NL8500277A - NEW PHOSPHATES AND PHOSPHONATES AND METHODS FOR PREPARING AND USING THESE COMPOUNDS. - Google Patents

Description

I

Novel phosphinates and phosphonates and methods of preparing and using these compounds.

The present invention relates to new 5- (substituted amino) anilinoalkyl phosphinates and phosphonates, syntheses thereof, intermediates therefor and to the use of these new compounds to control weeds.

The novel compounds of the invention are particularly represented by formula 1, wherein 10 W is a group of formula W1, W2, W3, W4, W5 or W6, IQ N or CH, each of the substituents X and Y, independently of each other , a hydrogen or halogen atom, Z 0 or NH, each of the substituents R and R 1, independently, a hydrogen atom or an alkyl group with 1-8 carbon atoms, an alkyl group with 1-8 carbon atoms or an alkoxy group with 1 -8 carbon atoms, a hydrogen atom, an alkyl group with 1-8 I carbon atoms, an alkenyl group with 2-8 carbon atoms, a cycloalkyl group with 3-8 carbon atoms, a C 1-8 alkoxyalkyl group, a C 1-8 alkylthioalkyl group, a C 1-8 alkoxycarbonylalkyl group or a dialkylaminocarbonylalkyl group and each of the substituents R, Rc, Rc, R, R, and 4 5a 6 6a R 4, independently, represent a hydrogen atom or an alkyl group of 1-8 carbon atoms.

The designation "an alkenyl group with 2-8 carbon atoms" refers to an alkenyl group with one or two double bonds.

The term halogen denotes a fluorine, chlorine or bromine atom, in particular a fluorine or chlorine atom.

The invention also provides methods of preparing a compound of formula I, which comprises a) preparing a compound of formula Ia, 8500277

BAD ORIGINAL

- 2 - wherein W 'is selected from the previously defined groups W1, W2 and W4, and X, Y, R, Rj, Rg, Rg and Z have the previously defined meanings, by reaction of a compound of formula II, wherein X , Y, R, Rj, Rg, Rg eh Z have the meanings defined above, with a compound of formulella, III or IV, wherein R ^, Rg, Rg and Q have the meanings previously defined and Rg has an alkyl group with 1- Represents 5 carbon atoms, or b) preparing a compound of formula Ib, wherein Wf * is selected from the groups W2 or W3, and X, Y, R, Rj, R2> Rg and Z have the meanings defined above, by intramolecular cyclization of a compound of formula V, wherein X, Y, R, Rj, R2> Rg and Z have the previously defined meanings and W'1 is selected from the groups of formulas VI or VII wherein Q and R'de meanings defined above

O

or c) preparing a compound of formula Ic, wherein X, Y, R, Rj, R 2, Rg, Rg and Z have the previously defined meanings, by reacting a compound of formula 20 VIII, wherein X, Y , R, Rj, R2> Rg, Rg and Z have the meanings defined above, with phosgene or a reactive functional derivative thereof, or d) preparing a compound of formula Id, wherein R, R., R, R, , Rc, R,, X, Y and Z have the meanings defined above-1 Δ3 da ba 25 by reaction of a compound of formula IX, wherein X, Y, R, Rj, Rg, Rg and Z have the previously defined have meanings, with a compound of formula X, wherein R ^ ^ has a previously defined meaning

N

optionally followed by N-alkylation of the thus obtained 1,2,4-triazol-5-ones in the 4-position.

The reaction according to method a) is suitably carried out at a temperature above room temperature, for example 100 ° C or the reflux temperature. If the reaction participant is an anhydride (a compound of formula II or IV), the reaction becomes suitable in the presence of an acid, such as 8500277

BAD ORIGINAL

- 3 - acetic acid, which can also serve as a solvent for the reaction.

The intramolecular cyclization of the compounds of formula V according to method b) can be effected under acidic conditions, for example in the presence of hydrogen chloride. The compounds of formula V are suitable in the

An acid addition salt is reacted, for example, as hydrochloride, and in a solvent which is inert under the conditions, for example, an alcohol such as ethanol.

A suitable reaction temperature is between room temperature and the reflux temperature.

The reaction according to method c) is suitably carried out in a solvent that is inert under the reaction conditions, such as dioxane, and at a temperature above room temperature. A reactive, functional derivative of phosgene which is particularly suitable for use in this reaction is trichloromethyl chloroformate, preferably in the presence of an organic base, such as triethylamine.

The reaction according to method d) can be carried out according to the Gold-Aubert method or modifications thereof. A suitable solvent is decahydronaphthalene, while a suitable reaction temperature is a temperature above room temperature, for example the reflux temperature.

