CH, can be prepared by the route shown in Equation 4.

Equation 4

(

The reaction is carried out by reacting IV with hydrogen chloride in an alcohol to form an imidate which is converted to the amidine salt, VIII, with ammonia. The pyrimidinol IX is formed by

condensation with a diketone/ester. This sequence of reactions and similar modifications can be found in H. C. van der Plas et al., Tetrahedron, 1989, 45,

6511-6518. Compounds of Formula IX can be converted to instant compounds I by preparation of the

chloropyrimidine with phosphorus oxychloride and a catalytic amount of DMF and subsequent displacement with sodium methoxide or ethoxide.

Heterocycles of Formula III are generally known in the art or can be prepared by simple modifications thereof. For example, preparation of chlorotriazines is described in J . Am. Chem. Soc . , 1951 , 73, 2989, while chloropyrimidines are described in J. Chem. Soc. (C), 1966, 2031. General references,

particularly to aminoheterocycles, can be found in "The Chemistry of Heterocyclic Compounds", a series published by Interscience Publishers, Inc., New York and London. The alkylsulfonyl and benzylsulfonyl heterocycles can also be prepared by the general reference above and more specifically by alkylation of thiols, as described in J. Med. Chem., 1984, 27, 1621-1629, followed by oxidation, most commonly by m-chloroperoxybenzoic acid.

The arylmethanes of Formula II are known in the art or easily prepared by methods therein.

The R¹ groups of Equations 1 to 4 can be converted into the claimed R¹ groups by techniques well known to one skilled in the art. For example, benzyl alcohols can be oxidized to aldehydes with many reagents, including pyridinium chlorochromate (PCC) and/or further oxidized to the carboxylate with potassium permanganate (KMnO₄). A sample procedure involving a phase transfer reagent is found in

Can. J. Chem., 1989, 67, 1381.

Additionally, conversion to and from various preferred R¹ groups are well known to one skilled in the art. Many are described in T. Greene, Protective Groups in Organic Synthesis, 1981, John Wiley and Sons, New York.

Carboxylic acid salts of Formula I (R¹ is CO₂M) can be prepared by reacting the carboxylic acid of Formula I (R¹ is CO₂H) with a base in the presence or absence of a solvent within a temperature range from room temperature to the boiling point of the solvent from 5 minutes to 24 hours. The solvent may be a hydrocarbon such as benzene or toluene, a halogenated hydrocarbon such as methylene chloride or chloroform, an alcohol such as methanol, ethanol or isopropanol, and other solvents, such as ethyl ether, THF,

acetone, methyl ethyl ketone, ethyl acetate or acetonitrile. The base may be an alkali metal such as sodium metal or potassium metal, an alkali metal or alkaline earth metal hydride such as sodium hydride, potassium hydride or calcium hydride, a carbonate such as sodium carbonate, potassium

carbonate or calcium carbonate, or a metal hydroxide such as sodium hydroxide or potassium hydroxide. The organic base may be ammonia, an alkylamine (primary amine), a dialkylamine (secondary amine) or a

trialkylamine (tertiary amine).

Example 1

2-[(4,6-Dimethoxy-2-Pyrimidinyl)methyl]-6-methyl- benzoic acid

To a cooled (15°C) suspension of sodium hydride (8.79 g, 0.183 mol), prewashed with dry hexanes, in 300 mL anhydrous THF under an N₂ atmosphere was added 2,6-dimethylbenzoic acid (24.5 g, 0.166 mol), portionwise. Additional THF (300 mL) was added to facilitate stirring in the resultant slurry. Then 142 mL of 1.4 M methyllithium (0.199 mol) was added dropwise at room temperature. One-twelfth of the resultant red solution (50 mL, 0.0138 mol), was added to 1.50 g of 4,6-dimethoxy-2-(methylsulfonyl)- pyrimidine (0.068 mol) under N₂ at room temperature. After 4 hours, the reaction was diluted with 100 mL IN HCl and 100 mL brine. The layers were separated; the aqueous layer was extracted with 100 mL ethyl acetate. The combined organic layers were dried

(MgSO₄), filtered and concentrated to give 2.5 g of a yellow oil. Addition of Et₂O gave a small amount of white precipitate, which was removed by filtration. The filtrate was subjected to flash column

chromatography (40 mm x 6" of SiO₂), eluted with 25% ethyl acetate/hexanes (v/v), initially, then 50:49:1 ethyl acetate in hexane/methanol. The fractions containing product were collected and concentrated under reduced pressure. The resultant oil

crystalized on standing to give 0.41 g solid, m.p. 122-124°C.

IR (nujol) = 1710 cm^-1.

Mass Spec. m/e = 289 (100, M+1).

PMR (200 MHz, CDCl₃) δ 2.49 (s, CH₃, 3H), 3.5-3.9 (bs, OH, 1H), 3.93 (s, OCH₃, 6H), 4.15 (s, CH₂, 2H), 5.91 (s, pyrm-H, 1H), 7.0-7.3 (m, ArH, 3H).

Example 2

2-[Cyano(4,6-dimethoxy-2-pyrimidinyl)methyl]- benzoic acid a) To a suspension of 60% NaH (0.38 g, prewashed with hexanes) in 50 mL dry THF was simultaneously added methyl 2-cyanomethylbenzoate (1.6 g) and

4,6-dimethoxy-2-methylsulfonylpyrimidine (1.99 g) in dry THF. After addition, the reaction was refluxed for 2 days, then 1.0 g of potassium t-butoxide was added. After 1 day, the reaction was quenched with 25 mL of brine and neutralized with 1 N HCl. The organic layer was concentrated under reduced pressure to give 2.87 g of an oil. The oil was subjected to flash column chromatography (SiO₂), eluted with

EtoAc/hexane (1:9) to give 0.75 g of solid, m.p.

