GB2146025A

GB2146025A - Novel phenoxyalkylphosphinates and -phosphonates

Info

Publication number: GB2146025A
Application number: GB08418971A
Authority: GB
Inventors: Shy-Fuh Lee
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1983-07-29
Filing date: 1984-07-25
Publication date: 1985-04-11
Also published as: PH20348A; GB2146025B; IL72526A0; IT1199167B; HUT36688A; AU3122884A; ES8601226A1; ES534664A0; DK369984D0; NL8402253A; FR2549841A1; BR8403746A; DE3426634A1; DK369984A; GB8418971D0; IT8448641A0

Abstract

Novel 5-(substituted amino)phenoxyalkyl-, phenylthioalkyl-, phenylsulfinylalkyl-, and phenylsulfonylalkylphosphinates and phosphonates, synthesis thereof, intermediates therefor, and the use of said novel compounds for the control of weeds.

Description

SPECIFICATION Novel phenoxyalkylphosphinates and -phosphonates The present invention relates to novel 5-(substituted amino)phenoxy-alkyl-, phenylthioalkyl-, phenylsulfinylalkyl-, and phenylsulfonylalkyl- phosphinates and phosphonates, synthesis thereof, intermediates therefor, and the use of said novel compounds for the control of weeds.

More particularly, the novel compounds of the present invention are represented by the following formula I:

wherein M is O, S, S(O) or SO2, W is selected from the groups

Q is N or CH; each of X and Y is independently hydrogen or halogen; Z is O, S or NR'; each of R' and R is independently hydrogen or C1-salkyl; R2 is C1-8alkyl or C1-salkoxy; R3 is hydrogen, C1-salkyl, C2-salkenyl, C2.salkynyl, C3-scycloalkyl, C2-8alkoxyalkyl, C2-8alkylthioalkyl, C3-9 alkoxycarbonylalkyl or C4-sdialkylaminocarbonylalkyl; and each of R4, R5, R5a, R6, R6a and R7 independently are hydrogen or C1-8 alkyl.

The term "C2-salkenyl" referres to an alkenyl group, having one or two double bonds.

The term "C2-salkynyl" refers to an alkynyl group having one or two acetylenic bonds.

The term halogen refers to F, Cl and Br, especially to F and Cl.

The invention also provides processes for producing a compound of formula I which comprises a) obtaining a compound of formula la

wherein W' is selected from the groups W1, W2 and W4 as defined above.

by reacting a compound of formula II

wherein X, Y, M. Ri, R2, R3 and Z are as defined above, with a compound of formula II, Ill or IV

wherein R4, R5, R6 and Q are as defined above and Ra is C1-salkyl, or b) obtaining a compound of formula Ib

wherein W" is selected from the groups W2 or W3, and X, Y, M, R, R2, R3 and Z are as defined above, by intramolecular ring closure of a compound of formula V

wherein X, Y, M, R1, R2, R3 and Z are as defined above, and W" ' is selected from the groups of formula VI or VII

CH3-N-CH2COOR8 VII wherein Q and Ra are as defined above or c) obtaining a compound of formula Ic

wherein X, Y, R, R2, R3, R7, M and Z are as defined above by reacting by reacting a compound of formula VIII

wherein X, Y, R, R2, Ra, R, M and Z are as defined above with phosgene or a reactive functional derivative thereof or d) obtaining a compound of formula Id

wherein R', R2, Ra, R5a, R6a, X, Y, M and Z are as defined above by reacting a compound of formula IX

wherein X, Y, R', R2, R3, M and Z are as defined above with a compound of formula X R6n CO-NH-CO-NH2 X followed, where desired, by N-alkylation of the thus obtained 1,2,4-triazole-5-ones in the 4-position e) obtaining a compound of formula le

wherein M' is 5(0) or SOa and W, X, Y, Ri, R2, R3 and Z are as defined above by oxydation of a compound of formula If

with a peroxyde.

The reaction according to process a) is conveniently effected at a temperature above room temperature e.g. 100" or reflux temperature. Where the reaction partner is an anhydride (compound of formula II or IV), the reaction is conveniently carried out in the presence of an acid such as acetic acid; the latter can also serve as solvent for the reaction.

The ring closure of the compounds of formula V can be effected under acid conditions, e.g. in the presence of hydrochloric acid. The compounds of formula V are conveniently reacted in the form of an acid addition salt, e.g. as hydrochloride and in a solvent which is inert under the reaction conditions, e.g.

an alcohol such as ethanol. A suitable reaction temperature is between room temperature and reflux temperature.

The reaction according to process c) is conveniently effected in a solvent which is inert under the reaction conditions such as dioxane, and at a temperature above room temperature. A reactive functional derivative of phosgene particularly appropriate for use in this reaction is trichloromethylchloroformate, preferably in the presence of an organic base such as triethylamine.

The reaction according to process d) may be carried out following the procedure of Gold-Aubert or modifications thereof. A suitable solvent is decahydronaphthalene; a suitable reaction is above room temperature, e.g. reflux temperature.

Subsequent N-alkylation can be effected according to methods known per se. Suitable alkylating agents are alkyl halides or reactive functional derivatives thereof such as for example CHaNa.

