The way to obtain the complete esters of acids alkylphosphonic

 

(57) Abstract:

The inventive products - full esters alkylphosphonic acids of the formula RP(O) (OR') (OR"), where R is alkyl (C1- C2or haloalkyl: R' and R"are alkyl (C4- C8. Reagent 1: RP(O)Cl2. Reagent 2: alcohol. Reaction conditions: in the midst of solvent - ultimate hydrocarbon normal structure, such as petroleum ether, hexane at 0 - 30oC.

The invention relates to organic chemistry, particularly to a technology for higher esters alkylphosphonic acids of General formula

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where

R is alkyl (C1-C2halogenated;

R', R" are alkyl (C4-C8.

These esters are extractants and are used for the separation of rare earths, as well as treatment of copper electrolytes from arsenic.

A method of obtaining higher esters alkylphosphonic acids by the interaction of dichlorohydrin alkylphosphonic acid with an excess of the higher alcohol, taken in the ratio of 1:2,2 (mol), respectively, when heated to 100oC in inert solvent (dichloroethane).

The disadvantage of the prototype method is the low yield and the formation of a mixture of acidic and high vacuum is not possible to obtain pure products. The output of the full ether 60 - 70%.

The aim of the invention is to increase the output and quality of a full ether.

Goal achieved:

a) introducing into the reaction mixture for the most efficient solvent - saturated hydrocarbons of normal structure, or mixtures thereof, such as hexane, petroleum ether;

b) conducting the process at a temperature of 0 - 30oC, better than 10 - 20oC.

The process of interaction of anhydride alkylphosphonic acid with a higher alcohol, taken in a molar ratio of 1:2,2, respectively, in the solvent - limiting hydrocarbons of normal structure at a temperature of 0 - 30oC, better than 10 - 20oC, allowing you to increase the output of the full ether, such as "gachsaran", at the stage of synthesis to 92 - 97%, reduce the content in the reaction mass, acidic impurities, which, in turn, leads to increased product yield and reduce the amount of wastewater generated in the process of neutralization and subsequent selection of the target product.

The output of the entire product according to the proposed method 90 - 96%.

The total amount of wastewater 4 m3/t of finished product.

The proposed method of obtaining esters of alkylphosphine the th and refrigerator, pour the higher alcohol and the solvent. In alcohol at a temperature of 0 to 10oC and a residual pressure of 200 to 760 mm RT.article dispense dichlorohydrin. After dosing the reaction mass is kept in solution at the temperature of 0 - 30oC, better than 10 - 20oC, for 3 to 4 h to complete the reaction, after which it when mixing the metered 15 - 20% solution of sodium hydroxide in the amount of 100 - 150 mg/g-mol source dichlorohydrin.

The resulting mixture was separated with a separating funnel, the organic layer washed twice with water to a total volume of 700 - 850 ml/g-mol source dichlorohydrin and after separation in a separating funnel from the organic layer to remove the solvent and unreacted alcohol by distillation with water vapor.

The remainder represents the finished product - fluids containing not less than 95% of the basic substance. In the process of separating the unreacted alcohol get 150 - 200 ml of condensate, which is an aqueous-alcohol emulsion. Alcohol after emulsion breaking and drying recycled. Total wastewater 0,9 - 1,2 l/g-mol source dichlorohydrin or 4 m3/t of finished product.

Example 1. To 93,2 g (0,715 g-mol) 2-ethylhexanol alcohol when peremeshivanie ether and after exposure for 4 h 90 ml of 17% aqueous solution of sodium hydroxide.

After separation emit 250 ml organic and 90 ml of water-salt layer. The organic layer is washed twice with water to a total volume of 250 ml and washed organic layer is distilled petroleum ether. Unreacted alcohol is removed by distillation with water vapor. You get a finished product in the amount of 100.2 g containing diapir is 95.2%. The output diapir source dichlorohydrin 90%. Total wastewater 1.2 l/g-mol of dichlorohydrin or 3.8 m3/t of finished product.

