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    • 专利摘要:
    O-aryl N-phosphonomethylglycinonitriles are described as well as a process for producing same. These phosphonomethyl substituted glycinonitriles are useful as herbicides.
    公开号:SU810066A3
    申请号:SU772543205
    申请日:1977-11-18
    公开日:1981-02-28
    发明作者:Энтони Дютра Джерард
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    (5) HERBICIDE STRUCTURE
    The invention relates to chemical means of controlling undesirable vegetation, namely, a herbicidal composition based on derivatives of N-phosphonomethylglycinonitrile. The herbicidal composition known to be N-phosphonomethylglycinonitrile and the usual additives are known l. However, its efficiency is insufficient. The purpose of the invention is to find a new derbicidal composition based on derivatives of N-phosphonomethylglycinonitrile, which has an enhanced herbicidal action. This goal is achieved by using as a derivative of N-phosphonomethylglyncinonitrile a compound of the general formula g, h II (arsh1-La-o) ji-P-CHa-1 f-CHi-CH-L C where aryl is phenyl, p-naphthyl, Biphenyl X - chlorine, fluorine, methyl, methoxy, methylthio, methylenedioxy, cyan, trifluoromethyl, nitro; Z is oxygen or sulfur; a is an integer from O to 3; b is an integer of O or 1; R - hydrochloric, hydrobromic, hydroiodic, perchloric, fluoroboric, nitric, sulfuric, phosphoric, oxalic, p-toluenesulfonic, phlorbenzosulfonova, trihlormetilfosfonova, trichloroacetic, trifluoroacetic acid or trifluoromethanesulphonic acid, methanesulphonic acid; X - O or 1, provided that X is equal to O, if b is equal to 1, in the amount of 5-95 parts by weight The formulations for the use of the compounds of the compound of formula (I) can be obtained by the interaction of diarylfoss 1,3,5-tritsnanomethylhexagide, 3,5-triazine. -phosphonomethylglycinonitriles of the formula (1), where x and b-0, are made by forming a mixture, mainly from a phosphoric ester of the structural formula (vril-XB-.0) (P) where X, Z and a have the above values, and 1,3,5-tricinomethylhexahydro-1, 3,5-triaine of structural formula y. (P1). ns-cng-Nftj-CHjCK, with the mixture heated to a temperature sufficient to initiate the reaction and maintain it for the interaction of the phosphoric ester with tri-Ein to obtain the N-phosphonomethylglycinonitrile, structural form-; ly (I). . In some cases, it is recommended to work with a solvent for simplicity and ease of reaction. The reaction temperature can range from 25 to. The ratio of phosphoric ester to triaine in order to achieve optimal results should be 3: 1. To obtain compounds of structural formula (1), where b 1, x "simply form a solution of a compound of structural formula (/) al-ha-o) gr-cHj-i-CHi-cH k where X, Z and a have the above value, in a solvent containing at least 1 mol / eq; water, maintaining the solution at room temperature, at which one of the (aryl-XC (-O) -groups is hydrolyzed. A preferred solvent for this is acetone. The desired product is isolated by conventional means — fractionated crystallization or vacuum evaporation of the solvent and other volatile products hydrolysis, the desired product is crystallized from the corresponding solvent to obtain compounds of structural formula (1), where b is O, X 1, i.e. compounds of structural formula gk, V (V) (o / Jun- Xa-o) j - P-CKj-V-CHj-CK -R compound structures Formula (IV) is dissolved in an anhydrous solvent like chloroform, by adding a strong acid to this solution, or in a solvent, in some cases, in pure form with stirring at rooms of: temperature for a time sufficient for the structural compound to react. Formula {IV) with an acid. The desired product of formula (v) is precipitated in crystalline form. In some cases, a mixture of chloroform and diethyl ether (50/50% by volume) is added to induce crystallization of the product or its isolation from the reaction mixture as an oil. In the preparation of salts of strong acids of structural formula (I), phosphoric acid diesters and strong acid are used in an equimolar ratio relative to each derivative of a strong acid salt. Complex aryl diesters of structural formula (IV) are preferably prepared according to one of the two methods described below. A. Acetonitrile solution (50 ml) of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine 3.4 g (0.0167 mol) and diarylphosphite (0.050 mol) are mixed in a reaction vessel, heating 1-90 h at 45-85 ° C until consumption of total phosphite or triazine, which is verified by NMR analysis. If NMR analysis no longer contains impurities, the product is isolated by concentration in a vacuum. If the impurities are still present, the product is precipitated and purified by crystallization or chromatography, in some cases, the diester is difficult. It is difficult to isolate in high-purity form, due to the hydrolysis that occurs during the purification. B: A mixture of diarylphosphite (0.05 mol) and 1,3,5-tricyanomethyl-hexahydro-triazine 3.4 g (0.0167 mol) is loaded into the reactor and heated at 60lOO C for 20-60 minutes to consume the total α-phosphite or triazine as determined by NMR analysis. The products are purified by crystallization or chromatography. Monoaryl esters of N-phosphonomethylglycinonitrile are obtained by dissolving the diaryl ester in acetone containing a small amount of water (usually about 2% by weight of water) with stirring the reaction mixture for 18-72 hours. The monoesters are usually crystalline in form; they are collected by filtration, washed with acetone and dried in air. Strong acid salts of diaryl esters are prepared according to the following general method. A solution of the strong acid (or pure acid) (0.01 mol) is added dropwise to the chloroform solution of the diester complex, keeping at room temperature. If crystals form, they are collected by filtration, washed with a 50% by volume mixture of chloroform and ether. In another case, 50% by volume of the mixture is added in order to achieve the crystallization of the salt or its precipitation from solution in the form of an oil. Example 1. Di (para-chlorphenium phosphite 23.32 g, 78% purity 0, The threshing is mixed in a reactor at room temperature, heating to 20 m. Obtain 27 g of O, 0-di- (para-chlorophenyl) -M-phosphonomethylglycinonitrile and 1.5747. Yield 100%. Example 2. Acetonitrile solution (10 ml) DI (3,4-dimethylphenyl) phosphite 8.7 g (0.03 mol) was added to an acetonitrile solution (50 ml) 1.3 , 5-tricyanomethyl-hexa. Hydro-1,3,5-triazine 2, 04 g (0, 01 mol of heating the mixture at 90 h. By filtering the solid product and evaporating the solvent, an oil the color of red Burgundy wine is obtained, which, according to I P-analysis contains the desired product and the amine product. Chromatography of the oil (8.0 g), on silica gel (450 g) / s cyclohexane / ethyl acetate (50/50%, 60 ml fraction) gives 0.0-di (3,4-dimethylphenyl) -N-phosphonomethylglycinonitrile in fractions 30-41, mp 61-64 to remove the solvent. The solid product is recrystallized from carbon tetrachloride / isooctane to give the product with mp bz-bb C. Yield 40%. Example 3. A stirred mixture of 0.02 mol of di (para-methylthiophenyl) phosphite and 0.0067 mol of 1,3,5-tricyanomethyl-hexahydro-1, 3,5-three-azine is heated to 80c for 1 h, yielding a dark red -Brown oil. Half of the sample is placed in the fridge for 8 days to obtain semi-solid masses. The sample is recrystallized from 70 ml of carbon tetrachloride to obtain a pink solid product. It is dissolved in 100 ml of hot tetrachloromethane and filtered through celite coated with 5.0 g of silica gel. The filtrate is concentrated to 50 ml and placed in a refrigerator overnight. The suspension is filtered to obtain 1.8 g of a white solid product 0,0-di (para-methylthiophenyl) -M-phosphonomethylglycinonitrile, m.p. 64 65 ° C. Yield 45%. Found,%: C 51.7; H 4.9; N 7.1 Calculated,%: C51.8; H 4.9; N 7.1. Example 4. A solution of di (ortho-methoxyphenyl) phosphite 8.5 g, 91% purity (0.025 mol) and 1,3,5-tricigt anomethyl-hexahydro-1,3,5-triazine 1.7 g (0.0083 mol) heated to 55 ° C for 73 hours, then filtered. The filtrate is concentrated to a dark brown oil (9.6 g). The oil of 5.8 g is applied on 8 g of silica gel by adhesion, and extracted with 80 ml of ethyl acetate. An ethyl acetate solution is concentrated with applying the resulting oil by adhesion on 4.0 g of silica gel. Silica gel was extracted with 70 ml of ethyl acetate, and the solution was concentrated in vacuo to give a pale yellow solution, Pr 1.5542. The yellow oil is 0,0-di (ortho-methoxyphenyl) -N-phosphonomethylglycinonitrile, containing a small amount of ortho-methoxyphenol. Example 5. A solution of 1,3,5tricyanomethyl-hexahydro-1, 3,5-triazine 13.6 g (0.06b mol) and diphenylphosphite 46.8 g (0.2 mol) in acetonitripe (100 ml) is heated at 55 ° C 48 h The NMR spectrum shows complete conversion to O, O-diphenyl-N-phosphonomethylglycinonitrile. Aceto-nitrile was removed in vacuo to give 57 g (94.4%) of a viscous black oil, which was dissolved in chloroform by adding 114 g of silica gel; the mixture is evaporated to dryness in vacuo. The silica gel impregnated with the product is placed in a column containing chloroform slurry and silica gel (200 g) and eluted until the product is no longer in the eluate. The chloroform eluents are concentrated, dissolved in methylene chloride, and washed twice with cold 5% KOH (100 ml), then with water. The methylene chloride layer is dried with magnesium sulfate, filtered and evaporated to form 57.9 g of a light yellow oil, which gradually hardens. The solid is O, O-diphenyl-N-phosphonomethylglycine nitrile, m.p. 64-67 ,. 75% yield. Example 6. Acetonitrile solution (100 ml) of di (m-tolyl) phosphite 10.7 g (0.04 mol) and 1,3,5-tricyanomethyl-hexahydro-1, 3,5-triazine- 2.72 g (0.0133 mol) heated to 3 days. The solution takes on the color of a red Burgundy wine, the solvent is evaporated to give 12.4 g of red oil (92; 4% regeneration). The oil (9.0 g) is chromatographed on silica gel, eluting with cyclohexane / ethyl acetate (60/40%) to obtain 60 ml fractions. Fractions 45-63 are pure O, 0-di (metatyl) -N-phosphonomethylglycinonitrile, p25 1.54567. Yield 1.25 g. (14%). ° Found,%: C 61.75; H 5.81; N 8.41. Calculated,%: C, 61.81; H 5.80; N 8.48. Example 7. A solution of di (methanitrophenyl) phosphite 15.2 g, 83% of the numbers (0.0392 mol) and 1,3,5-tricyanoethyl-hexahydro-1, 3,5-triazine 2.66 g (0.013 mol) in Acetonitrile agregayut 20 hours to 50 ° C. .-. NMR analysis: complete conversion. The solution is filtered, the solvent is removed in vacuo. 13 g of an amber oil, O-di (m-nitrophenyl) -N-phosphonomeylglycinonitrile, are obtained.