The oxydation according to process e) may be effected with one or two equivalents of a peroxyde, such as m-chloroperbenzoic acid to give a compound of formula Ic wherein M' is S(O) or SO2 resp. A suitable solvent for this reaction is CH2CI2.

The compounds of formula I may be recovered from the reaction mixture in which it is formed by working up by established procedures.

The compounds of the present invention have one or more asymmetric carbon atoms. The present invention includes each of the optically active isomers and racemic mixtures thereof. In the examples hereinafter, unless otherwise specified, the compound prepared is a racemic mixture.

The starting materials may be obtained in a manner analogous to known processes.

Examples of suitable reaction schemes for the preparation of various compounds of formula II are given below (M" is O or S, Alk is C1-salkyl, Hal is halogen (e.g. Cl), Rs is H or C1-salkyl and X, Y, R, R2, R3 and Z are as defined above).

H2N- Y XI J R1 0 O RO 11 + CH3SO20CH-P-OAlk + HO-CH-P-Oalk Alk XII R 6Alk XIII A H2N XIV M-CH-P-OAlk I" R1 F;;2 lhalogenation X X x R3ZH > -Y -CH-P-a1 XV R'1 R2 XVI Ri ' 2 al X R1 R2 1) hydrolysis 1 2) + HalCH(R9)-COOAlk 2) + HalCH(R9)-COOAlk H2N M"-CH-P-O-CH(R9)COOAlk XVII Ri R2 Analogously, compounds of formula XVIII

wherein X' is H, Cl or Br, and Y, R', R2, Alk and M" are as defined above, may be obtained by reaction of a compound of formula XII or Xlli with the corresponding nitrophenol or -thiol. The nitro compounds of formula XVIII may be hydrogenated to the corresponding amino compounds and/or halogenated and further reacted with R3ZH resp.

hydrolysed and reacted with HalCH(Rs)COOAlk as outlined above for the amino compounds of formula XV. The starting materials and reagents employed in the processes described above are either known or, insofar as they are not known, they may be produced in analogous manner to the processes described herein or to known processes.

The novel compounds of formula I are useful for the control of weeds, using pre- and/or post-emergent treatments. The compounds can be applied in the form of dusts, granules, solutions, emulsions, wettable powders, flowables and suspensions. Application of a compound of the present invention is made according to conventional procedure to the weeds or their locus using an herbicidally effective amount of the compounds, usually from about 100 g to 10 kg/ha.

The optimum usage of a compound of the present invention is readily determined by one of ordinary skill in the art using routine testing such as greenhouse testing and small plot testing. However, in general, satisfactory results are usually obtained when the compound is applied at a rate in the range of from about 0.01 to 5 kg/ha (e.g. at 0.01, 0.033, 0.1 or 0.33 Ib/acre after post-emergence application and 0.1, 0.33, 1.0 or 3.3 Ib/acre after pre-emergence application).

While the compounds of the present invention have activity on grass weeds, the compounds, in general, demonstrate a higher level of herbicidal activity on broadleaf plants. Broadleaf plant (weed) species on which the compounds of the present invention show effective herbicidal activity include, but are not limited to, mustard (Brassica spp.), pigweed (Amaranthus spp.), velvetleaf (Abutilon theophrasti), jimsonweed (Datura stramonium), cocklebur (Xanthium spp.), sicklepod (Cassia obtusifolia) and annual morning glory (Ipomoea purpurea). Many of the compounds of formula I exhibit excellent tolerance for corn (maize).

The compounds of the present invention, in view of their broadspectrum broadleaf weed herbicidal activity, can be advantageously combined with grass weed herbicides for broadspectrum postemergence weed control in most grass crops. Examples of herbicides which can be combined with a compound of the present invention include those selected from the carbamates, thiocarbamates, chloroacetamides, dinitroanilines, benzoic acids, glycerol ethers, pyridazinones, uracils and ureas for controlling a broad spectrum of weeds.

The term "herbicide", as used herein, refers to an active ingredient which modifies the growth of plants because of phytotoxic or plant growth regulating properties so as to retard the growth of the plant or damage the plant sufficiently to kill it.

Preferred compounds of formula I have one or more of the following features: W is W1, W2, W3 or W5, particularly W1 or W3, preferably W1 X is H, F or Cl, particularly F or Cl, preferably F Y is F, Cl, Br, particularly F or Cl, preferably Cl M is O or S, particularly 0 O is CH, R' is H or C1-3alkyl, particularly H or C1-nalkyl, R2 is C1-3alkyl, e.g. CHa, CaHe or nOaH7, R3 is C1-4alkyl, CH2-CH=CH2, CH,-CICH C1-4a I koxy-carbonyl-C1-4a I kyl or C1-4alkoxy-C1-4al kyl, particularly Oi-4alkyl (e.g. CH3, CaH5, iQH7 or iC4He), CH2CH2OCH3 or CH2C(O)OCH3, R4 is H, Re, Re, R6 and R6a independently are H or C1-4alkyl, R7 is H, CH3, iOaH7 or tC4Hg, Z is 0.

The compounds of formula I are conveniently employed as herbicidal compositions in association with agriculturally acceptable diluents. Such compositions also form part of the present invention. They may contain, aside from a compound of formula I as active agent, other active agents, such as herbicides.

