HU184655B - Herbicide compositions containing o-aryl- or 0,0-diaryl-n-/phosphono-methyl/-glycine nitriles and process for preparing the active substances - Google Patents

Abstract

The herbicide contains at least one compound of the formula <IMAGE> and an inert extender or diluent. The diesters of the formula I (b = 0, x = 0) are prepared by reacting a corresponding compound of the formula <IMAGE> with 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine. The monoesters of the formula I (b = 1, x = 0) are prepared by dissolving a diester, prepared as above, in an inert solvent which contains an equivalent amount of water to cause hydrolysis of one (aryl-Xa-O) group. The salts of the formula (b = 0, x = 1) are prepared by dissolving a diester of the formula I in an anhydrous solvent which contains a strong acid of the formula R. In the formulae, aryl, X, Z, a, b and x are as given in Claim 1.

Description

The present invention relates to herbicidal compositions containing O-aryl or 0,0-diaryl-N-phosphonomethylglycinitrile and to a process for the preparation of the active ingredient.

U.S. Patent No. 3,923,877 discloses that N-phosphonomethylglycine is prepared by treating a dihydrocarbonyl phosphite with

1.3.5-Tricyanomethylhexahydro-1,3,5-triazine is reacted in the presence of a catalyst such as hydrogen halide, Lewis acid, carboxylic acid halide or carboxylic anhydride and the resulting product is hydrolyzed. The yield of this process is extremely unfavorable. It is apparent from the description of the invention that the reaction takes place between the phosphite and the triazine to form an intermediate, the N-phosphonomethylglycinitrile ester. Esters prepared by the process of the present invention are esters containing C 1-6 aliphatic groups or phenyl-substituted aliphatic groups such as benzyl and preferably C 1-6 alkyl. These esters are hydrolysed to yield N-phosphonomethylglycine, which can be used as an active ingredient in post-emergence herbicides. It has been found that 0,0-diethyl-N-phosphonomethylglycinitrile produced by the process described in that patent has no post-emergence herbicidal activity at 4.48 kg / ha and no pre-emergence herbicidal activity. , 60 kg / ha when used.

It has been found that 0.0-diaryl-N- (phosphonomethyl) glycine nitriles can be prepared without any catalyst by reacting a diaryl phosphite with 1,3,5-tricyanomethylhexahydro-1,3,5-triazine. It has also been found that the glycerol nitriles thus prepared, as well as the corresponding monoaryl esters of these compounds, obtained by mild hydrolysis, exhibit pre-emergence and post-emergence herbicidal activity, which is completely surprising since O, O-diethyl-N-phosphonomethyl- glycinitrile is ineffective.

The N-phosphonomethylglycine nitriles used as active ingredients in the herbicidal compositions of the present invention correspond to formula (I). In the formula, R _is phenyl or naphthyl optionally substituted with one, two or three halogen atoms, C 1-4 alkyl, C 1-3 alkoxy or alkylthio, methylenedioxy, trifluoromethyl and / or nitro. substituted,

Z is oxygen or sulfur, b is 0 or 1

R is a strong acid and

X is 0 or 1, with the proviso that X is when b is 1.

According to the above limitation, strong acid salts are formed only with a diester. When a strong acid is added to a monoester (compound of formula IV), the only aryl ester group can be cleaved from the molecule by hydrolysis.

N-phosphonomethylglycinitriles according to formula (I). in the general formula X and b are 0; is prepared from the phosphoric acid ester of formula II.

- Z and R _a are as defined above -, and

1.3.5-Tricyanomethylhexahydro-1,3,5-triazine (also called N-methyleneglycine) nitrile trimer, which is represented by the formula (III), is made into a standing mixture and heated to a sufficiently high temperature. to initiate the reaction and maintain the temperature 2 sufficiently high for the reaction between the phosphorous acid ester and the triazine to take place and form the N-phosphonomethylglycinitrile of formula (I).

_5. The herbicidal compositions according to the invention the active substance of the preparation of the same there is no need to use a solvent, but its use is sometimes preferable to use a solvent for convenience and to facilitate the course of the reaction. The solvent is also useful for controlling the reaction temperature. For this purpose, a solvent may be used in which the triazine is soluble and does not react with the reactants. Examples of such an inert solvent include acetonitrile, ethyl acetate, tetrahydrofuran.

It has been found that the reaction temperature may be low and be in the range of about 25 ° C to 110 ° C. Higher temperatures can be used, but no measurable benefits are obtained as the reaction is substantially complete at a time when the temperature rises to about 85 ° C.

The above formulas (II) and (III) show that the best results are obtained when the ratio of the phosphoric acid ester to the triazine is 3: 1. Higher or lower ratios may be used, but there is no appreciable advantage, since higher ratios require the isolation of excess phosphoric acid ester, and lower ratios allow the formation of by-products.

The reaction is usually carried out at atmospheric pressure as it is economical. While working at higher or lower pressures, we do not get measurable benefits.

For the preparation of compounds of formula I wherein b is 1 and x is 0, that is, for the preparation of compounds of formula IV, Z and R _a are as defined above, a compound of formula V is Z and R _a is as defined above, prepared with a solvent containing at least one molar equivalent of water and maintained at ambient temperature where one of the groups (R _a -O) is hydrolyzed. The preferred solvent for hydrolysis is acetone. The desired product is isolated by known methods such as fractional crystallization or vacuum distillation of the solvent and other volatile hydrolysis products and the desired product can be crystallized from a suitable solvent.

For the preparation of compounds of formula I wherein b is 0 and x is 1, that is, compounds of formula VI - Z, R _a and R are as defined above - are prepared by reacting a compound of formula V in anhydrous solvent, dissolved in chloroform and a strong acid is added to the solution. The acid is added alone or, in some cases, alone, to the solution, and the mixture is stirred at ambient temperature for a period of time sufficient to allow the compound of formula (V) and the acid to react to form the compound of formula (VI). In some cases, the desired product precipitates in crystalline form from the reaction mixture. In other cases, a mixture of chloroform and diethyl ether (50% to 50% by volume) is added to the reaction mixture to start crystallization of the product or to isolate the product as an oil.

Compounds of formula (VI) are compounds of formula (V), i.e. salts of diesters may also be represented by formula (VII).

-21,184

In the formula, Z and R _a are as defined above and R _{1 is} an anion of a strong acid.

Examples of substituents on phenyl or naphthyl include halogen such as chlorine, fluorine and bromine, alkyl such as methyl, ethyl, propyl and butyl; alkoxy groups such as methoxy, ethoxy and propoxy; alkylthio groups such as methylthio, ethylthio, and propylthio; and methylenedioxy, trifluoromethyl, and nitro. These groups on the same ring may be the same or different from each other. ₁

Strong acids which can be used to prepare the salts of the compounds of formulas I, VI and VII are those having a pK _a in water of 2.5 or less, such as p-toluenesulfonic acid, p-chlorobenzenesulfonic acid, trichloro -acetic acid, oxalic acid, fluoroboric acid, hydrochloric acid, -j hydrobromic acid, hydrogen iodide, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, trifluoromethanesulfonic acid, nitric acid, sulfuric acid, phosphoric acid, trifluoromethane, , methanesulfonic acid.

In the preparation of salts with the strong acids of the formulas I, VI and VII, the diester of the phosphonic acid and the strong acid are preferably used in molar equivalents to facilitate the isolation of the strong acid salt. Higher or lower ester / acid ratios may be used, but isolation of the product becomes more difficult due to the excess of one of the reagents.

The compounds of formula (I) may be used as active ingredients in both pre-emergence and post-emergence herbicidal compositions.

The following general embodiments illustrate 3 preferred methods for preparing compounds of formula (I).

The diaryl esters of formula (V) are preferably prepared by one of the following two methods:

A) A solution of 3.4 g (0.0167 mole) of 1,3,5-tricyanomethylhexahydro-3 -1,3,5-triazine and 0.050 mole of diaryl phosphate in 50 ml of acetonitrile was stirred in a reaction vessel and Heat at 85 ° C for 1 to 90 hours until all phosphites and triazines have reacted, as determined by NMR analysis. In the 4 cases where the NMR spectral analysis shows no impurities present in the solution, the product is isolated by vacuum evaporation. If impurities are present, the product is isolated and purified by crystallization or chromatography. In some cases, isolation of the diester product in high purity form is difficult, since hydrolysis may occur during the isolation.

B) A mixture of 0.05 moles of diaryl phosphite and 3.4 g (0.0167 moles) of 1,3,5-triacinomethylhexahydro-1,3,5-triazine was placed in a rocking vessel and for 20 min. The mixture is heated at 60-100 ° C for 1 hour. During this time, all phosphite and triazine undergoes conversion, as determined by NMR spectral analysis. The product is purified by crystallization or chromatography. 5

The N-phosphonomethylglycinitrile monoaryl ester is prepared by dissolving the diaryl ester in acetone. The acetone contains a small amount of water (typically about 2% by weight) and the reaction mixture is stirred for 18-72 hours. The monoester usually crystallizes, the crystals are collected on a filter, washed with acetone and air dried.

The strong acid salts of the diaryl esters are preferably prepared by the following general method.

Strong acid solution (or strong acid alone) 6

655 2

0.01 M is added dropwise to the chloroform solution at room temperature at room temperature and the solution is allowed to stand. When crystals form, they are collected by filtration, washed with chloroform-ether (1: 1) and air-dried. Otherwise, chloroform-ether (1: 1) is added to the solution to induce crystallization or to precipitate an oily product. The following examples and experiments are intended to illustrate in greater detail the herbicidal compositions of the present invention and their preparation θ. Unless otherwise specified, parts in the examples and the experimental part are parts by weight.

Example 7

23.32 g (0.06 mol) of 78% pure di (p-chlorophenyl) phosphite and 4.08 g (0.02 mol) of 1,3,5-tricyanomethylhexahydro-1, 3,5-Triazine is stirred in a reaction vessel at ambient temperature and then heated at 100 ° C for 20 minutes. 27 g of 0.0-di-p-chlorophenyl-N- (phosphonomethyl) glycinitrile are thus obtained, which corresponds to a 100% yield.

