CS239903B2 - Processing of aminomethyl phosphoric acid derivatives - Google Patents

Abstract

The invention relates to compounds containing phosphorus- carbon-nitrogen bond of the general formula I <IMAGE> wherein R1 and R2 are the same or different and stand for hydrogen or an organic radical, R3 and R4 are the same or different and stand for hydrogen, hydroxy or an organic radical. The compounds are prepared by reacting a phosphorus halide with ammonia, water soluble ammonium salts, primary or secondary amine in the presence of water and further with aldehyde or ketone. The product is recovered by reducing the reaction volume or by adding a water miscible organic solvent to the reaction mixture. The process is preferably suitable for the preparation of N-phosphono- methylglycine and derivatives thereof, which are significant in plant protection as herbicidally active compounds.

Description

The present invention relates to a process for the preparation of compounds having a P-C-N bond (i.e. phosphorus-carbon-nitrogen), in particular N-phosphono-methyl-glycine and derivatives thereof. The latter compounds are known as herbicidal active compounds in plant protection.

PCN-binding compounds are widely used in plant protection due to the wide spectrum of their herbicidal activity · Herbicidal activity is accompanied by low residual activity, ie the active ingredient decomposes relatively rapidly in the soil · 7 literature describes some methods for producing PCN-bound compounds, in particular N-phosphono-methyl-glycine and its derivatives.

According to U.S. Pat. No. 2,635,222, compounds having a P-C-N bond are produced by treating a primary or secondary amine with an aldehyde or ketone and dialkylester phosphoric acid. When the phosphotyric acid dialkyl ester, ester production, isolation and subsequent hydrolysis are used, long processes are involved · The active ingredient produced is acid and base resistant, thus product isolation is complicated · Another disadvantage of using phosphoric acid dialkyl ester is that that its processing requires special supervision due to its toxicity ·

In Belgian Patent No. 774,349, compounds having a P-C-N bond, i.e., N-phosphonomethylglycine, are produced by treating chloromethylphosphonic acid with an amine, i.e., glycine. However, the reactivity of chloromethylphosphonic acid is rather low. The processing is therefore carried out under more drastic conditions, thus avoiding the formation of by-products ·

According to DE 2 355 351, a cyclic amine such as tricyanomethyl-hexahydro-triazine is treated with phosphorous diester in the presence of a catalyst. The ester of N-phosphono-methyl-glycine-nitrile is obtained, which is hydrolyzed to N-phosphono-methyl-glycine in the second step. However, this process is again disadvantageous due to the complicated production of phosphoric acid diester and the processing of the starting material, i.e. tricyanetriazine derivatives.

According to U.S. Pat. No. 3,567,768, P-C-N bonded compounds which additionally contain a C-PO 4 group are produced by treating a reactive nitrogen compound, an aldehyde, and an orthophosphoric acid in the presence of concentrated hydrochloric acid. The addition of acid is necessary to keep the pH of the reaction mixture below 2. Above this pH, orthophosphoric acid oxidizes to orthophosphoric acid, which is to the detriment of the reaction of the orthophosphoric acid with the aldehyde and the nitrogen compound. Oxidation can cause significant losses in yield as by-products are formed. The addition of concentrated hydrochloric acid to the reaction mixture to ensure a suitable pH value increases the risk of corrosion.

All of the above methods and other known methods use phosphoric acid or a reactive derivative thereof as the reactant. Due to the hydrolysis of orthophosphoric acid, there is a possibility of by-products formation in all processes. This reduces the quality of the desired end product and reduces the yield.

Compounds with a P-C-N bond are usually produced in a concentrated mineral acid environment. This increases the risk of corrosion. The reaction conditions must be strictly maintained in order to obtain reproducible end products. The processing is very slow.

The disadvantages of all known processes are thus: high risk of orthophosphoric acid hydrolysis, by-product formation, low quality end product desired, low yield, possibility of increased corrosion and low reaction rate.

