CS204014B2 - Process for preparing o-aryl-n-phosphonomethylglycinonitriles - Google Patents

Description

The invention relates to a process for the preparation of novel O-aryl-N-phosphonomethylglycinonitriles of the general formula I,

Z (Xa-Aryl-O) 2-P-CH 2 NHCH 2 CN (I) wherein Aryl is phenyl, naphthyl or bifehylyl, X is a substituent of said aryl

Z H

II I (Xa-Aryl-O) 2-P-CH2-NH-CH 2-CN R 6

H wherein Aryl, X, and Z are as defined above and R 1 is a strong acid anion.

According to U.S. Patent No. 3,923,877, N-phosphonomethylglycine can be prepared by reacting a dialkyl phosphite with 1,3,5-tricyanomethylhexahydro-1,3,5-triazine in the presence of a catalyst such as hydrogen halide, Lewis acid, halide % carboxylic acid or carboxylic anhydride, and the product obtained is subjected to hydrolysis. The yields of this process are extremely low. According to the patent, phosphite is reacted with triazine to form an N2 ester selected from the group consisting of halogen, C1-C4 alkyl, alkoxy or C1-C3 alkylthio, C2-C3 alkoxycarbonyl, methylenedioxy, cyano, trifluoromethyl and nitro, Z is oxygen or sulfur and and is an integer from zero to 3.

The invention also relates to a process for the preparation of salts of these compounds of the general formula Ia, (Ia)

-phosphonomethylglycinonitrile as an intermediate. Suitable esters according to said patent are those having an aliphatic alkyl group having 1 to 6 carbon atoms or esters having a phenyl-substituted aliphatic group, for example benzyl esters; esters with an alkyl group having 1 to 6 carbon atoms are particularly preferred. These esters, upon hydrolysis, yield N-phosphonomethylglycine, which is a post-emergence herbicide. It has also been found that the O, O-diethyl-N-phosphonomethylglycinonitrile produced by the method of the cited invention 204014 has neither postemergence herbicidal activity (at 4.48 kg / ha) nor preemergence herbicidal activity (at 5.60 kg / ha).

The inventor has found that O, O-diaryl-N-phosphonomethylglycinonitriles can be produced by treating diaryl phosphites with 1,3,5-tricyanomethylhexahydro-1,3,5-triazine in the absence of any catalyst. He further found that the glycinonitriles so produced, as well as the related monoaryl esters obtained by mild hydrolysis of said diesters, had pre-emergence and post-emergence herbicidal activity, which were completely unexpected due to the inefficiency of N-phosphonomethylglycinonitrile diethyl ester.

The principle of the preparation of the O-aryl-N-phosphonomethylglycinonitriles of the formula I by the process according to the invention is that the diaryl phosphite of the formula II

OF

II (Xa-Aryl-Oja-P-Η (II) wherein X, Z and a are as defined above) with 1,3,5-tricyanomethylhexahydro-1,3,5-triazine of formula III.

 (III)

The reaction is carried out at a temperature in the range of 25 to 110 ° C. The reaction is carried out in the presence of an inert solvent such as diarylphosphites diphenylphosphite, di (m-chlorophenyl) phosphite, di: p-methoxyphenyl) phosphite, di (3,4-dimethylphenyl) phosphite or di (p-fluorophenyl) phosphite.

The salt of the compound of formula (Ia) is prepared by the process of the invention by preparing a diester of formula (I),

OF

II (Xa - Aryl - O) 2 - P - CH 2 - NH - CH 2 - CN (I) in which Aryl, X, a, Z are as defined above, dissolved in a perfect solvent containing a strong acid having pK _and water equal to or less than 2.5 and capable of forming a salt with an amino group. This reaction is performed essentially with equimolar ratios of strong acid and diesters.

Although it is not necessary to use solvents in the process of the present invention, its use is sometimes suitable for a more convenient and easier reaction. The use of a solvent is also advantageous because it allows the reaction to be carried out at a controlled temperature. Solvents which can be used are those in which the triazine is soluble and which does not react with any of the reactants; a suitable inert solvent is, for example, acetonitrile, ethyl acetate, tetrahydrofuran and the like.

