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    • 专利摘要:
    Alkyl-[di(benzyl) or di(aryl)]esters of N-phosphonomethyl glycine are produced by the reaction of a dibenzyl or diaryl phosphite with an N-methylene alkyl glycinate trimer. These esters and the hydrolysis products thereof containing at least one benzyloxy or aryloxy group bonded to phosphorus are novel compounds having the formula <IMAGE> wherein R is a member of the group consisting of phenyl, benzyl, naphthyl, biphenylyl, benzyloxyphenyl and phenyl, benzyl or naphthyl groups substituted with from 1 to 3 groups selected from the class consisting of hydroxyl, lower alkyl, lower alkoxy, lower alkylthio, trifluoromethyl, carbo (lower alkoxy), nitro, or halo; R1 is hydrogen or an R group, and R2 is a lower alkyl group or hydrogen, and the strong acid salts of the compounds wherein neither R1 or R2 is H. These compounds are useful as post-emergent herbicides.
    公开号:SU843755A3
    申请号:SU772518560
    申请日:1977-09-09
    公开日:1981-06-30
    发明作者:Антони Дутра Джерард
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a new process for the preparation of new derivatives of N-phosphonomethylglycine, namely the N-phosphonomethylglycerides of the general formula OO IIII (RO) p-CHg-T-CHg-C-s where R is phenyl, benzyl, naphthyl, benzyloxyphenyl, biphenyl as well as their derivatives containing from 1 to 3 substituents selected from the group: hydroxyl, lower alkyl, lower alkoxy, lower alkylthio, trifluoromethyl carbo, (lower alkoxy).,. nitro or halogen; R is lower alkyl, which can be used as herbicides. The trialkyl esters of N-phosphoromethylglycine are known and methods for producing such esters. For example, tetraalkyl complex. N-phosphonomethylaminodiacetic acid esters can be converted by the electrolytic method into the trialkyl esters by means of trialkyl esters. Most N-phosphonomethylglycine trialkyl esters are usually not effective as post-emergent herbicides. N-phosphonomethylglydine esters containing an alkyl group bound to a carboxyl group and aromatic or benzyl groups bound to a phosphorus atom are not described in the literature. A method of producing N-phosphonomethylglycine is known, wherein 1,3,5-tricyanomethyl hexahydro-1, 3,5-triazine is reacted with a phosphoric ester in the presence of a catalyst, which is hydrohalic acid, Lewis acid, carboxylic acid anhydride, or the N-phosphonomethylglycinonitrile thus obtained is hydrolyzed to give N-phosphonomethylglyion 2. However, no esters are formed in this case. The purpose of the invention is to develop a new method for producing new N-phosphonomethylglycine tri-esters of general formula I containing aryl or benzyl groups on the phosphorus atom and alkyl groups on the carboxyl group. This goal is achieved due to the fact that the phosphite ester of the formula (CO), P-H. where T, as indicated above, is reacted with tris- (1,3,5-alkoxycarbonyl-methylene) hexagidrotriazine (hereinafter N-methylylishkylglycinate-trimer) of the general formula, ROOCH C- -H-CHHCOOH NgC / SNg: bT -CHiC; ooR where R is as indicated above, in an aprotic organic solvent medium, preferably benzene, at room temperature. to boiling point of the reaction mixture. Phosphite and tris- (1,3-lkoxycarbonylmethylene) hexahydrotriazine esters are preferably taken in a molar ratio of 3: 1. The tri-esters of N-phosphonomethyl glycine of formula I can then be treated with a strong acid to form salts, or they can be treated with water to obtain a hydrolysis product containing hydroxyl groups bound to a phosphorus atom, and the remaining groups remain unchanged. This hydrolysis product can then be treated with water to obtain a derivative of N-phosphonomethylglycine containing a single aryl or b.isyl ester group bound to the phosphorus atom. Compounds of formula I in which R is R and means an ester group can be treated with a strong acid to obtain strongly acidic salts of the formulas OO, f,) IIII 1 (ROJ-P-CHx-T - Shg C - OR O H L where R is the lower alkyl group, and X is a strong acid. The triesters of formula 1 can be hydrolyzed under mild conditions, yielding compounds of the formula RV O H O o II I II., PCHg-11-CHGC-s 1, where R. and R are as defined above. Compounds of formula iu can still be hydrolyzed by heating with water and acetone to form N-phosphonomethylglycine esters P-CH N-CH2COOH where R has the above meaning.The expression halogen or halogen means chlorine, bromine, iodine and fluorine.The expression lower alkyl means an alkyl group with 1-4 carbon atoms, for example methyl, ethyl, propyl, isopropyl, primary , secondary and tertiary butyl. Trister esters of the formula I can be isolated by removal of the solvent or they can be used as a solution in a solvent. In order to obtain the best yields and in order to simplify the preparation of the product, the ratio of phosphite ester to hexahydrotriazine derivative is not less than 3: 1. Solvents that can be used to obtain the proposed triester are anhydrous aprotic solvents that do not react neither with a hexahydrotriazine derivative, nor with a phosphite. The solvents must be anhydrous in order to prevent the premature hydrolysis of the trifere. Examples of such aprotic A solvent are acetonitrile, benzene, toluene, xylene, mono- and dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, ethyl acetate, dimethylformamide, tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether, dimethyl {diethyleneglycol, dimethyl ether diethylene glycol i and the like Dnmethyl sulfoxide, although it is an aprotic solvent, is not suitable because it reacts with phosphite esters. Preference is given to operating at temperatures ranging from to the boiling point of the reaction mixture. Usually, the solvent used is operated at the reflux temperature. The proposed method is carried out at atmospheric pressure. The strongly acid salts of the compounds of formula I are obtained by dissolving the compound in a suitable solvent, for example acetone or chloroform, and strong acid is added. The salt precipitates. Diethyl ether can be added and the salt forms a solid or insoluble oil. Strong acids that can be used to obtain strongly acidic salts of compounds of the formula I, where R and
    R does not mean hydrogen, these are acids that have a pK value of 2.2 or less, as measured in an aqueous solution. Acids with a pK value of 0.1 (or even less) can also be used. Examples of such acids are hydrochloric, bromistovo-d corpulence, hydroiodic, sulfuric acid, chlorosulfonic acid, methanesulfonic acid, benzenesulfonic acid, trichloroacetic acid, trifluoroacetic acid, p tiftorpropionova acid, heptafluorobutyric acid, trifluoromethanesulfonic acid ,. oxalic acid, etc.