The subsequent N-alkylation can be carried out by methods known per se. Suitable alkylating agents are alkyl halides with 1-8 carbon atoms or reactive, functional derivatives thereof, such as, for example, C 1-4.

The compounds of formula I can be recovered from the reaction mixture in which they are formed by working-up according to known methods.

The compounds of the present invention have one or more asymmetric carbon atoms. The present invention includes any of the optically active isomers and racemic mixtures thereof. In the following Examples 35, the compound is prepared in the form of a racemic mixture. 8500277

BAD ORIGINAL

- 4 - unless stated otherwise.

Examples of suitable reaction schemes for preparing various compounds of formula II are shown under X on the formula sheet, where Hal represents a halogen atom, R 1 'a lower alkyl group, a hydrogen atom or a lower alkyl group, and Alk represents a lower alkyl group, and X, Y , R, Rj, R ^, R ^ and Z have the previously defined meanings.

The compounds of formula IX are obtained by reacting a compound of formula II with sodium nitrite and then with stannous chloride in HCl at a temperature below room temperature. The reaction of compounds of formula IX with R 2 COCl in the presence of a base such as triethylamine and a solvent such as methylene chloride and at room temperature or lower temperature provides compounds of formula VIII.

The starting materials and reagents used in the above-described methods are known or, if not known, can be prepared analogously to the methods described herein or to known methods.

The new compounds of formula I are useful for weed control, using treatments before and / or after hatching. Application of a compound of the present invention is by conventional methods for the weeds of the area, using a herbicidally effective amount of the compounds, usually from about 100 g to 10 kg / ha.

The optimal use of a compound according to the present invention can be easily determined by a person skilled in the art, using a routine examination, such as an investigation in a greenhouse or in a small area. In general, however, satisfactory results are usually obtained when the compound is applied in an amount between about 0.1-5 kg / ha (e.g. 0.1 or 0.33 pounds / acre).

8500277

BAD ORIGINAL

Although the compounds of the present invention exert an effect on grassy weeds, the compounds generally exhibit a greater degree of herbicidal activity on broadleaf plants. Broad-leaved plants (weeds) species on which the compounds according to the present invention exert an effective herbicidal effect I include mustard (Brassica spp.), Melgan foot (Amaranthus spp.), Room maple (Abutilon theophrasti), thorn apple (Datura stramonium), burdock (Xanthium spp.), Arabis Canadensis 10 (Cassia obtusifolia) and annual day flower (Ipomoea purpurea), but are not limited thereto.

In view of their broad spectrum herbicidal action on broadleaf weeds, the compounds of the present invention may be suitably combined with herbicides for grassy weeds for broad spectrum weed control after hatching in most grassy crops. Examples of herbicides that can be combined with a compound of the present invention include those selected from carbamates, thio-carbamates, chloroacetamides, dinitroanilides, benzoic acids, y- ....

glycerol ethers, pyndazmones, uracil and urea compounds, to combat a wide spectrum of weeds.

The term "herbicide" as used herein refers to an active ingredient that modifies the growth of plants by phytotoxic or plant growth regulating properties, to slow down the growth of plants or to cause sufficient damage to the plant causing it to die. .

Recommended compounds of formula 1 have some or all of the following characteristics: V is N1, W2, W3, W5 or W6, especially W1 or W5, preferably W1, X is H, F or Cl, especially H , Y is F, Cl, Br, especially F or Cl, preferably Cl,

R is H or C 1-4 alkyl, especially H

8500277

BAD ORIGINAL

- 6 - Q is CH,

R 1 is H or C 1-6 alkyl, in particular H or C 1-6 alkyl, preferably C 1-6 alkyl, R 2 is C 1-6 alkyl or C 1-6 alkoxy, especially C 1-6 alkyl, R 1 is C 1-6 alkyl, C 1-6 alkenyl, Cj_ ^ alkoxy-carbonyl-

C 1-4 alkyl, C 1-4 alkoxy-C 1-6 alkyl, C 1-6 alkylthio-C 1-6 alkyl, C 3-8 cycloalkyl, (di-C 12alkylamino) carbonyl-C 1-6 alkyl, especially C 1-6 alkyl, C 1-6 alkoxycarbonyl-C 1-4 alkyl or di-C 1-6 alkylamino-carbonyl-C 1-2 alkyl, especially C 1-6 alkyl, R 10 is H, R 1, R 2, R 9 and R 8 independently, are hydrogen or an alkyl group of 1-4 carbon atoms, R ^ is H or C1-4 alkyl, especially tC ^ Hg, Z is 0.