They may be employed in either solid or liquid forms e.g. in the form of a wettable powder, an emulsion concentrate, a water dispersible suspension concentrate ("flowable"), a dusting powder, a granulate, a delayed release form, incorporating conventional diluents. Such compositions may be produced in conventional manner, e.g. by mixing the active ingredient with a diluent and optionally other formulating ingredients sch as surfactants.

The term diluents as used herein means any liquid or solid agriculturally acceptable material which may be added to the active constituent to bring it in an easier or improved applicable form, respectively to a usable or desirable strength of activity. It can for example be talc, kaolin, diatomaceous earth, xylene, or water.

Particularly formulations to be applied in spraying forms such as water dispersible concentrates or wettable powders may contain surfactants such as wetting and dispersing agents, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylaryl-sulphonate, a lignin sulphonate, a fatty alkyl sulphate, an ethoxylated alkylphenol and an ethoxylated fatty alcohol.

In general, the formulations include from 0.01 to 90% by weight of active agent from 0 to 20% by weight of agriculturally acceptable surfactant and 99.99 to 10% by weight (solid or liquid) diluent(s), the active agent consisting either of at least one compound of formula i or mixtures thereof with other active agents. Concentrate forms of compositions generally contain between about 2 and 90%, preferably between about 5 and 70% by weight of active. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent.

The following examples are provided to illustrate the practice of the present invention. Temperature is given in degrees centigrade and parts and percentages are by weight. RT means room temperature.

Formulation Example 1: Wettable powder 25 Parts of a compound of formula I, are ground with 3 parts of lauryl sulphate, 5 parts sodium lignin sulphonate, 22 parts of silica and 45 parts of finely divided kaolinite until the mean particle size is below 5 microns. The resulting wettable powder so obtained is diluted with water before use.

Formulation Example 2: Emulsion concentrate 25 Parts of a compound of formula 1, 65 parts of xylene, 10 parts of the reaction product of an alkylphenol with ethyleneoxide and calciumdodecylbenzene sulphonate are thoroughly mixed until a homogeneous solution is obtained. The resulting emulsion concentrate is diluted with water before use.

FINAL COMPOUNDS Example 1 : N-{5-[α(ethyl P-methylphosphino)ethoxy]-2,4-dichlorophenyl}tetrahydrophtalimide Ethyl P-methyl[α-(2,4-idchloro-5-aminophenoxy) ethyl] phosphinate (500 mg, 1.6 mmol) is dissolved in glacial acetic acid. 3,4,5,6-Tetrahydrophthalic anhydride (292 mg, 1.9 mmol) is added to the solution.

The mixture is heated at 100 under N2 overnight and then at 140 for an additional 6 hours. It is allowed to cool to RT, adjusted to pH 5-6 with potassium carbonate, diluted with water and extracted with methylene chloride. The extracts are combined, dried over sodium sulfate and evaporated to dryness to give, following purification by prep. thin layer chromatography (TLC), N-{5-[(x-(ethyl P-methylphosphino)ethoxy]- 2,4-dichlorophenyl) tetrahydrophthalimide, MS m/e 446.3 (M+) (compound 1, Table A).

Example 2 : N-[(Ethyl P-ethylphosphinomethox) 4-chloro-2-fluorophenyl]-tetrahydrophtalimide A mixture of ethyl P-ethyl(2-chloro-4- fluoro-5- aminophenoxy) methyl-phosphinate (0.77 g, 2.61 mmol) and 3,4,5,6-tetrahydrophthalic anhydride (0.52 g, 3.39 mmol) in 5 ml of acetic acid is heated under reflux for 9 hours. Excess anhydride and acetic acid are removed in vacuo. The oily product is purified by prep. TLC to give N-[(ethyl P-ethyiphosphinomethoxy)- 4-chloro-2-fluorophenyl] tetrahydrophthalimide, MS m/e 429 (M+) (compound 23, Table A).

nmr (CDCI3) T 8.87, 8.65 (tt, 3H, P-CH2-CH3), 8.70 (t, 3H, O-CH2-CH2), 5.93 (q, O-CH2-CH3), 5.82 (d, 2H, P-O-CH2-CH3), [3.15 (d, 1H), 2.77 (d, 1H)-aromatic H].

Example 3 Analogous to the procedure of Example 1 or 2, the following compounds of formula Ig are obtained by reaction of 3,4,5,6-tetrahydrophthalic anhydride with the corresponding aminophenoxy compound of formula II.