    Monooxy derivatives of the compounds of formula 1 are prepared by hydrolysis under mild conditions according to one of the following well-known methods.
    a) A mixed solution of ester phosphite of hexahydrotriazine derivative is heated with reverse chr: g in a suitable pacTBOHF for 1-2 h and cooled to room temperature. After that, it is kept in the atmosphere for a certain period of time (usually within 18-60 hours) to obtain a suspension of the solid hydroxy ester. The solid test powder is washed with acetone and dried to obtain an analytically pure sample.
    b) The triester of formula 1 is dissolved in acetone containing 5% by volume of water and heated to reflux for about 24 hours. After cooling to ambient temperature, the resulting solid oxyester is removed by filtration) and washed once or twice with acetone , and receive analytically pure test. The resulting monoxy ester is converted. a monoester of formula E by heating under reflux for a time sufficient to hydrolyze the carboxylic ester in acetone-water. The monoester of formula 5 is obtained in solid form by filtration,
    The resulting compounds are suitable as pre-sag herbicides.
    Example 1. Di-4-methoxyphenylphosphite 11.72 g (0.04 mol) and N-methylene ethylglycyltrimer 4.60 g (0.0133 mol) are dissolved in 50 ml of benzene and heated under reflux for 3 hours and 15 minutes. Veisole is removed in vacuo and the residue is filtrugo through diatomaceous earth, in which 12 g of ethyl-K-Cdi are obtained; (oxyphenoxy) -phosphonomethyl glycinate as a light yellow oil.
    Calculated,%: C 55.75, H 5.91; . N 3.42: C 55.50; H 6.00;
    Found,% 3.45
    N Di-4-nitrobenyl 2
    Example
    phosphite 17.6 g (0.05 mol) dissolved
    800 CMi of benzene 1 ml at, is added M methylene ethyl 1: 11 11 trimer 5.75 g (0.0167 mol) dissolved in benzene (50 ml) and the mixture is heated under reflux for 16 hours. The benzene is removed by evaporation in vacuo at and get ethyl-H- (di-4-nitrobenzyloxyphosphonomethyl) glycinate in the form of a yellow oil. Calculated,%: C 48.72; H 4.95;
    N 8.97.
    0
    C 48.95; H 4.83;
    Found%
    N 8.70.
    3. Diphenylphosphine
    Example 11. 71 g (0.050 mol) and N-methylene ethyl glycinate trimer (0.0167 mol) are dissolved in. benzene (200-300 ml) and heated under reflux for 1-3 hours. The reaction mixture is evaporated in vacuo to remove benzene and ethyl-N- (difenoxig osp fo and ome.tyl) glycinate are obtained, yield 70%.
    0
    Calculated%: C 58.45; H 5.77, N 4.03 Haido%: G 58.47; H 5.80;
    N 4.01.
    Example 4: Di-4-chlorobenyl phosphite is reacted with
    5 N-methylethylglycinate trimer, using benzene as a solvent in accordance with the method described above, and ethyl-M- (di-4-chlorobenzyloxyphosphonomethyl) glycinate is obtained in
    0 as a yellow liquid.
    Calculated,%; C 51.14; H 4.97;
    N 3.14.
    C 50.99; H 4.80;
    Found%:
    N 3.19.
    5 Example
    5. Di-2-methylphenylphosphite is reacted with an N-methylethylglycinate trimer. using benzene as a solvent, M- (di-2-methyl-phenoxyphosphoiomethyl) is obtained. glycinate is obtained as yellow
    0 oil.
    C, 60.47; H 6.41;
    Calculated,%: N 3.71.
    C, 60.35; H 6.64; Found,% N, 3.51.
    five
    6.Di-4-tert-butyl. An example of phenyl phosphite is reacted with an N-methylethylglycinate trimer, using benzene as a solvent according to the method described above,
    0
    k receive ethyl N- (di-4-tert-butylphenoxyphosphonomethyl) glycinate as a clear viscous liquid.
    Calculated,%: C 65.60; H 7.86;
    N 3.03.
    five
    Found,%: C 65.28; H 8.24; N 3.02.
