WO1990003731A1

WO1990003731A1 - Herbicidal phosphorylaminophenyl-substituted heterocycles

Info

Publication number: WO1990003731A1
Application number: PCT/US1989/004542
Authority: WO
Inventors: George Theodoridis
Original assignee: Fmc Corporation
Priority date: 1988-10-14
Filing date: 1989-10-10
Publication date: 1990-04-19
Also published as: KR900701164A; IL91894A0

Abstract

The present application discloses herbicidal phosphorylaminophenyl-substituted heterocycles, compositions of them, methods of preparing them, and methods for controlling undesired plant growth by preemergence or postemergence application of the herbicidal compositions to the locus where control is desired. The herbicidal compounds are compounds of formula (I), in which Q is selected from α, β, γ, δ; X and Y are independently F, Cl, or Br; R is lower alkyl or lower haloalkyl; R1 is selected from lower alkyl, lower haloalkyl, cycloalkyl of 3 to 7 ring carbon atoms, lower alkenyl, lower haloalkenyl, lower alkynyl, lower haloalkynyl, and benzyl which is unsubstituted or substituted on the phenyl ring with one or more substituents selected from halogen, lower alkyl, lower alkoxy, lower alkoxycarbonyl, cyano, and nitro; R2 is independently selected from among -OR1 or is hydroxy, amino, lower alkylamino, or lower dialkylamino; R3 is H, lower alkyl, or lower alkenyl; or a base addition salt of the compound as defined above in which R2 is hydroxy.

Description

HERBIClDAL PHOSPHORYLAMl NOPHENYL-SUBSTlTUTED

HETEROCYCLES

The invention described in this application pertains to weed control in agriculture, horticulture, and other fields where there is a desire to control unwanted plant growth. More specifically, the present application describes certain herbicidal phosphorylaminophenyl-substituted heterocycles, compositions of them, methods of preparing them, and methods for controlling undesired plant growth by preemergence or postemergence application of the herbicidal compositions to the locus where control is desired. The present compounds may be used to effectively control a variety of both grassy and broadleaf plant species.

U.S. Patent 4,613,675 discloses, as intermediates for herbicidal compounds, aryltetrahydrophthalimides of the formula

in which each of X and Y is independently hydrogen or halogen, M is oxygen, sulfur, sulfinyl, sulfonyl, or N-R, each of R and R¹ is independently hydrogen or lower alkyl, R⁹ is lower alkyl, and R³ is lower alkyl, alkoxyalkyl, or alkoxycarbonylalkyl.

Japanese Kokai 61-103,887, published May 22, 1986, discloses (as reported in Derwent Abstracts, accession No. 86-172208/27) herbicidal compounds of the formula

in which X is chlorine or bromine and R¹ and R² are independently 1-4C alkyl.

Japanese Kokai 60-246,392, published December 6, 1985, discloses (as reported in Chemical Abstracts, 104, 149,169k, 1986) herbicidal compounds of the formula

in which R is hydrogen or fluorine, R ¹ is chlorine or bromine, and R² and R³ are chlorine, hydroxy, alkyl, alkoxy, alkenyloxy, or alkylamino.

Japanese Kokai 60-228,494, published November 13, 1985, discloses (as reported in Derwent Abstracts, accession No. 86-003058/01) herbicidal compounds of the formula

in which X is hydrogen, fluorine, or chlorine, Y is chlorine or bromine, and R is hydrogen or 1-4C alkyl.

Japanese Kokai 59-033,293, published February 23, 1984, discloses (as reported in Derwent Abstracts, accession No. 84-084464/14) herbicidal compounds of the formula

in which X is oxygen or sulfur, Y is oxygen, sulfur, or amino, Z is halogen, R¹ is alkyl or alkoxyalkoxyalkyl, and R², is alkyl, alkoxy, haloalkyl, alkoxyalkoxyalkoxy, or phenyl.

The herbicidal compounds of the present invention are compounds of the formula

in which:

Q is selected from

X and Y are independently F, Cl, or Br,

R¹ is selected from lower alkyl (e.g. -CH₃ or -CH(CH₃)CH₂CH₃), lower haloalkyl (e.g. -CH₂CH₂CI), cycloalkyl of 3 to 7 ring carbon atoms (e.g. cyclopentyl), lower alkenyl (e.g. -CH₂CH=CE₂), lower haloalkenyl (e.g. -CH₂C(Cl)=CH₂), lower alkynyl (e.g. -CH₂C≡CH), lower haloalkynyl (e.g. -CE₂C≡CBr), and benzyl which may be substituted on the phenylring with one or more substituents selected from halogen, lower alkyl, lower alkoxy, lower alkoxycarbonyl, cyano, and nitro;

R² is independently selected from among -OR¹

or is hydroxy, amino, lower alkylamino (e.g. -NHC₂H₅), or lower dialkylamino (e.g. -N(CH₃)C₂H₅);

R³ is hydrogen, alkyl (e.g., lower alkyl such as -CH₃), or alkenyl (e.g., lower alkenyl such as -CH₂CH=CH₂); and

R is lower alkyl (e.g. -CH₃) or lower haloalkyl (e.g. -CHF₂ or

-CH₂CH₂CH₂F); or

a base addition salt of the compound as defined above in which R² is hydroxy.