79-81°C.

PMR (200 MHz, CDCl₃) δ 3.86 (s, OCH₃, 6H), 3.90 (s, OCH₃, 3H), 5.89 (s, pyrm-H, 1H), 6.74 (s, CHCN, 1H), 7.35-8.05 (m, ArH, 4H). b) The product of 2a (0.43 g ) was dissolved in a solution of 1.6 mL of 12% aqueous NaOH and 12 mL of ethanol. After 12 hours, the reaction mixture was diluted with 15 mL of .4 M NaOH and washed with

Et₂O. The aqueous layer was acidified, then

extracted with EtOAc. The organic layer was

concentrated under reduced pressure and the residue was triturated with butyl chloride to give 0.15 g solid, m.p. 214-216°C.

NMR (90 MHz, CDCl₃) δ 3.9 (s, OCH₃), 6.0 (s,

pyrm-H, 1H), 6.9 (s, CHCN, 1H), 7.4-8.3 (m, ArH, 4H), 11.0 (bs, CO₂H, 1H).

Example 3

2-[(4,6-Dimethoxy-2-pyrimidinyl)methyl]-3- pyridinecarboxylic acid

To a cooled (-78°C) suspension of

2-methylnicotinic acid (1.4 g, 10.2 mmol) in 100 mL dry THF was added 11.25 mL 1.95 M LDA dropwise. The reaction turned purple and warmed to -65°C. Allowed to recool to -78°C, then added 2-chloro-4,6-dimethoxy- pyrimidine (1.75 g, 10 mmol). The reaction was allowed to warm to room temperature over 2 days. The solvent was removed under reduced pressure. The residue was partitioned between Et₂O and water, which was basified to pH 8-9. The aqueous layer was acidified, then extracted with EtOAc, dried (MgSO₄); and concentrated under reduced pressure to give 1.33 g of a brown oil. This oil was subjected to flash column chromatography on SiO₂, eluted with 97:2:1 (EtOAc:MeOH:HOAc), to give after trituration with BuCl/hexanes a solid, 0.29 g, m.p. 182-186°C.

Mass Spec: m/e 276 (100, MH⁺).

PMR (acetone-d₆, 200 MHz) δ 3.8 (s, OMe, 6H), 4.8 (s, CH₂, 2H), 5.9 (s, pyrm-H, 1H), 7.4 (m) + 8.3 (m) + 8.7 (m)[pyrH, 3x 1H].

Example 4

4,6-Dimethoxy-α-phenyl-2-Pyrimidineacetic acid, ethyl ester.

To a cooled (-78°C) solution of ethyl phenyl- acetate (0.79 ml, 5mmol) in 30 mL anhydrous THF under an N₂ atmosphere was added 2.86 mL of 1.9M LDA dropwise, followed by 1.0 g of 4,6-dimethoxy-2- methylsulfonylpyrimidine. The reaction mixture was allowed to warm to room temperature over 6 h then quenched with 20 mL brine and 5 mL of 1 NHCl. The layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed once with brine, dried (MgSO₄), filtered and concentrated under reduced pressure to give 1.6 g of a brown oil. The oil was subjected to flash column chromatography (SiO₂), eluted with

Et₂O/hexanes (1:9) to give 0.63g of the product as an oil. PMR (200 MH_z, CDCl₃) δ 1.24 (t, CH₃, 3H), 3.89 (S, OCH₃, 6H), 5.08 (S, CH, 1H), 5.89 (s, pyrmH, 1H) 7.2-7.6 (m, ArH, 5H).

Using the procedures of Equations 1 to 4 and Examples 1 to 4, the compounds of Tables 1 to 7 can be prepared by one skilled in the art.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

TABLE 6

TABLE 7

Formulations

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable

concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of

(a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). More

specifically, they will contain these ingredients in the following approximate proportions:

Table 8

Active ingredient plus at least one of a

Surfactant or a Diluent equals 100 weight percent Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New

Jersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and

Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example. Littler, U.S. Patent

3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Patent 3,235,361, February 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Patent 3,309,192,

March 14, 1967, 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;

H. Gysin and E. Knusli, U.S. Patent 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 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.

In the following examples, all parts are by weight unless otherwise indicated.

Example A

Wettable Powder

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 80%

sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 13%

The ingredients are blended, hammer-milled until all the solids are essentially under 50

microns, reblended, and packaged. Example B

Wettable Powder

2-[4,6-dimethoxy-2-pyrimidinyl)methyI]-6- methyl-benzoic acid 50% sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2% diatomaceous earth 46% The ingredients are blended, coarsely hammermilled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging. Example C

Granule

Wettable Powder of Example B 5% attapulgite granules 95%

(U.S.S. 20-40 mesh; 0.84-0.42 mm)

A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged. Example D

Extruded Pellet

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 25% anhydrous sodium sulfate 10% crude calcium ligninsulfonate 5% sodium alkylnaphthalenesulfonate 1% calcium/magnesium bentonite 59%

The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.

Example E

Oil Suspension

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 25% polyoxyethylene sorbitol hexaoleate 5% highly aliphatic hydrocarbon oil 70% The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.

Example F

Wettable Powder

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 20% sodium alkylnaphthalenesulfonate 4% sodium ligninsulfonate 4% low viscosity methyl cellulose 3% attapulgite 69%

The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged. Example G

Low strength Granule

2-[4, 6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 1%

N,N-dimethylformamide 9% attapulgite granules 90%

(U.S.S. 20-40 sieve)

The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.

Example H

Aqueous Suspension

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 40% polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol ether 0.5% disodium phosphate 1% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7%

The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size. Example I

Solution

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 5% water 95% The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use. Example J

Low Strength Granule

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 0.1% attapulgite granules 99.9%

(U.S.S. 20-40 mesh)

The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.