TABLE A

Cpd X Y RI R2 Ra MS (mule) 1 Cl Cl CH3 CH3 CH2CH3 446.3 2 Cl Cl CH2CH3 CH3 CH2CH3 3 Cl Cl CH2CH3 CH3 CH3 446.27 4 H Cl CH2CH3 CH3 CH3 411.0 5 F F CH2CH3 CH3 CH3 6 F Cl CH2CH3 CH3 CH3 7 Cl Br CH2CH3 CH3 CH3 8 Cl Cl H CH3 CH3 418.22 9 Cl Cl CH3 CH2CH3 CH3 446.29 10 Cl Cl CH3 CH2CH2CH3 CH3 460.30 11 Cl Cl CH(CH3)2 CH3 CH3 12 Cl Cl CH2CH2CH3 CH3 CH3 13 Cl Cl CH3 CH3 CH2C(O)OCH3 490.28 14 Cl Cl CH3 CH2CH3 CH2C(O)OCH3 504.31 15 Cl Cl CH2CH3 CH3 CH2C(O)CCH3 504.31 16 Cl Cl CH2CH3 CH3 CH2CH = CH2 17 Cl Cl CH2CH3 CH3 CH2CH2OCH3 18 Cl Cl CH3CH3 CH3 CH 19 Cl Cl CH3CH3 CH3 CH2SCH3 20 F Cl CH2CH3 CH3 CH2CH3 21 Cl Cl CH2CH3 CH2CH3 CH3 460.00 22 Cl Cl H CH3 CH2C(O)OCH3 476.25 23 F Cl H CH2CH3 CH2CH3 429.0 24 F Cl H CH2CH3 CH(CH3)2 443 25 F Cl CH3 CH2CH2CH3 CH2CH3 457 26 F Cl CH3 CH2CH3 CH2CH3 443 27 F Cl CH3 CH3 CH2CH3 429 28 F Cl CH2CH3 CH2CH3 CH2CH3 457 29 F Cl H CH2CH3 CH2CH(CH3)2 457 30 F Cl H CH2CH3 CH2CH2OCH3 459 31 F Cl CH2CH3 CH3 CH2CH=CH2 455 32 F Cl CH3 CH2CH2CH3 CH2CH2OCH3 487 33 F Cl CH2CH3 CH3 CH2CH2OCH3 473 34 F Cl CH2CH3 CH3 CH2CCH 453.6 35 H Cl CH2CH3 CH2CH3 CH3 425.8 36 H Cl CH2CH3 CH2CH3 CH2CH3 439.9 37 Cl Cl CH3 CH3 CH3 432.2 38 F Cl H CH3 CH2CH3 415.8 39 F Cl CH3 CH(CH3)2 CH2CH3 457.8 40 F Cl CH2CH2CH3 CH3 CH2CH3 457.8 41 F Cl H CH2CH2CH3 CH3 429.8 42 F Cl H CH2CH3 CH3 415.8 43 H Cl CH2CH3 CH3 CH2CH3 425.8 44 H Cl H CH2CH3 CH2CH3 411.8 45 H Cl CH3 CH2CH2CH3 CH2CH3 439.9 46 H Cl CH3 CH2CH3 CH2CH3 425.8 47 H Cl CH3 CH2CH3 CH3 411.8 48 H Cl H CH2CH3 CH3 397.8 49 H Cl CH2CH3 CH3 CH2C(O)OCH3 487.8 50 F Cl CaHe CH3 CH2-CH(CH3)2 51 F Cl O3H5 CH3 CH(CH3)2 52 F Cl nC3H7 CH3 CH3 53 F Cl H nC3H7 O2He A selection of the compounds of Table A is further characterised as follows:: Compound No. NMR (CDCI3)T 29 9.04 (d, 6H, CH(CH3)2), 8.92, 8.54 (tt, 3H, P-CH2-CHa),j8.20 (m, 8H, CH2-CH2, P-CH=CH3, O-CH2-CH(CH3)2), 5.77 (d, 2H, OCH2-P), [3.15 (d, 1H), 2.80 (d, 1H)-aromatic H].

30 8.92, 8.52 (tt, 3H, P-CH2-CH3), 8.16 (m, 6H, CH2-CH2, P-CH=CH2), 6.70 (s, 3H, O-CH3(, 6.47 (t, 2H, O-CH2-CH2-O-CH3(, 5.87 (t, 2H, O-CH2-CH2-O-CH3), 5.70 (d, 2H, O-CHrP), [3.10 (d, 1H), 2.77 (d, 1H)-aromatic H].

35 8.78 (m, 6H, P-CH2-CH3, O-CH(CH2CH3)-P, 8.07 (m, 8H, CH2-CH3, O-CH(CH2CH3)-P), 6.32 6.12 (dd, 3H, P-OCH3), 5.42 (m, 1H, O-H, O CH(CH2CH3)-P), 2.87 (m, 3H, aromatic H).

36 8.77 (m, 9H, O-CH2-CH3, P-CH2-CH3, O-CH{CH2CH3)-PJ, 8.20 (m, 8H, CH,-CH, P-CH2-CH3, O CH(CH2CH3)-P, 5.70 (m, 3H, O-CH(CH2CH3)-P, O-CH2-CH3), 2.87 (m, 3H, aromatic H).

Example 4 : 3-{5-[α-(Ethyl P-methylphosphino)-n-propoxy]-4-chloro-2-fluorophenyl}-1,5-teramethylenehydantoin A mixture of ethyl P-methyl-1-(2-chloro-4-fluoro-5-aminophenoxy)- propylphosphinate (1.00 g, 3.2 mmol) and trichloromethyl chloroformate (0.76 g, 0.46 ml, 3.9 mmol) in dioxane (50 ml) and triethylamine (0.36 g, 0.49 ml, 3.5 mmol) is heated for 3 hours. The dioxane is then removed in vacuo to give the corresponding isocyanate, which residue is taken up in methylene chloride (35 ml). [2-(Ethoxycarbonyl) hexahydropyridine] (0.754 g, 0.75 ml, 4.8 mmol) is added and the mixture is stirred at RT overnight. The reaction mixture is diluted with methylene chloride, washed with water, dried and evaporated to dryness.