It is often preferable that any alkyl group or alkyl portion of any group herein have 1-6 carbon atoms and that any alkenyl or alkynyl group or alkenyl or alkynyl portion of any group herein have 3-6 carbon atoms.

The substituent X is advantageously F or Cl, preferably F. Y is preferably Cl or Br, more preferably Cl. In preferred embodiments X is F and Y is Cl, X is F and Y is Br, or X and Y are both Cl.

Compounds in which R² is hydroxy are acidic and form herbicidal base addition salts upon treatment with a base. Typical cations of such salts include sodium, potassium, calcium, ammonium, magnesium, and mono-, di- , and tri (C₁-C₄ alkyl) ammonium, sulfonium, or sulfoxonium ions.

When Q is (a) or (b), the R substituent is preferably a lower haloalkyl group, e.g., a lower fluoroalkyl group such as CHF₂ or CH₂CH₂CH₂F; however, when Q is (d), the R substituent is preferably lower alkyl, e.g., CH(CH₃)₂.

The compounds of this invention may be prepared by the use of steps generally described in the literature or by methods analogous or similar thereto and within the skill of the art.

Intermediates useful in the preparation of the compounds of this invention are compounds of the general formula

in which X, Y, and Q are as defined above.

Intermediate amino compounds II may be converted into final products I by known general methods, for example by a method similar to that described by R.M. Caven, J. Chem. Soc. 81, 1362 (1902). For example, II may be treated with a phosphoryl dihalide containing the R ² group (or -OR¹ group), in the presence of a base (e.g. triethylamine) to produce a halophosphoramide derivative of II, followed by reaction with R ¹-OH (or R²H) in the presence of a base to give final product I, where R³ is H, as illustrated in the following chemical equations:

A particularly useful alternative method for producing the products of formula I in which R² is the same as OR and R³ is H comprises reacting the amine intermediate (II) with a phosphorus oxyhalide, such as POCl₃, followed by treatment of the resulting dihalophosphoramide derivative with at least 2 equivalents of R ¹-OH in the presence of a base (e.g. NaHCO₃). The compounds in which R³ is alkyl or alkenyl may be prepared by alkylating or alkenylating the corresponding compounds in which R³ is H, for example, by treating the compound in which R³ is H with a base (such as sodium hydride) in the presence of an inert solvent (such as

dimethylformamide) followed by treatment with R ³-Z in which Z is good leaving group (such as Cl, Br, or I).

The intermediates of general formula II in which Q is (a) include a number of previously described compounds which may be prepared by methods disclosed in the art for those known compounds or by methods analogous thereto. For example, Example 1 of PCT Patent Application Publication No. WO87/03782, published July 2, 1987, describes the preparation of the compound of formula II above in which X is F, Y is Cl, and R is CHF₂, Example 8 describes the preparation of the corresponding compound in which Y is Br, Example 11 describes preparation of the compound in which X is F, Y is Cl, and R is CH₃, and Example 13 describes preparation of the compound in which X and Y are each Cl and R is CHF₂.

The intermediates of general formula II in which Q is (b) include a number of previously described compounds which may be prepared by methods disclosed in the art for those known compounds or by methods analogous thereto. For example, Example 1 of PCT Patent Application Publication No. WO87/03873, published July 2, 1987, describes the preparation of the compound of formula II above in which X is F, Y is Cl, and R is CH₂CH₂CH₂F. The preparation of other compounds of formula II is discussed in PCT Patent Application Publication No. WO85/01939, published May 9, 1985. The disclosures of WO85/01939 and WO87/03873 are incorporated herein by reference.

The intermediates of formula II in which Q is (c) may be prepared as illustrated in the following chemical equations:

The appropriate 2,4-dihalophenylamine may be combined with tetrahydrophthalic anhydride to give the corresponding 2,4- dihalophenyltetrahydrophthalimide IN. The C-5 amino group may be introduced by nitration (H₂SO₄/ΗΝO₃) to give the corresponding 5-NO₂ compound V, followed by reduction of the NO₂ group (FGICH₃CO₂H) to give the 5-NH₂ compound II. The NO2 reduction with Fe/CH₃QCO₂H is disclosed in Japan Patent Publication No. 59-067,261, published April 16, 1984 for the compounds in which X is F and Y is respectively Cl and Br. The 5-NO₂ compound V may also be made directly by reaction of the appropriate 2,4-dihalo-5-nitrophenylamino with tetrahydrophthalic anhydride.

The intermediates of formula II in which Q is (d) may be prepared by the method illustrated in the following chemical equations:

A 2,4-dihaloaniline is treated first with trichloromethyl chloroformate in toluene, then with glycine ethyl ester hydrochloride and triethylamine in chloroform to give ethyl 2,4-dihalophenylaminocarbonylaminoacetate (VI). Treatment of (VI) with R-X¹ (X¹ is a leaving group such as Cl, Br, I, or OSO₂CH₃) and a base (e.g., sodium hydride) forms the 3-(2,4- dihalophenyl)-1-(alkyl or haloalkyl)hydantoin (Vll). Nitration of (Vll) with sulfuric acid and nitric acid produces the 3-(2,4-dihalo-5-nitrophenyl)-1- (alkyl or haloalkyl)hydantoin (VIII). Treatment of (NIII) with iron powder and acetic acid in water produces the corresponding 3-(5-amino-2,4- dihalophenyl)-1-(alkyl or haloalkyl)hydantoin [ll(d)].