15

The compounds of the formula I can be suitably used as herbicidal compositions together with acceptable agricultural diluents. Such preparations are also part of the invention. In addition to a 20 or a number of compounds of the formula I as active ingredient, they may also contain other active agents, such as herbicides. They can be used in either solid or liquid form, for example in the form of a wettable powder or an emulsifiable concentrate, in which conventional diluents are present. Such compositions can be prepared or prepared in a conventional manner, for example, by mixing the active ingredient with a diluent and, if desired, other processing ingredients, such as surfactants.

The term diluent used herein refers to any liquid or solid agricultural material which can be added to the active ingredient to bring it into a more convenient or improved usable form, or a conventional or desired degree of activity, respectively. . For example, it can be talc, 8500277

BAD ORIGINAL

7 - kaolin, diatomaceous earth, xylene or water.

In particular, preparations to be applied in spray forms, such as water-dispersible, concentrated products or wettable powders, cpper-1¾ 5 surfactants, such as wetting agents or dispersants, for example the condensation product of formaldehyde with naphthalene sulfonate, an alkyl aryl sulfonate a lignin sulfonate, a higher alkyl sulfate, an ethoxylated alkyl phenol, and an ethoxylated higher alcohol.

Generally, in the compositions will be 0.01-90 wt% active ingredient, 0-20 wt% of an agriculture acceptable surfactant, and 9.9.99-10 wt% (solid or liquid) diluent (s). the active ingredient is either at least one compound of formula I, 115 or mixtures thereof with other active ingredients.

Concentrated forms of the compositions generally contain about 2-90% by weight, preferably about 5-70% by weight, of the active ingredient. The use forms of the preparation may contain, for example, 0.01-20% by weight, preferably 0.01-5% by weight, of the active ingredient.

The parts and percentages mentioned in the following examples are parts by weight and percentages by weight, respectively. RT is room temperature.

125 Sample Preparations

Example A - Emulsifiable concentrated preparation.

13 parts of a compound of formula I, for example the example 37 mentioned above, were mixed with 10 parts of an emulsifier (for example 5 parts of Atlox 3404 F and 5 parts of Atlox 8916 TF, which are mixtures of anionic and non-ionic emulsifiers of ICI America and 77 parts of an organic solvent (for example, xylene or Tenneco 500-100, a mixture of trimethylbenzene and xylene solvents from Tenneco Corpora 85 0 0 2 7 7

BAD ORIGINAL

- 8 - tion), intimately, until a homogeneous solution is obtained. Example B - wettable powder.

25 parts of a compound of formula I, for example the compound 34 mentioned below, 70 parts of kaolin clay, 4 parts of sodium lignosulfonate and 1 part of sodium dialkyl naphthalene sulfonate (for example Sellogen HR from Diamond Shamrock) were mixed and ground in a hammer mill until the particle size became smaller. 10 then 325 ^ u.

Example C - Granular preparation.

2 parts of dipropylene glycol were dissolved in 10 parts of a liquid compound of formula I, for example the compound 38 mentioned below, and the mixture was impregnated by spraying onto 88 parts of a calcined granular attapulgite clay such as Attapulgus Granular LVM from Engelhard Minerals and Chemicals.

20

Compounds of the invention.

Example 1 N-3- (diethylphosphono-1-ethylamino) -4-chloropheny-17-tetrahydrofalimide

1.20 g (3.9 moles) of diethyl 1- (2-chloro-5-aminoanilino) ethylphosphonate were dissolved in 0.5 ml glacial acetic acid. Then 774 mg (5.1 mmol) of 3,4,5,6-tetrahydrophthalic anhydride 30 was added to the solution and the mixture was refluxed for 15 hours. The acetic acid and excess anhydride were then removed under reduced pressure and the crude product obtained was purified by preparative thin layer chromatography to obtain the title compound (Compound 1, Table 35 A).

8500277

BAD ORIGINAL

^ Hi 'Η ^ nmr (CDCl ^ Y 8.74 (t, 6H, P-OCH2CH3), 8.40 (d, 3H, 7Hz, NHCH (CH3)), 8.24 (m, 4H, CH2C = CCH2), 7.64 (m, .4H, CH2CH2), I 5.87 (m, 6H, NHCH (CHJ), £ 3.40 (dd, 1H), 3.32 (s, 1H), 2, 75 (d, B j 1H, 8Hz) aromatic h7. EXAMPLE 2 I Analogous to the method of example 1, compounds 2-48 of formula Ie were obtained by reacting 3,4,5,6-tetrahydrophthalic anhydride with the corresponding aminoanilino compound of formula II (Table A).

Example 3 3- (5- (ethyl P-methylphosphino-1-propylamino) -4-chloro-2-fluoro-115-phenyl-1,5-tetramethylene-hydrantoin.