Example K

Granule

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 80% wetting agent 1% crude ligninsulfonate salt (containing 10%

5-20% of the natural sugars)

attapulgite clay 9%

The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and

packaged for use. Example L

High Strength Concentrate

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 99% silica aerogel 0.5% synthetic amorphous silica 0.5%

The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

Example M

Wettable Powder

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 90% dioctyl sodium sulfosuccinate 0.1% synthetic fine silica 9.9% The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged. Example N

Wettable Powder

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 40% sodium ligninsulfonate 20% montmorillonite clay 40%

The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged. Example O

Oil Suspension

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 35% blend of polyalcohol carboxylic 6% esters and oil soluble petroleum

sulfonates

xylene 59%

The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.

Example P

Dust

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 10% attapulgite 10%

Pyrophyllite 80%

The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.

Example Q

Emulsifiable Concentrate

2-[4,6-dimethoxy-2-pyrimidinyl)methyl]-6- methyl-benzoic acid 10% chlorobenzene 84% sorbitan monostearate and polyoxyethylene

condensates thereof 6% The ingredients are combined and stirred to produce a solution which can be emulsified in water for application. Utility

Test results indicate that compounds of this invention are active postemergence and preemergence herbicides. These compounds are useful for the control of selected grass and broadleaf weeds with tolerance to important agronomic crops which include, but are not limited to barley (Hordeum vulgare), corn (Zea mays), cotton (Gossypium hirsutum), and wheat

(Triticum aestivum). Weed species controlled include, but are not limited to cocklebur (Xanthium

pensylvanicum), teaweed (Sida spinosa), and velvetleaf (Abutilon theophrasti).

These compounds also have utility for complete control and/or selected control of vegetation in specified areas such as around storage tanks, parking lots, highways, and railways, and in fallow crop, citrus, and plantation crop areas. Alternatively, these compounds are useful to modify plant growth.

A herbicidally effective amount of the compounds of this invention is determined by a number of

factors. These factors include: formulation

selected, method of application, amount and type of vegetation present, growing conditions, etc. In general terms, a herbicidally effective amount of the compounds of the invention is applied at rates from 0.004 to 20 kg/ha with a preferred rate range of 0.025 to 2 kg/ha. One skilled in the art can easily

determine the application rate needed for the desired level of weed control.

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. Common Name Chemical Name

acetochlor 2-chloro-N-(ethoxymethyl)-N-

(2-ethyl-6-methylphenyl)acetamide acifluorfen 5-[2-chloro-4-(trifluoromethyl)- phenoxy]-2-nitrobenzoic acid acrolein 2-propenal

alachlor 2-chloro-N-(2,6-diethylphenyl)-N- (methoxymethyl)acetamide

anilofos S-4-chloro-N-isopropylcarbaniloyl- methyl-0,0-dimethyl phosphorodithioate

ametryn N-ethyl-N'-(1-methylethyl)-6-

(methylthio)-1,3,5-triazine-2, 4- diamine

amitrole 1H-1,2,4-triazo1-3-amine

AMS ammonium sulfamate

asulam methyl [(4-aminophenyl)sulfonyl]- carbamate

atrazine 6-chloro-N-ethyl-N'-(1-methylethyl)- 1,3,5-triazine-2,4-diamine

barban 4-chloro-2-butynyl 3-chlorocarbamate benefin N-butyl-N-ethyl-2,6-dinitro-4-(tri- fluoromethyl)benzenamine

bensulfuron 2-[[[[[(4,6-dimethoxy-2-pyrimimethyl dinyl)amino]methylcarbonyl]- amino]sulfonyl]methyl]benzoic acid, methyl ester

bensulide 0,0-bis(1-methylethyl) S-[2- [(phenylsulfonyl)amino]- ethyl]phosphorodithioate

bentazon 3-(1-methylethyl)-(1H)-2,1,3- benzothiadiazin-4(3H)-one,

2,2-dioxide

benzofluor N-[4-(ethylthio)-2-(trifluoro- methyl)phenyl]methanesulfonamide Common Name Chemical Name

benzoylprop N-benzoyl-N-(3,4-dichlorophenyl)-DL- alanine

bifenox methyl 5-(2,4-dichlorophenoxy)-2- nitrobenzoate

bromacil 5-bromo-6-methyl-3-(1-methylpropyl)- 2,4(1H,3H)pyrimidinedione

bromoxynil 3,5-dibromo-4-hydroxybenzonitrile butachlor N-(butoxymethyl)-2-chloro-N-(2,6- diethylphenyl) acetamide

buthidazole 3-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-4-hydroxy-1-methyl-2- imidazolidinone

butralin 4-(1,1-dimethylethyl)-N-(1-methylpropyl)-2,6-dinitrobenzenamine butylate S-ethyl bis(2-methylpropyl)- carbamothioate

cacodylic dimethyl arsinic oxide

acid

CDAA 2-chloro-N,N-di-2-propenylacetamide

CDEC 2-chloroallyl diethyldithiocarbamate

CGA 142,464 3-(4,6-dimethoxy-1,3,5-triazin-2-yl)- 1-[2-(2-methoxyethoxy)-phenyl- sulf onyl] -urea

chloramben 3-amino-2,5-dichlorobenzoic acid chlorbromuron 3-(4-bromo-3-chlorophenyl)-1-methoxy-1- methylurea

chlorimuron 2-[[[[(4-chloro-6-methoxy-2-pyrimiethyl dinyl)ethylamino]carbonyl]- amino]sulfonyl]benzoic