ηέ * = 1.5747.

Example 2

A solution of 8.7 g (0.03 mol) of di (3,4-dimethylphenyl) phosphite in 10 ml of aceto- ⁵ nitrile is added 2.04 g (0.01 mol) of 1,3,5-tricyanomethylhexahydro -1, 3,5-triazine in 50 ml of acetonitrile and the mixture was heated at 55 ° C for 90 hours. The solid present was removed by filtration and the solvent evaporated to give a red ⁰ oil having the NMR analysis shows that it contains the following items. 8.0 g of the oil obtained are chromatographed on 450 g of silica gel eluting with 50% cyclohexane / 50% ethyl acetate and collecting 60 ml fractions. 30-41. Fractions 1 to 4 yield 0.0-di (3,4-dimethylphenyl) -N- (phosphonomethyl) glycine nitrile after removal of the solvent. M.p. 61-64 ° C. The solid was recrystallized from carbon tetrachloride isooctane to give 3.1 g of product. M.p. 63-66 ° C. Yield 40%.

Example 3

A mixture of 0.02 mol of di-p-methylthiophenylphosphite and 0.0067 mol of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine was stirred at 80 ° C for 1.0 hour. heat to length to obtain ⁵ sticks of red-brown oil. Half of the product is kept in the refrigerator for 8 days, whereupon a semi-solid mass is formed. The material was then recrystallized from 70 ml of carbon tetrachloride to give a pink solid. The resulting solid was dissolved in 100 mL of warm carbon tetrachloride and filtered through 5.0 g of silica gel-covered celite. The filtrate was concentrated to 50 ml and allowed to stand overnight in a refrigerator. The resulting suspension was filtered to give 1.8 g of a white solid, which was identified as 0.0-di- (p-methylthiophenyl) -N-) phosphonomethyl) glycine nitrile.

Mp 64-65 ° C. Yield 45%.

Analysis

Calculated: C, 51.8; H-4.9: N, 7.1%

Found: C, 51.7; H, 4.9; N, 7.1%. Example 4

8.05 g (0.025 mol) of 91% pure di (o-methoxyphenyl) phosphite and 1.7 g (0.0083 mol) of 1,3,5-tricyanomethyl-hecahydro-1,3,5- The triazine solution was heated at 55 ° C for 73 hours and then filtered. The filtrate was concentrated and 3

This gave 9.6 g of a dark brown oil. 5.8 g of the oil were bound on 8 g of silica gel and extracted with 80 ml of ethyl acetate. The ethyl acetate solution was concentrated and the resulting oil was triturated on silica gel (4.0 g). The silica gel was extracted with ethyl acetate (70 mL) and the solution concentrated in vacuo to give a pale yellow oil. .

= 1.5542.

The yellow oil is 0.0-di (o-methoxyphenyl) -N- (phosphonomethyl) -glynitrile containing a small amount of o-methoxyphenol 1.

Example 5

13.6 g (0.066 mole) of 3,5-triciano-methyl-hexahydro-l, 3,5-triazine, and 46.8 g (0.2 mol) of diphenyl phosphite was treated with 100 ml acetonit- ₁ Linezolid 55 'C. is heated for 48 hours.

NMR analysis showed complete conversion to 0.0-diphenyl-N- (phosphonomethyl) glycine nitrile. The acetonitrile was then removed from the reaction mixture in vacuo to give 57 g of a black viscous solid; Oil was obtained in 94.4% yield. The oil was dissolved in chloroform, silica gel (114 g) was added and the mixture was evaporated to dryness in vacuo. The product impregnated silica gel is then applied to a column containing 200 g of silica gel saturated with chloroform and eluted with chloroform until no product can be detected in the eluent by NMR analysis. The chloroform eluate was concentrated, the residue was dissolved in dichloromethane and the solution was washed twice with 100 ml of 5% potassium hydroxide solution and then with water. The dichloromethane layer was dried over anhydrous magnesium sulfate and evaporated. This gave 37.9 g of a pale yellow oil which solidified on standing. The product was 0.0-diphenyl-N- (phosphonomethyl) glycinitrile, m.p. 64-67.5 ° C. '

Yield 75%.

example

10.7 g of di (m-tolyl) phosphite (0.04 mole) and 2.72 g (0.0133 mole) of 3,5-triciano-methyl-hexahydro-l, 3,5-triazine in 100 ml of acetonitrile ^z The mixture was heated at 50 ° C for 3 days. The color of the solution changes to wine red. The solvent was evaporated to give 12.4 g of a red oil in 92.4% yield. 9.0 g quantity of the oil was chromatographed on silica eluting with 60% ^z cyclo- hexane / 40% ethyl acetate as eluent, and 60 ml fractions up. 45-63. fractions yield pure 0.0-di (mtolyl) -N- (phosphonomethyl) glycine nitrile. 1.25 g of product are obtained, corresponding to a yield of 14%. '= 1.5467,

Analysis

Calculated: C, 61.81; H, 5.80; N, 8.48%

Found: C, 61.75; H, 5.81; N, 8.41%

Example 7

15.2 g (0.0392 mol) of 83% pure di (m-nitrophenyl) phosphite and 2.66 g (0.013 mol) of 1,3,5-tricyanomethylhexahydro-1,3, A solution of 5-triazine in acetonitrile was heated at 50 ° C for 20 h. At this point, NMR analysis showed the reaction was complete. The solution was then filtered and the solvent removed in vacuo to give 13 g of an amber oil which was 0.0-di (m-nitrophenyl) -N- (phosphonomethyl) glycine nitrile. í

655 2

Analysis

Calculated: C, 45.93; H, 3.34; N, 14.28%

Found: C, 45.80; H, 3.39; N, 14.27% & Example

15.63 g (0.05 mole) of 94% pure di (p-methoxyphenyl) phosphite and 3.4 g (0.0167 mole) of 1,3,5-tricyanomethylhexahydro-1, 3,5-Triazine is dissolved in acetonitrile and the solution is refluxed for 1 hour. The solvent was then evaporated in vacuo to give a dark pink oil (19.0 g). 5 g of this oil was separated by high pressure liquid chromatography eluting with 40/60% (v / v) cyclohexane / ethyl acetate to give 4.1 g of 0.0-di (p-methoxyphenyl) -N-phosphonomethylglycinnitrile. Yield 82%.

N ^2! = 1.5541.

Example 9 ₀ 2.04 g (0.01 mol) of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine and 8.8 g (0.03 mol) of 91.6% of a mixture of pure purity di-p-fluorophenylphosphite in 50 ml of acetonitrile was heated at 55 ° C for 70 hours. The reaction mixture was then filtered and the solvent removed in vacuo.

_5, giving a brown oil which is 92% pure 0,0-di (p-fluorophenyl-N- (phosphonomethyl) -glicinnitril. N £ ⁵ = 1.5270.

Example 10

9.93 g (0.03 mol) of 91.5% pure di (m-chlorophenyl) phosphite is dissolved in 20 ml of acetonitrile and 2.05 g (0.01 mol) of 1.3.5 is added. trichloromethylhexahydro-1,3,5-triazine and then heated at 55 ° C for 70 hours. The acetonitrile is then removed in vacuo to the brim to leave a light pink oil which is 92% pure 0.0-dichlorophenyl-N- (phosphonomethyl) glycine nitrile. n £ ^s = 1.5656.

Example 11

4.0 g (0.099 mol) of the diester prepared in Example 10 are dissolved in 100 ml of 2% aqueous acetone and the solution is stirred at ambient temperature for 6 days during which time a solid is formed. The resulting solid was collected, washed with acetone and dried. 1.55 g of O-m-chlorophenyl-N- (phosphonomethyl) glycine nitrile are obtained in the form of a solid.

Mp 181-182 'C. Yield 60%.

Analysis calculated for C 41.5; H, 3.9; N, 10.8%

Found: C, 41.5; H, 3.9; N, 10.8%

Example 72

2.38 g (0.069 mol) of the> 5 diester prepared in Example 9 are dissolved in 100 ml of 2% aqueous acetone and stirred at ambient temperature for 3 days. The resulting slurry was filtered and the solid washed with acetone to give 0.87 g of a tan-red solid, m.p. 258-262 ° C. The mother liquor was allowed to stand for 6 weeks and the resulting solid was collected and washed with acetone. 0.8 g is obtained, m.p. of the compound identified as O- (p-fluorophenyl) -N- (phosphonomethyl) glycine nitrile.

»5 Yield 98%.

184,655

Analysis

Calculated: C, 44.3; H, 4.1; N, 11.5%

Found: C, 44.3; H, 4.2; N, 11.5%

Example 13

0.01 Diphenyl-N- (phosphonomethyl) glycine nitrile (51 g, 0.005 mol) was dissolved in 50 ml of 2N hydrochloric acid with stirring for 2 hours. At the bottom of the vessel an amber oil is formed which is phenol. The vessel was cooled to room temperature and the hydrochloric acid solution was washed twice with 25 ml of methylene chloride to remove starting material and phenol formed during the reaction. The hydrogen chloride solution was then cooled in an ice bath.

During cooling, crystallization begins. The crystals were collected, washed with cold water and air dried. The crystals were identified as 0-phenyl-N-phosphonomethylglycinitrile by the same melting point values. Analysis of the crystals gives the following composition:

Analysis

Calculated: C, 47.49; H, 4.90; N, 12.39%

Found: C, 47.52; H, 4.93; N, 12.12%

Example 14

0.0 g (0.012 mol) of 0.0-di-m-tolyl-N- (phosphonomethyl) glycine nitrile is dissolved in 50 ml of acetone containing 1 ml of water and the solution is stirred at ambient temperature for 60 days. Three crystalline fractions are obtained. The crystals of the first two fractions have a melting point of 161-166 ° C and are determined to be impure. The third fraction had a melting point of 179-179.5 ° C and was analytically pure 0- (m-tolyl) -N- (phosphonomethyl) glycine nitrile, available in 53% yield.