3.2 moles of 5-ethyl P-methyl-1- 2-chloro-4-fluoro-5- (2-ethoxycarbonyl-1-hexahydropyridinylcarboxamido) -anilino / propylphosphinate were dissolved in 15 ml of ethanol. 20 ml of 2N hydrochloric acid were then added to the reaction mixture and the solution was first refluxed for 5 hours and then at 90 ° C overnight. The ethanol was removed under reduced pressure, the resulting residue was diluted with water and extracted three times. with methylene chloride. The combined extracts were dried and evaporated to dryness. The crude product was purified by thin layer preparative chromatography to give the title compound (compound 49).

Example 4 Analogous to the method of Example 3, the following compounds of formula Ib were prepared by intramolecular cyclization of a compound of formula V, wherein Rg represents the ethyl group.

8500277

BAD ORIGINAL

-10-

Connection input W '' X Y R Rj R2 ZR3 50 W3 Cl Cl H C2H5 CH3 OC ^ 51 W3 F Cl H C2H5 CH3 OC ^ 5 52 W2 (Q = N) F Cl H 0 £ Η CH3 0C2H5

Example 5 2-t-butyl-4-t5-methyl β-ethylphosphinomethylamino) -4-chloro-2-fluorophenyl-Δ ~ 1,3,4-oxadiazoline-5-one.

10

3.2 moles of methyl P-ethyl-2-chloro-4-fluoro-5- (N'-pivaloylhydrazino) anilino-7-methylphosphinate, 3.9 moles of trichloromethylchloroformate and 3.5 moles of triethylamine in 50 ml were heated dioxane for 3.5 hours. The dioxane was then removed under reduced pressure. The product was diluted with methylene chloride, washed, dried, evaporated to dryness and purified by preparative thin layer chromatography to obtain the title compound (compound 53).

Example 6 2-t-butyl-4- / 5-O-ethyl P-ethyl-phosphino-1-ethylamino) -4-chlorophenyl-7-2 A, -1,3,4-oxadiazolin-5-one.

According to the method of Example 5, a mixture of 0.62 g (1.6 mmol) of methyl P-ethyl-1-2-chloro-5- (N'-pivaloylhydrazino) anilinethylphosphinate and 0.39 g ( 2.0 m.mol) trichloromethyl chloroformate in 8 ml dioxane heated at 60 ° C for about 8 hours, whereby, after solvent removal and purification, the title compound MS m / e 401 30 (M +) ( compound 54) was obtained.

Example 7 3-t-butyl-1 - 5- (methyl β-methylphosphino-1-propylamino) -2,4-dichloro-2-phenyl-Δ-1,2,4-triazolin-5-one.

35 8500277

BAD ORIGINAL

-11-

A mixture of 9.6 moles of methyl P-methyl-1- (2,4-dichloro-5-hydrazinoanilino) propyl phosphinate and 9.6 moles of pivaloylurea in 12 ml of decahydrohaphthalene (decalin) was heated for about 8 hours under stirring under reflux, according to the method of Gold-Aubert et al., Helvetia Chimica Acta 47 (5): 1188 (1964), whereby, after purification, the title compound (compound 55) was obtained.

EXAMPLE 8: 10 1- (5-methyl β-ethylphosphinomethylamino) -4-chloro-2-fluorophenyl / -1 A -1,2,4-triazolin-5-one.

According to the method of Example 7, methyl H P-ethyl (2-chloro-4-fluoro-hydrazinoanilino) -methylphosphinate 15 was reacted with formyl urea to give the title compound (compound 56).

Example 9 4-Methyl-1- / 5- (methyl-P-ethylphosphinomethylamino) -4-chloro-2-20 fluorophenyl-7-1,2,4-triazolin-5-one.

3.0 mole mole methyl chloride, 2.5 mmole sodium hydride and 15 ml dimethylformamide were added to compound 56. Afterwards

The mixture was heated at 80 ° C for 2 hours. After cooling to room temperature, the reaction mixture was poured into water and extracted with methylene chloride. The combined extracts I were washed with water, dried, evaporated to dryness and purified by preparative thin layer chromatography to obtain the title compound (compound 57).

