Process for preparing aminomethylphosphonic acid

[Detailed Description of the Invention]

The present invention is a following formula:<img file="JPH03397B2_D0001.tif" />It comes out and is related with the manufacturing method of aminomethylphosphonic acid with which it is expressed. Aminomethylphosphonic acid is indicated as an active substance which has on vegetable growth until now as producing intermediate of a (refer to German patent public presentation No. 2315886 specification) and weeding-out active substance (refer to the German patent public presentation No. 2555573 specification). Aminomethylphosphonic acid makes 3 phosphorus chlorides or trialkyl phosphite react to carboxylic acid-N-hydroxy methylamide. Then, it is already proposed that it can manufacture by hydrolyzing the acquired reaction product [in U.S. Pat. No. 2304156 and the No. 2328358 specification, Bull, Akad.Sci., and 1968 (USSR), refer to the 585th page]. A publicly known process makes N-bromomethyl Phthal imide react to sodium diethyl phosphite or phosphorous acid triethyl. then, the thing for which phthalimidomethyl sulfonic acid diethyl ester is hydrolyzed -- a basis -- [Bull.Soc.Chim. (France) which is a Sly thing, the 778page(1948): -- Ann.Chim (Paris) [12] -- 4th volume and the 372page(1954):J.Am.Chem.Soc. -- the 75th volume, 5278th page (1953);J.Chem.Soc (c), and refer to the 1349th page (1966) ]. O and O-Diet roux halomethyl phosphonate is made to react to ammonia. then, hydrolyzing-acquired reaction product [Chem.Abat. -- the 45th volume, the 8444page(1951): -- said -- the 46th volume and the 421page(1952); -- said -- the 48th volume, The manufacturing method of the aminomethylphosphonic acid by making it react to refer to the 564th page (1954)] or Krol methylphosphonic acid, and ammonia (refer to the German patent public presentation No. 2315886 specification) is also publicly known. The process of the aminomethylphosphonic acid by the Curtius (Curtius) decomposition of O and O-Diethylphosphonic acetyl hydrazine is also proposed [refer to J.Org.Chem., the 29th volume, and the 832nd page (1964)]. It is made to react to the 3rd butylamine and formaldehyde first, and the 3rd corresponding butylamine of base [ of Sif ]:, i.e., N,-methylene is obtained, This is transformed to N-tertiary butyl aminomethyl phosphonate by an addition reaction with phosphorous acid diester, and [Synth.Inorg.MetalOrg.Chem. also with a publicly known manufacturing method of the aminomethylphosphonic acid by making hydrolysis of an ester group, simultaneously a reaction with hydrobromic acid separate a tertiary butyl machine from this compound under active conditions, and the 2nd volume, Refer to the 317th page (1972).] Other publicly known methods of obtaining aminomethylphosphonic acid, Dibenzylamine is made to react to formaldehyde and phosphorous acid ester, N and N-dibenzylamino methyl phosphonate is obtained, this is hydrolyzed, and it is a method according to desorbing N-benzyl group in hydrogenation decomposition continuously. After making Krol acetic acid react to dibenzylamine and considering it as N and N-Dibenzyl Grishin instead of this, This is made to react with 3 phosphorus chlorides and phosphorous acid, and N and N-dibenzylamino methylphosphonic acid is obtained as an intermediate in the inside of this process, Subsequently, the 7th volume of [Phos phorus and Sulfar, the 333rd page which is the method of desorbing N-benzyl group in hydrogenation decomposition more nearly similarly than the obtained intermediate (refer to it 1979.]) If a publicly known method is followed, acetonitrile and formaldehyde (paraformaldehyde) will be made to react with phosphorous acid and 3 phosphorus chlorides. Make the acquired reaction product react to water further, and it is made to change into N-acetylamino methylphosphonic acid, and aminomethylphosphonic acid is continuously obtained by desorption by hydrolysis of an acetyl