The resulting urea compound (1.5 g, 3.2 mmol) is dissolved in ethanol (15 ml). 2N HCI (20 ml) is added, and the solution is heated under reflux for 5 hours and then at 90 overnight. The ethanol is removed in vacuo, and the residue is diluted with water, extracted with methylene chloride (3X). The combined extracts are dried and evaporated to dryness. The crude product is purified by prep. TLC to give the title compound, MS m/e 446 (M+) (Compound 54).

Example 5 : l-Methyl-3-{5[a-(ethyl P-methylhposphino-n-propoxy]-2,4-dichlorophenyl} hydratoin A mixture of ethyl P-methyl-(2,4-dichloro-5-aminophenoxy) propylphosphinate (2.20 g, 6.7 mmol) and trichloromethyl chloroformate (1.60 g, 0.97 ml, 8.1 mmol) in dioxane (50 ml) and triethylamine (0.81 g, 1.1 ml, 8.1 mmol) is heated for 3.5 hours. The dioxane is removed in vacuo and and the resulting isocyanate is taken up in methylene chloride (60 ml). Triethylamine (1.02 g, 1.4 ml, 10.1 mmol) and methyl methylaminoacetate hydrochloride (1.40 g, 10.1 mmol) are added, and the mixture is stirred at RT for 1 hour. The reaction mixture is diluted with methylene chloride, washed with water, dried and evaporated to dryness.To the resulting urea compound (2.5 g), dissolved in ethanol (15 ml), is added 2N HCI (20 ml) and the mixture is stirred at RT for # 60 hours. The mixture is then heated under reflux for 7 hours, followed by stirring at RT overnight. The ethanol is then removed in vacuo, and the residue is diluted with water and extracted with methylene chloride. The combined extracts are dried and purified by prep.

TLC to give the title compound, MS m/e 423 (M+) (Compound 55).

Example 6 : 1-Methyl-3-{5-[α-(ethyl P-methylphosphino) -n-propoxyj -4chlorn-2-fluornpheny!\ hy dan to in In the same manner, ethyl P-methyl-1-(2-chloro-4-fluoro-5-amino-phenoxy) propylphosphinate (1.00 g, 3.2 mmol) and trichloromethylchloroformate (0.76 g, 0.46 ml, 3.9 mmol) are reacted together, and the resulting isocyanate is reacted with methyl methylaminoacetate hydrochloride (0.67 g, 4.8 mmol). The resulting urea compound (3.2 mmol) is heated together with 2N HCI (8 ml) and purified to give the title compound, MS m/e 406 (M+) (Compound 56).

Example 7 : 4- 5-[α-(Ethyl P-methylphosphino)-n-propoxy]-4-chloro-2-fluorophenyl}-1,2-tetramethilenetriazolidine-3,5-dione Following the procedure of Example 4, ethyl P-methyl-1-(2-chloro-4- fluoro-5-aminophenoxy) propylphosphinate is treated with trichloromethyl-chloroformate, and the resulting isocyanate is reacted with N-ethoxy-carbonylhexahydropyridazine hydrochloride, followed by heating to give the title compound (Compound 57).

Example 8 : 2-t-Butyl-4-[5-(methyl P-ethylphosphinomethoxy)-4-chloro-2-fluorophenyl]-#-1,3,4- oxadiazolin-5-one A mixture of methyl P-ethyl-[2-chloro-4-fluoro-5- (N'-pivaloylhydrazino) phenoxy] methylphosphinate (3.2 mmol), trichloromethylchloroformate (3.9 mmol) and triethylamine (3.5 mmol) in dioxane (50 ml) is heated for 3.5 hours. The dioxane is then removed in vacuo. The product is diluted with methylene chloride, washed, dried, evaporated to dryness and purified by prep. TLC to give the title compound (Compound 58).

Example 9 : 3-t-Butyl- 1-{5[a-(methyl P-methylphosphino)- n-propoxy]-2, 4-dichlorophenyn -A7 1,2,4-triazolin-5-one A mixture of methyl P-methyl-1-(2,4-dichloro -5-hydrazinophenoxy)- propylphosphinate (9.6 mmol) and pivaloylurea (9.6 mmol) in decahydronaphthalene (Decalin; 12 ml) is heated under reflux, with stirring, for about 8 hours, following the procedure of Gold-Aubert et.al., Helvetia Chimica Acta 47(5):1188 (1964), to give, after purification, the title compound (Compound 59).

Example 10: 1-[5-Methyl P-ethylphosphinomethoxy)-4chloro-2- fluorophenyl] - 9 1,2,4 triazolin-5- one Following the procedure of Example 9 methyl P-ethyl-(2-chloro-4-fluoro- 5-hydrazinophenoxy) methylphosphinate is reacted with formylurea to give the title compound (Compound 60).