18500277

BAD ORIGINAL

-12-Table A

Compounds of Formula Ie

Connection MS m / e XYRZ ^ (M * + 1) 1 H Cl H CH3 0CH2CH3 0 CH2CH3 441 2 H Cl H CH3 CH2CH3 0 CH3 411 3 H Cl Η H CH2CH3 0 C »3 397 4 H Cl H CH2CH3 CH2CH3 0 CH3 425 5 Cl Cl H CH3 CH2CH3 0 - CH3 6 F Cl H CH3 CH2CH3 0 CH-j 7 FFH CH3 CH2CH3 0 CH3 8 Cl Br H CH3 CH2CH3 0 CH3 9 H Cl Η H CH3 0 CH2CH3 10 H Cl Η H CH2CH (CH3) 2 0 CH2CH3 11 H Cl Η H CH2 (CH3) 2 0 CH3 12 H Cl Η H 0CH3 0 CH3 13 H Cl Η H CH2CH3 0 CH (CH3) 2 14 H Cl Η H CH2CH3 '0 CH2CH (CH3) 2 15 H Cl Η H CH2CH3 0 CH2CH2CH (CH3) 2 16 H Cl Η H CH2CH3 0 CH2C (0) 0CH3 17 H Cl Η H CH2CH3 0 CH (CH3) C (0) 0CH2CH3 18 H Cl Η H CH3 0 CH2C ( 0) 0CH3 19 H Cl H Or CH2CH3 O CH2C (0) 0CH3 20 F Cl Η H CH2CH3 O CH2C (0) 0CH3 21 H Cl Η H CH2CH3 O CH2CH = CH2 22 H Cl Η H CH2CH3 O CH2CH20CH3 23 H Cl Η H CH2CH3 O CH-CHg ch2 24 H Cl Η H CH2CH3 O CH2CH2SCH3 25 F Cl Η H CH2CH3 NH CH2CH2CH3 26 F Cl Η H CH2CH3 NH CH2CH2CH (CH3) 2 27 F C1 HH CH2CH3 NH CH (CH3) C (0) N ( CH3) 2 8500277

BAD ORIGINAL

I * V

(continued) Table A

128 H Cl H CH2CH3 0CH3 0 CH3 427 29 H Cl H CH3 0CH3 0 CH3 413 30 H Cl H CH3 0CH (CH3) 2 0 _ CH (CH3) 2 469 '31 H Cl Η H 0CH (CH3) 2 0 CH ( CH3) 2 455 32 H Cl H CH3 CH2CH2CH3 0 CH2CH3 439 33 H Cl H CH2CH2CH3 CH2CH3 0 CH2CH3 453 34 H Cl H CH2'CH2CH3 CH3 0 c H * 39 135 H Cl H CH2CH2CH3 CH3 0 CH3 5 425 36 H Cl H CH2CH2CH3 CH2CH3 0 CH3 439 37 H Cl H CH (CH3) 2 CHgCH-j 0 CH3 439 38 H Cl H CH (CH3) 2 CH3 0 CH3 425 39 H Cl H CH (CH3) 2 CH3 0 CH2CH3 439 40 H Cl H CH (CH3) 2 CH2CH3 0 CH2CH3 453 41 H Cl H CH3 CH3 0 CH3 397 42 H Cl H CH2CH3 CH3 0 CH3 411 43 H Cl H CH3 CH3 0 CH2CH3 411 44 H Cl H CH2CH3 CH3 0 CH2CH3 425 45 H Cl Η H CH2CH3 0 CH2CH3 411 46 H Cl H CH3 CH2CH3 0 CH2CH3 425; 47 H Cl H CH2CH3 CH2CH3 0 CH2CH3 439 148 Cl F H CH2CH3 CH3 O CH2CH3 443 8500277

BAD ORIGINAL

V

% - -14-

The selection of the compounds of Table A was characterized by the nuclear magnetic resonance spectrum as follows:

Connection no.

2 NMR (COCl3) r 7.84-9.17 (m, 12H, PCH2CH3, NHCH (CH3), CH2C = CCH2), 7.64 (m, 4H, CH2CH2), 6.25 (d, 3H, 10Hz, P0CH3), 6, 30 (m, 1H, NHCH (CH 3)), 5.14 (m, 1H, NH), [3.40 (dd, 1H)., 3.32 (s, 1H), 2.75 (d, 1H .8Hz) aromatic 3 NMR (C0Cl3) r 9.00, 8.70 (tt, 3H, PCH2CH3), 8.24 (m, 4H, CH2C = CCH2), 7.64 (m, 4H, CH2CH2), 6.50 (tt, 2H, NHCHg), 6.25 (s, 3H, POCH3), 5.37 (m, 1H, NH), [3.40 (dd, 1H, 2Hz), 3.32 (s, 1H) , 2.75 (d, 1H, 8Hz) aromatic 4 NMR (COCl3) X 9.00, 8.70 (tt, 3H, PCH2CH3), 8.97 (t, 3H, NHCH (CH2 CH3)), - 8 .24 (m, 4H, CHgC-CCHg), 7.94 (sextet, 2H, PCHgCH-g), 7.64 (m, 4H, CH2CH2), 6.30 (m, 1H, NHCH), 6.25 (d, 3H, 10Hz, P0CH3), 5.54 (m, 1H, NH), [3.40 (dd, 1H, 2Hz), 3.32 (s, 1H), 2.75 (d, 1H, 8Hz) aromatic 33 NMR (CDCl3) X 9.07 (m, 6H, (CH2) 2-CH3, P-CH2CH3), 8.68 (t, 3H, P-0CH2CH3), 8.19 (µL, 4H , CHgCHgCHg), 7.59 (m, 4H, Ct ^ OCCHg), 6.34 (m, 1H, NH-CH-P), 5.87 (m, 2H, P-0CH2CH3), 5.48 (dd , 1H, NH) [3.34 (d, 1H), 3.28 (s, 1H), 2.70 (d, 1H) phenyl H].