Representative compounds of this invention are shown in Tables 1-4. Preparation of the compounds of this invention is further illustrated in the following Examples. EXAMPLE 1

1-[4-CHLORO-2-FLUORO-5-(O,O-DIETHYLPHOSPHORYLAMINO)

PHENYL]-4-DEFLUOROMETHYL-4,5-DLHYDRO-3-METHYL-

1,2,4-TRIAZOL-5( 1H)-ONE

A stirred mixture of 1.0 g (0.0041 mole) of 1-(5-amino-4-chloro-2- fluorophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl- 1,2,4-triazol-5( 1H)- one in 10 mL of phosphorus oxychloride was heated at reflux for

approximately 18 hours. The reaction mixture was cooled, and the excess phosphorus oxychloride was removed by distillation under reduced pressure, leaving an oil. The oil was dissolved in approximately 10 mL of ethanol, and solid sodium bicarbonate was added until a neutral mixture was obtained. The mixture was filtered, and the filtrate was evaporated under reduced pressure leaving a residue. The residue was purified first by column chromatography on silica gel, eluting with methylene chloride:acetone

(80:20), then by recrystallization from n-heptane:ethyl acetate (95:5) to give 0.25 g of 1-[4-chloro-2-fluoro-5-(0,0-diethylphosphorylamino)phenyl]-4- difluoromethyl-4,5-dihydro-3-methyl- 1,2,4-triazol-5(1H)-one, m.p. 96-97°C, compound la of Table 1 below.

The nmr and ir spectra were consistent with the proposed structure.

EXAMPLE 2

1-[4-CHLORO-2-FLUORO-5-(O,O-DIMETHYLPHOSPHORYL- AMINO)PHENYL]-4-DIFLUOROMETHYL-4,5- DIHYDRO-3-METHYL- 1,2,4-TRIAZOL-5(1H)-ONE

In a manner similar to that described in Example 1, treatment of 1-(5- amino-4-chloro-2-fluorophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl- 1,2,4-triazol-5(1H)-one with phosphorus oxychloride, followed by treatment with methanol produced the desired product, m.p. 134-136°C, compound d 2a of Table 1 below.

The nmr and ir spectra were consistent with the proposed structure.

EXAMPLE 3

1-[2,4-DICHLORO-5-(O,O-DIMETHYLPHOSPHORYLAMINO)-

PHENYL]-4-(3-FLUOROPROPYL)-1,4-DIHYDRO-5H- TETRAZOL-5-ONE

A stirred mixture of 2.0 g (0.0065 mole) of l-(5-amino-2,4- dichlorophenyl)-4-(3-fluoropropyl)-1,4-dihydro-5H-tetrazol-5-one in 25 mL of phosphorus oxychloride was heated at reflux for approximately 18 hours. The reaction mixture was cooled, and the excess phosphorus oxychloride was removed by distillation under reduced pressure, leaving an oil. The oil was dissolved in 50 mL of methanol, and solid sodium bicarbonate was added until a neutral mixture was obtained. The mixture was stirred at room temperature for approximately 18 hours, then was heated at reflux for one hour. The mixture was cooled and filtered, and the filtrate was evaporated under reduced pressure leaving a solid. This solid was purified by column chromatography on silica gel, eluting with methylene chloride:acetone (80:20), to give 1.5 g of 1-[2,4-dichloro-5-(0,0- dimethylphosphorylamino)phenyl]-4-(3-fluoropropyl)-1,4-dihydro-5H- tetrazol-5-one, m.p. 96-99°C, compound lb of Table 2 below.

The nmr and ir spectra were consistent with the proposed structure. The corresponding diethyl ester (R² = OR¹ = OC₂H₅) was prepared in a similar manner (using ethanol in place of methanol in the last step), mp 79- 82°C, compound 2b of Table 2. The ir and nmr spectra were consistent with the proposed structure. EXAMPLE 4

1-[4-CHLORO-2-FLUORO-5-(O,O-DIMETHYLPHOSPHORYLAMINO)- PHENYL]-3,4,5,6-TETRAHYDROPHTHALIMIDE A stirred mixture of 2.0 g (0.0068 mole) of 1-(5-amino-4-chloro-2- fluorophenyl)-3,4,5,6-tetrahydrophthalimide in 25 mL of phosphorus oxychloride was heated at reflux for approximately 18 hours. The reaction mixture was cooled, and the excess phosphorus oxychloride was removed by distillation under reduced pressure, leaving an oil. The oil was dissolved in 50 mL of methanol, and solid sodium bicarbonate was added until a neutral mixture was obtained. The mixture was stirred at room temperature for approximately 18 hours, then was heated at reflux for one hour. The mixture was cooled and filtered, and the filtrate was evaporated under reduced pressure leaving a solid. This solid was purified by column chromatography on silica gel, eluting with methylene chloride :acetone (80:20), to give 1.1 g of 1-[4-chloro-2-fluoro-5-(0,0-dimethylphosphorylamino)phenyl]-3,4,5,6- tetrahydrophthalimide, m.p. 158-161°C, compound lc of Table 3 below.

The nmr and ir spectra were consistent with the proposed structure.

The corresponding diethyl ester (R² = OR¹ = OC₂H₅) was prepared in a similar manner (using ethanol in place of methanol in the last step), mp

123-124°C, compound 2c of Table 3. The ir and nmr spectra were consistent with the proposed structure.