Example 11: 4Methyl 1J5(methyl P-ethylphosphinomethoxy)- 4chloro-2-fluorophenyl]- 7 1,2,4 triazolin-5-one To the title compound of Example 10 (2.5 mmol) is added methyl iodide (3.0 mmol), sodium hydride (2.5 mmol) and dimethylformamide (DMF; 15 ml). The mixture is heated at 80" for 3 hours. Upon cooling to RT, the reaction mixture is poured into water and extracted with methylene chloride. The combined extracts are washed with water, dried, evaporated to dryness and purified by prep. TLC to give the title compound (Compound 61).

Example 12 : N-[5-lethyl P-ethylphosphinomethylthio) -4-chloro -2-fluorophenyl] tetrahydrophthalimide Following the procedure of Example 2, 2-chloro-4-fluoro-5-amino-phenylthiol is reacted with ethyl Pethyl(methylsulfonyl oxymethyl) -phosphinate to give ethyl P-ethyl(2-chloro -4-fluoro-5- aminophenylthio)- methylphosphinate, which is then reacted with 3,4,5,6-tetrahydrophthalic anhydride to yield the title compound.

HERBICIDAL USE Example 13 Pre-emergent herbicidal activity of compounds 1 and 3 of the present invention was determined as follows: Seeds of selected weeds were planted and the soil was drenched with a solution of water (17%), surfactant (0.17%) and the test compound at a rate equivalent to 10 Ib/acre and 3.3 Ib/acre. Scoring was made two weeks after treatment. In the 10 Ib/acre test, the grasses (GR) green foxtail, watergrass, shattercane and wild oats and the broadleafs (BL) annual morning glory, mustard nightshade and velvetieaf were treated. In the 3.3 Ib/acre test, the grasses green foxtail, barnyard grass, bermuda grass, wild oats and downy brome and the broadleafs mustard, pigweed, velvetleaf, jimsonweed, cocklebur, sticklepod and annual morning glory were tested. The average pre-emergent activity of the two compounds is presented in Table B below.

Example 14 Post-emergence herbicidal activity of compounds 1 and 3 was tested as follows: Seedlings of selected weeds were sprayed with a solution of water/acetone (1:1), surfactant (0.5%) and the test compound at a rate equivalent to 10 Ib/acre and 3.3 Ib/acre. Scoring was made two weeks after spraying. In the 10 Ib/acre test, the grasses (BR) green foxtail, water grass, shattercane and wild oats and the broadleafs (BL) annual morning glory, mustard, soybean and velvetleaf were treated. In the 3.3 Ib/acre test, the grasses green foxtail, barnyard grass, bermuda grass and wild oats and the broadleafs annual morning glory, pigweed, velvetleaf, cocklebur and sicklepod were treated. The average post-emergent activity of compounds 1 and 3 are presented in Table B below.

Example 15 Following the procedure of Example 13, compounds 23, 25 and 30 are tested for pre-emergent herbicidal activity at 10 Ib/acre and at 3.3 Ib/acre. The average activity of the three compounds is presenting in Table B below.

Following the procedure of Example 14, compounds 23, 25 and 30 are tested for postemergent herbicidal activity, at 10 Ib/acre for grasses and at 10 Ib/acre and 3.3 Ib/acre for broadleafs. The average activity is presented in Table B below.

TABLE B % Average Herbicidal Activity Pre Post Cpd Ib/acre GR BL GR BL 1 10 77 100 67 100 3.3 63 93 73 100 3 10 82 100 100 90 3.3 89 100 88 100 23 10 92 100 100 100 3.3 90 100 - 100 25 10 100 100 100 100 3.3 84 100 - 100 30 10 93 100 87 100 3.3 76 100 - 100 INTERMEDIA TES Example 16: Ethyl P-methyl-[os-r2,Sdichloro-initrophenoxy) ethyl]-phosphinate To a solution of 2,4-dichloro-5-nitrophenol (630 mg, 3.0 mmol) dissolved in 7 ml of dimethylsulfoxide (DMSO) is added potassium carbonate (538 mg, 3.9 mmol) and ethyl P-methyl-(or methyisulfonyloxyethyl) phosphinate (966 mg, 4.2 mmol). The mixture is stirred at 75" under N2 overnight. The reaction is diluted and acidified with 10% HCI and extracted (3X) with methylene chloride.The combined extracts are washed with water (3X), dried over sodium sulfate and evaporated to dryness. The resulting crude product is purified by column chromatography to give the title compound.

Example 17 The nitrophenoxy starting compounds of formula XVIII for the compounds 2 to 22 and 37 of Table A are obtained in a manner analogous to that described in Example 16.

Example 18: Ethyl P-methylja-(2,4dichloro -Saminophenoxy)ethyiJ -phosphinate Iron metal powder (1.5 g) is added in small portions to a stirring solution of ethyl P-methyl-[a-(2,4- dichloro-5- nitrophenoxy) ethyl]phosphinate (1000 mg, 2.9 mmol) in 5% aqueous acetic acid, and the mixture is heated at 115-1200 for 35 minutes. The reaction mixture is allowed to cool to RT and is made alkaline with potassium carbonate, filtered and extracted with methylene chloride. The combined extracts are washed with water (3X), dried over sodium sulfate and evaporated to dryness to give the title compound.