Analysis

Calculated: C, 50.0; H, 5.5; N, 11.7%

Found: C, 50.0; H, 5.5; N, 11.7%

Example 15

3.15 g (0.008 mol) of 0.0-di (m-nitrophenyl) -N- (phosphonomethyl) glycine nitrile are dissolved in 50 ml of acetone containing 1 ml of water and the solution is stirred for 16 hours at room temperature. A solid formed which was collected and washed with acetone to give 1.1 g of product, 51% yield. The product obtained is 0- (m-nitrophenyl) -N-phosphonomethylglycinitrile, m.p. 174-176 ° C.

Analysis

Calculated: C, 40.0; H, 3.4; N, 15.6%

Found: C, 40.0; H, 3.4; N, 15.5% / 6 examples

II, 64 g (0.0314 mol) of di (m-trifluoromethyl) phosphite and 2.15 g (0.0105 mol) of 1,3,5-tricyanomethylhexahydro-1,3,5, - A solution of triazine in 100 ml of acetonitrile was heated at 50 ° C overnight. The acetonitrile is then evaporated in vacuo and a solid begins to precipitate. The residue was dissolved in a mixture of 50 ml of acetone and 1 ml of water and the solution was stirred overnight at ambient temperature. A solid precipitates, which is collected and washed with acetone to give 3.5 g (39.5%) of a white solid. The product is

0- (m-trifluoro-tolyl) -N- (phosphonomethyl) -glicinnitril.

195-196 ° C.

Analysis

Calculated: C 40.8; H, 3.4; N 9.5% ⁵ Found: C, 41.0; H, 3.5; N, 9.7%

Example 17

9.0 g (0.024 mol) of 0,0-di (p-chlorophenyl) -N- (fosztbno methyl) -glicinnitrilt dissolved in 50 ml of acetone was stirred and 1 ml of a mixture of ⁰ precipitate filtered and the solution at room temperature for two days. The resulting solid was collected, weighing 2.35 g and melting at 170 ° C with decomposition. The solid is 0- (p-chlorophenyl) -N- (phosphonomethyl) glycine nitrile. The mother liquor was allowed to stand for a few weeks to give 5 additional 0.85 g of product. All products were 3.2 g, which corresponds to a yield of 51%.

Example 18 g (0.05 mol) of 83.8% di (3-methyl-4-nitrophenyl) phosphite and 3.4 g (0.0167 mol) of 1,3,5- tricyanomethylhexahydro-1,3,5-triazine was dissolved in 100 ml of acetonitrile and the solution was heated at 70 ° C for 1 hour. The acetonitrile solvent is then removed in vacuo and the residue is dissolved in 50 mL of acetone containing 1 mL of water and the solution is stirred at ambient temperature. This gives 4.3 g of crystalline product which is 0- (3-methyl-4-nitrophenyl) -N- (phosphonomethyl) glycine nitrile.

Mp 181-182 ° C. Yield 30%.

“Analysis

Calculated: C, 42.1; H, 4.2; N, 14.7%

Found: C, 42.2; H, 4.3; N, 14.7%

Example 19

3.0 g (0.0082 mole) of 0.0-di-p-methoxyphenyl-N- (bisphonomethyl) glycine nitrile is dissolved in 50 ml of acetone and 1 ml of water and the solution is stirred at ambient temperature for three months. The resulting solid was collected by filtration, washed with acetone and dried. The solid is 0- (p-methoxyphenyl) -N- (phosphonomethyl) glycine nitrile, m.p. 185-195 ° C.

Analysis

Calculated: C, 46.9; H, 5.1; N, 11.0%

Found: C, 47.1; H, 5.2; N, 10.8%

Example 20

19.5 g (0.05 mol) of 80% di (o-chlorophenyl) phosphite are added 3.4 g (0.01640 mol) of 1,3,5-tricyanomethylhexahydro-1 3,5-triazine in 50 ml of acetonitrile and the solution was heated at 70 ° C for 2 hours. A solution (15 ml) was concentrated and the residue was dissolved in a mixture of acetone (50 ml) and water (1 ml) and the solution was stirred overnight. A solid formed which was collected, washed with acetone and dried. 3.2 g of O - (o - chlorophenyl) - N - (phosphonomethyl) glycine nitrile are thus obtained.

Mp 170-171 ° C. Yield 82%.

Analysis: Calculated: C, 41.5; H, 3.9; N, 10.8%

Found: C, 41.4; H, 3.9; N, 10.7%

184,655

Example 27

0.08 M (0.069 mol) of 0.0-di-p-fluorophenyl-N- (phosphonomethyl) glycine nitrile was stirred in a mixture of carbon tetrachloride and methylene chloride (1: 1), filtered and filtered. 67 g (0.069 mol) of methanesulfonic acid are added to the filtrate. The solution is then allowed to stand overnight and the crystals formed are collected on a filter and washed with carbon tetrachloride. This gives 2.68 g of white crystalline material which is 0.0-di-p-fluorophenyl-N- (phosphonomethyl) glycine nitrile methanesulfonic acid.

132-132.5 ° C.

Analysis

Calculated: C, 44.2; H, 4.0; N, 6.5; S 7.4%

Found: C, 44.0; H, 4.0; N, 6.6; S 7.5%

Example 22

1.9 g (0.01 mol) of p-toluenesulfonic acid in 100 ml of benzene are refluxed and the water is removed in the form of an azeotropic mixture with benzene. This benzene solution was then added to a solution of 0.02 g (0.1 mol) of 0.02-diphenyl-N-phosphonomethylglycinitrile in 100 ml of a 50/50 by volume mixture of benzene / methylene chloride. The mixture is stirred for one minute at room temperature while crystallization begins. The resulting slurry was stirred at room temperature overnight and then the solid was collected by filtration. 4.38 g of 0.0-diphenyl-N- (phosphonomethyl) glycine nitrile p-toluenesulfonic acid salt are obtained in the form of a white solid, m.p. 151-153 ° C.

Yield 92.4%

Analysis

Calculated: C, 55.7; H, 4.9; N, 5.9%

Found: C, 55.4; H, 4.9; N, 5.7%

Example 23

A solution of p-chlorobenzenesulfonic acid (1.92 g, 0.01 mol) in chloroform was added to a solution of 3.0 g (0.01 mol) of 0.0-diphenyl-N- (phosphonomethyl) -glycinitrile in chloroform. After 10 minutes, crystallization begins, and the resulting slurry is stirred overnight, filtered and the solid remaining on the filter is washed with chloroform to give 4.0 g of 0.0-diphenyl-N-phosphonomethyl-glycine nitrile-p-chloro bengolsulfonic acid salt was obtained in 81% yield

149-151 ° C.

Analysis

Calculated: C, 51.0; H, 4.1; N, 5.7%

Found; C, 50.7; H, 4.1; N, 5.7%

Example 24

A solution of trichloroacetic acid (1.63 g, 0.01 mol) in chloroform (20 ml) was added to a solution of O-diphenyl-N-phosphonomethylglycinitrile (3.0 g, 0.01 mol) in chloroform (100 ml), and then stirred at room temperature overnight. The solvent was then removed in vacuo to give 3.75 g of a yellow oil, which was O.O-diphenyl-N-ylphosphonomethyl-O-glycine nitrile trichloroacetic acid. Yield 80%.

N '= 1.5410.

Analysis

Calculated: C, 43.9; H, 3.5; N, 6.0%

Found: C, 43.9; H, 3.5; N, 5.9%

Example 25

A solution of oxalic acid dihydrate (1.26 g, 10 mmol) in acetone (25 mL) was added to a solution of 0.02 g (10 mmol) of 0.02-diphenyl-N- (phosphonomethyl) glycine nitrile in acetone. After 10 minutes, crystallization begins in the oil. After stirring overnight and cooling, the precipitated crystalline material was collected to give 1.9 g of product. The mother liquor was then evaporated to give an additional 0.8 g of product. The total yield was 2.7 g, which corresponds to a yield of 69%. The product obtained is 0.0-diphenyl-N-phosphonomethyl) glycine nitrile oxalic acid salt.

165 DEG C. (dec.).

Analysis

Calculated: C, 52.1; H, 4.4; N, 7.1% Found: C, 52.1; H, 4.4; N, 7.1% Example

An ethereal solution of perchloric acid was added to a solution of 3.0 g (10 mmol) of _n- 0.0-diphenyl-N- (phosphonomethylglycinitrile in chloroform-ether) and the perchlorate salt crystallized slowly as white prisms. The diphenyl-N- (phosphonomethyl) -glycine nitrile perchloric acid salt was collected by filtration, washed with ether-chloroform2g to give 0.73 g of product, 18% yield.

Mp 166-168 ° C.

Analysis

Calculated: C, 44.7; H, 4.0; N, 7.0%. Found: C, 44.8; H, 4.0; N, 7.0%

Example 27

A solution of trichloromethane-phosphonic acid (1.99 g, 0.01 mol) in chloroform-metalone mixture was added to a solution of 3.0 g of 35 (10 mmol) of 0.0-diphenyl-N-phosphonomethyl-glycinnitrile in chloroform. Ether was added to the solution 10 minutes after the addition but no crystallization started. Light petroleum is then added to the solution until the cloud point is reached. At this point, crystallization begins after 10 minutes. The mixture was allowed to stand for an additional 10 minutes and the crystals formed were collected. This gives 2.9 g of the product, which is the 0.05-diphenyl-N-phosphonomethyl-glycinitrile trichloromethane-phosphinic acid salt.

145-146 ° C. Yield 58% ⁴⁵ Analysis

Calculated: C38.3; H, 3.4; N, 5.6%

Found: C, 38.3; H, 3.5; N, 5.6%

2 & example

To a solution of 3.0 g (10 mmol) of 0.0-diphenyl-N- (phosphonomethyl) glycine nitrile in chloroform-ether mixture is added a solution of fluoroboric acid in ether. The solution was then stirred overnight, and the resulting solid was filtered and washed with ether-chloroform (50:50). This gives 1.1 g of crystalline material which is the 0.0-diphenyl-N- (phosphonomethyl) glycine nitrile fluoroboronic acid salt.