    C 45.80; H 3.39; N
    Found,%: 4.27. C 45.93; H 3.34;
    Calculated,%: 14.28.
    8. Dee (p-metoksiffepri er
    or) 15.33 g phosphate, 94% purity (0.05 mol) and 1,3,5-tricyanomethyl hexahydro-1, 3,5-triazine 3.4 g (0.0167 mol) is dissolved in acetonityl, the solution is heated 1 h with reflux. The solvent was evaporated in vacuo to give a dark rosy oil (19.0 g). 5 g of the oil is subjected to high pressure liquid chromatography using a mixture of cyclohexane / ethyl acetate (40/60% by volume) to give 4.1 g of O, 0-di (p-methoxyphenyl) -N-phospho-. nomethylglycinonitrile in the form of oil, 1,5541. Yield 82%.
    Example 9. A mixture of .., 3,5-tricyanomethyl-hexahydro-1, 3,5-triazine 2.04 g (0.01 mol) and di (para-fluorophenyl) phosphite 8.8 g, 91.6% - purity (0.03 mol) in acetonitrile is heated 70 h to 55 ° C. The reaction mixture is filtered, the solvent is removed in vacuo to give a brown oil, which is pure 0.0-di (parafluorophenyl) -N-phosphonomethylglycinonitrile, p25 1.5270. The degree of purity is 92%.
    Example 10. Di (methyl chlorophenyl). Phosphite 9.93 g, 91.5% purity (0.03 mol) dissolved in 20 ml of acetonitrile is added to 1,3,5-tricyanomethyl-hexahydro-1U3, 5- triazine 2.04 g (0.01 mol), dissolved in 50 ml of acetonitrile. The mixture is heated for 70 hours to 55c. The acetonitrile is removed in vacuo to give a light pink oil, which is O, 0-di (m-chlorophenyl) -N-phosphonomethylglycinonitrile, 1.5656. The degree of purity is 92%.
    The above methods can be obtained:
     O, 0-di (p-cyanophenyl) -N-phosphogomeglymethylglycinonitrile;
    O, 0-di (para-biphenyl) -N-phosphonomethylglycinonitrile.
    Example 11. A diester of 4.0 g (0.099 mol) obtained in Example 10 was dissolved in 100 ml of 2% aqueous acetone, and the solution was stirred for 6 days at room temperature. A solid is formed. It is collected, washed with acetone and dried to obtain 1.55 g of O-m-chlorophenyl-M-phosphonomethylglycinonitrile as a solid, m.p. 181-182 ° C. Yield 60%.
    C 41.5; H 3.9; N 10.8.
    Found : C 41.5; H 3, -9; N
    Calculated 10.3.
    Example 12. The diester obtained according to Example 9, 2.38 g (0.069 mol) was dissolved in 2% aqueous acetone (100 ml) and stirred for 3 days at room temperature. The resulting slurry is filtered, the solid is washed with acetone to obtain 0.87 g of a reddish solid, m.p. 258-262 ° C. The mother liquor was incubated for 6 weeks, the resulting solid was collected and washed with aqueous acetone to obtain an additional 0.8 g of material, which is 0-para-fluorophenyl-N-phosphonomethylglycinonitrile with the same T.njf. Exit 98%.
    Found,%: C 44.3; H 4.2; N 11.5
    Calculated,%: with 44.3; H 4.1; N 11.5.
    Example 13. 0.0-Diphenyl-N-phosphonomethylglycinonitrile 1.51 g (0.005 mol) is stirred in 50 ml of 2N hydrochloric acid with heating until all the product is completely dissolved (2 hours). An amber colored oil is formed at the bottom of the flask, which is phenol. The flask is cooled to room temperature, the hydro-acidic solution is washed twice with methylene chloride (25 ml in order to remove any starting material and phenol obtained during the reaction. The hydro-acidic solution is cooled on an ice-bath; Crystals. The crystals are collected, washed with cold water and air-dried, they are 0-phenyl-N-phosphonomethylglycinonitrile without a definite mp.
    4.93; N
    C 47.52; H
    Found,%: 12.12.
    Calculated,%: C 47/79; N 4.90; N 12.39.
    Example 14. O, 0-Di (m-tolyl) -M-phosphonomethylglycinonitrile 4.0 g (0.012 mol) was dissolved in acetone (50 ml) containing water (1 ml), stirred for 60 days at room temperature. Receives three portions of crystals. The first two with impurities, so pl. 161-166 s. The third portion is analytically pure 0-m-tolyl-N-phosphonomethylglycinonitrile, m.p. 179-179.5 ° C. Yield 53%.
    Found,%: C 40.0; H 3.4; N 15.5
    Calculated,%: C 40.0; H 3.4; N 15.6.
    Example 15 O, 0-Di (m-nitrophenyl) -N-phosphonomethylglycinone nitrile 3.15 g (0.008 mol) was dissolved in 50 ml of acetone and 1 ml of water, stirring at room temperature for 16 h. A solid was collected, which was collected and washed acetone to obtain 1.1 g O-m-nitrophenyl-N-phosphonomethylglycinonitrile, so pl. 17417bs (with decomposition). Yield 51%.
    Found,%: C 50.0; H 5.5; N 11.7.
    C 50.0; H 5.5; N
    Calculated,% 11.7.
    Example 16. Acetonitrile solution (100 ml) of di (.m-three (|) torolyl) -phosphite 1G, 64 g (0.0314 mol) and 1,3,5-tricyano Methyl-hexahydro-1, 3.5- triazine 2.15 g (0.0105 mol is heated overnight at. Acetonitrile is evaporated in vacuo, a solid begins to form. The residual material is dissolved in 50 ml of acetone and 1 ml of water, stirring then overnight at room temperature. A solid is formed product. It was collected and washed with acetone to obtain 3.5 g of a white solid, mp 195ige C, defined as Ohm-trifluoromethyl-M-phosphonomethylglycinonitrile Yield 39.5%.