The reaction temperature may range from about 25 ° C to about 110 ° C. It is possible to work at higher reaction temperatures, but this does not result in a proportional improvement, since the reaction is substantially complete when the temperature reaches about 85 ° C.

As can be seen from the above formulas II and III, a molar ratio of phosphorous acid ester to triazine of 3: 1 is required for optimum results. Higher or lower molar ratios may also be used, but these component ratios are uneconomical because at higher molar ratios it is necessary to remove excess phosphorous acid ester from the product and undesired byproducts may be formed at lower molar ratios of ester to triazine.

The reaction is usually carried out for economy at atmospheric pressure. Higher or lower reaction pressures may be used, but no improvement is achieved.

Examples of X groups which may be substituted phenyl, naphthyl or biphenylyl include halogen, such as chlorine, fluorine or bromine; an alkyl group such as methyl, ethyl, propyl or butyl; alkoxy such as methoxy, ethoxy or propoxy; an alkylthio group such as methylthio, ethylthio or propylthio group; as well as methylenedioxy, cyano, trifluoromethyl and nitro. As can be seen from the general formula, the groups represented by X may be the same or different on the same aryl ring.

Strong acids which are suitable for the preparation of the salts of the general formulas (I) include acids having a pK _and in water of 2.5 or less, for example p4 toluenesulfonic acid, p-chlorobenzenesulfonic acid, trichloroethic, oxalic, fluoroboric, hydrogen chloride, hydrogen chloride, hydrogen iodide, trifluoroacetic, pentafluoropropionic, heptafluorobutyric, trifluoromethanesulfonic, nitric, sulfuric, phosphoric, trichloromethanephosphonic, perchloric, methanesulfonic and the like.

In the preparation of the salts of the strong acids of the general formula I, it is advantageous to use diesters of phosphonic acid and strong acid in a molar ratio of 1: 1 _, since the corresponding salt is then easily isolated. Higher or lower molar ratios of ester to acid may be used, but isolation of the product is more difficult due to the excess of one reactant.

Hydrolysis of the N-phosphonomethylglycinonitriles of formula I to N-phosphonomethylglycine can conveniently and rapidly be accomplished by heating glyeinonitrile at a slightly elevated temperature (60-100 ° C) in the presence of at least slightly more than one mole equivalent (e.g.

S in the presence of 1.01 equivalents) of aqueous hydrochloric acid or aqueous hydrobromic acid, which is at least 1.0 normal and preferably at least 2.0 normal. When using concentrated aqueous hydrochloric or hydrobromic acid, satisfactory hydrolysis to N-phosphonomethylglycine occurs within 24 hours at room temperature.

The compounds of formula (I) may be used as herbicides, both in pre-emergence and post-emergence applications.

General procedures described below represent particularly preferred methods of preparing various compounds of Formula I. ¹

The diaryl esters of formula I are preferably prepared by one of the following two processes:

A) A solution of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (3.4 g, 0.0167 mol) in acetonitrile (50 mL) was treated with diaryl phosphite (0.050 mol) in a reaction flask and heated. 45 to 85 ° C for 1 to 90 hours until all phosphite or triazine has reacted; progress of the reaction was monitored by NMR (nuclear magnetic resonance) spectral analysis. If, according to NMR spectral analysis, impurities are not present in the reaction mixture, the product is isolated by distilling off the volatiles under reduced pressure. If impurities are present, the product is isolated and purified by crystallization or chromatography. In some cases, the diester obtained is difficult to isolate in highly pure form because the product hydrolyzes during isolation.

B) Charge the reaction flask with diaryl phosphite (0.05 mol) and 1,3,5-tricyanomethylhexahydra-1,3,5-triazine (3.4 g, 0.0165 mol) and mix. Heat to 60-100 ° C for 20 min. up to one hour until all phosphite or triazine has reacted (progress of the reaction is monitored by NMR spectral analysis). The product is purified by crystallization or chromatography.