The above disadvantages are overcome in the method of the invention, where the oxidation of orthophosphoric acid is prevented using phosphorus trichloride and water. Thus, orthophosphoric acid formed in a non-state state can be reacted immediately with suitable reactants and oxidation potential is practically eliminated. PCN-binding compounds, preferably N-phosphono-ethyl-glycine and its derivatives, optionally directly in pure form, are produced. by synthesis ·

A process for the preparation of aminomethylphosphonic acid derivatives of the general formula I

HIM

OH and ₂

EID in which

R ₂ and R ₂ are hydrogen or phenyl;

R _@ 1 and R _{@ 4} which may be the same or different, which may be one of the following, by reacting an amine with a phosphorous compound, are according to the invention in that the radical X, cyclohexyl, phosphonoyl at am.n of the general formula

HMR3R4, where

R is as defined above, treated with phosphorus pentachloride and simultaneously reacting the mixture with a compound of the formula with water, whereupon

R ₁ R ₂ CO where ^{R 1 R} 2 is as defined above, 8 the product is isolated by reducing the mixture or addition of a water-miscible solvent · reaction volume. The system is saturated with hydrogen chloride under given reaction conditions. If R @ 1 or R @ 2 is hydrogen, a suitable reactant is an aldehyde such as formaldehyde, acetaldehyde, capronaldehyde, benzaldehyde, 2-bromoacetaldehyde, and the like. Ri and R ₂ is an organic group, then the reactant ketone ·

Ketones include acetone, ethoxybutyl acetophenone, butyron, 2-pentanone,

3-Pentanone and 1-chloro-S-propane · Aldehyde not containing more than 30 carbon atoms and ketone not containing more than 20 carbon atoms are usually used as the reactant ·

If a primary or secondary amine is replaced by an ammonium reactant, the component may be an aqueous amoid or a well-soluble ammonium salt such as ammonium chloride, ammonium acetate, ammonium bromide, ammonium carbonate, ammonium phosphate or other ammonium salts,

The product produced according to the invention is easy to crystallize, is chemically homogeneous and neither the NMR nor the spectra show any contamination. The yield is higher than 90 t. The content of compounds with P-C-N bond in the product is higher than 98%.

239903 4

Way can? The latter can be used advantageously for the production of the P-C-N bond of known compounds.

The ryooxec method has the following advantages:

1. L ™ removes: unwanted by-products which are formed by the support of orthophosphoric acid- ¹ '.

2. During processing, it is not possible to add acids, since the acid concentration can be controlled

3. Processing can be influenced by processing temperature. Optimal processing conditions can be used. Thus, the yield and the flow of the product can be improved.

4. Chemically homogermous, pure product can be obtained. Thus, compounds with a P-C-N bond are not contaminated with the by-products formed which are chemically similar to no products. This is of great importance because the physiological activity of homo-organic compounds not of the plant is substantially different. By producing numerous products, selective activity can be achieved in place of a wide spectrum of total herbicidal activity.

Other details of the invention are illustrated in the following examples.

Example 1

Place 300 ml of water in a flask with stirrer. For stirring! 137 g of phosphorus trichloride is added. To the elevated temperature solution is added 75 g of a 50% aqueous glycine solution. The reaction mixture is heated to the boiling point from constant temperature. After 30 minutes, 200 g of a 37% aqueous solution of phthalmaldehyde was added slowly. After the reaction, the water is separated off. The obtained syrup is dissolved in hot ethanol. The ethanolic solution is cooled to give a crystalline product containing N-diphenoxymethyl-glycine in a purity of 97% · Decomposition temperature: 210 ° C. Yield: 93%.

Example 2 ‘

Place 125 ml of water in a flask with a thermometer, stirrer and reflux condenser. While stirring and cooling, 51.7 g of phosphorus trichloride are added. The temperature is kept below 40 ° C. When all the phosphorous trichloride is added, 50 g of diamine diacetic acid are added to the sine, and the mixture is heated to the boiling point. To the brine which was refluxed, 119 g of 38% aqueous methyldehyde was added over 45 °. After the addition of all formidehyde, the mixture is believed for 3 hours. Two thirds of water are separated, the solution is diluted with ethanol and the mixture is allowed to stand with cooling. The precipitated crystals are filtered off, triturated with ethanedeo and water and dried. Very pure N-phosphonone-polyethylene glycine is obtained, which decomposes at 208 ° C. Yield: 95%.

