The method of obtaining methylenephosphonic acids or their salts

 

(57) Abstract:

The inventive products f-ly Q1Q2C[P(O)(OH)2]2where Q1and Q2-independently of one another, hydrogen or halogen, or their salts. Reagent 1: compound f-ly Q1Q2C[P(O)(OR)2]2where R is an unbranched or branched C1-C4-alkyl. Reagent 2: water. Reagent 3: HCl. Reaction conditions: aqueous hydrolysis is carried out at boiling in the presence of hydrochloric acid, taken in an amount of 1.0 to 5.0 by weight of the reaction mixture. 3 C.p. f-crystals. 1 Il.

The invention relates to a new method of obtaining methylenephosphonic acids of the formula I,

where Q1and Q2independently from each other are hydrogen or halogen, by hydrolysis of the corresponding complex tetraeder methylenephosphonic acid of the formula II

where R represents a branched or unbranched alkyl group containing 1-4 carbon atoms, and Q1and Q2have these values.

In previously known methods of obtaining bisphosphonic acids by hydrolysis of the corresponding complex tetrapyrrol used such strong acids as the acid halide. For example, complex tetrevi the UNT VE N 672205, example VI/B/). Also known hydrolysis of tetrapyrrol policecontributing hydrochloric acid at high pressure and temperature 130-145about(Houben-Weul, Methods der Orgnischen Chemie XII, I, 352-356). The disadvantages of this method include the lack of purity of the products and a large number of stages of purification is required to remove by-products and excess acid. Furthermore, the method causes corrosion. From EP patent application 0200980 known method, in accordance with which methylenephosphonate acid is produced by hydrolysis of tetrapyrrol plain water when boiling the reaction mixture under reflux. This substantially reduces the aforementioned problems associated with impurities and corrosion, significantly increases the processing time up to 16 h, which is economically disadvantageous.

A new method is proposed to obtain these methylenephosphonic acids and their salts corresponding to formula 1, with good yield and high purity in which it is possible to avoid corrosion problems associated with the use of strong acids. Additionally, according to the method of the invention, the process time is reduced to one quarter or less compared with the method known from EP-patent saferafrica and hydrochloric acid, moreover, this solution contains 1.0 to 5 wt. HCl in the calculation of the entire mixture. Below the specified limit of hydrolysis is very slow from a practical point of view, and above the specified limit is not noticeable speed increase relative to the number of chloride ions added to the mixture.

The hydrolysis is advantageously carried out at the boiling aqueous solution of terrafire and hydrochloric acid at the boiling temperature under reflux. So, the reaction mixture contains an excess of water compared with the stoichiometric amount of water required for complete hydrolysis of terrafire. This excess water is not critical, and can therefore be used multiple excess water compared to stekhiometricheskom number. Almost necessary volumetric quantity of an aqueous solution of hydrochloric acid from the point of view of carrying out hydrolysis is approximately 6 or 7 weights therefire, which, on the one hand, achieve sufficient dissolution of tetraeder in the aquatic environment, and on the other hand, it is possible to avoid the difficulties associated with the volume increase at later stages of hydrolysis.

The preferred amount of hydrochloric acid in a mixture of turmoil formation of by-products and reaction time.

Free tetracyclone obtained by hydrolysis, can be converted into its salt, partial salt, by methods known in the art, using a suitable organic or inorganic base, for example, hydroxides of alkaline or alkaline-earth metals, carbonates or bicarbonates. Salt is obtained after separation of the acid, or by adding the necessary basis directly in the reaction mixture after the hydrolysis step, without isolation of the free acid.

P R I m e R 1. Dynamiteraver dichlorodibenzofuran acid.

In triggerlevel flask equipped with thermometer, stirrer and condenser, load 420 ml of 3% hydrochloric acid and 65 g tetraisopropylphosphorodiamidite. The concentration of Hcl, the reaction mixture is about 2.6 wt. HCl. This mixture is refluxed, and over the course of the hydrolysis is monitored, determining the concentration of the resulting acid according to the31P-NMR. The solution is cooled to 20-25aboutWith, and treated with activated carbon. To this solution add the calculated amount of sodium hydroxide solution to a pH of 3.2. This solution is concentrated and cooled, resulting crystallized Dina is I approximately 50 g of the product, the degree of purity of more than 99%

Conducting the hydrolysis described above, but using instead of 3% hydrochloric acid aqueous solution of hydrochloric acid of various forces, receive the results of hydrolysis is shown in the drawing. Next to each curve on the one hand indicated the strength of the acid hydrolysis mixture, and on the other side, in parentheses, the strength of the acid used is an aqueous solution of hydrochloric acid. In the drawing, the output of hydrolysis (mol. free acid) is represented as function of the reaction time, and for comparison, hydrolysis with plain water according to the method of EP-patent application 0200980. As can be seen from the drawing the full outputs of the gain, using the method of the invention, using catalytic amounts of hydrochloric acid, in a significantly shorter period of reaction time compared with the method specified EP-patent application.

1. The method of obtaining methylenephosphonic acids of General formula

< / BR>
where Q1and Q2independently from each other, hydrogen or halogen,

or their salts, water hydrolysis of the corresponding tetraeder methylenephosphonic acid of General formula

< / BR>
where R is an unbranched or branched C1C4-alkyl;

Q1and Q2are these C the lot take in the amount of 1.0 to 5.0% by weight of the reaction mixture, followed by separation of the target product in the form of the acid or its salt by the action of the base.

2. The method according to p. 1, characterized in that use 6 7-fold excess of an aqueous solution of hydrochloric acid relative to the weight of terrafire methylenephosphonic acid.

3. The method according to PP.1 and 2, characterized in that use hydrochloric acid in a quantity of 2.5 to 5.0% by weight of the reaction mixture.

4. The method according to p. 1, characterized in that as tetraeder methylenephosphonic acid is used tetraisopropyl ether dichlorodibenzofuran acid.

 

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