    Example 7  Di-2-methoxyphenylphosphite is reacted with M-methylene. using a benzene as solvent / according to the method described above, ethyl-N-DI-2-methoxyphenoxyphosphonomethyl) glycinate is obtained as a yellow oil.  C 55.75; H 5.91; Calculated,%: N 3.42.  C 55.60; H 5.99; Found,%: N, 3.54.  Example 8  Ethyl H- (di-4 nitrobenzyl-oxyphosphonomethyl glycyate, prepared according to Example 2, was kept at room temperature and exposed.  atmosphere around; a white, solid substance forms within 7 days at this time.  This white solid is ethyl-L-hydroxy (4-nitrobenzyloxy) phosphonomethyl glycetate with a melting point of 202-20b - C.  Calculated,%: C 43.48; H 5.16; N 8.43.  Found,%: C 43.58; N. 5.00; N8.30.  Example 9  Ethyl M- (difenoxypho. sphonomethyl-glycinate is dissolved in acetone and enough water is added to form a cloudy mixture.  The mixture is heated under reflux for 4 hours and then evaporated to dryness.  The residue is extracted with a mixture of chloroform water. The aqueous layer is evaporated in vacuum to dryness and then recrystallized from chloroform-acetone, and a white solid is obtained with m. square  in 187-199C with decomposition.  The white solid is e5: yl-H-hydroxy (phenoxy) phosphonomethyl glycinate.   X.  Calculated,%: C 48.36; H 5.90; N 5.13.  Found,%: C 47.93; H N 5.16.  Example 10  The ethyl (di-4-chlorobenzyloxy-phosphonomethyl) glycinate prepared in Example 4 was dissolved in acetone containing 1-3 vol. % water as a solvent, and stirred for 24 hours under the influence of the atmosphere.  The solvent was removed by evaporation in vacuo and the residue was dissolved in chloroform.  Isooctane is added and a fine precipitate is obtained, which is removed by filtration. The filter is evaporated and the oil is obtained, which after incubation for about 3 days, and stirring in toluene gives a white solid which is collected by filtration under vacuum. This white solid is ethyl H-goxy- (4-chlorobenzyloxy) phosphonomethyl glycinate c; X. square  185-190 With decomposition, i.  Calculated,%: C 44.80; H 5.33 N, 4.35.  C, 44.78; H 5 ;, Found,% N 4.19.  eleven.  A solution of Example 5.76 g (0.0167chmol) of N-methylethylglycine trimer and 14.50 g (0.05 mo of Di (4-methylbenzyl) phosphite in benzene. heated under reflux for 17 h, concentrated, isolated for 6 weeks as an oil.  A solid is obtained.  The mixture is stirred in acetone, then filtered and a white solid is collected. (1D g), which is ethyl-N-hydroxy (4-methylbenzyloxy) phosphonomethyl glycinate with m. square  157.5-159.50s.  Calculated,%: C, 51.83; H 6.69; N 4.65.  Found,%: C 52.00; H 6.66; N 4.70.  Example 12  A mixed solution of di- (3-nitrophenyl) phosphite and N-methylethylglycinate trimer in 30 ml of benzene is heated under reflux for 4 hours and cooled to room temperature with stirring.  A solid suspension is obtained.  The mixture is filtered to give 2.0 g of a tan solid, which is ETIH-M-EOXI- (3-nitrophenoxy) phosphonomethyl glycinate. with t. square  171-1720  C 41.52; H 4.75; Calculated,%: N 8.80.  C 41.54; AND. 4.57; Found,%: N 8.62.  Example 13  A suspension of 5.5 g of ethyl N-di- (4-methoxyphenoxyphosphonomethylglycinate in a mixture of water-acetone solvents (10 wt. h to 15 weight. h  acetone by volume) mix.  within 21 hours to obtain a clear, slightly yellow solution.  This solution is added to 30 ml of water and extracted with methylene chloride, m.  The aqueous solution is concentrated in vacuo and a solid is obtained which is an ethyl-M-hydroxy- (4-methoxy-phenoxy) hemihydrate.  phosphonomethyl glycinate.  The chloromethylene extract is evaporated to dryness and then dissolved in 5 m. n acetone and 30.  ml of water and heated under reflux (70-75-s) for approximately 17 hours.  The mixture is extracted with chlorine; methylene gas, and the aqueous solution is evaporated, to dryness, in vacuo, and 1.6 g of a white solid are obtained, which is a hemihydrate with m. square  1b2-164c.  C 46.16; H 6.13; Calculated,%; N 4.49.  C 46.11; H 5.83; Found,%; N 4.66.  Example 14  According to. to the above method (but using di- (4-chlorophenyl) phosphite, I get ethyl-N-Toxic (4-chlorophenoxy) phosphonomethyl glycinate as a white solid, t. square  205-207-C, yield 11%.  Calculated,%: C, 42.94; H 4.91; N 4.55.  Found,%: C 42.94; H 4.70; N 4.31.  Example 15  Di- (biphenyl) phosphate 6.73 g and N-methylene ethyl hydroxycinate trimer 2.3 g (0.00667 mol) are dissolved in 50 ml of benzene and heated under reflux for 2.5 hours.  Another 1 g of phosphite (total 0.02 mol) is added and heated under reflux for an additional 30 minutes.  The filter is filtered through diatomaceous earth and concentrated, whereby 3.2 g of oil are obtained.  Oil bath, add 25 ml of acetone, add 10 ml of water and heat with a reverse tank overnight.  Formed suspension.  The suspension is filtered, washed with acetone and dried to give a white solid, which is ethyl N-hydroxy (4-phenyl-phenoxy) phosphonomethyl glycyst with m. square  209-210С.  Calculated,%: C 58.45; H 5. , 77; N 4.01.  Found,%: C 58.78; H 5.70; N3.87. .  PRI and meper 16.  Di- (4-carbethoxyphenyl) phosphite (0 °, 02 mol) and N-methylene ethylglycinate trimer (0.00667 MO solution c. benzene is added and the hydrochloride salt is added to the mixture. under reflux for 2.5 hours, with the ethyl chlorine salt of ethyl-y-di- (4-carbethoxyphenoxy) phosphonomethyl being obtained.  glycinate.  The hydrochloride salt of glycinate is dissolved in 45 ml of thermally benzene, and 1 ml of ethyl ethyl amine is added.  The resulting suspension is filtered after keeping for 20 minutes at room temperature and the filtrate is concentrated in vacuo, and a yellow oil is obtained containing some amount of solid matter.  2 are added to the yellow oil. 5 ml of benzene and 3 drops and the mixture is kept at room temperature (approximately 25 seconds) for 6 days.  