Example 19 The aminophenoxy starting compounds of formula II for the compounds 2 to 22 and 37 of Table A are obtained in a manner analogous to that of Example 18.

Example 20 : Methyl P-methyl-[(x- 62,4-dichloro-initrophenoxy) -n-propyl]-phosphinate Thionyl chloride (8 ml) is added to ethyl P-methyl-[a-(2,4-dichloro-5- nitrophenoxy)-n-propyl] phosphinate and the mixture is allowed to stand at RT overnight. The thionyl chloride is removed and the resulting P-methyl-[a- (2,4-dichloro-5-nitrophenoxy) -n-propyl] phosphinic acid chloride is treated with 2.0 g of sodium hydroxide in water (100 ml). The aqueous solution is acidified and extracted with ether, and the ether extracts are dried and evaporated to dryness to give P-methyl-[a- (2,4-dichloro-5- nitro phenoxy) -l-n-propyl] phosphinic acid.

The above phosphinic acid (1.7 g) is dissolved in 10 ml of ether, and an excess of diazomethane is added. After reaction is complete, excess diazomethane is decomposed with acetic acid and the solution is concentrated to dryness to give the title compound.

Example 21 : Methoxycarbonylmethyl P-methylfa-(2,4 dichloro-initrophenoxyJethyl] phosphinate Following the procedure of Example 20, methyl[a-(2,4-dichlorn-5 nitrophenoxy) ethyl] phosphinic acid is prepared from ethyl P-methyl[a-(2,4-dichloro-5- nitrophenoxy) ethyl] phosphinate.

A mixture of the above phosphinic acid (1.5 g, 5.59 mmol), potassium carbonate (0.9 g), methyl bromoacetate (1.2 g, 0.74 ml, 7.80 mmol) and acetone (20 ml) is heated under reflux overnight. The reaction mixture is allowed to cool to RT and filtered, and the filtrate is concentrated. The oily residue is extracted in methylene chloride and rhe extracts are washed, dried and evaporated to dryness to give the title compound.

Example 22 : Ethyl P-ethyl(2-chloro-4-fluoro-5-aminophenoxy) methyl-phosphinate A mixture of 2-chloro-4-fluoro-5-aminophenol (0.60 g, 3.72 mmol) in 10 ml of DMSO, potassium car bonate (0.62 g, 4.40 mmol) and ethyl P-ethyl(methylsulfonyloxymethyl) phosphinate (1.19 g, 5.21 mmol) is heated to 100" for 48 hours. The reaction mixture is diluted with ether and filtered, and the filtrate is washed with brine, dried and evaporated to dryness. The crude product is purified by prep. TLC to give the title compound.

Example 23 The aminophenoxy starting compounds of formula 11 for the compounds 24 to 28, 35, 36, 38 to 48 and 51 to 53 are obtained in a manner analogous to that described in Example 22.

Example 24: Isobutyl P-ethyl-t2-chloro-4-fluoro-5-aminophenoxyJ methylphosphinate A solution of ethyl P-ethyl(2-chloro-4-fluoro-5- aminophenoxy)- methylphosphinate (1.50 g, 5.10 mmol) in thionyl chloride (6 ml) is heated under reflux with stirring and under N2 for 1.5 hours. The excess thionyl chloride is removed in vacuo and methylene chloride (12 ml) is added, followed by dropwise addition of isobutyl alcohol (6 ml). After addition is complete, the mixture is stirred at RT under N2 for 18 hours. The reaction mixture is diluted with methylene chloride, washed with potassium carbonate and sodium chloride and evaporated to dryness. The crude product is purified by prep. TLC to give the title compound.

Example 25 Following the procedure of Example 24 the aminophenoxy starting compounds of formula II for the compounds 30 to 34 and 50 are obtained by reaction of the appropriate alkyl phosphinate with thionyl chloride followed by reaction of the thus obtained chloride with 2-methoxyethanol, allyl alcohol, propargyl alcohol or isobutyl alcohol.

Example 26: Methyl P-ethyl-[2chloro-4- fluoro-5-{N'- pivaloylhydrazino)- phenoxy] methylphosphinate Methyl P-ethyl-(2-chloro-4-fluoro-5-aminophenoxy) methylphosphinate (3.4 mmol) is dissolved in 6N HCI (10 ml). Temperature of the solution is maintained at -15" to -20" as sodium nitrite (0.24 g, 3.5 mmol) in 2 ml of water is added dropwise. The mixture is warmed to 0 and is stirred at 0 for 1 hour. An ice-cooled solution of stannous chloride/2H2O in 2 ml of conc. HCI is quickly added to the mixture, and stirring at 0 is continued for 2.5 hours. The reaction mixture is neutralized with saturated sodium bicar bonate and is extracted with methylene chloride. The combined extracts are washed with water, dried, evaporated to dryness and purified by prep. TLC to give methyl P-ethyl- (2-chloro-4-fluoro-5- hydrazinophenoxy) methylphosphinate.

To the above phosphinate (2.5 mmol) in methylene chloride (10 ml) is added pivaloyl chloride (3.0 mmol) and triethylamine (3.0 mmol). The mixture is stirred at RT for 4 hours, after which it is washed with water, dried and evaporated to dryness to give the title compound.