group (refer to the German patent public presentation No. 2829046 specification). Ben Jill Ule Tan is heated with the acetic anhydride in acetic acid, and paraformaldehyde, and it is made to change into N-acetoxy methyl Benzyl urethane as a manufacturing method of aminomethylphosphonic acid. The method which makes this react to phosphorous acid truffe enyl, and obtains N-(O and O-diphenyl phosphono methyl) Ben Jill Ule Tan and into which it makes a benzyloxycarbonyl group separate from this by hydrolysis is also publicly known [refer to the 906th page (1980) of Synthesis]. It is impossible to manufacture in a commercial scale by yield which can be satisfied with the above-mentioned method of aminomethylphosphonic acid. As for no these methods, an overall yield attains 70% or more of theoretical values. The overall yields of most are 20~50% of theoretical values. There is a fault that it is expensive again that the starting material to be used cannot obtain easily some of processes mentioned above again. In a certain case, adaptation of severe reaction conditions is needed, and expensive equipment is needed. Therefore, it leaves from the starting material which is easy to come to hand easily, and the object of the present invention is to provide the manufacturing method obtained by yield which may satisfy aminomethylphosphonic acid simply. For this artificer, aminomethylphosphonic acid is a following formula:<img file="JPH03397B2_D0002.tif" />(R expresses a Alkyl machine or a phenyl group with 1 thru/or 4 carbon atom among a formula.) -- hexahydro 1,3,5-triazine N and N' which are expressed, and N''-tris carboxylate ester -- the bottom of existence of the Lewis acid as a catalyst, and the temperature of 90 thru/or 150 degreeC -- following formula:<img file="JPH03397B2_D0003.tif" />(Inside of a formula, R)₁A Alkyl machine with 1 thru/or 5 Is a carbon atom, a phenyl group, a benzyl group, 2-cyanoethyl group or 2 and 2, and 2-Tori Krol ethyl group are expressed. It is made to react to the ester of phosphorous acid expressed, and is a following formula:<img file="JPH03397B2_D0004.tif" />(Inside of a formula, R and R)₁The same meaning as Is is expressed. It found out that it could obtain with simply and sufficient yield (aminomethylphosphonic acid) by coming out, obtaining N-Calvo Ix- aminomethylphosphonic acid derivative expressed, and hydrolyzing this derivative under existence of strong acid in a water medium continuously. Hexahydro 1,3,5-triazine N and N' which are denoted by the formula demanded as a starting material by the present invention method, and N''-tris carboxylate ester, It is [ whether formaldehyde is made to react to corresponding urea in a water chloride medium, and ] [journal. of American The 68th volume of chemical society (J. Am.Chem.Soc.), To refer to the 1681st page (1946)] or urea, and paraformaldehyde are made into a catalyst, and it is under existence of p-toluenesulfonic acid, [the 1st volume of journal of heterocyclic chemistry (J. Heterocyc.chem.) and refer to the 937th page (1974)] -- it can obtain with sufficient yield by the easy method according to things. [ which it makes it react in toluene as a solvent ] Thus, R of especially a suitable compound is a compound of methyl or ethyl as a starting material for the method of the present invention among hexahydro 1,3,5-triazine N and N' which are denoted by the obtained formula, and N''-tris carboxylate ester. Suitable Lewis acid which catalyst-izes a reaction with the ester of phosphorous acid denoted by hexahydro 1,3,5-triazine N and N' which are denoted by the formula by the present invention, N''-tris carboxylate ester, and a formula, They are 3 fluoridation boron ether complex salt, titanium tetrachloride, tin tetrachloride, and ferric chloride () and an aluminium chloride especially. It became clear that 3 fluoridation boron ether complex salt was an especially suitable catalyst. Lewis acid is generally used