The salts of the diaryl esters with strong acids are preferably prepared by the following general procedure. A solution of the strong acid (or acid itself) (0.01 mol) was added dropwise to the chloroform solution of the diester at room temperature and the reaction mixture was allowed to stand. If a crystalline salt precipitates, it is filtered off, washed with a 1: 1 (v / v) mixture of chloroform and ether and dried in air. When the product does not precipitate, a 1: 1 (v / v) mixture of chloroform and ether is added to the solution, whereby the salt crystallizes or precipitates out of solution in oily form.

The process according to the invention is illustrated in more detail by the following non-limiting examples. All “parts” mean “parts by weight” unless otherwise stated.

He did

Di (p-chlorophonyl) phosphite (23.32: g, 78 percent purity, 0.06 mol) and 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (4.08 g, 0.02 mol) The mixture was added to the reaction flask at room temperature and the mixture was heated to 100 ° C for 20 minutes. 27 g (100% yield), Q, O-di. (P-ehlorf enyl) -Nf Qnomethylglycinonitrilu phosphonate as an oil N _D ²¹ - 1.5747.

Example 2

A solution of di (3,4-diethylphenyl) phosphite (8.7 g, 0.03 mol) in acetonitrile (10 mL) was added to an acetonitrile solution (50 mL) of 1,3,5-tricyanomethylhexahydro-1,3,5- trialamine (2.04 g, 0.01 mol) and the mixture was heated at 55 ° C for 90 h. The precipitated solid is filtered off and the solvent is distilled off; An oily red oil is obtained which, according to NMR spectral analysis, contains a mixture of the desired product with the aminalein of this product. For chromatography the crude product (8.0 g) on a column of silicic (450 g) using a mixture of cyclohexane (50%) and ethyl acetate (5.0%) to eluei substances (fractions Θ0 ¹ mL), transferred O O-di (3,4-dimethylphenyl) -Nphosphinomethylgenetonitrile in fractions of numbers 30 to 41; after evaporation of the solvents, the product has a mp of 61-64 ^° C. After recrystallization from a mixture of carbon tetrachloride and isooctane, 3.1 g (40%) of the pure product are obtained with a mp of 63-66 ° C.

Example 1 a d 3

A mixture of 0.02 mol of di, (p-methylthiophenyl) phosphite and 0.0067 mol of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine was heated to 80 ° C with stirring for 1.0 hour to give a dark red-brown color Half of the crude product is placed in a refrigerator where, after 8 days, a semi-solid precipitates, the product is recrystallized from 70 ml of carbon tetrachloride, the obtained pink colored crystalline substance is dissolved in 100 ml of hot carbon tetrachloride and filtered through celite. The filtrate is concentrated to about 50 ml and the solution is stored overnight in the refrigerator for crystallization. The colorless precipitate formed is filtered off to give 1.8 g (yield 45%) of O, O-di (p). (methylthiophenyl) -Nfphosphonomethylglycinonitrile, mp 64-65 ° C.

Elementary analysis:

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

A solution of di (o-methoxyphenyl) phosphite (8.05 g, 91% purity, 0.025 mol) and 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (1.7 g, 0.0083 mol) in acetonitrile was added. The mixture was then filtered from the filtrate and the solvent was distilled off to give a dark brown oil (9.6 g), and the crude oil (5.8 g) was adsorbed onto a 8 g silica gel column. and the product was eluted with 80 mL of ethyl acetate. From the eluate ethylacetátovébo distilling off the solvent, the oily residue is re-adsorbed onto 4.0 g of silica gel and the silica was extracted with 70 ml of ethyl acetate. the ethyl acetate extract gives, after evaporation of the solvent under reduced pressure to a light yellow-colored oily product N _D ²² = 1.5542. The oily product obtained is 0, 0-di (o-methoxyphenyl) -N-phosphonomethylglycinonitrile containing a small amount of o-methoxyphenol.