    Found,%: C41.0; H3.5; N9.7.
    Calculated,%: C 40.8; H 3.4; N 9.5.
    Example 17. O, 0-Di (p-chlorophenyl) -N-phosphonomethylglycinonitrile 9.0 g (0.024 mol) was dissolved in 50 m of acetone and 1 ml of water, stirring at room temperature for two days. 2.35 g of solid 0-p-chlorophenyl-N-phosphonomethylglycine nitrile are formed, m.p. 170s (with decomposition). The mother liquor was incubated for several weeks, then another 0.85 g was collected. The overall yield was 3.2 g (51%).
    Example 18: 21 g of a solution containing 83.8% by weight of di (3-methyl-4-nitrophenyl) phosphite (0.05 mol) and 1,3,5-tricyanomethyl-hexahydro-1.3, 5-triazine, 3.4 g (0.0167 mol), is dissolved in 100 ml of acetonitrile and heated to 70 ° C for 1 hour. The acetonitrile solvent was then removed in vacuo, the residue was dissolved in 50 ml of acetone containing 1 ml of water, and stirred at room temperature. Crystals (4.3 g) are defined as O- (3-methyl-4-nitrophenyl) -H-phosphonomethylglycinonitrile, m.p. 181182 ° C. Yield 30%.
    Found,%: C 42.2; H, 4.3; N, 14.7.
    Calculated,%: C 42.1; H 4.2; N 14.7.
    Example 19. 0.0-Di (p-methoxyphenyl) -N-phosphonomethylglycinonitrile 3.0 g (0.0082 mol) was dissolved in 50 ml of acetone and 1 ml of water, stirring for three months at room temperature. A solid is formed which is removed by filtration, washed with acetone and dried. The solid product is defined as 0-p-methoxyFeNYL-N-phosphonomethylglycine nitrile, m.p. 185-195s (with decomposition).
    Found,%: C 47.1; H 5.2; N 10.8.
    Calculated,%: C 46.9; H 5.1; N 11.0.
    Example 20 Di (o-chlorophenyl) phosphite 19.5 g, 80% by weight (0.05 mol) was added to an acetonitrile solution (50 ml) of 1,3,5-tricyanomethyl hexahydro-1, 3, 5-triazine 3 , 4 g (0.01640 mol), and heated to 70 ° C for 2 hours. Concentrate the solution to 15 ml, dissolve
    in 50 ml of acetone and 1 ml of water and stirred overnight. A solid is formed. It is collected, washed with acetone, and dried to obtain 3.2 g of product, defined as O- (o-chlorophenyl) -N-phosphonomethylL-glycine nitrile, mp. 170-171 C. Yield 82%.
    Found,%: C 41.4; H 3.9; N 10
    Calculated,%: C41.5; H3.9; N 10.8.
    Example 21. 0-0-Di (para-fluorophenyl) -N-phosphonomethiglycinonitrile 2.38 g (0.069 mol) is stirred in a 50% by volume mixture of carbon tetrachloride and methylene chloride, filtered with methanesulfonic acid 0, 67 g (0.069 mol). The solution is held overnight, the crystals formed are collected by filtration and washed with carbon tetrachloride to obtain 2.68 g of a white crystalline product, defined as 0.0-di methanesulfonic acid salt (pfluorophenyl-1-M-phosphonomethylglycinonitrile, mp 132-132.5 ° WITH.
    Found,%: C 44.0; H 4.0; N 6.6 S 7.5.
    Calculated,%: C 44.2; H 4.0; N 6.5; S 7.4.
    Example 22. p-Toluenesulfonic acid 1.9 g (0.01 mol) is heated under reflux in 100 ml of benzene, removing the water present by an azeotropic route using benzene. The benzene solution is added to the benzene-methylene chloride solution (50/50% by volume, 100 ml) of 0,0-diphenyl-M-phosphonomethylglycinonitrile 3.02 g (0.1 mol). The mixture is stirred for 1 min at room temperature; crystallization occurs during this time. The resulting slurry is stirred overnight at room temperature, then filtered to obtain 4.38 g of a white solid product, defined as the p-toluenesulfonic acid salt of O, O diphenyl-M-phosphonomethylglycininitrile, m.p. 152-153 ° C. The yield is 92.4%.
    Found,%: C 55.4; H 4.9; N 5.7.
    Calculated,%: C 55.7; H 4.9; N 5.9.
    Example 23. Chloroform solution of p-chlorobenzenesulfonic acid 1.92 g (0.01 mol) was added into the chloroform solution of 0, O-diphenyl-N-phosphonomethylglycinonitrile 3.0 g (0.01 mol). The mixture is stirred, after 10 minutes crystallization begins. The slurry is stirred overnight, filtered, the solid product is washed with chloroform to obtain 4.0 white solid product, soluble as p-chlorobenzenesulfonic acid salt O, O-diphenyl. -N-phosphonomethylglycinonitrile, so pl. 149-151 ° C. Exit 81i.
    Found,%: C 50.7; H 4.1; N 5.7.