in the amount of 1~10 mol % to hexahydro 1,3,5-triazine N and N' which are denoted by a formula, and N''-tris carboxylate ester, and preferably% of the amount of 4~6 mol is used. The reaction with the ester of phosphorous acid denoted by hexahydro 1,3,5-triazine N and N' which are denoted by a formula, N''-tris carboxylate ester, and a formula can be performed under existence of an inactive solvent or absence. It is like [ a suitable solvent is hydrocarbon and halogenated hydrocarbon which have the boiling point of 110 degreeC, for example even if not small, and ] toluene, xylene, chlorobenzene, and o-dichlorobenzene. The reaction of the ester of phosphorous acid denoted by hexahydro 1,3,5-triazine N and N' which are denoted by the formula by the present invention, N''-tris carboxylate ester, and a formula is performed in 90 thru/or 150 degrees of the temperature ranges C, and 120~150 degreeC is preferred. The desirable ester of phosphorous acid denoted by a formula is R.₁It is a Alkyl machine with 1 thru/or 3 Is a carbon atom. A very suitable thing is the Screw- (2-cyano ethyl) ester and Screw- (2, 2, and 2-Trichlor ethyl) ester of phosphorous acid similarly. It is because it can be especially desorbed from 2-cyanoethyl group, 2 and 2, and 2-Tori Krol ethyl group easily by hydrolysis. The ester of phosphorous acid denoted by hexahydro 1,3,5-triazine N and N' which are denoted by a formula, N''-tris carboxylate ester, and a formula reacts in the amount of theories generally. Slightly superfluous use to 10-mol% of the ester of phosphorous acid denoted by a formula is performed especially advantageously. For the hydrolysis of N-Calvo Ix- aminomethylphosphonic acid derivative denoted by the formula obtained at a reaction with the ester of phosphorous acid denoted by hexahydro 1,3,5-triazine N and N' which are denoted by a formula, N''-tris carboxylate ester, and a formula, A water reaction medium like the mixture of water or water, and an organic solvent, for example, water, acetonitrile and methanol, or ethanol can be used. As strong acid which can be used, they are chloride, hydrobromic acid, hydriodic acid, sulfuric acid, phosphoric acid, and p-toluenesulfonic acid, for example. especially hydrogen halide acid is preferred -- especially -- chloride and bromination -- it is water hydrogen acid. It is preferred for hydrolysis of N-Calvo Ix- aminomethylphosphonic acid derivative denoted by a formula to be performed at high temperature, and to be carried out under the flowing-back temperature of a reaction solvent. R and R as a Alkyl machine₁Then of a basis is good in a straight chain or a branch chain. R and R₁Un-active substitution machine, for example, halogen atom, low-grade Alkyl, and alkoxy , cyano and nitroglycerine can also replace a of phenyl group with un-replacing or a reaction. The same thing is R.₁It is applicable also to a of benzyl group. It will be aminomethylphosphonic acid if a desirable example is followed by the present invention According to method, The compound in which R expresses methyl or an ethyl group in hexahydro 1,3,5-triazine N and N' which are denoted by a formula, and N''-tris carboxylate ester, In the ester of phosphorous acid denoted by temperature of 120 thru/or 150 degreeC by a formula to hexahydro 1,3,5-triazine [ of the formula to be used ] N, N', and N''-tris carboxylate ester under existence of 4 thru/or 6-mol% of a 3 fluoridation boron ether complex, it is R.₁The inside of N-Calvo Ix- aminomethylphosphonic acid derivative which makes react to the compound showing a Alkyl machine with 1 thru/or 3 Is a carbon atom, 2-cyanoethyl group or 2 and 2, and 2-Tori Krol ethyl group, and is denoted by a formula, and R are methyl or an ethyl group, and it is R.