Example 5

A solution of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (13.6 g, 0.066 mol) and diphenylphosphite (46.8 g, 0.2 mol) in acetonitrile (100 mL) was heated at 55 ° C for 48 hours. ° C; according to NMR spectral analysis of the crude reaction mixture, the reactants were completely converted to O, O-diphenyl-N-phosphonomethylglycinonitrile. The acetonitrile was distilled off under reduced pressure to obtain 57 g (yield 94.4%) of a viscous black oil. The crude oil was dissolved in chloroform, 114 g of silica gel was added, and the solvent was distilled off under reduced pressure. The product-impregnated silica is applied to a column prepared from a suspension of silica gel (200 g) in chloroform and the product is eluted with chloroform until it is no longer detectable in the eluate by NMR. The chloroform eluates were combined, the solvent was distilled off, the residue was dissolved in methylene chloride, washed twice with cold 5% potassium hydroxide solution (100 ml) and then with water. The methylene chloride fraction was dried over anhydrous magnesium sulfate, the desiccant was filtered off and the solvent was distilled off; 37.9 g of a pale yellow oily O, O-diphenyl-N-phosphonomethylglycinonitrile are obtained, which solidifies on standing; b. mp 64-67.5 ° C, yield 75%.

Example 6

Acetonitrile solution (100 mL) of difm-tolyl] phosphine (10.7 g, 0.04 mol) and 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (2.72 g, 0.0133 mol) was heated with 3 mL of water. days at 50 ° C; the solution turns burgundy red. The solvent was distilled off to give 12.4 g (92.4 percent yield) of a red oil. The crude oily product (9.0 g) is chromatographed on silica gel, eluting with a mixture of cyclohexane (60%) and ethyl acetate (40%); 60 ml fractions were collected. Fractions 45 to 63 contain the desired product; after distilling off the solvent afforded 1.25 g (14% yield) of pure 0,0-di (m-toyl) -N-fosfonomethylglycinonitrilu as an oil N _D ²⁵ = 1.5467.

Elementary analysis:

H, 5.80; N, 8.48. Found: C, 61.75; H, 5.81; N, 8.41. Example 7

A solution of di (m-nitrophenyl) phosphine (15.2 grams, 83% purity, 0.0392 mol) and 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (2.66 grams, 0.013 mol) in acetonitrile heated at 50 ° C for 20 hours; after this time, the reaction is complete according to NMR spectral analysis. The solution is filtered and the solvent is distilled off under reduced pressure; 13 g of O, O-di (m-nitrophenyl) -N-phosphonomethylglycinonitrile are obtained in the form of an amber-yellow oil.

Elementary analysis:

H, 3.34; N, 14.28. Found: C, 45.80; H, 3.39; N, 14.27

Di (p-methoxyphenyl) phosphite (0.05 mol, 15.63 grams, 94% purity) and 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (3.4 g, 0.0167 mol) ) was dissolved in acetonitrile and the solution was heated under reflux for 1 hour. The solvent was distilled off under reduced pressure to give a dark pink oil (19.0 g). The crude oily product (5.0 g) was subjected to high pressure liquid chromatography using a mixture of cyclohexane and ethyl acetate (40/60 volume percent) to elute the substances. There were obtained 4.1 g (82% yield) of O, O-di (p-methoxyphenyl) -N-fosfonomethylglycinonitrilu as an oil N _D ²⁵ = 1.5541.

Example 1 9

A solution of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (2.04 g, 0.01 mol) and di (p-fluorophenyl) phosphite (8.8 g, purity 91.6% / o, 0.03 mol) in acetonitrile (50 mL) was heated at 55 ° C for 70 hours, then the reaction mixture was filtered and the solvent was distilled off under reduced pressure to give a brown oil oily on _D ²⁵ = 1.5270 containing 92 percent O, O-di (p-fluorophenyl) -N-phosphonomethylglycinonitrile.

Example 10

A solution of di (m-chlorophenyl) phosphite (9.93 g, purity 91.5%, 0.03 mol) in acetonitrile (20 mL) was added to a solution of 1,3,5-tricyanomethyl204014 hexahydro-1,3, Of 5-triazine (2.04 g, 0.01 mol) in acetonitrile (50 mL) and heated at 55 ° C for 70 h. The acetonitrile was distilled off under reduced pressure to give O, O-di (m-chlorophenyl) -Nfphosphonomethylglycinonitrile as a light pink oil, 92% o, n _D ²⁵ = 1.5656.

The following compounds can also be prepared by this procedure:

O, O-di (p-cyanophenyl) -N-phosphonomethylglycinonitrile,

O, O-di (p-biphenylyl) -N-phosphonomethylglycinonitrile.