    Calculated,%: C 51.0; H 4.1; N 5.7. Example 24. Chlorophoremic solution (20 ml) of trichloroacetic acid 1.63 g (0.01 mol) was added to the chloroform solution (100 ml) of 0.0-diphenyl-N-phosphonomethylglycinonitrile 3.0 g (0.01 mol) and stir overnight at room temperature. Crystallization does not start, the solvents are removed in vacuo to give 3.75 g of a light yellow oil. 1.5410, defined as 0.0-diphenyl-N-phosphonomethylglycinonitrile salt of trichloroacetic acid. You move 80%. Found,%: C 43.9; H 3.5; N 5.9. Calculated,%: C 43.9; H 3.5; N 6; P m and m. P 25. Acetonitrile solution (25 ml) of oxalic acid dihydrate, 1.2G g (10 mol) is added to an acetone solution of 0., O-diphenyl-N-phosphonomethylglycinonitrile 3 , 02 g (10 mol). After 10 minutes, the salt begins to crystallize out of solution. The solution is stirred overnight, cooled, the solid product is collected (-1, 9 g) and washed with acetone. The second portion is obtained by condensing the mother liquor (0.8 g). The crystals are defined as the salt of oxalic acid O, O-diphenyl-N-phosphonomethylglycinonitrile, m.p. (with decomposition). Yield 2.7 g (69%). Found,%: C 52.1; H 4.4; N 7.1 Calculated.,%: C 52.1; H 4.4; N 7.1. Example 26. Perchloric acid ether solution was added to chloroform-ether solution of 0,0-diphenyl-N-phosphonomethylglycinonitrile 3.0 g (10 mol). Perchlorate slowly crystallizes as white prisms. The solid product, defined as the perchloric acid salt of 0,0-diphenyl-N-phosphonomethylglycinonitrile, is collected and washed with ether-chloroform to obtain 0.73 g, m.p. 166-168C. Yield 18%. Found,%: C 44.8; H 4.0; N 7.0 Calculated,%: C 44.7; H 4.0; N, 7.0. Example 27. Chloroform-methanol solution of trichloromethane-phosphonic acid 1.99 g (0.01 mol) was added into chloroform solution of 0,0-diphenyl-M-phosphonomethylglycinonitrile 3.0 g (10 mol). After 10 minutes ether was added, no crystals formed. Petroleum ether is then added until the cloud point is reached. After 10 minutes, crystals begin to form, and the solution is held for another 10 minutes. The crystals are collected in two portions (2.9 g). The crystals are defined as the salt of trichloromethane phosphonic acid O, O-diphenyl-M-phosphonomethylglycinonitrile, m.p. 145146 S. The yield is 58%. Found,%: C 38.3; H 3.5; N 5.6 Calculated,%: C 38.3; H 3.4; . N 5.6. Example 28. An ethereal solution of fluoroboric acid was added into chloroform-ethereal solution of 0,0-diphenyl-N-phosphonomethylglycine 3.0 g (10 mol). The solution is stirred overnight, the solid is filtered, washed with ether / chloroform (50/50%) to obtain white crystals (1.1 g), defined as fluoroboric acid salt O, O-diphenyl-N-phosphonomethylglycinonitrile, mp . 156-158 p. Yield 28%. Found,%: C 46.0; H 4.2; N 7.2. Calculated,%: C, 46; H 4.1; N 7.2. Example 29. -Gas-like hydrogen broth is introduced into a chloroform solution of O, O-diphenyl-N-phosphonomethylglycinonitrile 3.0 g (10 mol). The solution was removed overnight after the hydrobromide crystallized, the crystals were collected and washed with ether to obtain 3.0 g of O, O-diphenyl-M-phosphonomethylglycinonitrile hydrogen bromide. The yield is 78%. Found,%: C 47.1; H 4.3; N 7.4. Calculated,%: С 47.0; H 4.2; N 7.3. Example 30 A 57% solution of hydroiodic acid (2 ml) was added to a chloroform solution of 0, 0-diphenyl-N-phosphonomethylglycinonitrile 3, O-g (10 mol). The solution becomes cloudy and golden. After 2 hours, the three products are not formed, so ether is added until the cloud point is reached and crystallization begins. A stirring solution} from 1 more hour, a solid product, defined as the salt of hydroiodic acid O, 0-diphenyl-N-phosphonomethylglycinonitrile, is collected in the form of light yellow tiles, so pl. 153-164 ° C (2.4 g. Yield 56%. Found,%: C 41.8; H 3.8; I 29.3. Calculated,%: C 41.9; H 3.8; I 29 , Example 5. Trifluoroacetic acid 1.13 g (10 mol) was added to chloroform solution of 0,0-diphenyl-N-phosphonomethylglycinonitrile 3.0 g (10 mol). The solution was stirred overnight, the solvent was evaporated in vacuo with obtaining 4.0 g of a light yellow oil, p 1.5172, defined as the salt of trifluoroacetic acid O, O-diphenyl-N-phosphonomethyl- .. glycinonitrile. Yield 96%. P. p and me 32. Trifluoromethanesulfonic acid ( smoked) 1.50 g (Humol) O, 0-diphenyl M phosphonate is added to the chloroform solution Ilglycinonitrile 3, O g (10 mol). The reaction mixture is stirred for 2 hours at room temperature, then ether is added until the cloud point is reached. The product crystallizes. After 1 hour, the solid product is collected and washed with chloroform-ether (50%), obtaining 3.8 g of trifluoromegansulphonic acid salt o, O-diphenyl-M-phosphonone methylglycinonitrile, mp 119-120 84% yield. Found: C 42.7; H 3.6; N 6, Calculated,%: C 42.5; H 3.6; N 6.2. Example 