acid, ethyl ester

chlormethoxy2,4-dichlorophenyl 4-nitro-3- nil methoxyphenyl ether

chlornitrofen 2,4,6-trichlorophenyl-4-nitro- phenyl ether Common Name Chemical Name

chloroxuron N'-[4-(4-chlorophenoxy)phenyl]-N,N- dimethylurea

chlorpropham 1-methylethyl 3-chlorophenylcarbamate chlorsulfuron 2-chloro-N-[[(4-methoxy-6-methyl-1,3,5- triazin-2-yl)amino]carbonyl]benzene- sulfonamide

chlortoluron N'-(3-chloro-4-methylphehyl)-N,N- dimethylurea

cinmethylin exo-1-methyl-4-(1-methylethyl)-2-[(2- methylphenyl)methoxy]-7-oxabicyclo- [2.2.1]heptane

clethodim (E,E)-(+)-2-[1-[[(3-chloro-2-propenyl)- oxy]imino]propyl]-5-[2-(ethylthio)- propyl]-3-hydroxy-2-cyclohexen-1-one clomazone 2-[(2-chlorophenyl)methyl]-4,4-dimethyl- 3-isoxazolidinone

cloproxydim (E,E)-2-[1-[[(3-chloro-2-propenyl)oxy)- imino]butyl]-5-[2-(ethylthio)propyl]- 3-hydroxy-2-cyclohexen-1-one

clopyralid 3,6-dichloro-2-pyridinecarboxylic acid

CMA calcium salt of MAA

cyanazine 2-[[4-chloro-6-(ethylamino)-1,3,5-tri- azin-2-yl]amino]-2-methylpropanenitrile cycloate S-ethyl cyclohexylethylcarbamothioate cycluron 3-cyclooctyl-1, 1-dimethylurea

cyperquat 1-methyl-4-phenylpyridinium

cyprazine 2-chloro-4-(cyclopropylamino)-6-(iso- propylamino)-s-triazine

cyprazole N-[5-(2-chloro-1,1-dimethylethyl)-1,3,4- thiadiazol-2-yl]cyclopropanecarbox- amide

cypromid 3',4'-dichlorocyclopropanecarboxanilide Common Name Chemical Name

dalapon 2,2-dichloropropanoic acid

dazomet tetrahydro-3,5-dimethyl-2H-1,3,5-thiadiazine-2-thione

DCPA dimethyl 2,3,5,6-tetrachloro-1,4-benzene- dicarboxylate

desmediphan ethyl [3-[[(phenylamino)carbonyl]oxy]- phenyl]carbamate

desmetryn 2-(isopropylamino)-4-(methylamino)-6- (methylthio)-s-triazine

diallate S-(2,3-dichloro-2-propenyl)bis(1- methylethyl)carbamothioate

dicamba 3,6-dichloro-2-methoxybenzoic acid dichlobenil 2,6-dichlorobenzonitrile

dichlorprop (±)-2-(2,4-dichlorophenoxy)propanoic

acid

diclofop- (±)-2-[4-(2,4-dichlorophenoxy)phenoxy]- methyl propanoic acid, methyl ester

diethatyl N-(chloroacetyl)-N-(2,6-diethylphenyl)- glycine

difenzoquat 1,2-dimethyl-3,5-diphenyl-1H-pyrazolium dimepiperate S-1-methyl-1-phenylethylpiperidine- 1-carbothioate

dinitramine N³,N³-diethyl-2,4-dinitro-6-(trifluoro- methyl)-1,3-benzenediamine dinoseb 2-(1-methylpropyl)-4,6-dinitrophenol diphenamid N,N-dimethyl-α-phenylbenzeneacetamide dipropetryn 6-(ethylthio)-N,N'-bis(1-methylethyl)- 1,3,5-triazine-2,4-diamine

diquat 6,7-dihydrodipyrido[1,2-a:2',1'-c]- pyrazinedium ion

diuron N'-(3,4-dichlorophenyl)-N,N-dimethylurea Common Name Chemical Name

DNOC 2-methyl-4,6-dinitrophenol

DSMA disodium salt of MAA

dymron N-(4-methylphenyl)-N'-(1-methyl- 1-phenylethyl)urea

endothall 7-oxabicyclo[2.2.1]heptane-2,3-dicarbox- ylic acid

EPTC S-ethyl dipropylcarbamothioate

esprocarb S-benzyl-N-ethyl-N-(1,2-dimethyl)- (SC2957) propyl)thiolcarbamate

ethalfluralin N-ethyl-N-(2-methyl-2-propenyl)-2,6- dinitro-4-(trifluoromethyl)- benzenamine

ethofumesate (±)-2-ethoxy-2,3-dihydro-3,3-dimethyl- 5-benzofuranyl methanesulfonate fenac 2,3,6-trichlorobenzeneacetic acid fenoxaprop (±)-2-[4-[(6-chloro-2-benzoxazolyl)oxy]- phenoxy]propanoic acid

fenuron N,N-dimethyl-N'-phenylurea

fenuron TCA Salt of fenuron and TCA

flamprop N-benzoyl-N-(3-chloro-4-fluorophenyl)- DL-alanine

fluazifop (±)-2-[4-[[5-(trifluoromethyl)-2-pyridinyl]oxy]phenoxy]propanoic acid fluazifop-P (R)-2-[4-[[5-(trifluoromethyl)-2-pyridinyl]oxy]phenoxy]propanoic acid fluchloralin N-(2-chloroethyl)-2,6-dinitro-N-propyl- 4-(trifluoromethyl)benzenamine

fluometuron N,N-dimethyl-N'-[3-(trifluoromethyl)- phenyl]urea Common Name Chemical Name

fluorochlor- 3-chloro-4-(chloromethyl)-1-[3-(tri- idone fluoromethyl)phenyl]-2-pyrrolidinone fluorodifen p-nitrophenyl α,α,α-trifluoro-2-nitro- p-tolyl ether