34 NMR (CDCl 3) V 9 ^, 08 (t, 3H, (CH 2) 2 -CH 3), 8.72 (t, 3H, P-0CH 2 CH 3), 8.53 (d, 3H, P-CHg), 8 .20 (m, 4H, CH 2 CH 2 Hj), 7.60 (m, 4H, C 1 C-CCHg), 6.32 (m, 1H, NH-CH-P), 5.90 (m, 2H, P-OCHgCH2, 5.57 (dd, 1H, NH) and [3.34 (d, 1H), 3.22 (s, 1H), 2.66 (d, 1H) phenyl H].

8500277

BAD ORIGINAL

I compound 35 NMR (CDCl 3) Tr 10 (t, 3H, (CH 2 -CH 3), 8.54 {d, 3H, P-CH 3), 8.20 (m, 4H, CH 2 -CH 2 -CH 3), 7 .60 (m, 4H, CH2C = CCH2), 6.34 (m, 1H, NHCH-P), 6.26 (d, 3H, P-OCf ^), 5.60 (m, 1H, NH) and [3.3O (d, 1H), 3.30 (s, 1H), 2.70 (d, 1H) phenyl H].

37 NMR (CD 13) ΐ 8.92 (m, 9H, CH () 2, P-CH2CH3), 7.58 (m, 4H, 6.32 (m, 1H, NH-CH-P), 6, 24 (dd, 3H, P-0CH3), 5.27 (dd, 1H, NH), and [3.36 (d, 1H), 3.30 (s, 1H), 2.70 (d, 1H) phenyl H].

38 NMR (CDCl3) ^ 8.90 (m, 6H, CH (CH3) 2), 8.54 (d, 3H, P-CH-j), 7.59 I (m, 4H, CH ^) C ^ C-CHg), 6 ^, 34 (m, 1H, NH-CH-P), 6.26 (d, 3H, P-OC ^), 5.33 (dd, 1H, NH) and [1.34 (d, 1H), 3.30 (s, 1H), 2.70 (d, 1H) phenyl H].

18500277

BAD ORIGINAL

-16-

Intermediates.

Example 10

Diethyl 1- (2-chloro-5-nitroanilino) ethyl phosphonate.

5

A mixture of 1.20 g (6.9 mole) of 2-chloro-5-nitroaniline, 1.7 ml of acetaldehyde, 3.46 g (20.8 mole) of triethyl phosphite, 0.4 ml of boron trifluoride was heated in ether and 30.0 ml of toluene under reflux for 2 hours, after which the reaction mixture was cooled and poured into aqueous sodium bicarbonate. The solution was then extracted with ether. The ether extracts were combined, washed with water, dried and evaporated to dryness. The crude product was purified by preparative thin layer chromatography to give the title compound (crystalline).

Example 11

Analogous to the procedure of Example 10, the starting material of formula XI for compounds 2-15 and 28-48 of Table A and for compounds 49-52 was obtained by reaction of the corresponding aniline, aldehyde and phosphite or phosphonite.

Similarly, methyl P-ethyl-2-chloro-4-25 fluoro-5-nitroanilinomethylphosphinate (starting material for compounds 20, 53, 56 and 57) and methyl P-ethyl-1- (2,4-dichloro-5 nitroanilino) propyl phosphinate (the starting material for compound 55).

30 Example 12

Methoxycarbonylmethyl P-ethyl-2-chloro-5-nitroanilinomethyl phosphinate.

8 ml of thionyl chloride was added to methyl P-35 ethyl-2-chloro-5-nitroanilinomethyl phosphinate and the mixture was left to 85 0 0 2 7 7

BAD ORIGINAL

Staan stand overnight at room temperature. The excess thionyl chloride was then removed to give P-ethyl-2-chloro-5-nitroanilinomethylphosphinic acid chloride. This acid chloride was treated with 2.0 g of sodium hydroxide in 100 ml of water. The aqueous solution was then acidified and extracted with B ether, the combined ether extracts dried and evaporated. giving P-ethyl-2-chloro-5-nitroanilinomethylphosphinic acid

I was obtained.