156-158 ° C. Yield 28%

Analysis

Calculated: C, 46.2; H, 4.1; N 7.2%

Found: C, 46.0; H, 4.2; N 7.2%

-6184655

Example 29

Gaseous hydrobromide was bubbled through a solution of 3.0 g (10 mmol) of 0.0-diphenyl-N- (phosphonomethyl) glycine, cinnitrile in chloroform. The solution was then allowed to stand overnight. Meanwhile, the hydrogen bromide salt crystallizes, the crystals are collected and washed with ether. In this way, 3.0 g of the 0.0-diphenyl-N-phosphonomethylglycinitrile hydrobromide salt is obtained, corresponding to a 78% yield.

Analysis

Calculated: C, 47.0; H, 4.2; N, 7.3%

Found: C, 47.1; H, 4.3; N, 7.4%

Example 30. 2 ml of 57% hydrogen iodide was added to a solution of 3.0 g (10 mmol) of 0.0-diphenyl-N- (phosphonomethyl) glycine nitrile in chloroform. The solution becomes cloudy and its color turns golden yellow. After two hours no crystals form, so ether is added until the cloud point is reached and crystallization begins. The solution was stirred for an additional 1 hour and the solid was collected. In this way, 2.4 g of the 0.0-diphenyl-N-phosphonomethylglycinitrile hydrogen iodide salt are obtained, which appear as light yellow sheets.

163-164 ° C, 56% yield.

Analysis

Calculated: C, 41.9; H, 3.8; I 29.5%

Found: C, 41.8; H, 3.8; I 29.3%

Example 31

Trifluoroacetic acid (1.14 g, 10 mmol) was added to a solution of O-diphenyl-N- (phosphonomethyl) glycine nitrile (3.0 g, 10 mmol) in chloroform. The solution was stirred overnight and the solvent was evaporated in vacuo to give 4.0 g of the 0.0-diphenyl-N- (phosphonomethyl) glycine nitrile trifluoroacetic acid salt as a light yellow oil in 96% yield. equivalent to.

n ^ ⁵ = 1.5172.

Example 32

Trifluoromethanesulfonic acid (1.50 g, 10 moles) was added as a smoke to a solution of 3.0 g (10 moles) of 0.0-diphenyl-N- (phosphono-methylglycinitrile chloroform) and the mixture was stirred at room temperature for 2 hours. After stirring for 1 hour, the solid was collected and washed with chloroform-ether (50:50) to give 3.8 g of 0.0-diphenyl-N-. (phosphonomethyl) glycine nitrile trifluoromethanesulfonic acid salt, 84% yield, m.p. 119-120 ° C.

Analysis

Calculated: C, 42.5; H, 3.6; N 6.2%

Found: C, 42.7; H, 3.6; N 6.2%

Example 33

To a solution of 15.1 g (0.05 mol) of 0.0-diphenyl-N- (phosphonomethyl) glycinitrile in chloroform was added 5.0 g (0.051 mol) of methanesulfonic acid and the solution was stirred for 2 hours at ambient temperature. The precipitated solid precipitate was collected, washed with ether and dried. 15.90 g of 0.0-diphenyl-N- (phosphonomethyl) -nitrile-methanesulfonic acid salt are obtained, corresponding to a yield of 82.1%.

147-150 ° C.

Analysis

Calculated: C, 44.2; H, 4.0; N, 6.5; S 7.4%

Found: C, 44.0; H, 4.0; N, 6.6; S 7.5%

Example 34

A solution of 0.9 g (0.01 mol) in 70% nitric acid in ether was added to a solution of 3.0 g (0.01 mol) of 0.0-diphenyl-N- (phosphonomethyl) glycine nitrile in 100 ml of Idoroform. Diethyl ether was added to the solution, followed by addition of 20 ml of isocyanate. At this point, crystal formation begins. After stirring for 1 hour at room temperature, the resulting crystals were collected, washed with chloroform and air dried. Thus, 2.66 g of 0.0-diphenyl-N- (phosphonomethyl) glycine nitrile nitric acid salt are obtained, corresponding to a yield of 72%.

116-116.5 ° C.

Analysis

Calculated: C, 49.32; H, 4.42; N, 11.5%

Found: C, 49.2; H, 4.42; N, 11.6%

Example 35

To a solution of 3.2 g (0.01 mol) of 0.0-diphenyl-N- (phosphonomethyl) glycine nitrile in 100 ml of chloroform was added a solution of 1.01 g (0.01 mol) of 98% sulfuric acid in ether. Additional chloroform was added and the mixture was stirred for 2 hours. The precipitated solid was collected by filtration, washed first with chloroform and then with food and dried. Yield: 3.9 g of 0.0-diphenyl-N- (phosphonomethyl) glycine nitrile sulfuric acid salt, corresponding to 100% yield.

151-151,5 ° C.

Analízié

Calculated: C, 45.0; H, 4.28; S 8.1%

Found; C, 44.90; H, 4.27; S, 8.05%;

A solution of phosphoric acid in ether (0.01 mol) was added to a solution of 0.0 g (0.01 mol) of 0.0-diphenyl-N- (phosphonomethyl) glycine nitrile in chloroform and the mixture was stirred at ambient temperature. The solution immediately becomes cloudy and an oil appears on the bottom of the vessel. The reaction mixture was cooled, the solvent was decanted, evaporated to dryness and the residue was dried over anhydrous magnesium sulfate. The resulting solid represents the 0.0-diphenyl-N-phosphonomethylglycine nitrile phosphoric acid salt, m.p. 74.5-78.5 ° C.

Yield 25%.

Analysis

Calculated: C, 45.0; H, 4.5; N, 7.0%

Found: C, 44.8; H, 4.6; N, 7.1%

Example 37

A heterogeneous solution of 0.04 g (0.2 mol) of 0.0-diphenyl-N- (phosphonomethyl) glycine nitrile in 500 ml of ethanol was cooled in an ice bath and bubbled with dry hydrogen chloride gas. The solution was then allowed to stand, ethyl ether was added and the white solid collected by suction. An additional white solid is formed when additional dry hydrogen chloride gas is bubbled through the solution, the ethanol-ether mother liquor, at about 0 ° C. The solid was collected and washed with ether. Dy way, 62.7 g of 0.0-diphenyl-N- (phospho

-7184655 is obtained with the phosphomethyl) glycine nitrile hydrochloride salt, which corresponds to a 93% yield.

112-123 ° C.

Analysis

Calculated: C, 53.19; H, 4.79; N, 8.27%

Found: C, 53.51; H, 4.78; N, 8.30%

3 & example

17.8 g (0.05 mole) of di (2,4,6-trimethylphenyl) phosphite are added 3.4 g (0.0164 mole) dissolved in 50 ml of acetonitrile.

1.3.5-Tricyanomethylhexahydro-1,3,5-triazine and the mixture was heated at 80 ° C for 18 hours. The resulting black solution was filtered and concentrated to an oil, 7 g of which was chromatographed on 450 g of silica gel. Elution was carried out with 70% cyclohexane / 30% ethyl acetate (60 mL fractions) and fractions 28-40, 1.0 g of 0.0-di (2,4,6-trimethylphenyl) -N- (phosphono- methylglycine nitrile was obtained which corresponds to a yield of 14%.

Mp 118-120 ° C.

Analysis

Calculated: C, 65.27; H, 7.04; N, 7.25%

Found: C, 65.38; H, 7.07; N, 7.18%

Example 39

A solution of the diester of Example 3 (0.025 mol) in wet acetone (50 ml) was heated at reflux for 2 hours and then allowed to stand at ambient temperature for 5 days. The suspension was filtered to isolate 0.9 g of an impure pink solid. The filtrate was left in a stoppered container for an additional 30 days at ambient temperature. The resulting slurry was filtered and the separated solid was washed with 50 mL of acetone. 4.5 g of O- (p-methylthiophenyl) -N- (phosphonomethyl) glycine nitrile are thus obtained in the form of a white solid, corresponding to 66% yield.

M.p. 250-253 ° C (dec.).

Analysis

Calculated: C, 44.12; H, 4.81; N, 10.29%

Found: C, 44.26; H, 4.86; N, 10.22%

Example 40

8.2 g (0.0246 mole) of diphenylthiophosphite and 1.68 g (0.0023 mole) of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine are dissolved in 50 ml of acetonitrile and the solution is heated at 60-65 ° C for 2 hours. The resulting oil was chromatographed on silica gel (450 g) eluting with 60% cyclohexane / 40% ethyl acetate to collect 60 mL fractions. 1.6 g of 0.0-diphenyl-N- (thiophosphonomethyl) glycine nitrile are thus obtained in 20% yield from fraction 30.

n "= 1.5847.

Analysis

Calculated: C, 56.60; H, 4.75; N, 8.80; S 10.07%

Found: C, 56.40; H, 4.80; N, 8.73; S 10.26%

Example 41

33.5 g (0.1 mol) of di (3-naphthyl) phosphite and 20.4 g (0.1 mol)

A solution of 1.3.5-tricyanomethyl-hexahydro-1,3,5-triazine in 100 ml of acetonitrile was heated at reflux for 1 hour and then concentrated. This gave a red-brown oil, from which 10 g was purified by high performance liquid chromatography on silica gel. Elution was carried out with 60% cyclohexane / 40% ethyl acetate and 20 ml fractions were collected. 45-64. fractions were combined and concentrated. and the product is crystallized from the resulting oil. This way

1.1 g of 0.0-di ((3-naphthyl) -N- (phosphonomethyl) glycine nitrile are obtained in the form of a light yellow solid.

104-105 ° C.