fluorogly- carboxymethyl 5-[2-chloro-4-(tri- cofen fluoromethyl)phenoxy]-2-nitrobenzoate fluridone 1-methyl-3-phenyl-5-[3-(trifluoro- methyl)phenyl]-4(IH)-pyridinone fomesafen 5-[2-chloro-4-(trifluoromethyl)phenoxy]- N-(methylsulfonyl)-2-nitrobenzamide fosamine ethyl hydrogen (aminocarbonyl)- phosphate

glyphosate N-(phosphonomethyl)glycine

haloxyfop 2-[4-[[3-chloro-5-(trifluoromethyl)-2- pyridinyl]oxy]phenoxy]propanoic acid hexaflurate potassium hexafluoroarsenate

hexazinone 3-cyclohexyl-6-(dimethylamino)-1-methyl- 1,3,5-triazine-2,4(1H,3H)-dione imazametha- 6-(4-isopropyl-4-methyl-5-oxo-2- benz imidazolin-2-yl)-m-toluic acid,

methyl ester and 6-(4-isopropyl- 4-methyl-5-oxo-2-imidazolin-2-yl)- E-toluic acid, methyl ester

imazapyr (±)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3- pyridinecarboxylic acid

lmazaqum 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3- quinolinecarboxylic acid

imazethapyr (±)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-5- ethyl-3-pyridinecarboxylic acid Common Name Chemical Name

ioxynil 4-hydroxy-3,5-diiodobenzonitrile

isopropalin 4-(1-methylethyl)-2,6-dinitro-N,N- dipropylbenzenamine

isoproturon N-(4-isopropylphenyl)-N',N'-dimethylurea isouron N'-[5-(1,1-dimethylethyl)-3-isoxazolyl]- N,N-dimethylurea

isoxaben N-[3-(1-ethyl-1-methylpropyl)-5- isoxazolyl]-2,6-dimethoxybenzamide karbutilate 3-[[(dimethylamino)carbonyl]amino]- phenyl-(1,1-dimethylethyl)carbamate lactofen (±)-2-ethoxy-1-methyl-2-oxoethyl 5-[2- chloro-4-(trifluoromethyl)phenoxy]- 2-nitrobenzoate

lenacil 3-cyclohexyl-6,7-dihydro-1H-cyclopenta- pyrimidine-2,4(3H,5H)-dione

linuron N'-(3,4-dichlorophenyl)-N-methoxy-N- methylurea

MAA methylarsonic acid

MAMA monoammonium salt of MAA

MCPA (4-chloro-2-methylphenoxy) acetic acid MCPB 4-(4-chloro-2-methylphenoxy)butanoic acid

MON 7200 S,S-dimethyl-2-(difluoromethyl)-4-

(2-methylpropyl)-6-(trifluoromethyl)- 3,5-pyridinedicarbothionate

mecoprop (±)-2-(4-chloro-2-methylphenoxy)- propanoic acid

mefenacet 2-(2-benzothiazolyloxy-N-methyl-N- phenylacetamide

mefluidide N-[2,4-dimethyl-5-[[(trifluoromethyl)- sulfonyl]amino]phenyl]acetamide methal- N-(2-methyl-2-propenyl)-2,6-dinitro-N- propalin propyl-4-(trifluoromethyl)benzenamide Common Name Chemical Name

methabenz- 1,3-dimethyl-3-(2-benzothiazolyl)urea thiazuron

metham methylcarbamodithioic acid

methazole 2-(3,4-dichlorophenyl)-4-methyl-1,2,4- oxadiazolidine-3,5-dione

methoxuron N'-(3-chloro-4-methoxyphenyl)-N,N- dimethylurea

metolachlor 2-chloro-N-(2-ethyl-6-methylphenyl)-N- (2-methoxy-1-methylethyl)acetamide metribuzin 4-amino-6-(1,1-dimethylethyl)-3-(methyl- thio)-1,2,4-triazin-5(4H)-one

metsulfuron 2-[[[[(4-methoxy-6-methyl-1,3,5-tri- methyl azin-2-yl)amino]carbonyl]- amino]sulfonyl]benzoic acid,

methyl ester

MH 1,2-dihydro-3,6-pyridazinedione

molinate S-ethyl hexahydro-1H-azepine-1-carbothioate

monolinuron 3-(p-chlorophenyl)-1-methoxy-1-methyl- urea

monuron N'-(4-chlorophenyl)-N,N-dimethylurea monuron TCA Salt of monuron and TCA

MSMA monosodium salt of MAA

napropamide N,N-diethyl-2-(1-naphthalenyloxy)- propanamide

naptalam 2-[(1-naphthalenylamino)carbonyl]- benzoic acid

neburon 1-butyl-3-(3,4-dichlorophenyl)-1-methyl- urea

nitralin 4-(methylsulfonyl)-2,6-dinitro-N,N- dipropylaniline

nitrofen 2,4-dichloro-1-(4-nitrophenoxy)benzene Common Name Chemical Name

nitrofluorfen 2-chloro-1-(4-nitrophenoxy)-4-(tri- fluoromethyl)benzene

norea N,N-dimethyl-N'-(octahydro-4,7-methano- 1H-inden-5-yl)urea 3aα,- 4α, 5α, 7α, 7aα-isomer

norflurazon 4-chloro-5-(methylamino)-2-[3-(tri- fluoromethyl)phenyl]-3(2H)- pyridazinone

oryzalin 4-(dipropylamino)-3,5-dinitrobenzenesulfonamide

oxadiazon 3-[2,4-dichloro-5-(1-methylethoxy)- phenyl]-5-(1,1-dimethylethyl)- 1,3,4-oxadiazol-2(3H)-one