Example 11

Di (2,4,6-trimethylphenyl) phosphite (17.8 g, 0.05 mol) was added to an acetonitrile solution (50 mL) of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (3,4 g, 0.0164 mol) and heated at 80 ° C for 18 hours. The resulting dark solution was filtered and the solvent was distilled off; an oily product is obtained. A portion of the crude material (7 g) was chromatographed on a silica gel column (450 g) using a mixture of cyclohexane (70%) and ethyl acetate (30%) to elute the materials; 60 ml fractions were collected. Fractions 28-40 yielded 1.0 g (14%) of O, O-di (2,4,6-trimethylphenyl) -N-phosphonomethylglycinonitrile, which solidified on standing; mp 118-120 ° C.

Elementary analysis:

C, 65.27; H, 7.04; N, 7.25. Found: C, 65.38; H, 7.07; N, 7.18.

Example 12

A solution of 0.01 mole of an amber-colored oily product obtained as described in Example 32 in wet acetone (70 mL) was heated at reflux for 4 days. The amber-yellow solution was then allowed to stand at room temperature for one day and the precipitated product was filtered off. 1.7 g of O- (3,4-methylenedioxyphenyl) -N-phosphonomethylglycinonitrile are obtained in the form of a colorless crystalline substance, m.p. 160-161 ° C.

Example 13

A solution of di (3,4-dichlorophenyl) phosphite (0.04 mol) and 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (0.013 mol) in acetonitrile (40 ml) was heated to 80 ° with stirring for 18 hours. C. The solvent was distilled off from the reaction mixture, to the obtained oily product was added wet acetone (80 ml) and the mixture was heated under reflux for 80 hours. After cooling, the colorless precipitate formed was filtered off and washed with acetone (50 ml); 6.3 g (53% yield) of O- (3,4-dichlorophenyl) 10 are obtained

N-phosphonomethylglycinonitrile, m.p. 169-170 ° C.

Example 14

To the acetonitrile solution (300 mL) of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (68 grams, 0.333 mol) was added diphenylphosphite (234 g, 1.0 mol) and the mixture was heated at 75-75 for 3 hours. 82 ° C. The solution was cooled and the solvent was distilled off under reduced pressure; A dark colored oily residue is obtained which is substantially identical to the product obtained as described in Example 5. A sample of the crude oil (101 grams) is dissolved in chloroform, adsorbed onto silica gel and the solvent is distilled off. The product impregnated silica gel was loaded onto a silica gel column (1.1 kg) and eluted with chloroform; 1 liter fractions were collected. Fractions 13 to 14 are combined, the solvent is distilled off and the residue is recrystallized from a mixture of dichloromethane and cyclohexane; 51 g of O, O-diphenyl-N-phosphonomethylglycinonitrile are obtained.

Example 15

O-Di (p-fluorophenyl) -N-phosphonomethylglycinonitrile (2.38 g, 0.069 mol) was stirred with a mixture of carbon tetrachloride and methylene chloride [1: 1 by volume], the solution was filtered and methanesulfonic acid was added to the filtrate (0). , 67 g, 0.069 mol). The mixture was allowed to stand overnight, then the precipitated crystalline salt was filtered off and washed with carbon tetrachloride. 2.68 g of O, O-di (p-fluorophenyl) -N-phosphonomethylglycinonitrile methanesulfonate are obtained as a colorless crystalline solid, m.p. 132 DEG-132.5 DEG.

Elementary analysis:

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 16

P-Toluenesulfonic acid (1.9 g, 0.01 mol) was added to benzene (100 mL) and the mixture heated to boiling while the water present was distilled off as an azeotropic mixture with benzene. The obtained benzene acid solution was added to a solution of O, O-diphenyl-N-phosphonomethylglycinonitrile (3.02 g, 0.1 mol) in a mixture of benzene and methylene chloride (100 mL, 50/50 by volume), and the mixture was stirred at room temperature for one minute. rooms; a crystalline salt precipitates. The mixture was further stirred at room temperature overnight and then the precipitated product was filtered off. O, O-diphenyl-N-phosphonomethylglycinonitrile p-toluenesulfonate (4.38 g, 92.4% yield) was obtained as a colorless crystalline solid, m.p. 152-153 ° C.