EXAMPLE 5

3-[4-CHLORO-2-FLUORO-5-(O,O-DIMETHYLPHOSPHORYLAMINO)- PHENYL]-1-(1-METHYLETHYL)HYDANTOIN Step A Ethyl 4-Chloro-2-fluorophenylaminocarbonylaminoacetate

To a stirred solution of 20.0 g (0.137 mole) of 4-chloro-2-fluoroaniline in 300 mL of toluene was slowly added 16.2 g (0.082 mole) of

trichloromethyl chloroformate. The reaction mixture was heated at reflux for approximately 18 hours. The mixture was cooled, and the solvent was removed by distillation under reduced pressure leaving an oil. The oil was dissolved in 100 mL of chloroform, and 20.6 g.(0.15 mole) of glycine ethyl ester hydrochloride was added. Triethylamine (15.2 g, 0.15 mole) was added slowly, and the resultant mixture was stirred at room temperature for two hours. The reaction mixture was diluted with 300 mL of n-heptane and 100 mL of water, resulting in the formation of a precipitate. The precipitate was collected by filtration to give 36.4 g of ethyl 4-chloro-2- fluoropheπylaminocarbonylaminoacetate, m.p. 125-129°C Step B 3-(4-Chloro-2-fluorophenyl)-1-(1-methylethyl)hydantoin

A solution of 10.0 g (0.036 mole) of ethyl 4-chloro-2-fluorophenylaminocarbonylaminoacetate in 100 mL of N,N-dimethylformamide was added slowly to a stirred mixture of 2.0 g (0.044 mole) of sodium hydride in 125 mL of N,N-dimethylformamide. The mixture was stirred at 0°C for one hour, and then 7.1 g (0.040 mole) of 2-iodopropane was added. The resultant mixture was allowed to warm to room temperature and was stirred for approximately 18 hours and then was heated at 60°C for approximately four hours. The reaction mixture was cooled and poured into ice water. The aqueous mixture was acidified with dilute hydrochloric acid, then was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, filtered, and the filtrate evaporated under reduced pressure leaving a residue. The residue was purified by column

chromatography on.silica gel, eluting with ethyl acetate:n-heptane (30:70), to give 4.1 g of 3-(4-chloro-2-fluorophenyl)-1-(1-methylethyl)hydantoin as an oil.

Step C 3-(4-Chloro-2-fluoro-5-nitrophenyl)-1-(1-methylethyl)hydantoin The nitration of 1.0 g (0.037 mole) of 3-(4-chloro-2-fluorophenyl)-1-(1- methylethyl)hydantoin with 0.33 g (0.037 mole) of nitric acid in 6 mL of sulfuric acid produced 1.0 g of 3-(4-chloro-2-fluoro-5-nitrophenyl)-1-(1- methylethyl)hydantoin.

This reaction was repeated on a larger scale to produce an additional 3.4 g of 3-(4-chloro-2-fluoro-5-nitrophenyl)-1-(1-methylethyl)hydantoin.

Step D 3-(5-Amino-4-chloro-2-fluorophenyl)-1-(1- methylethyl)hydantoin

To a stirred mixture of 4.4 g (0.014 mole) of 3-(4-chloro-2-fluoro-5- nitrophenyl)-1-(1-methylethyl)hydantoin in 70 mL of acetic acid and 10 mL of water was added slowly 4.5 g (0.083 mole) of iron powder. The reaction mixture was heated briefly at 50°C, then was cooled to room temperature and was stirred for 0.5 hour. The mixture was diluted with diethyl ether and was filtered through a pad of Celite^R filter aid. The filter pad was rinsed with diethyl ether. The filtrate, containing the diethyl ether wash, was transferred to a separatory funnel and was washed with water and an aqueous dilute sodium bicarbonate solution. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate evaporated underreduced pressure to give 3.0 g of 3-(5-amino-4-chloro-2-fluorophenyl)-1-(1- methylethyl)hydantoin.

The nmr and ir spectra were consistent with the proposed structure.

Step E 3-[4-Chloro-2-fluoro-5-(O,O-dimethyl- phosphorylamino)phenyl]-1-(1-methylethyl)hydantoin

A stirred mixture of 1.45 g (0.00508 mole) of 3-(5-amino-4-chloro-2- fluorophenyl)-1-(1-methylethyl)hydantoin in 16 mL of phosphorus oxychloride was heated at reflux for approximately 18 hours. The reaction mixture was cooled, and the excess phosphorus oxychloride was removed by distillation under reduced pressure, leaving an oil. This oil was dissolved in 50 mL of methanol. Solid sodium bicarbonate was added until a neutral mixture was obtained. The mixture was stirred at room temperature for approximately 18 hours, then was heated at 50°C for two hours. The mixture was cooled, filtered, and the filtrate evaporated under reduced pressure leaving a solid. The solid was purified by column chromatography on silica gel, eluting with methylene chloride:acetone (80:20), to give 0.9 g of 3-[4- chloro-2-fluoro-5-(O,O-dimethylphosphorylamino)phenyl]-1-(1- methylethyl)hydantoin as an oil, compound Id of Table 4.

The nmr and ir spectra were consistent with the proposed structure.