Analysis

Calculated: C, 68.65; H, 4.76; % N, 6.96 ¹⁰ Found: C, 68.58; H, 4.79; N, 6.92%

Example 42

A solution of 0.05 mol of di (3,4-methylenedioxyphenyl) phosphite and 0.0167 mol of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine in 75 ml of acetonitrile was stirred. The mixture is heated at 75 ° C for 3 hours and then allowed to stand overnight at ambient temperature. The solution is then concentrated to give an amber oil. 7.6 g (0.02 mol) of the oil are dissolved in 100 ml of chloroform and 1.92 g (0.02 mol) of methanesulfonic acid are added dropwise. After stirring for 15 minutes, ether (200 mL) was added to give a white precipitate. The solid was recrystallized twice from acetone to give 4.6 g of 0.0-di (3,4-methylenedioxyphenyl) -N- (phosphonomethyl) glycine nitrile methanesulfonic acid salt (47% yield). a. 135-136.5 ° C.

Analysis

Calculated: C, 44.45; H, 3.94; N, 5.76%

Found: C, 44.26; H, 3.95; N, 5.71%

Example 43

A solution of the amber oil of Example 42 (0.01 mol) in wet acetone (70 ml) was heated at reflux for 4 days. The amber solution was then allowed to stand at ambient temperature for 1 day. The resulting suspension was filtered to give 1.7 g of 0- (3,4-methylene di q _4-yloxy) -N- (phosphonomethyl) -glicinnitrilt as a white solid.

160-161 ° C.

Example 44

A solution of 0.04 mol of di (3,4-dichlorophenyl) phosphite and 0.013 mol of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine in 40 ml of acetonitrile was heated to 80 ° C and kept at this temperature for 18 hours. The resulting solution was concentrated and the resulting oil was treated with 80 ml of wet acetone and heated to reflux for 80 hours. The resulting suspension was filtered and the white solid remaining on the filter was washed with 50 mL of acetone to give 6.3 g of O- (3,4-dichlorophenyl) -N- (phosphonomethyl) glycine nitrile (53%). yield.

169-170 ° C.

Example 45. 234 g (1.0 mol) of diphenylphosphite are added to a solution of 68 g (0.333 mol) of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine in 300 ml of acetonitrile and the mixture is stirred for 75 hours at 75- Heat at 82 ° C. The solution was then cooled and concentrated in vacuo to give a black oil, which was mainly the product of Example 5.

101 g of this oil are burned on silica gel

184,655 was added (which was dissolved in chloroform, silica gel was added and the solvent was evaporated). This material was chromatographed on 1.1 kg of silica gel eluting with chloroform (1 liter fractions were collected). 13-14. fractions were combined, concentrated, and recrystallized from dichloromethane-cyclohexane. 51 g of 0.0-diphenyl-N-phosphonomethylglycinitrile are thus obtained.

Recognition that O-aryl-N- (phosphonomethyl) glycine nitriles can be prepared in high yields by reacting a diaryl phosphite with 1,3,5-tricyanomethylhexahydro-1,3,5-triazine without it was not foreseeable in U.S. Patent No. 3,923,877. The process described in that patent requires the use of an acidic catalyst such as hydrogen halide, Lewis acid, carboxylic anhydride or acid halide. In one example, N- (phosphonomethyl) glycine nitrile diester can be prepared in only 6.12% yield with diethyl phosphite and 1,3,5-tricyanomethylhexahydro-1,3,5-triazine hydrogen. chloride-saturated solution. In contrast, the process of the present invention provides N- (phosphonomethyl) glycine nitrile diaryl esters in 45% to 100% yield. In contrast to the example of U.S. Patent No. 3,923,877, the reaction materials are reacted in stoichiometric amounts without leaving the hydrochloride catalyst at 40 ° C but at 100 ° C. nor after 24 hours of reaction time. The same negative result is obtained if the example is repeated without acidic catalyst but using acetonitrile as solvent and the reaction is carried out for 24 hours at 100 ° C. In another experiment, the same procedure as above was followed, with the modification that chloroform was used as a solvent. Again, no reaction occurs at 40 ° C or 100 ° C.

In the case of the acidic catalyst mentioned in U.S. Patent No. 3,923,877, a diaryl phosphite such as diphenyl phosphite and 1,3,5-tricyanomethylhexahydro-1,3,5, The reaction of the triazine, i.e. the reaction in the presence of hydrogen chloride as described in the example, yields the desired product in only 15% yield, as opposed to 75% in the method of the present invention.

These results show that there are significant differences in the reaction of dialkyl phosphite and diaryl phosphite with 1,3,5-tricyanomethylhexahydro-1,3,5-triazine, which are currently unexplained. Example 57

The post-emergence activity of the herbicidal agents containing the active compounds of the formula I is shown below. The composition is sprayed onto 14 to 21 day old plants of different varieties. The spray is a solution in 1% water or water / acetone (1: 1) containing 0.01% by weight of a surfactant (35 parts dodecylbenzenesulfonic acid butylamine salt and 65 parts condensation product, 11 moles ethylene). oxide and 1 mole of tall oil) and applied to plants in various bowls. The solutions are sprayed onto the plants at specific ratios per kg / ha (kilograms / hectare). The treated plants are then kept in a greenhouse and observed for approximately 2 or 4 weeks. The results are shown in Figures I and Π. Table.

I and II. In Table 1, the post-emergence herbicidal activity index is as follows:

plant response

0-24% mortality

25-49% mortality 50-74% mortality 75-99% mortality total mortality no treatment plant species index +

WAT (weeks after treatment) in the table indicates the number of weeks after treatment. The treated plant species and the letters used to designate them were as follows:

A - Field thistle B - Conch C - Silkworm D - Dawn E - Goat grass F - Bitter grass G - Slurry H - Millet wheat I - Sorghum J - Rye

K - Cocksfoot L - Soybeans M - Sugar Beets N - Wheat O - Rice P - Sorghum Q - Butterflies R - Butterfly S - Millet T - Muhar

The following tables show the letters of the active ingredient (preparation example), the number of weeks after treatment and the code numbers of the plant species indicated above.

Table 7

plant Variety

OD authorities material WAT kg / ha THE B C D E F G H I J K 1 4 11.2 3 4 4 1 4 4 3 2 3 3 3 4 5.6 3 3 4 2 4 4 2 1 1 2 3 40 2 4 11.2 4 4 3 2 4 3 3 2 0 .3 4 4 5.6 3 3 3 2 4 4 2 1 1 4 3 3 4 11.2 3 3 3 3 4 4 2 3 3 2 3 4 5.6 3 4 1 2 4 4 2 2 2 1 2 4 4 11.2 4 4 3 4 4 4 2 2 2 4 3 45 4 5.6 4 3 3 2 3 4 2 1 1 3 4 5 4 11.2 2 4 3 4 4 3 2 2 3 3 4 4 4.48 3 4 3 3 4 4 2 1 2 1 3 6 4 11.2 3 4 4 3 4 4 1 2 2 2 3 4 5.6 2 4 1 3 4 4 1 1 3 1 3 50 7 4 11.2 2 3 2 1 4 3 2 1 4 2 2 4 5.6 3 2 2 1 3 3 1 1 4 1 3 8 4 11.2 2 4 2 1 4 4 2 3 4 1 2 4 5.6 3 3 3 2 4 4 2 1 4 1 3 9 4 11.2 4 4 4 3 4 4 1 3 2 3 4 55 4 5.6 4 4 4 2 4 4 1 3 2 3 4 10 4 11.2 4 4 3 3 4 4 2 3 3 4 4 4 5.6 3 3 3 2 4 4 1 2 1 3 4 11 4 11.2 4 4 4 4 4 4 3 3 2 3 4 4 5.6 4 4 4 2 4 4 2 3 1 3 4 60 12 4 11.2 4 4 3 2 4 4 2 3 4 2 4 4 5.6 4 4 3 2 4 4 3 3 3 1 4 13 4 11.2 2 + 4 4 4 3 3 3 4 3 4 4 4.48 3 + 3 3 4 2 3 3 3 3 3

(Table continues)

-9Hatóanyag

WAT kg / ha AB (Continued from Table A) Plant varieties CDEFGHI JK

184 655 2 (Continuation of the table)