Elementary analysis:

calculated: 55.7% C, 4.9% H, 5.9% N; found: C 55.4%, H 4.9%, N 5.7%, Example 17

A chloroform solution of p-chlorobenzenesulfonic acid (1.92 g, 0.01 mol) was added to a chloroform solution of O, O-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 0.01 mol) and the mixture was stirred at room temperature; after about 10 minutes the salt begins to crystallize. The mixture was further stirred overnight and then the precipitated product was filtered off and washed with chloroform. 4.0 g (81% yield) of O, O-diphenyl-N-phosphonomethylglycinonitrile p-chlorobenzenesulfonate are obtained as a colorless crystalline solid, m.p. 149-151 ° C. Elementary analysis:

C, 51.0; H, 4.1; N, 5.7; Found: C, 50.7; H, 4.1; N, 5.7

Chloroform solution (20 ml) of trichloroacetic acid (1.63 g, 0.01 mol) was added to a chloroform solution (100 ml) of O, O-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 0.01 mol) and the mixture stir overnight at room temperature; no crystalline substance is deposited. The solvent was distilled off under reduced pressure to obtain 3.75 g (80 percent yield) of O, O-diphenyl-N-phosphonomethylglycinonitrile trichloroacetate as a pale yellow oil, n _D ²⁵ = 1.5410. Elementary analysis:

calculated: 43.9% C, 3.5% H, 6.0% N; found: 43.9% C, 3.5% H, 5.9% N. Example 19

Acetone solution (25 mL) of oxalic acid dihydrate (1.26 g, 10 mol) was added to an acetone solution of O, O-diphenyl-N-phosphonomethylglycinonitrile (3.02 g, 10 mol); in about 10 minutes the salt starts to crystallize out of solution. The mixture was stirred overnight, then cooled, the precipitated crystalline material was filtered off and washed with acetone; 1.9 g of product are obtained. A second crop of salt is obtained by concentrating the mother liquors (0.8 g). Total yield 2.7 g (69%) of O, O-diphenyl-N-phosphonomethylglycinonitrile oxalate, mp 165 ° C with decomposition. Elementary analysis:

calculated: 52.1% C, 4.4% H, 7.1% N; Found: C, 52.1; H, 4.4; N, 7.1.

Example 20

The ethereal perchloric acid solution was added to a solution of O, O-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 10 mol) in chloroform-ether and the mixture was allowed to crystallize; perchlorate in the form of colorless prisms is slowly released. The precipitated salt is filtered off and washed with ether / chloroform; 0.73 g (yield 18%) of O, O-diphenyl-N-phosphonomethylglycinonitrile m.p. 166 DEG-168 DEG C. was obtained.

Elementary analysis:

C, 44.7; H, 4.0; N, 7.0; found: 44.8% C, 4.0% H, 7.0% N. Example 21

A solution of trichloromethanephosphonic acid (1.99 g, 0.01 mol) in chloroform-methanol was added to a chloroform solution of O, O-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 10 mol). After 10 minutes, ether was added to the solution; no crystals are deposited. The solution is then diluted with light petroleum until the haze just begins; after 10 minutes the salt began to crystallize. The solution was allowed to stand for an additional 10 minutes and then the precipitated salt was filtered in two portions. A total of 2.9 g (58% yield) of the trichloromethanephosphonic acid salt of O, O-diphenyl-N-phosphonomethylglycinonitrile of m.p. 145-146 ° C was obtained.

Elementary analysis:

calculated: 38.3% C, 3.4% H, 5.6% N; found 38.3% C, 3.5% H, 5.6% N. Example 22

The ethereal solution of fluoroborife was added to a solution of O, O-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 10 mol) in chloroform-ether and stirred overnight. The precipitated crystalline salt was filtered off and washed with ether / chloroform (50/50). 1.1 g (yield 28%) of O, O-diphenyl-N-phosphonomethylglycinonitrile fluoroborate are obtained in the form of colorless crystals of m.p. 156-158 ° C.