EXAMPLE 6

3-[4-CHLORO-2-FLUORO-5-(O,O-DIETHYL-

PHOSPHORYLAMINO)PHENYL]-1-(1-METHYLETHYL)HYDANTOIN

In a manner similar to that of Step E of Example 5, the reaction of 1.45 g (0.00508 mole) of 3-(5-amino-4-chloro-2-fluorophenyl)-1-(1-methyl- ethyl)hydantoin with 15 mL of phosphorus oxychloride, followed by dissolution of the residual oil in 50 mL of absolute ethanol and treatment with solid sodium bicarbonate produced 1.0 g of 3-[4-chloro-2-fluoro-5- (O,O-diethylphosphorylamino)phenyl]-1-(1-methylethyl)hydantoin as an oil, compound 2d of Table 4.

The nmr and ir spectra were consistent with the proposed structure.

EXAMPLE 7

3-[4-CHLORO-2-FLUORO-5-(O,O-DIMETHYLPHOSPHORYLAMINO)- PHENYL]-1-(3-FLUOROPROPYL)HYDANTOIN

Step A Ethyl 4-Chloro-2-fluorophenylaminocarbonylaminoacetate To a stirred solution of 20.0 g (0.137 mole) of 4-chloro-2-fluoroaniline in 300 mL of toluene was slowly added 16.2 g (0.082 mole) of

trichloromethyl chloroformate. The reaction mixture was heated at reflux for approximately 18 hours. The mixture was cooled, and the solvent was removed by distillation under reduced pressure leaving an oil. The oil was dissolved in 100 mL of chloroform, and 20.6 g (0.15 mole) of glycine ethyl ester hydrochloride was added. Triethylamine (15.2 g, 0.15 mole) was added slowly, and the resultant mixture was stirred at room temperature for two hours. The reaction mixture was diluted with 300 mL of n-heptane and 100 mL of water, causing a precipitate to form. The precipitate was collected by filtration to give 36.4 g of ethyl 4-chloro-2-fluorophenylamino- carbonylaminoacetate, m.p. 125-129°C

Step B 3-(4-Chloro-2-fluorophenyl)-1-(3-fluoropropyl)hydantoin A solution of 15.0 g (0.055 mole) of ethyl 4-chloro-2-fluorophenylaminocarbonylaminoacetate in 40 mL of N,N-dimethylformamide was added slowly to a stirred mixture of 1.4 g (0.058 mole) of sodium hydride in 30 mL of N,N-dimethylformamide. The mixture was stirred at room temperature for four hours, then 10.3 g (0.066 mole) of 3-fluoropropyl methanesulfonate was added. The resultant mixture was heated at 80°C for approximately 18 hours. The reaction mixture was then cooled, poured into ice water, and the aqueous mixture was extracted with diethyl ether. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated under reduced pressure, leaving a residue. The residue was purified by column chromatography on silica gel, eluting with methylene chloride, to give 7.5 g of 3-(4-chloro-2-fluorophenyl)-1-(3- fluoropropyl)hydantoin as an oil. Step C 3-(4-Chloro-2-fluoro-5-nitrophenyl)-1-(3- fluoropropyl)hydantoin

Nitration of 7.5 g (0.026 mole) of 3-(4-chloro-2-fiuorophenyl)-1-(3- fluoropropyl)hydantoin with 2.4 g (0.026 mole) of nitric acid in 30 mL of sulfuric acid produced 6.0 g of 3-(4-chloro-2-fluoro-5-nitrophenyl)-1-(3- fluoropropyl)hydantoin as an oil.

Step D 3-(5-Amino-4-chloro-2-fiuorophenyl)-1-(3-fluoropropyl)- hydantoin

To a stirred mixture of 6.0 g (0.018 mole) of 3-(4-chloro-2-fluoro-5- nitrophenyl)-1-(3-fluoropropyl)hydantoin in 40 mL of acetic acid and 5 mL of water was added slowly 6.0 g (0.11 mole) of iron powder. The reaction mixture was stirred at 35 °C for two hours. The mixture was filtered throughh a pad of Celite^R filter aid, and the filter pad was rinsed with diethyl ether. The filtrate and washings were combined, transferred to a separatory funnel, and extracted with three 200 mL portions of water. The organic phase was dried over anhydrous magnesium sulfate and was filtered. The filtrate was evaporated under reduced pressure to give 3.4 g of 3-(5-amino-4-chloro-2- fluorophenyl)-1-(3-fluoropropyl)hydantoin as a solid, m.p. 89-91°C.

Step E 3-[4-Chloro-2-fluoro-5-(O,O-dimethylphosphorylamino)- phenyl]-1-(3-fluoropropyl)hydantoin

A stirred mixture of 1.6 g (0.0051 mole) of 3-(5-amino-4-chloro-2- fluorophenyl)-1-(3-fluoropropyl)hydantoin in 20 mL of phosphorus oxychloride was heated at reflux for approximately 18 hours. The reaction mixture was cooled, and the excess phosphorus oxychloride was removed by distillation under reduced pressure, leaving an oil. The oil was dissolved in 40 mL of methanol and solid sodium bicarbonate was added until a neutral mixture was obtained. The mixture was stirred at room temperature for approximately 18 hours, then was heated at reflux for one hour. The mixture was cooled and filtered, and the filtrate was evaporated under reduced pressure leaving an oil. The oil was purified by column chromatography on silica gel, eluting with methylene chloride:acetone (80:20), to give 1.2 g of 3- [4-chloroo2-fluoro-5-(O,O-dimethylphosphorylamino)phenyl]-1-(3-fluoro- propyl)hydantoin as an oil, compound 3d of Table 4.