Claims

1. A compound of formula I

wherein M is O, S, S(O) or SO2, W is selected from the groups

o is N or CH; each of X and Y is independently hydrogen or halogen; Z is O, S or NR'; each of R' and R1 is independently hydrogen or C1-aalkyl; R2 is C1-salkyl or C1-salkoxy; R is hydrogen, C1-8alkyl, C2-8alkenyl, C2-8alkynyl, C3-8cycloalkyl, C2-8alkoxyalkyl, C2-8alkylthioalkyl, C3-9 alkoxycarbonylalkyl or C4-sdialkylaminocarbonylalkyl; and each of R4, Re, Rq R6, R6a and R7 independently are hydrogen or C1-salkyl.

2. A compound of Claim 1 in which M is O, W is selected from the groups W1, W2, W3 and W5 and R, R, R6 and R' independently are H or C1-4alkyl,

3. A compound of Claim 2, in which X is H, F or Cl, Y is CI, Z is O, R1 is H, CH3 or C2H5, R2 is C1-3alkyl, R is alkyl, C1-4alkoxy-carbonyl- C1-4alkyl or C1-4alkoxy-C1-4alkyl.

4. A compound of Claim 3 in which W is the group W1 wherein R4 is H, and R is CH3, C2Hs, iC3H7, iC4H9 or methoxyethyl.

5. A compound of Claim 4 wherein X, Y, R', R and R are a) Cl, Cl, CH3, CH3, CH3 resp.

or b) F, Cl, H, C2H5, C3H5 resp.

or c) F, Cl, C3H5, OH3, C3H5 resp.

or d) F, Cl, CH3, nC3H7, C2H5 resp.

or e) F, Cl, H, C2H5, iC,H, resp.

or f) F, Cl, H, C2H5, iC4H9 resp.

or g) F, Cl, H, C2H5, CH2CH2OCH3 resp.

or h) H, Cl, C2H5, C2H5, C2H5 resp.

or i) H, Cl, C2H5, C2H5, CH3 resp.

6. A compound of Claim 4, in which W is the group W2 and Q is CH.

7. The compound 3-{5-[α-(ethyl P-methylphosphino) -n-propoxyl- 4-chloro-2- fluorophenyl}-1,5- tetramethylenehydantoin, according to Claim 6.

8. A compound of Claim 4 in which W is the group W3.

9. A compound of Claim 4 in which W is the group W5 and R7 is CH3, iC3H7 or tC4H9.

10. Processes for the production of a compound of formula I stated in Claim 1, which comprise a) obtaining a compound of formula la

wherein W' is selected from the groups W1, W2 and W4 as defined in Claim 1, by reacting a compound of formula II

wherein X, Y, M, Ri, R2, R3 and Z are as defined in Claim 1, with a compound of formula II, III or IV

wherein R4, R5, R6 and Q are as defined in Claim 1 and R6 is is C1-4alkyl, or b) obtaining a compound of formula Ib

wherein W" is selected from the groups W2 or W3, and X, Y, M, R1, R2, R3 and Z are as defined in Claim 1, by intramolecular ring closure of a compound of formula V

wherein X, Y, M, R1, R2, R3 and Z are as defined in Claim 1, and W"' is selected from the groups of formula VI or VII

CH3-N-CH2COOR8 VII wherein Q and Re are as defined in Claim 1, c) obtaining a compound of formula Ic

wherein X, Y, R1, R2, Ri, R7, M and Z are as defined in Claim 1, by reacting a compound of formula VIII

wherein X, Y, R1, R2, R , R7, M and Z are as defined in Claim 1, with phosgene or a reactive functional derivative thereof or d) obtaining a compound of formula Id

wherein R, R2, R , R', R6a, X, Y, M and Z are as defined in Claim 1, by reacting a compound of formula IX

wherein X, Y, Ri, R2, R , M and Z are as defined in Claim 1, with a compound of formula X R6a-CO-NH-CO-NH2 X followed, where desired, by N-alkylation of the thus obtained 1,2,4-triazole-5-ones in the 4-position e) obtaining a compound of formula le

wherein M' is 5(0) or SO3 and W, X, Y, Ri, R, RS and Z are as defined in Claim 1, by oxydation of a compound of formula If

with a peroxyde.

11. A process according to Claim 10, substantially as described herein by way of Example.

12. A compound obtained by a process according to Claim 10 or 11.

13. A herbicidal composition comprising a compound according to any one of Claims 1 to 9 and 12, and an agriculturally acceptable diluent.

14. A method of combatting weeds which comprises applying to the locus thereof a herbicidally effective amount of a compound according to any one of Claims 1 to 9 and 12.

15. A method according to Claim 14 wherein the locus is a crop locus.

16. A method according to Claim 15, wherein the locus is a maize locus.

17. A method according to Claim 15, wherein the locus is a grass crop.

18. A method according to Claim 17, wherein the compound is used in association with a grass weed herbicide.

19. A compound selected from the following formula Ila or formula XVIII:

wherein R1, R2 and R3 are as defined in Claim 1, each of X and Y is independently H or halogen, and X' is H, Cl or Br.