33. Methanesulfonic acid 5.0 g (0.051 mol) was added to a chloroform solution of O, O-diphenyl-M-phosphonomethyl glycinonitrile 15.1 g (0.05 mol). The solution is stirred for 2 hours at room temperature. A solid product precipitates, which is collected (washed, washed with ether and dried. The solid product weighs 15.90 g and is the methanesulfonic acid salt of 0,0-diphenyl-N-phosphonomethylglycinonitrile, mp. 147-150 s. Yield 82.1% Found,%: C 44.0; H 4.0; N 6, S 7.5. Calculated,%: C 44.2; H 4.0; N 6.5; S 7.4. Example 34. An ether solution (10 ml) of nitric acid, 0.9 g, 70% by weight (0.01 mol) is added to a chloroform solution (100 ml) is added to a chloroform solution (100 ml) containing O, O-diphenyl-M- glycinonitrile phosphonet 3.0 g (0.01 mol). No cloudiness is observed. Diethyl ether is added, then isooctane (20 ml); After this, the solid begins to crystallize. The mixture is stirred for 30 minutes at room temperature, the crystal is collected, washed with chloroform and dried in air. The crystals weigh 2.66 g and are the salt of nitric acid O, O-diphenyl-M-phosphonomethyl glycinonitrile, mp 116-116, Yield 72%. Found,%: C 49.2; H 4.42; N 11.6. Calculated,%: C 49.32; H 4.42; N 11.5 Example 35. To a solution of 0,0-diphenyl-M-phosphonomethylglycinonitrile 3.0 g (0.01 mol) in chloroform (100 ml) was added an ethereal solution of a 98% sulfuric acid 1.01 g (0.01 mol ). An additional amount of chloroform is then added, the mixture is stirred for 2 hours. The solid is removed by filtration and washed with chloroform and ether, then dried to obtain 3.9 g of product, determined as the salt of sulfuric acid O, 0-diphenyl-s-phosphonomethylglycinonitrile m.p. 151-151.5 ° C. The yield is 100%. Found,%: C 44.90; H 4.27; S 8.05. Calculated,%: C 45.0; H 4.28; S 8.01. Example 36. A phosphoric acid ester solution (0.01 mol) was added to a chloroform solution of 0,0-diphenyl-N-phosphonomethylglycinonitrile 3.0 g (0.01 mol) at room temperature. The solution instantly becomes cloudy. An oil forms at the bottom of the flask. After cooling, the solvent is drained, evaporated to dryness and dried with anhydrous magnesium sulphate. Solid material is defined as a phosphoric acid salt. O, O-diphenyl-N-phosphonomethylglycinonitrile, m.p. 74.578, 5 ° C. Yield 25%. Found,%: C 44.8; H 4.6; N 7.1. Calculated,%: C 45.0; H 4.5; N 7.0. EXAMPLE 37. A heterogeneous solution of O, O-diphenyl-Mt-phosphonomethylglycinonitrile 60.4 g (0.2 mol) in ethanol (500 ml) is cooled in an ice bath with dry hydrogen chloride gas flowing through it. The solution is allowed to stand, ethyl ether is added, and a white solid is collected by suction filtration. When passing through.:. an ethanol-ether mother liquor at approximately 0 ° C of dry hydrochloric gas, an additional amount of white solid is formed, which is collected and washed with ether; it is the hydrochloride salt of O, O-diphenyl-N-phosphonomethylglycinonitrile, m.p. 112.-123 ° C. Yield 62.7 g (93%). Found,%: C 53.51; H 4.78; N 8.30. Calculated,%: C 53.19; H 4.79; N, 8.27. Example 38. Di (2,4,6-trimethylphenyl) phosphite 17.8 g (0.05 mol) was added to an acetonitrile solution (50 ml) of 1,3,5-trithio-methyl-hexahydro-1, 3 , 5-triazine 3.4 g (0.0164 mol) with heating the mixture for 18 h at. The resulting black solution is filtered and concentrated to an oil. 7 g of this oil is chromatographed on silica gel (4.50 g) using cyclohexane / ethyl acetate (70/30%, 60 ml fractions) to obtain 1.0 g (14%) of 0.0-di (2,4,6-trimethylphenyl ) -Phosphonomethylglycinonitrile, m.p. 118-120 ° C in fractions 28-40, which crystallize from time to time. Found,%: C 65.38; H 7.07; N 7.18. Calculated,%: C 65.27; H 7.04; N 7.25. Example 39. A solution of the ester according to example 3 (0.025 mol) of moist acetone (50 ml) is heated under reflux for 2 hours, then kept at room temperature for 5 days. The slurry is filtered to obtain a pinkish product with impurities (0/9 g). The filtrate is placed in a closed flask and dispensed at room temperature for another 30 days. The resulting suspension is filtered, the solid product is rummed with 50 ml of acetone. Receive, 5 g of O- (para-methylthio) -N-phosphonoethylglycinonitrile as white
    solid product, so pl. 250-253С (with decomposition). Yield 66%.
    Found,%: C 44.26; H 4.86; N1.0.22.
    Calculated,%: C 44.12; H 4.81; N 10.29.
    PRI mere. 40. Diphenylthiophosphite .8.2 g (0.0246 mol) and 1,3,5-tricyanomethylhexahydro-1, 3,5-triazine 1.68 g (0.00823 mol) are dissolved in 50 ml of acetonitrile with heating at 60-65 ° C 2 days The resulting oil is chromatographed on silica gel (450 g), eluting using cyclohexane / ethyl acetate (60/40%, 60 ml fractions) to give 1.6 g (20%) of O, O-diphenyl-N-thiol
    phosphonomethylglycinonitrile, 1.5847 in fraction 40.
    Found,%: With 56,40; H 4.80; N 8.73; S 10.26.