A white solid is formed.  Solid matter filtered off, washed with hot acetone and dried.  This white solid is ethyl M-hydroxy- (4 carbethoxy) phosphonomethyl glycinate and has m. square 1901920c  Calculated,%: C, 48.70; H 5.84; . N 4.06.  Found,%: C 48.35; H 5.59; N 3.98.  Example 17, Mixed. a solution of DI-C4-methylthiophenyl) 4 osphite (0.04 mol) and ethyl N-methylene glycinate trimer (0.0133 mol) in 100 ml of benzene is dissolved under reflux for 3 hours and then cooled to room temperature.  Hydrochloric times are passed in the form. bubbles through solution in the first 30 minutes.  A simple diethyl ether (400 ml) was added and a dark yellow oil precipitated.  Mai -JK) kg-PPP t. with benzene in the form of aseoTponEiofi smosp for 2 hours, add carotene ester to precipitate the oil, which can be recovered and concentrated to give a yellow glass.  Benzene (50 ml) and triethylamine (5 ml) are added to the glass and the solution is filtered for 15 minutes.  The filtrate is concentrated to an oil.  Acetone (37 ml) and water (3 ml) were added to the oil and the mixture was heated under reflux overnight with stirring.  A suspension is formed, which is cooled to room temperature and filtered, and is prepared. white solid.  The solid is washed with acetone and dried, yielding 1.8 g of a white crystalline solid with m. square  201-202-C, which is ethyl-L-hydroxy (4-methylthiophenoxy) phosphonomethyl glycinate hemihydrate.  Calculated,%: C 45.14; H 5.68; N 4.13.  Found,%: C 44.73; H 5.45; N 4.19.  Example 18  According to Example 16, using di- (3-methyl-4-chlorophenyl) phosphite, the hydrochloride salt of ethyl m-di- (3-methyl-4-chlorophenoxy) phosphonomethyl glycinate is obtained.  Triethylamine (1 ml) was added to a solution of 2.8 g of the hydrochloride salt in 40 ml of benzene and the mixture was kept for 15 minutes.  The mixture is filtered and the filtrate is concentrated to obtain a dark oil. - Acetone (40 ml) and water (2 ml) were added to the oil and the resulting solution was heated under reflux for 18 hours.  The solution is cooled to room temperature and a white solid is obtained.  The mixture is filtered and the white solid washed twice with acetone and dried.  The white solid is ethyl M-hydroxy (3-methyl-4-chlorophenoxy) phosphonomethyl glycinate hemihydrate with m. square  195-1960С.  Calculated,%: C 43.58; H 5.49; N 4.24 Found: C 43.46; H 5.54; ; N 4.05.  Example l9.  Di- (4-tert-butylphenyl phosphite (0.02 mol) and ethyl N-methylene glycinetrimer (0.0067 mol) dissolved in benzene, heated under reflux for 1.5 h and then concentrated to an oil.  Acetone (30 ml) and water (30 ml) are added to the oil and the resulting emulsion is heated under reflux for 116 hours), and a semi-double system is obtained.  The mixture was held for about 5.5 days and then filtered, and a white solid was obtained, which was washed with hot acetone and dried.  The solid is ethyl M-hydroxy (4-tert-butylphenoxy) phosphonomethyl glycinate with m. pl, 1781790c. Calculated: C 54.71 | H 7.35; N 4.25.  Found,%: C 54.96; H 7.07; N 4.35. Example 20.  The mixed solution of di- (3-trifluormet. ylphenyl) phosphite (0.02 mol) and ethyl M-; methylene glycine trimer (0.0067 mol) in 40 ml of benzo is heated under reflux for 2 h and concentrated in vacuo.  about getting butter.  The oil is dissolved in. acetone (50 ml) and water (3 ml is heated under reflux for 20 minutes and then cooled overnight.  The resulting mixture.  filter and obtain 3.2 g of a white solid, which is ethyl N-hydroxy (3-trifluoromethylphenoxy) phosphonomethyl 3 glycinate with m. square  181-182,5Зс.  Calculated,%: C 42.24; H 4.43; N 4,10.  .   Found,%: C 42.23; H 4.44; N 4.15.  P, R i MER 21.  To a stirred suspension of 0.02 mol of di- (4-nitrophenyl) phosphite in benzene (40 ml), 0-, 02 equivalents of ethyl N-Methylene glycinate trimer are added and the mixture is heated under reflux for 2 times. A solid is formed.  The benzene is decanted further in the hot state and the solid is washed 3 times with 50 ml portions of acetone, acetone (150 ml) is added to the remaining solid matter and the acetone mixture is heated under reflux in a hot state and 2 are obtained. 0 g of a white solid which is ethyl m-hydroxy. (4-nitrophenoxy) phosphonomethylTglycinate with t. square  1931950s.   Calculated,%: C 41.52; H 4.75; N, 8.80; Found: C, 41.44; H 4.76; N 8.80.  Example 22  A stirring solution of 0.02 mol di- (3,4-dichlorophenyl; phosphite and 0.00667 mol (0.02 eq equivalent) ethyl-N-methylene glycinate trimer in 50 ml of oenzol containing 3 drops of water is heated under reflux for 3.5 hours, cool, add 10 mp of acetone, and incubate overnight at ambient temperature.  The resulting suspension is filtered and a solid is obtained which is washed with acetone.  The solid is boiled in benzene (30 ml) for 45 minutes and 20 ml of acetone are added and the filter is added.  The white solid (1.2 g) pg4eddsdal is ethyl-H-okoi (3,4-dichlorophenoxy) phosphonomethyl glycinate with t. square  190-192S.  Calculated,%: C 38.62; H 4.12; N 4.09.  Found,% J C 38.73; H 4.15; N 4.12.  Example 23  A solution of about 0.008 mol of 1,2-phenylene phosphite and 0.00267 mol of ethyl M-methylene glycinate trimer in 40 ml of acetone containing 1 ml of water,. reflux overnight.  Several crystals are obtained.  The solution is cooled, closed with a stopper and kept at room temperature for 10 days.  The solution is filtered and receive 0.3, g of a white solid, which. is ethyl N-oxy (2-oxiphenoxy) phospho-methyl glycinate with t. square  193-194 ° C. Calculated,%: C 45.68; H 5.58; N 4.84.  C 45.63; H 5.58; Found, i n 4.85.  24 According to Example 12, but using di- (3-chlorophenyl) phosphite, ethyl H-hydroxy- (3-chlorophenoxy) phosphonomethyl 3 glycinate is obtained in 70% yield as a white solid, t. square  187.5-189 C.  