The nmr and ir spectra were consistent with the proposed structure. HERBICIDAL ACTIVITY

The plant test species used in demonstrating the herbicidal activity of compounds of this invention include cotton (Gossypium hirsutum var.

DPLGI), soybean (Glycine max var. Williams), field corn (Zea mays var. Pioneer 3732), wheat (Triticum aestivium var. Wheaton), rice (Oryza sativa var. Labelle), momingglory (Ipomea lacumosa or Ipomea hederacea), wild mustard (Brassica kaber), velvetleaf (Abutilon theophrasti), bamyardgrass (Echinochloa crus-galli), green foxtail (Setaria viridis),and johnsongrass (Sorghum halepense).

Preparation of Flats

Preemergence:

Two disposable fiber flats (8 cm x 15 cm x 25 cm) for each rate of application for each candidate herbicide for preemergence testing are filled to an approximate depth of 6.5 cm with steam sterilized sandy loam soil. The soil is leveled and impressed with a template to provide six evenly spaced furrows 13 cm long and 0.5 cm deep in each flat. Seeds of cotton, soybean, corn, rice and wheat are planted in five of the furrows of the first flat (the sixth furrow is left unplanted), and seeds of wild mustard, momingglory, velvetleaf, bamyardgrass, green foxtail, and johnsongrass are planted in the six furrows of the second flat. The template is again employed to firmly press the seeds into place. A topping soil of equal portions of sand and sandy loam soil is placed uniformly on top of each flat to a depth of approximately 0.5 cm. The flats are first watered, then sprayed with a solution of test compound as described below.

Postemergence:

Two flats for each rate of application for each herbicide candidate are also prepared for postemergence application. The postemergence flats are prepared in the same manner as discussed above for the preemergence flats. The prepared flats are watered for 8-11 days, then the foliage of the emerged tests plants is sprayed with a solution of test compound as described below. Application of Herbicides

In both the preemergence and postemergence tests, the candidate herbicides are applied as aqueous acetone solutions, usually at rates equivalent to 8.0 kilograms/hectare (kg/ha) and/or submultiples thereof, i.e., 4.0 kg/ha, 2.0 kg/ha, and so on.

The four flats (2 preemergence, 2 postemergence) are placed together and sprayed with 30 mL of test solution containing an appropriate amount of the test compound, i.e., approximately 7.5 mL of the test solution is sprayed on each of the four flats. Preemergence applications are made as sprays to the soil surface. Postemergence applications are made as sprays to the foliage. After treatment, the two preemergence flats are watered regularly at the soil surface for approximately 2 weeks, at which time phytotoxicity data are recorded. In the postemergence test the foliage is kept dry for 24 hours after treatment, then watered regularly for approximately 2 weeks, and phytotoxicity data recorded.

Preparation of Test Solutions

For flats of the size described above, an application rate of 8.0 kg/ha of active ingredient is equivalent to 0.06 g of active ingredient/flat (0.24 g/4 flats). A stock solution of 0.48 g of the candidate herbicide in 60 mL of a 50:50 mixture of water and acetone containing 0.5% (v/v) of sorbitan monolaurate emulsifier/solubilizer is divided into two 30 mL portions, each containing 0.24 g of the candidate herbicide. For the 8.0 kg/ha application, one of the 30 mL portions is sprayed undiluted onto the four flats (7.5 mL/flat). The remaining 30 mL portion of the stock solution is diluted with an additional 30 mL of the aqueous acetone/emulsifier mixture to provide 60 mL of a solution containing 0.24 g of candidate herbicide. As above, this solution is divided into two 30 mL portions, each containing 0.12 g of candidate herbicide. One of the 30 mL portions is applied, without further dilution, to the four flats for the 4.0 kg/ha rate. The remaining 30 mL portion is further diluted with an equal amount of aqueous acetone/emulsifier mixture, and the resulting 60 mL solution of 0.12 g candidate herbicide is divided into two 30 mL portions each containing 0.06 g of candidate herbicide. One of the 30 mL (0.06 g active) portions is used for the 2.0 kg/ha application rate and the other is used in the preparation of lower rate test solutions by the same serial dilution technique.

Phytotoxicity data are taken as percent control. Percent control is determined by a method similar to the 0 to 100 rating system disclosed in "Research Methods in Weed Science," 2nd ed., B. Truelove, Ed.; Southern Weed Science Society; Auburn University, Auburn, Alabama, 1977. The rating system is as follows:

For herbicidal application, the active compounds are formulated into herbicidal compositions by admixture in herbicidally effective amounts with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the material in a given application. Thus, for agricultural use the present herbicidal compounds may be formulated as granules of relatively large particle size, as water-soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.

These herbicidal compositions may be applied either as water-diluted sprays, or dusts, or granules to the areas in which suppression of vegetation is desired. These formulations may contain as little as 0.1%, 0.2% or 0.5% to as much as 95% or more by weight of active ingredient.

Dusts are free flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful herein is one containing 1.0 part or less of the herbicidal compound and 99.0 parts of talc.