A mixture of 5.59 moles of the aforementioned phosphinic acid, 0.9 g of potassium carbonate, 1.2 g (0.74 ml, 7.80 moles) of methyl bromoacetate and 20 ml of acetone was heated under reflux overnight . The reaction mixture was then allowed to cool to room temperature and filtered and the filtrate concentrated. The residue was extracted into methylene chloride and the combined extracts were washed, dried and

Evaporated to dryness to give the title compound. The starting materials of formula XI for compounds 1.7, 18, 19 and 20 were obtained in the same manner.

Example 13

1.0 g of P-ethyl-2-chloro-5-nitro-anilinomethylphosphinic acid chloride, 1.3 g of 2-propenyl and 10 ml of methylene chloride were combined and this mixture was allowed to stand at room temperature for 2 hours, after which it was worked up in an aqueous medium, to obtain 2-propenyl P-ethyl-2-chloro-5-nitroanilinomethyl phosphinate.

The starting materials of formula XI for compounds 22, 23 and 24 (Table A) were similarly obtained using methoxyethanol, cyclopropanol and methylthioethanol as alcohol, respectively.

8500277

BAD ORIGINAL

-18-

Example 14

1.5 g of P-ethyl-2-chloro-4-fluoro-5-nitro-anilinomethylphosphinic acid chloride, 2.2 g of irpropylamine, 2.0 g of triethylamine and 10 ml of methylene chloride were combined and this reaction mixture was left for 3 hours at room temperature and worked up in an aqueous medium to give n-propyl P-ethyl-2-chloro-4-fluoro-5-nitroanilinomethylphosphinamide.

The starting materials of formula XI for compounds 26 and 27 (Table A) were obtained in the same manner, using 3-methylbutylamine and 1- (dimethyl-aminocarbonyl) ethylamine as amine, respectively.

Example 15 Diethyl 1- (2-chloro-5-aminoanilino) ethyl phosphonate.

A mixture of 1.74 g (5.7 mole) of diethyl 1- (2-chloro-5-nitroanilino) ethylphosphonate, 0.30 g (5.7 mole) of ammonium chloride and 1.26 g ( 22.7 moles) iron in 16.0 ml ethanol and 8.0 ml water under reflux for about an hour. The reaction mixture was then filtered and the filtrate was evaporated to dryness. The residue was taken up in methylene chloride, washed with sodium chloride solution, dried and evaporated to give the title compound after purification by preparative thin layer chromatography.

Example 16 The starting materials of formula II for compounds 1-15 and 17-57 were obtained in an analogous manner by hydrogenation of the corresponding nitro compound of formula XI.

35 8500277

BAD ORIGINAL

-19-

Example 17

Methoxycarbonylmethyl P-ethyl-2-chloro-5-amino-anilinomethyl phosphinate.

Methoxycarbonylmethyl P-ethyl-2-chloro-5-nitroanilinomethylphosphinate was suspended in 50 ml of 5% acetic acid and 2.0 g of iron powder was added. The mixture was then heated under reflux for 1 hour. After cooling to room temperature, the reaction mixture was filtered and the filtrate was extracted with methylene chloride. The combined extracts were dried over magnesium sulfate and evaporated to dryness, after which, after purification by preparative thin layer chromatography, the title compound was obtained.

15 Example 18

Ethyl P -methyl-1- / 2-chloro-4-fluoro-5- (2-ethoxycarbony1-1-hexa-hydropyridinylcarboxamido) anilinQ7propylphosphinate.

A mixture of 3.2 moles of ethyl P-methyl-1-20-1- (2-chloro-4-fluoro-5-aminoanilino) -propylphosphinate and 0.76 g (0.46 ml, 3.9 m) was heated. mol) trichloromethyl chloroformate. in 50 ml of dioxane and 0.36 g (0.49 ml, 3.5 mole) of triethylamine for 3 hours. The dioxane was then removed under reduced pressure to obtain the corresponding isocyanate, the residue of which was taken up in 35 ml of methylene chloride. 0.754g (0.75ml, 4.8mol) ethyl pipecolinate was added and the mixture was stirred at room temperature overnight. Finally, the mixture was diluted with methylene chloride, washed with water, dried and evaporated to dryness to give the title compound 30.

Example 19

Analogous to the method of Example 18, the starting material of formula V for compounds 50, 51 and 52 was 85 0 0 2 77

BAD ORIGINAL

-20- obtained by reaction of the corresponding isocyanate with methyl methylaminoacetate HCl / NiC 2 H 3) and N-ethoxycarbonylhexahydropyridazine HCl / NCC 2 H 3), respectively.