C 42.94; H 4.91; , Calculated,%; N 4.55.  Found,%: C 42.94; H 4.94; N 4.53.  25 According to example Sample frames 3 and 9. , but using methylme | Thyleneglycinate trimer, methyl-hydroxy (phenoxy) phosphonomethyl glycinate, t. square 201-2030s with decomposition.  Calculated,%: With 46,34; H 5.44; R 11.95.  Found,%: C 46.23; H 5.41; . .  R 11.79.   Example 26  According to example 20, but.  using methyl N-Methyleneglycinate trimer, methyl-N-oxy (3-trifopromomethyl phenoxy) phosphonomethyl glycinate with m are obtained. square  188190С.  , Calculated. %: N 4.28; P 9.47; Found,%: N 4.36; R 9.63.  Example 27  DN- (4-bromobenzyl) phosphite 8.4 g (0.020 mol) and 2.30 g 1 equivalent (0.0067 mol) M of methylene ethyl glycinate trimer are suspended in benzene, heated with a refrigerator for 16 h, stirred in acetone under the influence of the atmosphere and a white verdoid substance is formed that is collected,. square   with decomposition.  This solid substance is, according to UGIDRT 9TIL-} 4- OXY (4-brOMbVNZS11 xi), phosphonomethyl 1 ml Calculated,%: C 38.42; H 4.84; N 3.73.  Found,%; C 38.92; H 4.66; .  N 3.68.  Example 28  To ethyl M-di (4-methylphenoxy) phosphonomethyl 3 glycinate, prepared according to examples 1-7 (P, 07 g), add 20 ml of acetone and 30 ml of water the resulting emulsion is heated under reflux for 20 hours and then cooled .  The mixture is extracted twice with 16 ml of chloroform each time.  Water the naked layer is concentrated and 1.1 g of a tan solid are obtained.  The chloroform extras are evaporated to dryness and then 130 ml of acetone is added with stirring over 10 minutes.  The resulting suspension is filtered and a white solid is obtained.  The tan solid is stirred in 30 ml of acetone for 10. min and fil to create a white solid.  The combined amount of white solids is 2.5 g and this substance is ethyl M-hydroxy (4-methylphenoxy) phosphonomethyl C glycinate. square  186-188 ° C.  C 50.18; H 6.32; Calculated,%; N 4.88.  C 50.39; H 6.40; Found,% N 4.79 29.  mixed solution 0.03 mol of di- (2-methylphenyl) phosphite and 0.1 mol of ethyl n-methylene glycinate trimer in 50 ml of benzene is heated under reflux for 3.5 hours and the benzene solution is concentrated to give an oil.  30 ml of acetone and 25 ml of water are added to the oil and the mixture is heated under reflux overnight.  Two layers are formed.  The upper layer is concentrated, 50 ml of acetone is added, maintained for 1,. 5 h and then filtered and receive 0.5 g of solid substance.  The aqueous layer is then concentrated to give 3.0 g of a white solid.  Both solids are combined, 150 ml of acetone is added, then heated to boiling for 5 minutes and filtered while still hot, and 1.9 g of white solid are obtained. substances.  The white solid is dissolved in. hot mixture of water (25 ml) and ethanol (50 ml) is concentrated and then 15 ml of ethanol and 15 ml of acetone are added.  The ethanol-acetone product mixture is filtered and 0.5 g of a white solid is obtained with m. square  187.5-189 C. It is ethyl N-oxy (2-methylphenoxy) phosphonomethyl glycinate. .  Calculated,%: C 50.18; H 6.32; N 4.88.  Found,%: C 50.35; H 6.38;   N 4.8-5.  Example 30  Pereg 4eshanny race mol di ((. 3,4-dimethylphenyl) phosphite and 2 ,, OU lO-mole N-methylene ethyl glycinate trimer in 40 ml of benzene (heated under reflux for 1 h and then concentrated to an oil.  The oil is dissolved in 40 ml of acetone and 1 ml of water is heated under reflux for 18 hours.  Then the solution is dispensed at ambient temperature  Wednesday for 3 days.  After this, the solution is concentrated to obtain asla and the oil is dissolved in 120 ml of boiling water.  The solution is washed twice, each time with 50 ml of chloroform.  one layer is then concentrated and 75 ml of acetone is added to the Oil. The suspension obtained is filtered and semi-dried. 0.8 g of white solid N-hydroxy (3,4-dimethylfe. noxy) phosphonomethyl glycine, t. square  199 ° C, Calculated,%: C 45.52; H 5.90; N 4.83.  Found,% 45.93; H 5.96; N 4.98.  Example 31  A stirred solution of 4.0 × 10 mol of di- (o-naphthyl) phosphite and 4, OX10 mol of N-methylene ethyl glycinate trimer in 70 ml of benzene is heated under reflux for 2 hours and then aged. After being kept at ambient temperature for 13 days, 20 ml of water are added and the solution is again maintained for 20 days.  3.8 g of methanesulfonic acid was added to the solution, and an oil was precipitated on addition of 350 ml of ethyl ether.  The oil is washed three times with 300 ml of ethyl ether and then kept in 300 ml of ethyl ether for 64 hours.  The resulting gray mass is stirred in 200 ml of acetone for 15 minutes and then filtered. .  0.7 g of a white solid is obtained, which is y- (oxC d-naphthoxy) phosphonomethyl3glycine with t. square  : 200-2020s ; Calculated. %: C52.89; H 4.78; N 4.74.  Found,%: C 52.68; H 4.88; N 4.68.  Example 32  A mixed solution of 1,2) 410 mol.  ethyl H-Cd- (2-methoxyphenoxy) phosphonomethyl glycinate and 1.210 mol of water are heated under reflux for 2 days, in 5 ml of acetone and then kept at ambient temperature for 8 days.  After that, concentrate the solution. and get butter.  The oil is stirred in 250 ml of acetone overnight and the resulting suspension is filtered and 0.3 g of white solid is obtained, which is L-oxy 12-methoxyphenoxy) phosphonomethyl glycine, t. pl.  183.5-185-s (with the formation of gas).  Example 33  The mixed solution 2,0i40 mol di- (2-chlorfeiil) f. osphite and 2 mol of N-methylene ethyl glycinate trimer in 50 ml of benzene-.  reflux for 2.5 hours and then concentrated to an oil.  The oil is heated under reflux in 35 ml of acetone and 10 ml of water for 18 hours.  To the solution were added 70 ml of water and 30 ml of chloroform, the resulting bilayer solution was added over 15 minutes.  