oxyfluorfen 2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4- (trifluoromethyl)benzene

paraquat 1,1'-dimethyl-4,4'-dipyridinium ion pebulate S-propyl butylethylcarbamothioate pendimethalin N-(1-ethylpropyl)-3,4-dimethyl-2,6- dinitrobenzenamine

perfluidone 1,1,1-trifluoro-N-[2-methyl-4-(phenyl- sulfonyl)phenyl]methanesulfonamide phenmedipham 3-[(methoxycarbonyl)amino]phenyl (3- methylphenyl)carbamate

picloram 4-amino-3,5,6-trichloro-2-pyridine- carboxylic acid

PPG-1013 5-[2-chloro-4-(trifluoromethyl)- phenoxy]-2-nitroacetophenone

oxime-O-acetic acid, methyl ester pretilachlor α-chloro-2,6-diethyl-N-(2-propoxy- ethyl)acetanilide

procyazine 2-[[4-chloro-6-(cyclopropylamino)-1,3,5- triazine-2-yl]amino]-2-methylpropane- nitrile

profluralin N-(cyclopropylmethyl)-2,6-dinitro-N- propyl-4-(trifluoromethyl)benzenamine Common Name Chemical Name

prometon 6-methoxy-N,N'-bis(1-methylethyl)-1,3,5- triazine-2,4-diamine

prometryn N,N'-bis(1-methylethyl)-6-(methylthio)- 1,3,5-triazine-2,4-diamine

pronamide 3,5-dichloro-N-(1,1-dimethyl-2-propynyl)benzamide

propachlor 2-chloro-N-(1-methylethyl)-N- phenylacetamide

propanil N-(3,4-dichlorophenyl)propanamide propazine 6-chloro-N,N'-bis(1-methylethyl)- 1,3,5-triazine-2,4-diamine

propham 1-methylethyl phenylcarbamate

prosulfalin N-[[4-(dipropylamino)-3,5-dinitro- phenyl]sulfonyl]-S,S-dimethylsulfilimine

prynachlor 2-chloro-N-(1-methyl-2-propynyl)acetanilide

pyrazolate 4-(2,4-dichlorobenzoyl)-1,3-dimethyl- pyrazol-5-yl-p-toluenesulphonate pyrazon 5-amino-4-chloro-2-phenyl-3(2H)- pyridazinone

pyrazosulfuron ethyl S-[3-(4,6-dimethoxypyrimidin-2- ethyl yl)ureadosulfonyl]-1-methylpyrazole- 4-carboxylate

quinclorac 3,7-dichloro-8-quinoline carboxylic acid quizalofop (±)-2-[4-[(6-chloro-2-quinoxalinyl)- ethyl oxy]phenoxy]propanoic acid, ethyl

ester

secbumeton N-ethyl-6-methoxy-N'-(1-methylpropyl)- 1,3,5-triazine-2,4-diamine

sethoxydim 2-[1-(ethoxyimino)butyl]-5-[2-(ethyl- thio)propyl]-3-hydroxy-2-cyclohexen- 1-one

siduron N-(2-methylcyclohexyl)-N'-phenylurea Common Name Chemical Name

simazine 6-chloro-N,N'-diethyl-1,3,5-triazine- 2,4-diamine

SK-233 1-(α,α-dimethylbenzyl)-3-(4-methyl- phenyl)urea

sulfometuron 2-[[[[(4,6-dimethyl-2-pyrimidinyl)- methyl amino]carbonyl]amino]sulfonyl]- benzoic acid, methyl ester

TCA trichloroacetic acid

tebuthiuron N-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-N,N'-dimethylurea

terbacil 5-chloro-3-(1,1-dimethylethyl)-6- methyl-2,4(1H,3H)-pyrimidinedione terbuchlor N-(butoxymethyl)-2-chloro-N-[2-(1,1- dimethylethyl)-6-methylphenyl]- acetamide

terbuthyl- 2-(tert-butylamino)-4-chloro-6-(ethyl- azine amino)-s-triazine

terbutol 2,6-di-tert-butyl-p-tolyl methylcarbamate

terbutryn N-(1,1-dimethylethyl)-N'-ethyl-6- (methylthio)-1,3,5-triazine- 2,4-diamine

thifensul3-[[[[(4-methoxy-6-methyl-1,3,5-triazin- furon methyl 2-yl)amino]carbonyl]amino]sulfonyl]- 2-thiophenecarboxylic acid, methyl ester

thiobencarb S-[(4-chlorophenyl)methyl] diethylcarbamothioate

triallate S-(2,3,3-trichloro-2-propenyl) bis(1- methylethyl)carbamothioate

tribenuron 2-[[[[N-(4-methoxy-6-methyl-1,3,5- methyl triazine-2-yl)-N-methylamino]- carbonyl]amino]sulfonyl]benzoic acid, methyl ester Common Name Chemical Name

triclopyr [(3,5,6-trichloro-2-pyridinyl)- oxy]acetic acid

tridiphane 2-(3,5-dichlorophenyl)-2-(2,2,2- trichloroethyl)oxirane

trifluralin 2,6-dinitro-N,N-dipropyl-4-(tri- fluoromethyl)benzenamine

trimeturon 1-(p-chlorophenyl)-2,3,3-trimethylpseudourea

2,4-D (2,4-dichlorophenoxy) acetic acid

2,4-DB 4-(2,4-dichlorophenoxy)butanoic acid vernolate S-propyl dipropylcarbamothioate

xylachlor 2-chloro-N-(2,3 dimethylphenyl)-N- (1-methylethyl)acetamide

Herbicidal properties of the compounds that follow were determined in greenhouse tests. Test results and procedures follow.