    Calculated,%: C 56.60; H 4.75; N 8.80; S 10.07.
    Example 41. Acetonitrile solution (100 ml) of di ((} - naphthyl) phosphite 33.5 g (0.1 mol) and 1,3,5-tricyanomethyl-hexahydro-1, 3,5-triazine 20.4 g ( 0.1 mol) is heated under reflux for 1 hour and then concentrated to obtain a red-brown oil. 10 g of oil is purified by high-pressure liquid chromatography, eluting using cyclohexane / ethyl acetate (60/40%, fractions of 20 ml). Fractions 45-64 are combined and concentrated; the resulting oil is crystallized from carbon tetrachloride to obtain 1.1 g of O, 0-di (| 3-naphthyl) -N-phosphonomethylglycinonitropyl as a dark yellow solid. duct, mp 104-105 ° C. Found,%: C 68.58; H 4.79; N 6.92.
    Calculated,%: C 68.65; H 4.76; N 6.96.
    Example 42. A stirred solution of di (3,4-methylenedioxyphenyl) phosphite (0.05 mol) and 1,3,5-tricyanomethyl-hexahydro-1, 3,5-triazine (0.0167 mol) in 75 ml of acetonitrile is heated 3 h to 75 ° C, then again overnight at room temperature. The resulting solution is concentrated to obtain an amber oil. To the chloroform solution (100 ml) of this oil 7.6.g (0.02 mol) was added dropwise methanesulfonic acid 1.92 g (0.02 mol) After stirring for 1-5 minutes, ether (200 ml) was added; solid white product. It is recrystallized two times from acetone to obtain 4.6 g of methanesulfonic acid salt 0.04 dd (3,4-methylenedioxyphenyl) -H-phosphonomethylglycine, mp 135-136. Yield 47%.
    Found,%: C 44.26; H 3.94; N 5.71.
    Calculated,%: C, 44.45; H 3.94; . N 5.76.
    Example 43. A solution of 0.01 mol of amber oil in Example 42 in wet aceto {e (70 ml) is treated for 4 days with reflux, maintained at room temperature for 1 day. The resulting suspension is filtered to obtain 1.7 g of 0- (3,4-methylenedioxyphenyl) N-phosphonomethylglycinonitrile in the form of a white solid, so pl. 160-161 ° C.
    Example 44. A stirred solution of di- (3,4-dichlorophenyl) phosphite (o, 04 mol) and 1,3,5-tricyanomethyl-hexahydro-1, 3,5-triazine (O, 013 mol in acetonitrile (40 ml) is heated to 80 ° Cf then incubated for 18 hours. The resulting solution is concentrated to obtain an oil by adding wet acetone (80 ml), after which the mixture is heated under reflux for 80 hours. The resulting suspension is filtered to obtain a white product, which is washed with 50 ml of acetone, 6.3 g of 0- (3,4-dichlorophenyl) -M-phosphonomethylglycinonitrile, mp 169-170 ° C. Yield 53%.
    Example 45. Get 0,0-di (4-chloro-m-tolyl) -N-phosphonomethylglycinonitrile in the form of a rose oil, p 1.5588.
    Example 46. The methanesulfonic acid salt of O, O-di (4-chloro-m-tolyl) -N-phosphonomethylglycinonitropyl is obtained, m.p. 143-147 ° C.
    The post-emergence herbicidal action of the various compounds according to the invention is demonstrated as follows.
    The active ingredients are applied in the form of a spray solution to various plant species in the developmental stage for 14-21 days. The spraying solution — an aqueous or organic solvent solution in water containing the active ingredient and surfactant (35 parts of dodecylbenzenesulfonic acid butylamine salt and 65 parts of tall oil condensed with ethylene oxide in a ratio of 11 moles of ethylene oxide and 1 mole of tall oil) is applied on plants in different series of vegetative planar vessels with the use of different consumption rate (kg / ha) of the active ingredient. Treated plants are placed in greenhouse conditions, the action is registered after about two or four weeks.
    The post-emergence effect of the poisons is presented in table. 1 by changing the following code:
    Displacement of rativia,%
    0-24
    25-49
    50-74
    75-99 All plants
    destroyed
    During testing, plants not present + species of test plants in Table 1,
    2 and 3 are marked with letters: A - bad to the field; B - Cockerel; B — Limnocharis; G - ipome; D - Mari Bel; Pepper's Egor; J - Cyperus rotundus;
    3- wheatgrass; And - humay; And - In gothus tec to r urn; K - hedgehog; L.- with; M beet sugar; H - wheat; O rice; P - sorghum; R - field buckwheat; C - Hemp sesbania; T - millet; Rosy has a home on. 1411.234414432333 45.63342442112.3 2411.2 44324332234 45.633324421143 3411.2 33334423323 45.634124422212 4411.2443444 22233 246344322334 22113 24634 22 22344322334 44.444 34334421213 2411 233443441 2263 four . 5.6 32213311413 8411.2 24214423413 45.6333244 2. 1413 .. 9 4 11.244434413234. 45.6444424413234 10 411.2443344233 4 4 45.6 333244-12134
    Continued table. one.