The two-layer solution is incubated for 3; months and thereafter the layers are separated.  The aqueous layer is concentrated.  Get the oil and put it in 300 ml of acetone.  After incubation for 8 days, the acetone suspension is filtered and 0.8 g of a white solid is obtained, which is N (2-chlorophenoxy) phosphonomethyl glycine with m. square  173.5-180®С.  Example 34  The mixed solution of di-4-fluorophenylformate (0.03 mol and ethyl-N-methylethyleneglycinate tripe / 0.01 mol) is heated under reflux in benzene (40 ml) for 30 minutes, then it is kept at ambient temperature for 2.5 hours  The solution is then concentrated and acetone (45 ml) and water (1.5 ml) are added, then kept at ambient temperature overnight, and a suspension is formed.  The suspension is filtered and a white crystalline solid (3.7 g) is obtained, which is ethyl-M-1 | hydroxy (4-fluorophenoxy) phosphonomethylT glycinate with m. square  2012030С.  P r and m  e p 35.  A solution of di- (2,4dichlorophenyl) phosphite (O ,, 02 mol) and ethyl-m-methy lenglycinate trimer (0.0067 mol) ,. dissolved in benzene (40 ml) is heated under reflux for 20 minutes and a solid forms within 1 time.  The mixture is maintained at ambient temperature overnight, then it is filtered and 4.4 g of solid are obtained, which is ethyl m-hydroxy (2,4-dichlorophenoxy) phosphonomethyl glycinate with m. pl in 193.5-195 C.  Prim rzb.  The mixed solution of di- (4-biloxypropyl) phosphite (0.03 mol of ethyl-n-methyleneglycinate trimer (0.01 mol), dissolved in benzene (50 ml), is heated under reflux for 1 h, then concentrated and get butter.  The oil is dissolved in acetone (50 ml) containing approximately 0.1 ml of water, the solution is heated under reflux for 4 days and then cooled.  The resulting suspension is filtered and an off-white solid is obtained which is a crude ethyl M-L-hydroxy (4-benzyl-oxyphenoxy) phosphonomethyl) glycinate with m. square  192-195OS.  A solid substance is n t t d in each using acetone and a purified sample of the compound with t is obtained. square  197198 p.  Example 37  The ester of Example 5 is dissolved in a mixture of benzene and water (9-10 by volume) and heated under reflux for 90 days.  A white crystalline solid with m is isolated by filtration. square  214-21bs.  This material is (2-methylphenoxy) phosphonomethyl glycine.  Example 38  A mixed solution of 0.05 mol of dibenzylphosphite and 0.0167 mol of methyl-M-methylene glycinate trimer in 100 ml of benzene is heated under reflux for about 18. h and concentrated in vacuo.  Get it.  an oil which is dissolved in acetone and traces of WATER are added.  The mixture is held for about 60 days.  The acetone was concentrated in vacuo to give 72 g of oil, which was dissolved in 50 ml of chloroform and extracted 4 times with 30 ml of water.  The aqueous layer was extracted 4 times with ether, filtered through clay, concentrated in vacuo to give an oil, which was dissolved in ethanol, and acetone was added until the cloud point was reached.  The solid is precipitated overnight and collected by filtration.  The solid has t. square  186-189-C with decomposition, and it is a hemihydrate (. benzyloxy. a) phosphonomethyl} glycine.  Example 39  Di-4-methoxyphenylphosphite (0.05 mol) and ethyl-N-methylene glycinate trimer (0.0167 mol) are dissolved in dry benzene and heated under reflux for 1 hour.  An NMR analysis shows that ethyl M-di- (4-methoxyphenoxy) phosphonomethyl glycine is formed. Benzene removed in vacuo and the resulting oil was dissolved in diethyl ether.  Methanesulfonic acid (4.81 g) was dissolved in ether and added dropwise with stirring overnight.  Oil is formed, and the supernatant is decanted.  Diethyl ether is added at.  stirring and again decant from the oil.  The oil is dissolved in benzene and filtered, while keeping white solid crystallizes from solution.  It is a salt of methanesulfonic acid ethyl-H-di- (4-methoxyphenoxyphosphonomethylT-glycinate with m square 1091140s  Example 40  Ethyl M (diphenoxy) phosphonomatic glycinate (6.90 g). is dissolved in diethyl ether and anhydrous hydrogen chloride is bubbled through the solution for 5 minutes.  The solution becomes cloudy and the oil precipitates.  The supernatant is decanted, the oil is dissolved in methylene chloride and added
    isooctane to precipitate an oil. The supernatant is decanted and excess isooctane is removed in vacuo. The oil is dissolved in methylene chloride, filtered through clay and methylene chloride is distilled off from the filtrate on a rotary evaporator under vacuum. A yellow oil is obtained which is the hydrochloride salt of ethyl N- (difenoxy) phosphonomethylglycinate.
    Calculated,%: C 52.93; H 5.49; N 3.63.
    Found,%: C 52.76; H 5.44; N 3.82.
    Example 41. According to Example 39, but using the appropriate phosphite and then anhydrous hydrogen chloride, the hydrochloride salt of ethyl- (2-methyl-4-chlorophenoxy) phosphonomethyl glycinate is obtained. The material is washed with a mixture of chloroform and petroleum ether, decanted, and then washed with distil ether (200 ml). The washed substances are combined and incubated overnight. A tan solid is obtained. After boiling in diethyl ether, the tan solid becomes creamy in color and has so pl. 92-93 0. The solid is a hydrochloride salt.
    Example 42. According to Example 39, the methanesulfonic acid salt of ethyl M-di- (4-chlorobenzsux) phosphonomethylglycinate is obtained in the form of a solid with mp. 88-90SS.
    Example 43. Di- (4-fluorophenyl) phosphite 2.94 g (0.01 mol) and methyl-N-methylene glycinate trimer 1 .0 g (0.0033 mol) are dissolved in benzene; (100 ml) and heated under reflux for 1 hour. The reaction mixture is then concentrated by evaporation in vacuo to give methyl-N-DI- (4-fluorophenoxy) phosphonomethyl glycinate as a light yellow oil 1.5248.