Wettable powders, also useful formulations for both pre- and postemergence herbicides, are in the form of finely divided particles which disperse readily in water or other dispersant. The wettable powder is ultimately applied to the soil either as a dry dust or as an emulsion in water or other liquid. Typical earners for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents. Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion. For example, a useful wettable powder formulation contains 80.8 parts of the herbicidal compound 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. Other wettable powder formulations are:

Component: % by Wt.

Active ingredient 40.00

Sodium lignosulfonate 20.00

Attapulgite clay. 40.00

Total 100.00

Component: % by Wt.

Active ingredient 90.00

Dioctyl sodium sulfosuccinate 0.10

Synthetic fine silica 9.90

Total 100.00

Component: % by Wt.

Active ingredient 20.00

Sodium alkylnaphthalenesulfonate 4.00

Sodium lignosulfonate 4.00

Low viscosity methyl cellulose 3.00

Attapulgite clay 69.00

Total 100.00 Component: % by Wt.

Active ingredient 25.00

Base: 75.00

96% hydrated aluminum magnesium silicate

2% powdered sodium lignosulfonate

2% powdered anionic sodium alkyl- naphthalenesulfonate

Total 100.00 Frequently, additional wetting agent and/or oil will be added to the tank-mix for postemergence application to facilitate dispersion on the foliage and absorption by the plant.

Other useful formulations for herbicidal applications are emulsifϊable concentrates (ECs) which are homogeneous liquid or paste compositions dispersible in water or other dispersant, and may consist entirely of the herbicidal compound and a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvent. For herbicidal application these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the herbicidal composition.

The following are specific examples of emulsifiable concentrate formulations: Component: % by Wt.

Active ingredient 53.01

Blend of alkylnaphthalenesulfonate

and polyoxyethylene ethers 6.00

Epoxidized soybean oil 1.00

Xylene 39.99

Total 100.00

Component: % by Wt.

Active ingredient 10.00

Blend of alkylnaphthalenesulfonate

and polyoxyethylene ethers 4.00

Xylene 86.00

Total 100.00

Flowable formulations are similar to ECs except that the active ingredient is suspended in a liquid carrier, generally water. Flowables, like ECs, may include a small amount of a surfactant, and contain active ingredient in the range of 0.5 to 95%, frequently from 10 to 50%, by weight of the composition. For application, flowables may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated.

The following are specific examples of flowable formulations: Component: % by Wt.

Active ingredient 46.00

Colloidal magnesium aluminum silicate 0.40

Sodium alkylnaphthalenesulfonate 2.00

Paraformaldehyde 0.10

Water 40.70

Propylene glycol 7.50

Acetylenic alcohols 2.50

Xanthan gum 0.80

Total 100.00

Component: % by Wt.

Active ingredient 45.00

Water 48.50

Purified smectite clay 2.00

Xanthan gum 0.50

Sodium alkylnaphthalenesulfonate 1.00

Acetylenic alcohols 3.00

Total 100.00

Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of long-chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. The surface-active agent, when used, normally comprises from 1 to 15% by weight of the composition. Other useful formulations include simple solutions or suspensions of the active ingredient in a relatively non-volatile solvent such as water, corn oil, kerosene, propylene glycol, or other suitable solvents. The following illustrate specific suspensions:

Oil Suspension: % by Wt.

Active ingredient 25.00

Polyoxyethylene sorbitol hexaoleate 5.00

Highly aliphatic hydrocarbon oil 70.00

Total 100.00

Aqueous Suspension: % by Wt.

Active ingredient 40.00

Polyacrylic acid thickener 0.30

Dodecylphenol polyethylene glycol ether 0.50

Disodium phosphate 1.00

Monosodium phosphate 0.50

Polyvinyl alcohol 1.00

Water 56.70

Total 100.00

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freon fluorinated hydrocarbons, may also be used. Water-soluble or water-dispersible granules are also useful formulations for herbicidal application of the present compounds. Such granular formulations are free-flowing, non-dusty, and readily water-soluble or water-miscible. The soluble or dispersible granular formulations described in U.S. patent No. 3,920,442 are useful herein with the present herbicidal compounds. In use by the farmer on the field, the granular formulations, emulsifiable

concentrates, flowable concentrates, solutions, etc., may be diluted witii water to give a concentration of active ingredient in the range of say 0.1% or 0.2% to 1.5% or 2%.

The active herbicidal compounds of this invention may be formulated and/or applied with insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals and may be used as effective soil sterilants as well as selective herbicides in agriculture. In applying an active compound of this invention, whether formulated alone or with other agricultural chemicals, an effective amount and concentration of the active compound is of course employed; the amount may be as low as, e.g. about 1 to 250 g/ha, preferably about 4 to 30 g/ha. For field use, where there are losses of herbicide, higher application rates (e.g., four times the rates mentioned above) may be employed.