₁; Obtain the compound showing a Alkyl machine with 1 thru/or 3 Is a carbon atom, 2-cyanoethyl group or 2 and 2, and 2-Tori Krol ethyl group, and it is the method of hydrolyzing this derivative continuously under the flowing-back temperature of the bottom of existence of water medium Nakashio acid or hydrobromic acid, and reaction solution, and obtaining aminomethylphosphonic acid. The present invention method for manufacture of aminomethylphosphonic acid, A reaction with ester of phosphorous acid denoted by hexahydro 1,3,5-triazine N and N' which are denoted by both reaction stages, i.e., a formula, until now unlike a publicly known process, N''-tris carboxylate ester, and a formula, Then, in both reactions of N-Calvo Ix- aminomethylphosphonic acid derivative of hydrolysis denoted by a formula, it is an advantageous method. It is giving quantitive yield especially under reaction conditions which can be held easily. Hexahydro 1,3,5-triazine N and N' which are denoted by the formula as a starting material, and N''-tris carboxylate ester are simply by the reaction of corresponding urea and formaldehyde, Being able to obtain especially by quantitive yield, especially the present invention method is preferred at the point expanded as an economical manufacturing method of the aminomethylphosphonic acid in a commercial scale. Hereinafter, an example explains the manufacturing method of the present invention in detail. Example 1 20.22g (0.066 mol) of process hexahydro 1,3,5-triazine [ of O and O-Diethyl- N-ethoxycarbonyl aminomethyl phosphonate ] N, N', and N''-tris carboxylate ester, and 28.4 ml of diethyl phosphite Into the mixture of (0.22 mol), 2 ml of boron trifluoride ether complexes are added with internal temperature C of 125 degrees under churning. Subsequently, the temperature of a reaction mixture is raised to 150degreeC. 2 ml of boron trifluoride ether complexes are added after 1-hour churning in 150 degreeC. Although the temperature in a reaction mixture falls to 105degreeC temporarily in this stage, it is made to go up again to 150degreeC slowly succeedingly. A reaction mixture is again agitated in 150 degreeC after that for 1 hour. Subsequently, the ingredient which volatilizes easily is distilled off by advanced vacuum distillation, and 48.0 g (the amount of 100% theories) of O and O-Diethyl- N-ethoxycarbonyl aminomethyl phosphonate is obtained as a residual substance. A product can be directly used to the next hydrolysis, without further refining. The boiling points of this thing are 130degreeC/0.15Torr. Example 2 A process of aminomethylphosphonic acid 100 ml of chloride is added 20% into O and O-Diethyl- N-ethoxycarbonyl aminomethyl phosphonate (rough product from Example 1) 23.9g (0.1 mol), and channeling-back heating of the mixture is carried out for 20 hours. Decompression distilling off of the chloride is carried out after that, and 12.6 g of substantially pure aminomethylphosphonic acid is obtained as a residue. A residue is re-crystallized from water/Acenan, and 9.4 g (84.7% of the amount of theories) of pure aminomethylphosphonic acid is obtained as melting point 277-281"C. Example 3 In accordance with the method of a statement, the following output was obtained as a catalyst using the boron trifluoride ether complex in the Example 1. -Obtain from the reaction of O and O-Diethyl- N-methoxy carbonyl aminomethyl phosphonate and boiling point 130degreeC/0.08Torr., hexahydro 1,3,5-triazine N, N', and N''-tris carboxylic acid methyl ester and diethyl phosphite. -O and O-Dimethyl- N-methoxy carbonyl aminomethyl phosphonate and boiling point 125degreeC/0.08Torr.; obtain from the reaction of hexahydro 1,3,5-triazine N, N', and N''-tris carboxylic acid methyl ester and dimethyl phosphite. And -O and O-Dimethyl- N-ethoxycarbonyl aminomethyl phosphonate and boiling point 130degreeC/0.1Torr.; it obtains from the reaction of hexahydro 1,3,5-triazine N, N', and N''-tris carboxylic acid ethyl ester and diethyl phosphite. Hydrolysis by aqueous hydrochloric acid or hydrobromic acid solution of such output obtains aminomethylphosphonic acid by yield of 85~95% of the amount of theories.