TABLE OF COMPOUNDS

SPECTRAL DATA

Compound Data 3 PMR(CDCl₃,90MHz)δ 2.35(s,CH₃,3H),

3.9(s,OCH₃,6H), 4.25(s,CH₂,2H), 5.35(s,OCH₂,2H), 5.85(s,pyrmH,1H), 7.1-7.6 (m, ArH,OH).

10 PMR(CDCl₃,200MHz) δ 3.90(s,CO₂CH₃,3H)

4.00(s,OCH₃,6H), 6.99(S,CHCN,1H), 7.4-8.1(m,ArH,4H).

17 PMR(CDCl₃,200MHz) δ 1.35(t,CH₃,3H),

2.54(s,CH₃,3H), 3.96(s,OCH₃,6H), 4.2-4.4(M,CH₂O,2H), 5.49(s,CH,1H), 6.01(s, pyrmH,1H), 7.2-7.6(m.ArH,4H)

19 PMR(CDCl₃, 200MHz)δ 1.24 (t,CH₃,3H),

3.89(s,OCH₃,6H), 5.08(s,CH,1H), 5.89(s,pyrmH,1H), 7.2-7.6(m.ArH,5H).

20 PMR(CDCl₃, 200MHz) δ 1.24 (t,CH₃,3H),

2.33(s,CH₃,3H), 3.89(s,OCH₃,6H), 4.1(m,OCH₂,2H), 5.05(s,CH₂,1H), 5.89(s,pyrmH,1H), 7.1-7.4(m.ArH,4H) . Compound Data

21 IR (neat) v co 1740cm^-1

22 PMR(CDCL₃, 200MHz) δ 1.23 (t,CH₃, 3H),

2.55(S,CH₃,3H), 4.0(S,OCH₃,3H),

4.2(q,OCH₂,2H), 5.07(s,CH, 1H),

7.2-7.6(m,ArH,5H).

TEST A

Seeds of barley (Hordeum vulgare),

barnyardgrass (Echinochloa crus-galli), cheatgrass (Bromus secalinus), cocklebur (Xanthium

pensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria spp.), bedstraw

(Galium aparine), giant foxtail (Setaria faberii), morningglory (Ipomoea hederacea), rice (Orvza

sativa), sorghum (Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf

(AbutiIon theophrasti), wheat (Triticum aestivum), 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.

TEST B

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 (AbutiIon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), and 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 approximately twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table B, 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.

TEST C

Seeds of barley (Hordeum vulgare),

barnyardgrass (Echinochloa crus-galli), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium pensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass

(Dioitaria spp.), downy brome (Bromus tectorum), giant foxtail (Setaria faberii), green foxtail

(Setaria viridis), jimsonweed (Datura stramonium), johnsongrass (Sorghum halepense), lambsquarters

(Chenopodium album), morningglory (Ipomoea spp.), rape (Brassica napus), rice (Oryza sativa), sicklepod (Cassia obtusifolia), soybean (Glycine max), sugar beet (Beta vulgaris), teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polyoonum convolvulus), and 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 (two to three leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for approximately eighteen to twenty-four days, after which all species were compared to controls and visually evaluated. Plant response ratings,

summarized in Table C, are reported on a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

TEST D

The compound evaluated in this test was

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 (paddy 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 paddy test. Water depth was approximately 2.5 cm for the paddy 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 (Amaranthus

retroflexus), rape (Brassica napus), ryegrass (Lolium multiflorum), sorghum (Sorghum bicolor), soybean

(Glycine max), speedwell (Veronica persica), sugar beet (Beta vulgaris), velvetleaf (AbutiIon

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 postemergence portion of the test. Plant species in the paddy test consisted of barnyardgrass (Echinochloa crus-galli), rice (Oryza sativa), and umbrella sedge (Cyperus difformis). 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 D, were recorded on a zero to ten scale where zero is no injury and ten is plant death. A dash (-) response means no test result.

Claims

CLAIMS What is claimed:

1. A compound of the formula:

wherein

Q is

A is CR², N or N-O;

X is H, F, Cl, CH₃, OH, C(O)NR¹²R¹³, CO₂R¹⁴ or CN;

R¹ is H, CHO, C(OCH₃)₂H, CO₂R⁵ or C(O)SR¹¹;

R² is H, F, Cl, C₁-C₂ alkyl, C₁-C₂-alkoxy,

C₂-C₃ alkynyl, C₂-C₃ alkenyl, S(O)_nC₁-C₂ alkyl, NO₂, phenoxy, C₂-C₄ alkylcarbonyl, C(OCH₃)₂CH₃, or C(SCH₃)₂CH₃;

R³ is C₁-C₂ alkyl, C₁-C₂ alkoxy, OCF₂H or Cl;

R⁴ is C₁-C₂ alkyl;

R⁵ is H; M; C₁-C₃ alkyl; C₂-C₃ haloalkyl;

allyl; propargyl; benzyl optionally

substituted with halogen, C₁-C₂ alkyl, C₁-C₂ alkoxy, CF₃, NO₂, SCH₃, S(O)CH₃, or

S(O)₂CH₃; C₂-C₄ alkoxyalkyl; N=CR⁷R⁸; or CHR⁹S(O)_nR¹⁰;

R⁶ is H, F, Cl, CH₃, OCH₃ or S(O)_nCH₃;

R⁷ is Cl, C₁-C₂ alkyl or SCH₃; R⁸ is C₁-C₂ alkyl, CO₂(C₁-C₂ alkyl) or

C(O)N(CH₃)₂;

R⁹ is H or CH₃;

R¹⁰ is C₁-C₃ alkyl or phenyl optionally substituted with halogen, CH₃, OCH₃ or NO₂;