    Example 44. Di- (4-methoxyphenyl) phosphite 3.0 g (0.01 mol) and methyl N-methylene glycinate trimer 1.0 g (0.0033 mol) is dissolved in benzene (50 ml) and heated with reflux for 1 h. The reaction mixture is then concentrated by evaporation in vacuo to obtain 3.2 g (81%) of methyl M- {di- (4-methoxyphenoxy) phosphonomethyl glycinate as a pale yellow oil, p 1.5489.
    Calculated,%: C 54.71; H 5.57; N-.
    Found,%: C 54, 86; M 5.55; N.3,54. . .
    Example: 45- Di (3-chlorophenyl) phosphite 4.43 g (0.013 mol) and methyl N-methylene glycinate trimer 1.3, g (0.0043 mol) dissolved in benzene (100 ml) and heated under reflux for hours. The reaction mixture is concentrated by evaporation in vacuo to obtain methyl-M - f DI - (3, - chl orff and oh c and u) phosphorus I t and l glycinate as a viscous light yellow oil , 1.5574.
    PRI me R 46, Mixed solution of DI- (2,4,6-trimethylphenyl) phosphite 17, 8 g I0j05 mol) and ethyl M-methylene glycinate trimer 5, 8 g (0.0167 mol) in benzene (75 ml ) heated under reflux for 2 hours. The yellow solution is then concentrated and a dark yellow oil is obtained, which is filtered through a zeolite and 15.6 g (70%) of ethyl-L-di- (2.4, b-tri5 methylphenoxy) phosphonomethyl glycinate.
    , H
    1.5359.
    Calculated,%: C 63.73; H 7.44; N 3.23.
    Found,%: C 63.49; H 7.53; N 3.15.
    0
    Example 47. A mixed solution of DI- (3-methyl-4-nitrophenyl) phosphite 12.6 g (0.03 mol) and methyl N-methylene glycinate trimer 3.0 g (0.01 mol) in benzene (50 ml) is heated It is heated under reflux for 1 h and then concentrated to an oil. Acetone (70 ml) was added to the oil and the resulting solution was heated under reflux.
    0 for 0.5 h. The solution is then maintained at ambient temperature for 2 days. The resulting suspension is filtered and the resulting white solid is washed with ace5 in a tone (50 ml) and 3.2 g (33%) of methyl-M-hydroxy (3-methyl-4-nitrophenoxy) phosphonomethyl glycinate are obtained, m.p. 1911930c.
    Calculated,%: C 41.52; And 4.75; N 8.80.
    0
    Found,%: C 41.37; H 4.73, N 8.72.
    Example 48. Benzene solution .DI- (4-methoxyphenyl phosphite 3, O g (O, 01 mol) and 1.0 g (O, 0033 mol)
    Methyl N-methyleneglycinate trimer is heated under reflux for 2 hours and then concentrated to an oil. The oil is dissolved in acetone, heated at reflux for 18 hours, cooled and incubated overnight. The white solids that form are collected by filtration and washed with acetone, and 1.2 g of methyl 5 (4-methoxyphenoxy) phosphono is obtained. Thyl Glycinate, m.p. 194-196 S.
    Calculated,%: C 45.68; H 5.58;
    N 4.84.
    Found,%: C 45.64; H 5.61; N 4.82.
    0
    Ex. 49. A solution of the product of example 45 (2.29 g, 0.005 mol) in wet acetone (50 ml) is maintained at ambient temperature for 4.5 days before filtration. The solid obtained is washed with acetone (30 ml) and g (54%) methyl-N-hydroxy (3-chlorophenoxy) phosphonomethyl glycinate is obtained in the form of a light-colored solid, mp 181-1820C. Included,%: C 40.9.2; H 4.43; N 4.77. Found,%: C 40.77; H 4.41; N 4.68. Example 50. The solution of the product of example 43 (2.4 g, 0.0061 mol) in wet acetone (50 ml) is maintained at ambient temperature for 5.5 days. The resulting suspension is filtered, the solid is washed with hot acetone, and 1.0 g (62%) of methyl M-hydroxy (3-fluorophenoxy) phosphonomethyl glycinate is obtained in the form of a white solid, mp 204205 ° С. . . Calculated,%: C 43.34; H 4.69; N 5.05. Found,%: C 43.32; H 4.72; N 5.05. Example 51. The suspension of the product of example 49 (4.5 g, 0.016 mol) in acetone (50 ml) and water (300 ml) is heated to an oil bath and held for 80 h. The resulting yellow solution was concentrated to about 40 ml and acetone (300 ml) was added. The reaction mixture is stirred and incubated for 1 hour. The mixture is then filtered and 2.5 g (59.5%) of (3-chlorophenoxy) phosphonomethylglycine are obtained in the form of a monohydrate in the form of a cream-colored solid, mp.178180 ° C. Calculated,%: C 36.32; H 4, 40; 4.71. C, 36.26; H 4.44; Found,%: N 4.72. Example 52. A mixture of diphenylphosphite, 2.9 g (0.01 mol) and methyl N-methylene glycinate trimer, 1.0 g (0.0033 mol) is heated for 10 minutes before and cooled to ambient temperature. The resulting oil was dissolved in chloroform (45 m) and p-nitrobenzenesulfonic acid (2.0 g ° C) 01 mol was added to form a suspension, which was heated under reflux for 25 minutes and then cooled. Ethyl ether (200 ml) is added and the mixture is kept overnight. It is then filtered and a cream-colored solid is obtained, which is dissolved in hot chloroform (115 ml) and concentrated into 50 ml. Ethyl ether was added (60 ml) and the solution was kept for 30 minutes. The resulting suspension was filtered and 3.3 g of methyl-di-p-nitrobenzenesulfonic acid methyl salt was obtained (phenoxy-phosphonomethyl glycinate as cream-colored krigates, mp 1371380c Calculated,%: C 49.07; H 4.27; N 5.20. C 48.40; H 4.23; Found,%: N 5.25. 