plant Variety

WAT kg / ha ABCDEFGHI UK

14 - 4 4 11.2 5.6 4 3 4 4 3 4 4 2 4 4 4 1 2 1 2 3 4 2 3 4 5 32 4 4 11.2 5.6 4 4 4 4 4 4 2 2 4 4 4 3 3 2 4 4 4 4 4 2 2 2 4 4 15 4 11.2 4 4 4 2 4 4 4 3 3 4 4 33 4 11.2 4 4 3 4 4 4 3 4 4 3 4 4 5.6 3 4 0 1 3 4 2 2 4 3 3 4 5.6 4 + 4 2 4 4 3 3 4 3 4 16 4 11.2 4 4 3 1 4 4 3 4 4 2 4 34 4 11.2 4 4 4 4 4 4 2 3 3 3 4 4 5.6 4 4 2 1 4 4 2 3 4 0 3 10 4 5.6 2 3 4 2 4 3 2 3 3 3 3 17 4 11.2 4 4 4 3 4 4 3 3 4 3 4 35 4 11.2 4 4 3 3 4 4 2 3 3 3 4 4 5.6 3 4 4 3 4 4 2 2 • 4 3 4 4 5.6 4 3 4 2 4 4 2 3 3 3 3 18 4 11.2 3 3 3 2 4 4 2 2 3 2 3 36 4 11.2 3 4 4 3 4 4 3 3 4 4 4 4 5.6; 4 3 2 2 4 4 2 1 3 1 3 4 5.6 4 4 2 3 4 3 2 3 4 2 3 19 4 11.2 4 4 4 2 2 2 3 1 3 0 2 15 37 4 11.2 4 4 4 3 4 4 3 3 4 4 4 4 5.6 2 4 1 1 2 2 3 1 10 2 4 5.6 4 4 4 3 4 4 3 3 3 3 4 20 4 11.2 3 4 2 2 3 4 2 3 3 2 3 38 2 11.2 0 1 1 0 0 0 0 0 3 0 0 4 5.6 3 3 1 2 4 4 2 1 3 2 3 2 5.6 0 1 0 0 0 0 0 0 1 0 0 21 4 11.2 4 4 3 2 4 4 2 3 4 3 3 39 4 11.2 2 4 3 1 4 4 3 3 4 2 3 4 5.6 2 3 3 2 4 4 2 2 2 3 3 20 4 5.6 2 3 2 1 2 2 3 2 4 2 3 22 4 11.2 4 4 4 3 4 4 4 4 4 4 4 40 4 11.2 1 2 1 1 4 1 1 1 2 0 2 4 5.6 3 3 4 2 4 4 3 3 3 2 4 41 4 11.2 1 3 3 1 4 4 2 2 2 1 3 23 4 11.2 4 4 4 4 4 4 4 4 2 4 4 4 5.6 1 3 2 1 3 3 2 2 1 1 3 4 5.6 4 4 4 3 4 4 4 2 3 4 4 42 4 11.2 4 4 4 4 4 3 3 4 4 3 4 24 4 11.2 4 3 4 3 4 4 3 4 3 4 4 25 4 5.6 4 3 2 3 4 4 3 2 4 1 4 4 5.6 3 4 4 1 4 4 2 2 1 3 3 43 4 11.2 2 4 3 3 4 4 2 3 2 2 3 25 4 11.2 4 4 4 3 4 4 3 2 14 4 · 4 5.6 1 3 3 2 4 4 2 2 1 1 3 4 5.6 4 4 4 2 4 4 2 1 2 4 3 44 4 11.2 2 4 3 3 4 4 2 3 2 2 4 26 4 11.2 3 4 3 3 4 4 1 1 3 13 4 5.6 2 3 3 2 4 4 2 3 3 1 4 4 5.6 2 3 2 2 4 4 1 1 2 2 3 30 Die-0.0 4 4.48 0 0 0 0 0 0 0 0 0 0 0 27 4 11.2 2 3 3 2 4 4 1 1 1 3 3 methyl-N- 4 5.6 2 · 3 3 2 4 4 1 1 1 1 2 - (phospho- 28 4 11.2 2 4 4 3 4 4 2 1 3 4 4 no-me- 4 5.6 3 3 3 2 3 3 1 0 1 1 3 methyl) -gli- 29 4 11.2 3 3 4 2 3 4 2 1 4 2 4 35 cinnitril- 4 5.6 4 3 3 2 3 4 2 1 3 1 4 (3,923 4 11.2 0 1 0 1 0 0 0 0 0 0 0 30 4 11.2 3 3 3 3 4 4 3 2 2 2 3 No. 877 4 5.6 4 3 3 2 4 3 1 1 2 1 3 USA- 31 4 11.2 2 4 3 4 4 4 1 2 2 2 3 have US 4 5.6 2 3 2 2 3 3 1 SHE 4 1 2 40 tailor. leí- (Table continues) RAS)

II. Spreadsheet

authorities material WAT kg / ha plant Variety L M N 0 P B Q D R E F c J · s K T 1 4 5.6 4 2 2 3 3 3 1 1 1 3 3 3 2 2- 3 3 4 1.12 2 1 1 1 2 2 1 1 1 2 2 2 1 2 3 3 4 0.28 1 1 0 1 1 1 1 1 0 2 2 1 0 1 1 1 2 4 5.6 4 3 2 3 3 3 4 2 4 4 4 3 3 4 3 3 4 1.12 2 1 1 1 1 2 1 1 1 2 2 2 1 1 2 2 2 0.28 . 1 0 0 0 1 1 0 0 0 0 0 1 0 0 0 1 3 4 5.6 3 3 4 4 3 3 4 2 3 4 4 1 3 3 3 4 4 1.12 2 1 1 1 2 2 1 1 1 2 1 1 2 2 2 2 4 0.28 1 0 0 0 1 1 0 1 0 1 0 0 0 1 J 1 4 4 5.6 4 3 2 3 3 3 1 2 2 4 4 3 1 2 3 3 4 4.12 2 1 1 1 3 2 1 1 1 3 2 2 1 1 1 2 4 0.28 1 0 1 0 1 1 1 1 0 2 0 0 0 0 0 0 ¹ (Table continues)

-101

184,655

authorities material WAT kg / ha L M N 0 P B Q plant Variety E F C J (Continuation of the table) s K T D R 5 4 4.48 4 3 3 3 4 4 3 4 4 4 4 4 4 4 4 4 4 1.12 1 1 1 2 3 2 2 2 2 3 3 3 3 4 3 4 4 0.224 1 0 1 0 3 2 1 2 0 2 0 1 1 3 3 3 6 4 1.12 2 1 1 3 4 2 1 2 4 4 4 4 4 4 4 4 4 0.28 1 1 1 1 3 2 1 2 2 2 2 2 1 3 2 3 4 0,056 1 0 0 0 1 1 0 1 1 0 1 0 0 1 1 2 7 4 1.12 0 0 0 0 1 2 0 4 0 0 0 0 0 0 0 0 8 4 1.12 l 1 1 1 2 2 1 1 0 2 3 2 1 0 1 4 9 4 5.6 4 3 2 3 3 3 3 + 4 4 4 4 3 4 4 4 4 1.12 2 2 2 3 3 3 1 2 4 4 4 4 2 4 3 4 4 0.28 1 1 1 1 2 2 1 2 2 2 2 2 1 2 2 2 10 4 5.6 3 3 2 4 4 3 4 4 4 4 4 '4 4 4 4 4 4 1.12 2 3 2 3 3 2 2 3 2 4 4 2 2 4 3 4 4 0.28 1 1 1 1 1 1 2 1 1 4 2 2 0 2 1 2 13 4 4.48 3 3 3 3 3 3 3 3 3 4 3 4 3 4 3 4 4 1.12 1 2 1 2 2 3 2 2 2 3 1 1 2 4 3 3 4 0.224 1 0 0 2 2 1 1 1 1 3 1 1 1 4 2 3 14 4 5.6 3 3 3 3 3 2 1 2 4 4 4 4 2 4 4 4 4 1.12 2 2 1 2 2 2 0 2 4 3 3 2 1 2 3 4 15 4 1.12 1 0 0 0 3 2 0 1 0 2 4 1 2 4 1 3 16 4 5.6 2 1 1 2 3 3 1 2 2 2 4 1 0 2 2 3 4 1.12 1 1 1 1 3 2 1 1 1 3 2 1 0 2 1 2 4 0.28 1 0 0 0 1 1 0 1 1 1 1 0 0 0 0 0 17 4 5.6 2 1 4 4 4 3 1 2 2 4 4 3 3 4 4 4 4 1.12 2 0 1 2 4 3 1 2 2 4 3 2 2 2 2 4 4 0.28 1 1 1 1 2 1 0 1 0 2 2 1 1 1 1 2 18 4 5.6 2 2 3 3 4 2 2 2 1 4 4 1 3 3 3 4 4 1.12 1 1 1 1 3 2 1 1 1 3 2 1 1 2 2 3 19 4 5.6 3 1 1 4 3 3 2 2 3 4 4 3 1 4 3 4 4 1.12 1 1 1 1 3 2 1 1 1 2 2 1 0 3 1 3 4 0.28 1 0 0 0 1 1 0 0 0 1 1 1 1 1 1 1 20 4 5.6 1 2 3 4 4 2 4 . 2 2 4 4 3 3 4 4 4 4 1.12 1 1 1 1 2 2 1 1 1 4 4 2 l 2 2 3 21 4 5.6 2 1 l 3 3 2 1 1 1 2 2 1 1 2 2 3 4 1.12 1 2 1 1 1 1 0 1 0 1 1 1 0 1 1 1 22 4 5.6 3 3 2 4 4 3 1 1 4 4 4 4 3 4 4 4 4 1.12 1 1 1 1 3 2 1 1 2 3 1 2 1 3 2 3 4 0.28 1 0 1 1 2 1 1 1 1 2 1 1 0 1 1 2 23 4 5.6 3 2 3 3 4 4 1 3 2 4 4 3 3 4 3 4 4 1.12 2 1 1 2 3 2 1 2 2 4 4 2 1 3 2 4 4 0.28 1 1 1 0 1 1 0 1 1 4 2 1 0 1 1 2 24 4 5.6 4 4 2 4 4 4 2 4 3 4 4 4 3 4 4 4 4 1.12 2 1 1 3 4 2 1 2 3 4 4 2 1 4 4 4 4 0.28 1 0 0 1 2 1 0 1 1 4 2 1 0 1 1 2 25 4 5.6 3 3 2 4 4 3 1 4 3 4 4 4 4 4 4 4 4 1.12 1 1 1 3 3 2 1 2 2 4 3 3 1 3 2 3 4 0.28 1 0 0 0 2 1 0 1 2 3 2 1 0 1 1 2 26 4 5.6 4 3 4 4 4 3 2 4 4 4 4 4 3 4 4 4 4 1.12 2 1 1 3 3 2 1 2 2 4 4 4 2 4 4 4 4 0.28 1 1 1 1 2 2 1 2 1 2 2 2 1 4 3 3 27 4 5.6 4 4 3 4 4 3 2 4 3 4 4 4 4 4 4 4 4 1.12 2 1 1 1 3 2 2 2 2 3 3 2 2 4 3 4 4 0.28 2 0 0 0 2 1 1 1 1 2 2 2 1 2 2 2 28 4 5.6 3 4 3 3 4 3 2 4 3 4 4 4 4 4 4 4 4 1.12 2 1 1 2 3 2 1 2 2 3 3 2 2 4 3 3 4 0.28 1 0 1 1 2 2 1 1 2 2 2 2 1 2 2 2 29 4 5.6 4 4 4 3 3 4 1 4 3 4 4 4 4 4 4 4 4 1.12 2 2 1 2 3 2 1 2 2 4 4 2 2 3 3 4 4 0.28 1 0 1 1 2 1 1 1 2 2 2 1 0 2 2 2 (Table continues)

-111

184,655 (Continued from Table)