5 Example 20

Methyl P-ethyl-Z2-chloro-5-fluoro-5- (N, -pivaloylhydrazino) -am.linQ-methylphosphinate.

a) 3.4 moles of methyl P-ethyl- (2-chloro-4-10 fluoro-5-aminoanilino) methylphosphinate were dissolved in 10 ml 6N hydrochloric acid.

The temperature of the solution was kept between -15 and -20 ° C when 0.24 g (3.5 moles) of sodium nitrite were added dropwise into 2 ml of water. The mixture was heated to 0 ° C and stirred at 0 ° C for 1 hour. An ice-cooled solution of stannous chloride. 2 H 2 O in 2 ml of concentrated hydrochloric acid was then quickly added to the mixture and stirred at 0 ° C for an additional 2.5 hours.

The reaction mixture was neutralized with saturated sodium bicarbonate and extracted with methylene chloride. The combined extracts were washed with water, dried, evaporated to dryness and purified by preparative thin layer chromatography to give methyl P-ethyl (2-chloro-4-fluoro-5-hydrazino-anilino) -methylphosphinate.

b) To the aforementioned phosphinate (2.5 mole) 25 in 10 ml methylene chloride, 3.0 mole pivaloyl chloride and 3.0 mole triethylamine were added. The mixture was stirred at room temperature for 4 hours, after which it was washed with water, dried and evaporated to give the title compound.

The starting material of formula VIII for compound 54 was obtained in an analogous manner. The starting material of formula IX for compounds 55, 56 and 57 was obtained analogous to the method of example 20a).

35 8500277

BAD ORIGINAL

I, «* i

Assessment of the herbicidal action.

Example 21 The herbicidal action for hatching of selected I compounds of the present invention was as follows determined: Seeds of selected weeds were planted and the soil was soaked with a solution of water (17%), surfactant (0.17%) and the compound to be tested in an amount equivalent to 1.12 g / m ^. The evaluation! division occurred two weeks after treatment. The grasses (GR) Setaria vividis, Echinochloa, crus-galli, Sorghum bicolor and Avena fatua and the broadleaf crops (BL) Ipomoea purpurea, IBrassica juncea,. Solanum spp. and Abutilon theophrasti were treated. The average performance for hatching of the compounds is shown in Table B below.

Example 22 t i! The herbicidal activity after hatching of selected compounds was determined as follows: Seedlings of selected weeds were sprayed with a solution of a mixture of equal parts water and acetone, surfactant (0.5%) and the test compound in a amount equivalent to 1.12 g / m 2. The evaluation was made 2 weeks after spraying. The grass species (GR) Setaria vividis,

Echinochloa crus-galli, Sorghum bicolor * lfiPin: oval-leaved crops (BL) Ipomoea purpurea, Brassica juncea, glycine max and Abutilon theophrasti. The average activity 30 after hatching of the compounds is shown in Table B below.

35 8500277

BAD ORIGINAL

2

-22-Table B

the percentage of herbicidal activity at 1.12 g / m 5 before hatching

connection GR_BL GR_BL

4 100 100 95 100 32 100 100 96 100 10 33 100 100 100 100 34 100 100 91 100 35 100 100 91 100 37 100 100 100 100 38 100 100 95 100 15 39 100 100 100 100 40 100 100 100 100 42 100 100 100 100 43 100 100 98 100 1 S 5 0 ö 2 7 7

BAD ORIGINAL

Claims (7)

2. A compound of formula 1, wherein W represents a group 20 of formula WI, wherein R 1 and R 1. represent a hydrogen atom. A compound according to claim 2, wherein X represents a hydrogen, chlorine or fluorine atom, Y a chlorine atom and R j represents a hydrogen atom or an alkyl group with 1-3 carbon atoms. A compound according to claim 3., wherein Z represents an oxygen atom, R2 represents a methyl, ethyl, n-propyl or iso-I propyl group and Rg represents a methyl or ethyl group. 5. A herbicidal formulation comprising one or more compounds according to any one of claims 1 to 4, optionally together with an agricultural diluent acceptable. 8500277 BAD ORIGINAL -24- Method for controlling weeds, characterized in that a herbicidally effective amount of one or more compounds according to any one of claims 1-4 is applied in the field of these weeds. A compound selected from formula II as defined in claim 1 or formula XI, wherein X, Y, R, Rj, R ^, R ^ and Z have the meanings defined in claim 1. 8. Methods as described in the description and / or examples. 10 / 'Ϋ / ƒ 85 0 0 2 7 7 BAD ORIGINAL