53. Benzene Example of the product of Example 1 (3, 0 g, 0.0073 mol) is concentrated and dissolved in chloroform (50 ml). A 10% ethanol-chloroform solution (90 ml) of p-nitrobenzenesulfonic acid is added 1.5 g (0.0073 mol) and then added are simple to reach point of turbidity. The solids that are formed, collected, washed with ether and get 2.83 g of the salt of p-nitrobenzenesulfonic acid ethyl and-di- (4-methoxyphenoxy) phosphonomethyl glycinate in the form of a white solid, so pl. 11-75 C. Calculated, S: C 49.02; H 4.77; N 4.57; C 49.08; H 4.87; Found,% N 4.63. 54. Solution di- (o-ExampleLil) phosphite 24.8 g (0.075 mol) and methyl-m-methyl.englycinate trimer 8.63 g (0.025 mol) in dry benzene (300 ml under reflux for 2.5 h, cooled and filtered. A benzene (ethereal) solution of methanesulfonic acid, 7.2 g (0.075 mol) is added dropwise. The solids that are formed are collected by filtration in vacuo to give 28.7 g (81%) of methanesulfonic acid ethanethyl di-di ( o-tolyloxy) phosphonomethyl glycinate as a white solid, so pl. 138-14lc. Calculated,%; C, 50.73; H 5.96; N 2.96. C 50.95; H 5.99; Found,%: N 2.90. 55. Benzene solution Example 1 of the product of Example 1 (3.0 g, 0.0073 mol) was concentrated and an oil was obtained which was dissolved in chloroform (50 ml). Acetic acid solution (50 ml) of oxalic acid O, 95 g (O, 0073 mol) is added and the gelatinous precipitate that forms is dissolved in chloroform. Ether is added and a solid is formed upon evaporation under a stream of nitrogen. The solid is collected by filtration and washed with ether, and 2.6 g of the oxalic acid salt of ethyl M-di- (4-methoxyphenoxy) phosphonomethyl glycinate are obtained in the form of a white solid, mp. 13b, 5-138 C. Calculated,%: C 50.51; H 5.25; N 2.80. Found,%: C 50.49; H 5, .26; N 2.86. 56. Benzene solution Example 3 trichloroacetic acid, 2 g (0.0073 mol) was added to the benzene solution of the product of example 1
    权利要求:
    Claims (3)
    [1]
    Claim
    -1. The method of obtaining the esters of N-phosphonomethylglycine of the General formula (R0) P-CH, -N - CH, -C-ΌΒ ' 4 ' 2-11 g I 1 II
    О О О where R is phenyl, benzyl, naphthyl, benzyloxyphenyl, biphenyl, as well as their derivatives, containing from 1 to 3 substituents selected from the group: hydroxyl, lower alkyl, 15 lower alkoxyl, lower alkylthio, trifluoromethyl, carbo (lower alkoxyl ), nitroyl halogen, R - lower alkyl, 2Q consisting in the fact that the phosphite ester of the general formula (PO ^ -H, '
    About where R - as described above, is reacted with tris- (1,3,5-alkoxycarbonylmethylene) hexahydrotriazine of the general formula
    R'oOCH x cN Tti-CH 2 COOR 'n-r cN soov wherein R 1 - as stated above, in an aprotic organic solvent at a temperature adjusted to room kom40 from the reaction mixture boiling temperature.
    [2]
    2. The method according to claim 1, which consists in the fact that the ester
    45 phosphite and tris- (1,3,5-alkoxycarbonylmethylene) hexahydrotriazine are taken in a molar ratio of 3: 1.
    [3]
    3. The method of pop 1i2, which consists in the use of benzene as an aprotic organic solvent.
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    同族专利:
    公开号 | 公开日
    SE435386B|1984-09-24|
    FI63761B|1983-04-29|
    FI63761C|1983-08-10|
    IL51170A|1980-03-31|
    NL182881C|1988-06-01|
    FR2337142B1|1981-02-06|
    ATA971076A|1979-01-15|
    NO152874B|1985-08-26|
    GR62427B|1979-04-12|
    IL51170D0|1977-02-28|
    NZ183000A|1978-07-10|
    DE2659172A1|1977-07-07|
    ZA767654B|1977-11-30|
    PH16654A|1983-12-09|
    NL182881B|1988-01-04|
    SU639416A3|1978-12-25|
    IT1070047B|1985-03-25|
    PH14019A|1980-12-08|
    DD130857A5|1978-05-10|
    NO834498L|1977-06-30|
    SE7614619L|1977-06-30|
    CS196338B2|1980-03-31|
    YU318176A|1983-01-21|
    BR7608756A|1977-10-25|
    NO152861C|1985-12-04|
    US4120689A|1978-10-17|
    IE44325L|1977-06-29|
    NL7614431A|1977-07-01|
    PT66022B|1978-06-19|
    NO770935L|1977-06-30|
    HU185206B|1984-12-28|
    DE2659172C2|1986-01-09|
    IN145471B|1978-10-21|
    BE849907A|1977-06-28|
    JPS5726697A|1982-02-12|
    NO152861B|1985-08-26|
    NO764376L|1977-06-30|
    BG27533A3|1979-11-12|
    RO71484A|1982-12-06|
    FI763713A|1977-06-30|
    AT351858B|1979-08-27|
    TR19596A|1979-08-10|
    DK144215C|1982-07-12|
    MX3898E|1981-09-10|
    JPS5935919B2|1984-08-31|
    DK144215B|1982-01-18|
    PT66022A|1977-01-01|
    IE44325B1|1981-10-21|
    NO152874C|1985-12-04|
    JPS5654320B2|1981-12-24|
    DD136696A5|1979-07-25|
    FR2337142A1|1977-07-29|
    DK584476A|1977-06-30|
    OA05523A|1981-04-30|
    LU76475A1|1977-07-05|
    PL106856B1|1980-01-31|
    CH627922A5|1982-02-15|
    ES464928A1|1979-01-16|
    CA1070704A|1980-01-29|
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    JPS5297949A|1977-08-17|
    ES454604A1|1978-03-16|
    AU2089576A|1978-06-29|
    GB1538209A|1979-01-10|
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    AU507499B2|1980-02-14|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US64440675A| true| 1975-12-29|1975-12-29|
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