Native plant species ^{WAT k} S ^{/ ha} LMNOPBQDREFCJ SKT

30 4 5.6 4 4 1.12 1  4 0.28 1 31 4 5.6 3 4 1.12 2 4 0.28 1 32 4 5.6 4 4 1.12 2 4 0.28 1 33 4 5.6 2 4 1.12 0 4 0.28 1 34 4 5.6 3 4 1.12 2 4 0.28 1 35 4 5.6 2 4 1.12 1 4 0.28 1 36 4 5.6 3 4 1.12. 1 4 0.28 1 37 4 5.6 3 4 1.12 1 4 0.28 1 39 4 5.6 2 4 1.12 1 4 0.28 1 41 2 5.6 2 42 4 5.6 3 4 1.12 1 4 0.28 1 43 2 5.6 1 44 2 5.6 1

2 4 4 4 1112 1 1 1 12 1 3 2 2 3 3

114 4 0 0 12 1

3 4 4 4

1112 3 10 111 3 2 4 4 3

114 2 1 0 0 2 1

3 4 4 4 110 4 3 + 0 0 2 1 2 14 4 3 2 1,1 2 2 0 0 0 1 0

3 3 4 3 1112 2 0 0-111 113 4 3 11 1 3 2 0 113 2

3 4 4 3 2 112 1 0 10 11 11 1 1 1

2 4 3 4

1113 3 0 0 0 1 1 2 2 12 1 11112

4 4 4 4 1 2 2 4 4 112 2 2

3 3 4 4

2 2 4 4

1113 2 2 3 4 4 4 114 3 2 0 0 111 12 14 4 110 2 1 0 10 11 2 2 2 4 2

1114 2 11111

2 2 4 4 1113 2 0 0 0 0 0

2 2 3 4 1 2 1 2 1 0 1110 1 2 14 3 110 3 2 110 2 1

2 2 4 4 12 12 3 0 10 2 1 1 1 2 3 2 4 4 4 4 4 1 2 2 4 4 1 1 1 3 3 1113 4 1113 3

4 4 4 4 4 12 2 4 2 0 2 2 2 4 4 4 4 4 4 3 3 3 3 11112 4 4 4 4-4 3 12 3 3 10 12 2 3 4 4 4 3 111 1 2 0 0 0 0 2

3 4 4 4 1 2 2 2 2 0 0 1 1 1

2 4 3 4 112 2 2 0 0 10 0

3 3 3 4 1112 2 0 1 0 0 1

13 3 4

112 3 3 0 112 2

3 4 4 3 11 2 2 3 1 0 1 12 1 0.2 2 2

2 4 4 4

113 3 3 11113 112 2 3 112 2 3

Example 52

The pre-emergence herbicidal activity of the various herbicides containing the compounds of the formula I is investigated as follows:

Good quality soil is filled into aluminum bowls and compacted to a depth of 9-12 mm from the edge of the bowl. A predetermined number of seeds or propagating organs of each plant species are placed on the ground in each bowl and pressed into the soil. The solutions of Example 51 were mixed or introduced into the upper soil layer of the bowls.

For this purpose, the soil needed to cover the seeds and the reproductive organs is weighed and mixed with a solution containing a known amount of the active ingredient. The bowls are then covered with the mixture and smoothed. Water the soil in the bowls by allowing water to be absorbed through the opening at the bottom of the bowl. Bowls containing seeds and propagating organs are placed in a wet sand bed and kept there for about two weeks under conditions providing adequate sunlight and moisture. At the end of this period, the number of hatched specimens of each plant species is determined and compared with untreated control. The results are shown in Table III. Table.

The pre-emergence herbicidal activity index is determined on the basis of the average killing percentage of each variety:

Decompression Percent Index

0-25% 0

26-50% 1

51-75% 2

76-100% 3 ///. Spreadsheet

plant Variety

agent kg / ha ABC D E F GH 1 J K 1 11.2 3 0 0 0 0 0 0 0 0 0 0 2 11.2 2 0 0 0 0 0 1 0 3 0 0 3 11.2 3 0 0 0 10 1 10 0 0 4 11.2 2 0 0 0 0 0 0 0 0 0 0 5 11.2 3 0 3 0 10 0 12 1 0 6 11.2 1 0 0 0 0 0 0 0 0 0 0 7 11.2 1 0 0 0 0 0 0 0 0 0 0 (Table continues)

-121

184,655

Növényfíijták

agent kg / ha THE B c D E F G 1! I J K 8 11.2 1 0 0 0 0 0 0 0 1 0 0 9 11.2 3 0 0 0 0 0 1 1 0 0 0 10 11.2 3 0 0 0 0 0 0 0 0 0 0 11 11.2 3 0 0 0 0 0 0 0 0 0 0 12 11.2 1 0 0 0 0 0 0 0 0 0 0 13 11.2 2 0 0 3 3 0 0 0 1 0 0 14 11.2 3 0 0 0 3 0 0 0 1 0 1 15 11.2 0 0 0 0 0 0 0 0 0 0 0 16 11.2 0 0 0 0 0 0 0th 0 0 0 SHE 17 11.2 1 0 0 0 0 0 0 0 0 0 0 18 11.2 0 0 0 0 0 0 0 0 0 0 0 19 11.2 1 0 0 0 0 0 0 0 0 0 0 20 11.2 0 0 0 0 0 0 0 0 0 0 0 21 11.2 2 0 0 0 0 0 0 0 0 0 0 22 11.2 2 .0 0 0 0 0 1 1 0 0 0 23 11.2 3 0 0 0 3 1 0 0 0 0 0 24 11.2 1 0 0 0 0 0 0 1 0 0 0 25 11.2 2 0 0 0 0 0 0 0 0 0 0 26 11.2 2 0 0 0 0 0 0 0 0 0 0 27 11.2 2 0 0 1 0 0 1 0 0 0 0 28 11.2 1 0 0 0 0 0 0 0 0 0 0 29 11.2 2 0 0 0 0 0 0 0 0 0 0 30 11.2 2 0 0 1 0 0 0 1 1 0 0 31 11.2 2 0 0 0 0 0 0 0 0 0 0 32 11.2 3 0 0 0 0 0 0 0 0 0 0 33 11.2 3 0 0 0 0 0 0 0 1 0 0 34 11.2 3 0 0 0 0 0 0 0 1 0 0 35 11.2 3 0 0 0 0 0 2 2 3 0 0 36 11.2 3 0 0 0 0 0 1 1 0 0 0 37 11.2 3 0 0 0 1 0 0 1 0 0 0 38 11.2 0 0 0 0 0 0 0 0 0 0 0 39 11.2 3 0 0 0 0 0 0 0 0 0 0 40 11.2 0 0 0 0 0 0 0 1 1 0 0 41 11.2 0 0 0 0 0 0 0 0 0 0 0 42 11.2 3 0 0 0 0 0 0 0 0 0 0 43 11.2 3 0 0 0 3 0 0 1 0 0 0 44 11.2 3 0 0 0 0 0 0 0 3 0 0 0,0-diethyl-N- - (phosphono methyl) -glycine nitrile 5.6 0 0 0 0 0 0 0 0 0 0 0 (3,923,877 s. US szab.leírás)

In III. The letters used in Table 5 represent the same plant species as in Example 51.

II. and III. The experimental results shown in Table I show that although the herbicidal activity of the formulations containing the active compounds of the formula I is largely total, in some cases they exhibit some selectivity. Experimental results demonstrating the pre-emergence herbicidal activity clearly show the selective action of the field thistle and some other varieties.

The herbicidal compositions of the present invention, including concentrates to be diluted prior to application to plants, contain from 5 to 95 parts by weight of active ingredient and 95 to 5 parts by weight of a liquid or solid excipient, for example about 0.25 to 25 parts by weight of wetting agent. 25 parts by weight of dispersant and approx

4.5 to 94.5 parts by weight of an inert liquid filler, such as water, per 100 parts by weight of the composition. Where appropriate, from about 0.1 to about 2.0 parts by weight of an inert liquid filler may be replaced by a corrosion inhibitor, an antifoam agent, or both.

The formulations of the present invention are prepared by admixing the active ingredient with an excipient such as diluent, excipient, vehicle, and conditioning agents, and formulating the formulations into finely divided solid particles, pellets, solutions, dispersions or emulsions. Thus, the active ingredient in an excipient, namely finely divided solid, a liquid of organic origin, water, ₁₅ vesítőszerrel wetting, dispersing, or emulsifying them in combination, may be used.

The herbicidal compositions of the present invention, in particular liquid compositions and soluble powders, contain one or more surfactants as a conditioning agent in an amount that enables the compositions to be readily dispersed in water or oil. The incorporation of a surfactant into the compositions greatly enhances their effectiveness. The term "surfactant" includes both excipients, dispersants, suspending agents and emulsifying agents. Both anionic, cationic and nonionic agents are easy to use.

Preferred wetting agents are alkylbenzene and alkyl30 naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothiocyanate, polyoxyethylene derivatives of phenols (especially isooctylphenol and nonylphenol); and polyoxyethylene derivatives of higher carbon mono-fatty acid esters of hexitol anhydrides (e.g. sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonate, polymeric alkyl naphthalene sulfonate, sodium naphthalene sulfonate, polymethylene bisnaphthalenesulfonate and sodium N-methyl-N-long chain fatty acid.

Water dispersible powder formulations contain one or more active ingredients, an inert solid filler, one or more more wetting and dispersing agents. Inert solid diluents are usually of mineral origin, such as natural chalk, diatomaceous earth, and synthetic mineral products derived from silica. Such diluents include kaolinites, attapulgite chalk, and synthetic magnesium silicates.

The water-dispersible powders of the present invention will generally contain from 5 to 95 parts by weight of active ingredient, from about 0.25 to 25 parts by weight of wetting agent, from about 0.25 to 25 parts by weight of dispersant and 4.5 to 94.5 parts by weight of inert solid diluent. per part by weight. If desired, 0.1 to 2.0 parts by weight of the solid diluent may be replaced by an anti-corrosion agent, an antifoam agent, or both.