    10 11.2 44444433234 5.6 44424423134 11.2 44324423424 5.6 44324433314 11.2 2 + 444333434 4.48 3 + 33423 3333 11.2 44434442234 5.6 33324411234 11.2 44424443344 5.6 .34013422433 11.2443 144 34424 5.6 44214 423403 11.2 44434433434 5.6 34434422134 11.2 33324422323 5.6 4 3 2 2 4 4 2 1 3 1 3 11.244422231302 5.6 24112231102 11.23422342 3323 5.6 33124421323 11, 2 44324423433 5.6 23324422233 1.2 44434444444 5.6334 2 4433324 1.2 44444444244 1.2 24344412223 5.6 23223310412
    Continued table. one
    Continued table. one
    21
    81006622
    Continued table. 2
    81006624
    23
    Calculation of the working week, the norm, after k / g
    L
    m processing
    45,62144431224433444 41,122012431224322224 40,281111210102211112
    45.62233422214413334 41.121111321113211223
    45,63114332234431434 41,121111321112210313 40,281000110001100111
    45.612344-24224433444 41.121111221114421222
    45,62113321112211223 41,121211110101110111
    45,63324431144443444 41,121111321124321323 40,281011211112110112
    45.63233441324433434 41.122112321224421324 40.281110110114210112
    45,64424442434443444 41,122113421234421444 40.281001210114210112
    45.63324431434444444 41.121113321224331323 40.281 00 0210123210112
    45.64344432444443444 41,1221133212244 4 2444 40.261111221212221433
    4 5,64434432434444444
    4 1,122111322223322434
    4 0,282000211112221222
    Continued table. 2 Plant species
    and
    to
    E
    AT
    n
    25
    28
    29
    thirty
    31
    32
    33
    34
    35
    36
    37
    81006626
    Continued table. 2
    3433432434444444
    2112321223322433
    1011221122221222
    4443341434444444
    2212321224422334
    1011211122210222
    4424444444444444
    1111211224441224
    1111211122220222
    3322331334444444
    2311442224443333
    1001211113211112
    4434442344444444
    2111231143231233
    1101110011110122
    2324431214434443
    0211421102111112
    1100210101100002
    33-34442224213444
    2110431114212222
    1 + 00211111100111
    2214432224422434
    1211221113211222
    1000100000000100
    3233433223433334
    1111 2 21212111122
    1001110111001001
    3113431214321334
    H
    1111321103211233 1011321102101122
    27
    Table3
    81006628
    Continued table. 2
    Continued table. 3 29810066 Continuation of the table. 3Type of rastani Consumption rate, kg / ha
    11.2200000000
    11,220010001100
    11.2200000000
    11.2300000000
    11,230000000100
    11,230010000100
    11,230000022300
    11,230000011000
    11.230001001000
    11,200000000000
    11.2300000000 c. Pre-emergence herbicidal action of various compounds is demonstrated as follows. The appropriate amount of arable soil is placed in flat-shaped aluminum vegetation vessels and compacted to reach a level of 3/8 - 1/2 inches from the top of each vessel. A predetermined number of seeds or seedlings of each plant species is placed on the soil surface in each vessel, then pressed into the soil. Topsoil is treated with herbicidal compositions described in Example A, based on the active ingredients of the invention. According to the proposed method, the soil necessary for covering the seeds and seedlings is weighed and mixed with the herbicidal composition containing a known amount of the active ingredient. After that, the vegetative vessels are filled with a mixture, leveling the soil surface. Watering is carried out using holes in the bottom of the vessels through which the soil can absorb moisture. The vessels with seeds and seeds are placed on wet sand and kept for about two weeks under normal conditions in sunlight with irrigation. By the end of this period, the number of ascended plants is compared to the untreated control. This is given in table. 3 with the following code applied: 45
    11,200000001100
    40 41
    11,200000000000
    ten
    11.2300 billion. 42 43
    11.230003001000
    15 44 45 46
    11,230000000300
    11.230001000200
    11,230000100000
    20
    about;: p-CHiUHCHiCM
    CtHsO. CjHjOS2 (25 known) 5.6
    权利要求:
    Claims (1)
    [1]
    00000000000, more than the deeds imitated the dust of the deed (Ч where is the continuation of the table. 3 Type of planting is asymptomatic. Destruction of plants,% 0-25 26-50 51-75 76-100 thus, the proposed bicidal composition possesses a higher herbicidal activity. Claims of the Invention A herbicidal composition containing an origin based on a fluxed M-phosphonomethylglycinone and an additive selected from a group carrier, a diluent and fill, differing in that, in order to enhance the herbicidal structure, it contains as a processant N-phosphonomethylglycine nitrile of the general formula IV X -0) .- P-CHj-N-OC-SI Their aryl - phenyl, jj-naphthyl Sifenil; X is chlorine, fluorine, methyl, methoxy, methylthio, methylenedioxy, cyan, trifluoromethyl, nitro; Z is oxygen or sulfur; a is an integer from O to 3; b is an integer of O or 1; 31. 81006 R - hydrochloric, hydrochloric, hydroiodic, chloric, fluorophenol, nitric, sulfuric, phosphoric, oxalic, p-toluenesulfonic, p-chloroarbenzenesulfonic, hydrochloric acid, acetic acid or trifluormetmetkt, hydrochloric acid, hydrochloric acid 632 X - about or 1, provided that x is equal to O, if% is 1, in the amount of 5-95 parts by weight Sources of information taken into account in the examination 1. US patent 3,923,877, cl. 260-502.5, publ. 02.12.75.
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    同族专利:
    公开号 | 公开日
    BE860972A|1978-05-18|
    SU704457A3|1979-12-15|
    US4089671A|1978-05-16|
    US4083898A|1978-04-11|
    MY8100129A|1981-12-31|
    ZA776900B|1978-09-27|
    YU279877A|1983-02-28|
    ZA776903B|1978-09-27|
    US4067719A|1978-01-10|
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    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/750,327|US4067719A|1976-12-13|1976-12-13|O-Aryl N-phosphonomethylglycinonitriles and the herbicidal use thereof|
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