Elementary analysis:

C, 46.2; H, 4.1; N, 7.2; Found: C, 46.0; H, 4.2; N, 7.2

A chloroform solution of O, O-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 10 mol) was charged with hydrogen bromide gas and the solution was then allowed to stand overnight. The precipitated salt is filtered off and washed with ether; 3.0 g (78% yield) of 0,0-diphenyl-N-phosphonomethylglycinonitrile hydrobromide are obtained.

H, 4.2%; N, 7.3%. found: 47.1% C, 4.3% H, 7.4% N.

Example 24

To a chloroform solution of O, O-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 10 mol) was added a 57% solution of hydroiodic acid (2 mL); the solution becomes cloudy and turns golden yellow. After two hours standing does not crystallize; ether was added to the solution just beginning to turbidity, the mixture was stirred for an additional 2 hours and the precipitated crystalline salt was filtered off. 2.4 g (yield 56%) of O, O-diphenyl-N-phosphonomethylglycinonitrile hydroiodide are obtained in the form of pale yellow colored plates, m.p. 163-164 ° C.

Elementary analysis:

calculated: 41.9% C, 3.8% H, 29.5% I; found 41.8% C, 3.8 o / _o h, 29.3% I. Example 25

To a chloroform solution of O, O-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 10 mol) was added trifluoroacetic acid (1.14 g, 10 mol) and the solution was stirred overnight. After distilling off the solvent under reduced pressure, 4.0 g (96% yield) of O, O-diphenyl-N-phosphonomethylglycinonitrile trifluoroacetate are obtained in the form of a pale yellow oil; n _D ²⁵ - 1.5172 ..

Example 26

To a chloroform solution of O, O-di-phenyl-N-phosphonomethylglycinonitrile (3.0 g, 10 mol) was added trifluoromethanesulfonic acid (1.50 g, 10 mol) and the reaction mixture was stirred at room temperature for two hours. The ether was then added to turbidity and after standing for one hour, the precipitated salt was filtered off and washed with chloroform / ether (50/50). There was obtained 3.8 g (84% yield) of O, O-diphenyl-N-phosphonomethylglycinonitrile trifluoromethanesulfonate, m.p. 119-120 ° C.

Elementary analysis:

C, 42.5; H, 3.6; N, 6.2; Found: C, 42.7; H, 3.6; N, 6.2

To the chloroform solution of O, O-diphenyl-N-phosphonomethylglycinonitrile (15.1 g, 0.05 mol) was added methanesulfonic acid (5.0 g, 0.051 mol) and the mixture was stirred at room temperature for two hours. The solid was collected by filtration, washed with ether and dried to give 15.9 g of O, O-diphenyl-N-phosphonomethylglycinonitrile methanesulfonate, mp 147-150 ° C, yield 82.1%.

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 28

Etheric solution (10 ml) of nitrous acid (0.9 g, 70 wt%, 0.01 mol) was added to a chloroform solution (100 ml) of O, O-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 0, More diethyl ether and then isooctane (20 mL) were added, followed by precipitation of the crystalline salt, the mixture was stirred at room temperature for one hour, then the precipitated crystalline substance was filtered off, washed with chloroform and dried 2.66 g of O, O-diphenyl-N-phosphonomethylglycinonitrile of m.p. 116 DEG-116.5 DEG C. are obtained, yield 72% of theory.

Elementary analysis:

C, 49.32; H, 4.42; N, 11.5. found: C, 49.20; H, 4.42; N, 11.6. Example 29

To a solution of O, O-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 0.01 mol) in chloroform (100 mL) was added an ethereal solution of 98% sulfuric acid (1.01 g, 0.01 mol). The mixture was diluted with additional chloroform and stirred for two hours. The precipitated crystalline salt is filtered off, washed first with chloroform, then with ether and dried. 33 g (100% yield) of O, O-diphenyl-N-phosphonomethylglycinonitrile m.p. 151-151.5 ° C are obtained.

Elementary analysis:

calculated: 45.0% C, 4.28% H, 8.01% S; found: 44.90% C, 4.27% H, 8.05% S. Example 30

Etheric phosphoric acid solution (0.01 mol) was added at room temperature, with stirring, to a chloroform solution of O, O-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 0.01 mol). The solution became turbid immediately and an oily substance formed at the bottom of the flask. After cooling, the solvent was decanted off, evaporated and the residue was dried over anhydrous magnesium sulphate. There was obtained solid O, O-diphenyl-N-phosphonomethylglycinonitrile of m.p. 74.5-78.5 ° C, yield 25%.