R¹¹ is C₁-C₂ alkyl or benzyl;

R¹² is H or CH₃;

R¹³ is H or CH₃;

R¹⁴ is H, C₁-C₃ alkyl, C₂-C₅ haloalkyl, C₃-C₅ alkenyl, C₃-C₅ alkynyl, C₂-C₅ alkoxyalkyl or benzyl optionally substituted with CH₃, OCH₃, SCH₃, halogen, NO₂ or CF₃;

m is 0 or 1;

n is 0, 1 or 2;

M is a alkali metal atom or an alkaline earth metal atom, an ammonium group or an alkylammonium group; and

Z is CH or N.

and their agriculturally suitable salts;

provided that:

(a) when R¹ is H, then X is CO₂R¹⁴;

(b) when X is CO₂R¹⁴, then R¹ is H; and. (c) when Z is N, then R³ is C₁-C₂ alkyl or C₁-C₂ alkoxy.

2. The compounds of Claim 1 wherein Q is Q-1 or Q-2.

3. The compounds of Claim 2 wherein

is H, F, Cl, CH₃, SCH₃, OCH₃ or

OCH₂CH₃.

4. The compounds of Claim 3 wherein

R⁶ is H;

Z is CH;

R³ is OCH₃;

R⁴ is CH₃; and

X is H.

5. The compounds of Claim 3 wherein

R⁶ is H or 3-F;

Z is CH;

R³ is OCH₃;

R⁴ is CH₃;

X is CO₂R¹⁴; and

R¹⁴ is C₁-C₃ alkyl, allyl, propargyl or benzyl.

6. The compound of Claim 3 which is 2-[cyano(4,6-dimethoxy-2-pyrimidinyl)methyl]-benzoic acid.

7. The compounds of Claim 4 wherein Q is Q-1;

R¹ is CO₂R⁵; and

R⁵ is H or M.

8. The compounds of Claim 4 wherein Q is Q-2;

R¹ is CO₂R⁵; and

R⁵ is H or M.

9. The compound of Claim 5 which is ethyl 4,6-dimethoxy-alpha-phenyl-2-pyrimidineacetate.

10. The compound of Claim 7 which is

2-[(4,6-dimethoxy-2-pyrimidinyl)methyl]-6-methyl- benzoic acid.

11. The compound of Claim 7 which is

2-[(4,6-dimethoxy-2-pyrimidinyl)methyl]-6-methyl benzoic acid, sodium salt.

12. The compound of Claim 7 which is

2-[(4,6-dimethoxy-2-pyrimidinyl)methyl]-3-pyridine carboxylic acid.

13. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 1 and at least one of the following: surfactant, solid or liquid diluent.

14. A composition suitable for controlling the growth of undesired vegetation which compresses an effective amount of a compound of Claim 2 and at least one of the following: surfactant, solid or liquid diluent.

15. A composition suitable for controlling the growth of undesired vegetation which compresses an effective amount of a compound of Claim 3 and at least one of the following: surfactant, solid or liquid diluent.

16. A composition suitable for controlling the growth of undesired vegetation which compresses an effective amount of a compound of Claim 4 and at least one of the following: surfactant, solid or liquid diluent.

17. A composition suitable for controlling the growth of undesired vegetation which compresses an effective amount of a compound of Claim 5 and at least one of the following: surfactant, solid or liquid diluent.

18. A composition suitable for controlling the growth of undesired vegetation which compresses an effective amount of a compound of Claim 6 and at least one of the following: surfactant, solid or liquid diluent.

19. A composition suitable for controlling the growth of undesired vegetation which compresses an effective amount of a compound of Claim 7 and at least one of the following: surfactant, solid or liquid diluent.

20. A composition suitable for controlling the growth of undesired vegetation which compresses an effective amount of a compound of Claim 8 and at least one of the following: surfactant, solid or liquid diluent.

21. A composition suitable for controlling the growth of undesired vegetation which compresses an effective amount of a compound of Claim 9 and at least one of the following: surfactant, solid or liquid diluent.

22. A composition suitable for controlling the growth of undesired vegetation which compresses an effective amount of a compound of Claim 10 and at least one of the following: surfactant, solid or liquid diluent.

23. A composition suitable for controlling the growth of undesired vegetation which compresses an effective amount of a compound of Claim 11 and at least one of the following: surfactant, solid or liquid diluent.

24. A composition suitable for controlling the growth of undesired vegetation which compresses an effective amount of a compound of Claim 12 and at least one of the following: surfactant, solid or liquid diluent.

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

26. A method for controlling the growth of undesired vegetation which compresses applying to the locus to be protected an effective amount of a compound of Claim 2.

27. A method for controlling the growth of undesired vegetation which compresses applying to the locus to be protected an effective amount of a compound of Claim 3.

28. A method for controlling the growth of undesired vegetation which compresses applying to the locus to be protected an effective amount of a compound of Claim 4.

29. A method for controlling the growth of undesired vegetation which compresses applying to the locus to be protected an effective amount of a compound of Claim 5.

30. A method for controlling the growth of undesired vegetation which compresses applying to the locus to be protected an effective amount of a compound of Claim 6.

31. A method for controlling the growth of undesired vegetation which compresses applying to the locus to be protected an effective amount of a compound of Claim 7.

32. A method for controlling the growth of undesired vegetation which compresses applying to the locus to be protected an effective amount of a compound of Claim 8.

33. A method for controlling the growth of undesired vegetation which compresses applying to the locus to be protected an effective amount of a compound of Claim 9.

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

35. A method for controlling the growth of undesired vegetation which compresses applying to the locus to be protected an effective amount of a compound of Claim 11.

36. A method for controlling the growth of undesired vegetation which compresses applying to the locus to be protected an effective amount of a compound of Claim 12.