114 g of N-phosphone-O-1-glycine, prepared as described above, are placed in a flask and 150 ml of water are added. 50 g of concentrated sulfuric acid are added to the mixture. The mixture is heated to 90 ° C with stirring. 260 g of a 30% aqueous hydrogen peroxide solution are added at the same temperature. After the addition of hydrogen peroxide, the temperature was maintained at 90 ° C for an additional 3 hours.

After completion of the reaction, some of the water was removed by filtration. The calves are diluted with ethanes and cooled. By cooling, N-phosphonomethylglycine is precipitated in the form of crystals. Kutaly be sorry and vyuuuí. The purity of the product is 98%. The product decomposes at 230 ° C, yield: 9 ^ς % ·

Example 3

175 ml of water are placed in a flask with stirrer and reflux condenser. 69 g of phosphorus trichloride are added with stirring.

Next, 44.5 g of N-methyl-glycine is added. While stirring, 188.4 g of a 38% aqueous formaldehyde solution are added, maintaining the reaction temperature at the boiling point. When the addition is complete, the mixture is boiled for two hours, then not half the volume is evaporated. After addition of ethanol and cooling, the precipitated crystalline product is washed with water and dried. The obtained N-phosphono-methyl-N-methyl-glycine has a purity of 97% · Yield: 90%.

Example 4

Into a flask with stirrer and reflux condenser. While stirring and maintaining the temperature so as not to exceed 40 ° C, add 206 g of phosphorus trichloride. This is followed by the addition of 27 g of ammonium chloride, boiling, 565 g of a 38% aqueous solution of foaldehyde and boiling for 1 hour. After completion of the reaction, the mixture was cooled to room temperature. The precipitated crystalline material is filtered off the solution. The produced N-trimethylphosphonic acid has a purity of 97%.

Example 5

In a flask equipped with a stirrer and a reflux condenser was added 350 ml of water. While stirring, 138 g of phosphorus trichloride are added while maintaining the temperature at about 40 ° C. 62 g of cyclohexylamine hydrochloride are then added. The mixture is heated to boiling and, after boiling for 30 minutes, 108 g of benzaldehyde are added. The mixture was boiled for 2 hours and then finally cooled to room temperature. Cyclohexyl-amino-di- (benzylidene) phosphonic acid of 97% purity was prepared. Yield: 92%.

Example 6

To 350 ml of water in a flask with stirrer and reflux condenser was added 138 g of phosphorus trichloride such that the temperature did not exceed 40 ° C. 15 g of diethylenediemine are then added and the reaction mixture is heated to boiling. After three minutes of boiling, 170 g of a 38% aqueous solution of formaldehyde are added and the reaction mixture is cooled to room temperature. The white crystalline product produced is ttylenediamine-tetramethylene-phosphonic acid. Yield: 93%. Purity: 98%. Decomposes at 214 ° C.

Claims (1)

Р К В D M T T IS I 1 POINT A process for the preparation of aminoinoethylphosphonic acid derivatives of the general formula I (I) in which: R | and 2 2 represents hydrogen or phenfl, and R 3 and which may be the same or different, are methyl, cyclohexyl, phosphonoethyl, or N, N- (diphosphonoethyl-D-Biinoethyl group), by reaction of an amino with a phosphorous compound, characterized in that the amine of the formula HNR3R4, where R @ 4 to R @ 4 are as defined above, with phosphorus pentachloride present in water, and the resulting mixture is reacted with a compound of formula R.R3CO, | ! r where ’ R1 and Rg are as defined above, and the product is isolated by reducing the volume of the reaction mixture or adding a water-miscible solvent.