Elementary analysis:

calculated: 45.0% C, 4.5% H, 7.0% N; found: 44.8% G, 4.6% H, 7.1% N.

Example 31

To a suspension of O, O-diphenyl-N-phosphonomethylglycinonitrile (60.4 g, 0.2 mol) in ethanol (500 mL) was added anhydrous hydrogen chloride while cooling in an ice bath. Ethyl ether was added to the resulting solution, and the crystallized colorless salt was filtered off with suction. A further portion of the colorless crystalline solid was recovered by introducing anhydrous hydrogen chloride into ethanol-ether mother liquors at 0 ° C, filtered and washed with ether. g (93% yield) of O, O-diphenyl- N -phosphonomethylglycinonitrile hydrochloride, m.p. 112-123 ° C.

Elementary analysis:

calculated: 53.19% C _r 4.79% H, 8.27% N; found: C 53.51, H 4.78, N 8.30

A solution of di (3,4-methylenedioxyphenyl) phosphite (0.05 mol) and 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (0.0167 mol) in acetonitrile (75 ml) was stirred and stirred for 3 hours. 75 ° C and then allowed to stand overnight at room temperature, after distilling off the solvent, the crude product was obtained as an amber-yellow oil, and the oil (7.6 g, 0.02 mol) was dissolved in chloroform (100 mL). methanesulfonic acid (1.92 grams, 0.02 mol) was added dropwise and the mixture was stirred for 15 minutes, then ether (200 mL) was added and the colorless salt precipitated was filtered off. 6 grams (47% yield) of O, O-di (3,4-methylenedioxyphenyl) -N-phosphonomethylglycinonitrile methanesulfonate, mp 135-136.5 ° C.

calculated: 44.45% C, 3.94% H, 5.76% N; found: 44.26% C, 3.94% H, 5.71% N. Example 33

O, O-dl (4-chloro-m-tolyl) N-phosphonomethylglycinonitrile was obtained as a pink oil. Refractive index n _D ²² - 1.5588.

Example 34

The methanesulfo acid salt with O, O-di (4-chloro-m-tolyl) -N-phosphonomethylglycinone tril has a melting point of 143-147 ° C.

Claims (3)

SUBJECT A process for the preparation of O-aryl-N-phosphonomethylglycinonitriles of the general formula I, OF II (Xa-Aryl-O) 2-P-CH 2 NHCH 2 CN (I) wherein Aryl denotes phenyl, naphthyl or biphenylyl, X represents a substituent on said aryl group selected from the group consisting of halogen, C1-C4 alkyl, alkoxy or C1-C3 alkylthio, C2-C3 alkoxycarbonyl, methylenedioxy, cyano, trifluoromethyl and nitro, Z is an oxygen or sulfur atom and a is an integer from zero to 3, and their acid salts, characterized in that the diaryl phosphite of the formula II, Z (Π) (Xa-Aryl-O) 2-P-H VYNALEZU. 3. in which X, Z, and as hereinbefore defined, indicate at 25 to 110 ° C the action of 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine of formula III NC-C CO O ^ (III) and the isolated O-aryl-N-phosphonomethylglycinonitrile are optionally converted into a salt of formula (Ia), Z H II I (Xa — Aryl — Oj 2 —P — CH2 — NH2 —CH2 CN NR1 H (1a) wherein Aryl, X, a, Z are as defined above and R 1 is a strong acid anion by dissolving in an anhydrous solvent containing a strong acid having a pK value _and water of 2.5 or less and capable of forming a salt with an amino group. 2. A process according to claim 1 wherein the reaction is carried out in the presence of an inert solvent. 3. A process according to claim 1, wherein the diaryl phosphite is diphenylphosphite, di (m-chlorophenyl) phosphite, di (p-methoxyphenyl) phosphite, di (3,4-dimethylphenyl) phosphite or di (pf luorph). enyl jf osfitu.