Aqueous suspensions may be prepared by mixing a water-insoluble active ingredient of formula (I) in a water-slurried form with a dispersing agent and milling it into concentrated suspensions of very fine particles. The resulting concentrated aqueous suspension is of ordinary order

-131

184,655 has a very small particle size, which is easy to dilute and spray, and has a uniform coverage. These suspensions contain 5 to 95 parts by weight of active ingredient, about 0.25 to 25 parts by weight of a dispersant and about 4.5 to 94.5 parts by weight of water.

Emulsifiable oils are usually solutions of the active compounds in water-immiscible or water-immiscible solvents and a surfactant. Suitable solvents for the active compounds in the compositions of the invention include hydrocarbons, water immiscible ethers, esters and ketones. Emulsifiable oil formulations generally contain from 5 to 95 parts by weight of active ingredient, 1 to 50 parts by weight of surfactant and about 4 to 94 parts by weight of solvent, based on the total weight of emulsifiable oils.

The formulations may contain other additives, such as fertilizers, phytotoxic agents and plant growth regulators, as well as pesticides, but it is preferred that the formulations of the present invention be used separately and subsequently treated with other phytotoxic agents, fertilizers, to obtain the best possible effect. The sowing area may be sprayed before or after treatment with the composition of the invention, fertilizers or other phytotoxic agents. The active compounds and chemical substances which may be used at the same time as or after use of the compositions of the invention include triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acid derivatives, phenols, thiocarbamates, triazoles, benzoic acids, nitriles.

Fertilizers for use with the compositions of the invention include, for example, ammonium nitrate-containing urea, potassium compound, and superphosphate-containing fertilizers.

The compositions of the present invention containing glycine nitrile active ingredients are applied in effective amounts to the plants or to or in the soil. Liquid or granular solid compositions may be applied to plants or soil by conventional means such as sprayers, machine and hand sprayers and sprayers. The compositions of the invention may also be sprayed from an aircraft in powder or spray form as they are effective in small doses. When the herbicidal compositions of the present invention are used in aquatic plants, the compositions are added to the waters in which the plants to be treated grow.

An effective amount of the herbicidal compositions of the present invention plays a crucial and important role in the practical application of these compositions. The exact amount of active ingredient to be used will vary depending on the reaction of the treated plant and other factors such as the state of development of the plant species, the amount of rain that has fallen, and the active ingredient employed. To inhibit the vegetative development of plants, the herbicidal agent according to the invention containing about 0.112 kg and 22.4 kg or more of active ingredient is applied to the leaves of the plants per hectare. In the case of pre-emergence treatments, the application rates may be between 0.56 kg and 22.4 kg or more per hectare. For the control of aquatic plants, the herbicidal agents of the invention are used in an amount such that the aqueous medium contains the active ingredient in a ratio of 0.01 to 1000 ppm. The effective amount required for phytotoxic or herbicidal eradication will generally be that of total or selective eradication, for example phytotoxic or herbicidal. For example, the compositions of the present invention have the following composition:

Emulsion Concentrate

The active ingredient of Example 5 was 16.0

F10 Mo 14NP (Monsanto Company) 3.47

Tergitol XH (Union Carbide Co.) 0.69 F10 Mo 60H (Monsanto Combany) 0.84 Phenol 2.37 Monochlorobenzene 76.63

The active ingredient of Example 8 was 40.00

Atlas AL 1366 (Atlas Chemical Industries Inc.) 3.00 Atlas AL 1367 (Atlas Chemical Industries Inc.) 2.00 Monochlorobenzene 55.0

Example 40 5.00 calcium dodecylbenzene sulfonate 1.0 castor oil, polyoxyethylene glycol ether 2.2 xylene 91.5 MOISTURIZABLE POWDER Example 35 5.00 Marasperse C-21 (Lignin Chemie Waldhof GmbH) 2.00 Attapulgit 93.00 Example 11 95.00 Marasperse C-21 5.00 powder preparations (a) Diluted: Example 14 1.0 sodium dodecyl benzene sulfonate 0.5 mineral 98.5 (b) Concentrate: Example 13 40 bentonite 40 Igepon T-77 (GAF Corp., USA) 20 Example 43 95.0 Aerosol AT-B 4.0 Hi Sil 233 (finely divided silica) 1.0 LIQUID PREPARATIONS Example 8 5.00 Pluraflo 5EG (Wyandotte Chemical Co.) 3.50 Hi Sil 233 1.00 kaolinite] 4.50 xanthan rubber 0.15 WATER 86.35 Example 3 50.00 Pluronic P-105 (Wyandotte Chemical Co.) 4.00 lignin sulfonate 1.50 bentonite 2.00 water 53.00

-141

184,655

MOISTURIZING POWDER

The active ingredient of Example 15 was 25.00

Marasperse B 22 4.00

Kaolins 71.00

Example 33: 25.00

Marasperse G-21 4.00

Kaolins 71.00

Claims (16)

PATENT CLAIMS CLAIMS 1. A herbicidal composition comprising up to 95% by weight as an active ingredient of N-phosphonomethylglycinitrile of formula (I): R _is phenyl or naphthyl optionally substituted with one, two or three halogens, C 1-4 alkyl, C 1-3 alkoxy or alkylthio, methylenedioxy, trifluoromethyl and / or nitro, Z is oxygen or sulfur, b is 0 or 1, R is a strong acid and x is 0 or 1, with the proviso that x is 0 when b is 1 - and solid carriers and diluents, preferably attapulgite, kaolin and bentonite, liquid solvents and diluents, preferably monochlorobenzene and xylene, and at least one of surfactants, preferably sodium dodecylbenzene sulfonate. (Priority: 13 January 1976) 2. The herbicidal composition according to claim 1, wherein the active ingredient is a compound of formula I wherein R _is phenyl or naphthyl monosubstituted. (Priority: June 13, 1976) 3. The herbicidal composition of claim 1, wherein the active ingredient is a compound of formula I wherein x is 1 and b is 0. (Priority: 13 January 1976) 4. The herbicidal composition of claim 1, wherein the active ingredient is a compound of formula I wherein x is 0 and b is 1. (Priority: June 13, 1976) 5. The herbicidal composition according to claim 1, wherein the active ingredient is a compound of formula I wherein b and x are both 0. (Priority: 13 January 1976) 6. A herbicidal composition according to claim 1, characterized in that it contains as active substance (I) compound, wherein R, in water of 2.5 or less pK _a monobasic acid. (Priority: 13 January 1976) 7. The herbicidal composition according to claim 1, wherein the active ingredient is a compound of the formula I wherein R _is phenyl and Z is oxygen. (Priority: 13 January 1976) 8. The herbicidal composition according to claim 7, wherein the active ingredient is a compound of formula (I) wherein x is 1 and b is 0. (Priority: 13 January 1976) 9. An embodiment of the herbicidal composition according to claim 7, wherein the active ingredient is a compound of formula I wherein X is 0 and b is 1. (Priority: December 13, 1976) 10. A herbicidal composition according to claim 7, embodiment ₁₀ shape, characterized in that it contains as active substance (I) compound wherein X and b are each 0th (Priority: June 13, 1976) 11. The herbicidal composition according to claim 1, wherein the active ingredient is 0.0-diphenyl-N- (phosphonomethyl) glycine nitrile, O, O-di-methoxyphenyl-N- (phosphono- methyl) glycine nitrile, 0.0-di- (p-fluorophenyl) -N- (phosphonomethyl) glycine nitrile, O- (m-nitrophenyl) -N- (phosphonomethyl) glycine nitrile, - (o-chlorophenyl) -N 2 0 -phosphonomethyl j-glycinitrile, 0.0-diphenyl-N- (phosphonomethyl) -glycinitrile trifluoroacetic acid or 0.0-diphenyl-N- (phosphono- containing methyl) glycine nitrile methanesulfonic acid salt. (Priority: 13 January 1976) 25 12. A process for the preparation of 0,0-diaryl-N- (phosphonomethyl) glycine nitriles of formula (I) wherein R _is phenyl or naphthyl optionally substituted with one, two or three halogens, C 1-4 alkyl, Substituted with C 1-3 alkoxy or alkyl 30 thio, methylenedioxy, trufluoromethyl and / or nitro, Z is oxygen or sulfur, b is 0 or 1 R is a strong acid, and 35 x is 0 or 1 with the proviso that x is 0 when b is 1 - characterized in that (a) for the preparation of diesters of formula (V): R _is phenyl or naphthyl, optionally one, They are substituted with two or three halogen atoms, C 1-4 alkyl, C 1-3 alkoxy or alkylthio, methylenedioxy, trifluoromethyl or nitro. and Z is oxygen or sulfur - 45 diaryl phosphite of formula II wherein R _a and Z are as defined above and is reacted with 1,3,5-tricyanomethylhexahydro-1,3,5-triazine, or b) for the preparation of the 0.0-diaryl-N- (phosphonomethyl) -glycinitrile salts of the formula (VII), wherein R and Z are 50 The anion of formula V, wherein R _a and Z are as defined above, is dissolved in an anhydrous solvent containing a strong acid having a pK _a value of 2.5 in water or an anion of a strong acid. less than that, or C) for the preparation of 0-aryl-N- (phosphonomethyl) glycine nitriles of formula IV wherein R _a and Z are as defined above, a diester of formula V wherein R _a and Z are above - dissolved in an inert solvent containing 60 g equivalent water to hydrolyze a R _a -O- group. (Priority: January 3, 1977) 13. The process according to claim 12, wherein the reaction is carried out at a temperature of from 25 ° C to 110 ° C. 65 (Priority: January 3, 1977) -151 184,655 14. The process according to claim 13, wherein the diaryl phosphite and the triazine are reacted in the presence of an inert solvent. (Priority: January 3, 1977) 15. The process of claim 12 wherein the diaryl phosphite of formula II is diphenylphosphite; di (m-chlorophenyl) phosphite, di (p-methoxyphenyl) phosphite, di (3,4-dimethylphenyl) phosphite or di (p-fluorophenyl) phosphite. (Priority: January 3, 1977) ' 16. The process of claim 12, wherein the salt formation reaction is carried out with an equally strong strong acid and a diester.