The active herbicidal compounds of this invention may be used in combination with other herbicides, e.g. they may be mixed with, say, an equal or larger amount of a known herbicide such as chloroacetanilide herbicides such as 2-chloro-N-(2,6-diethylphenyl)-N- (methoxymethyl)acetamide (alachlor), 2-chloro-N-(2-ethyl-6-methylphenyl- N-(2-methoxy-1-methylethyl)acetamide (metolachlor), and N-chloroacetyl- N-(2,6-diethylphenyl)glycine (diethatyl-ethyl); benzothiadiazinone herbicides such as 3-(1-methylethyl)-(1H)-2,1,3-benzothiadiazin-4-(3H)-one- 2,2-dioxide (bentazon); triazine herbicides such as 6-chloro-N-ethyl-N-(1- methylethyl)-1,3,5-triazine-2,4-diamine (atrazine), and 2-[4-chloro-6- (ethylamino)-1,3,5-triazin-2-yl]amino-2-methylpropanenitrile (cyanazine); dinitroaniline herbicides such as 2,6-dinitro-N,N-dipropyl-4- (trifluoromethyl)benzeneamine (trifluralin); aryl urea herbicides such as N'- (3,4-dichlorophenyl)-N,N-dimethylurea (diuron) and N,N-dimethyl-N'-[3- (trifluoromethyl)phenyl]urea (fluometuron); and 2-[(2-chlorophenyl)methyl]- 4,4-dimethyl-3-isoxazolidinone.

It is apparent that various modifications may be made in the formulation and application of the compounds of this invention without departing from the inventive concepts herein as defined in the claims.

Claims

1. A compound of the formula

characterized in that

Q is selected from

X and Y are independently F, Cl, or Br;

R is lower alkyl or lower haloalkyl;

R¹ is selected from lower alkyl, lower haloalkyl, cycloalkyl of 3 to 7 ring carbon atoms, lower alkenyl, lower haloalkenyl, lower alkynyl, lower haloalkynyl, and benzyl which is unsubstituted or substituted on the phenyl ring witii one or more substituents selected from halogen, lower alkyl, lower alkoxy, lower alkoxycarbonyl, cyano, and nitro;

R² is independendy selected from among -OR¹ or is hydroxy, amino, lower alkylamino, or lower dialkylamino;

R ³ is H, lower alkyl, or lower alkenyl; or

a base addition salt of the compound as defined above in which R² is hydroxy.

2. The compound of claim 1 characterized in that X and Y are respectively F, Cl; Cl, Cl; or F, Br.

3. The compound of claim 2 characterized in that X and Y are respectively F, Cl or Cl, Cl.

4. The compound of claim 3 characterized in that R² is hydroxy, amino, lower alkylamino, or lower dialkylamino; or a base addition salt of die compound in which R² is hydroxy.

5. The compound of claim 4 characterized in tiiat R¹ is lower alkyl.

6. The compound of claim 5 characteπzed in that R³ is H or lower alkyl.

7. The compound of claim 6 characterized in diat Q is

8. The compound of claim 3 characterized in that R² is independently selected from among -OR¹.

9. The compound of claim 8 characterized in that RMs lower alkyl.

10. The compound of claim 9 characterized in that R² is lower alkoxy and is the same as -OR ¹.

11. The compound of claim 10 characterized in that R³ is H or lower alkyl.

12. The compound of claim 11 characterized in that Q is

and R is a lower haloalkyl group.

13. The compound of claim 12 characterized in that R is a lower fluoroalkyl group.

14. The compound of claim 13 characterized in diat R is -CHF₂.

15. The compound of claim 11 characterized in that Q is

and R is a lower fluoroalkyl group.

16. The compound of claim 15 characterized in that R is

-CH₂CH₂CH₂F.

17. The compound of claim 11 characterized in that Q is

18. The compound of claim 11 characterized in that Q is

and R is a lower alkyl group.

19. A herbicidal composition characterized in that it contains an herbicidally effective amount of the compound of claim 1 in admixture witii a suitable carrier.

20. A method for controlling undesired plant growth characterized by applying to die lccus where control is desired a herbicidally effective amount of the composition of claim 19.

21. A method for controlling undesired plant growth characterized by applying to the locus where control is desired a herbicidally effective amount of a compound of claim 1.

22. A process for producing a compound of formula I

in which

Q is selected from

X and Y are independently F, Cl, or Br,

R is lower alkyl or lower haloalkyl;

R¹ is selected from lower alkyl, lower haloalkyl, cycloalkyl of 3 to 7 ring carbon atoms, lower alkenyl, lower haloalkenyl, lower alkynyl, lower haloalkynyl, and benzyl which is unsubstituted or substituted on die phenyl ring with one or more substituents selected from halogen, lower alkyl, lower alkoxy, lower alkoxycarbonyl, cyano, and nitro;

R³ is H, lower alkyl, or lower alkenyl; or

a base addition salt of die compound as defined above in which R ² is hydroxy;

characterized by (a) (i) treating in die presence of a base, a compound of formula II

in which X, Y, and Q arc as defined above witii a compound of die formula

in which R¹ and R² are as defined above and each Z¹ is an independently selected halogen atom to produce die compound of die formula

(ii) treating, in the presence of a base, the compound of formula llla with R¹-OH or the compound of formula IX with R²-H, to produce the compound of formula I in which R³ is H; or

(b) (i) treating, in the presence of a base, a compound of formula II with a compound of the formula POZ ¹ ₃ in which each Z¹ is an independendy selected halogen atom to produce the compound of me formula

(ii) treating the compound of formula N with at least two equivalents of R ¹-OH to produce the compound of formula I in which R³ is H and R² is the same as OR¹; or

(c) treating, in the presence of a base, the compound of formula I in which R³ is H with a compound R³-Z in which Z is a halogen atom and R³ is a lower alkyl or alkenyl group to produce die compound of formula I in which R³ is a lower alkyl or alkenyl group; or

(d) treating die compound of formula I in which R² is OH with a base to produce the corresponding base addition salt.