The elemental composition of the finished product:

Found,%: P Of 9.21; C 64,21; H 11,72; O 14,86.

Calculated,%: P 9,67; C 63,72; H 11,64; O 14,97.

Example 2. Differs from example 1 in that the solvent used hexane (200 ml). The product is obtained from of 124.8 g (0,987 g-mol) of the alcohol and 59.6 g (0,448 g-mol) of dichlorohydrin.

To neutralize the acidic impurities serves 100 ml of a 16% aqueous solution of sodium hydroxide. Get 136,7 g of product with a basic substance content of 96.5%. The output diapir on dichlorohydrin 91,9%. Total wastewater 1.1 l/g-mol source dichlorohydrin or 3.4 m3/t of finished product.

The elementary composition of the original product:

Found,%: P was 9.33; C 63,99; H 11,80; O 1 is similar reagents take butyl alcohol and dichlorohydrin ethylphosphonic acid number 0,715 and 0,325 g-mol, respectively.

The output diapir of 92.5%.

The elementary composition of the original product:

Found,%: P 13,70; C 54,48; H 10,50; O 22,32.

Calculated,%: P 13,94; C 54,03; H 10,43; O 21,60.

Example 4. Carried out analogously to example 1.

As the initial reactant charge hexyl alcohol and dichlorohydrin chloromethylphosphonic acid number of 1,144 and 0,526 g-mol, respectively.

The output diapir 95,7%.

The elementary composition of the original product:

Found,%: P 9,89; C 53,14; H 9,60; O 16,06; Cl 11,31.

Calculated,%: P Accounted For 10.39; C 52,26; H 9,38; O 16,08; Cl 11,89.

Thus, the proposed method is a complete esters alkylphosphonic acids allows to increase the output of diapir 60 - 70% to 92 - 97% at the stage of synthesis of 1,2 times the total output, to improve the quality of the finished product (at least 95%) to reduce the amount of waste water.

The way to obtain the complete esters alkylphosphonic acids of General formula

< / BR>
where R is alkyl (C1- C2or haloalkyl;

R', R" are alkyl (C4- C8,

the interaction of dichlorohydrin alkylphosphonic acid with a higher alcohol in a solvent, characterized in that, to improve yield and quality of the target product in the solvent used limit ug

 

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< / BR>
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SUBSTANCE: invention relates to method for production of compounds having general formula , wherein R is lower alkyl and R1 is lower alkoxyl, phenoxyl, or group of formula . Claimed method includes reaction of pentavalent phosphorous acid chloroanhydride with glycydil methacrylate at 20-50°C in presence of titanium tetrachloride as catalyst in amount of 0.02-0.05 % calculated as reagent mass.

EFFECT: one-step method for production of phosphorous and chlorine containing methacrylates with improved water resistance.

2 tbl, 7 ex

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EFFECT: valuable properties of substance.

1 tbl, 2 ex

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SUBSTANCE: invention relates to the improved method for preparing N-phosphonomethylglycine. Method involves interaction of derivative of hexahydrotriazine of the formula (II):

wherein X represents CN, COOZ, CH2OY and others; Z and Y represent hydrogen atom and others with triacylphosphite of the formula: P(OCOR3)3 (III) wherein R3 means (C1-C18)-alkyl or aryl that can be substituted. The prepared product is hydrolyzed and (if X represents CH2OY) oxidized. The proposed method is a simple in realization, economy and provides high degree of the end product purity.

EFFECT: improved preparing method.

19 cl, 11 ex

FIELD: organic chemistry, chemical technology, medicine.

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16 cl, 10 tbl, 87 ex

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EFFECT: improved method of synthesis, improved and valuable properties of compounds.

2 tbl, 10 ex

FIELD: organic chemistry, biochemistry, medicine.

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64 cl, 5 tbl, 38 ex

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EFFECT: valuable medicinal and biochemical properties of compounds.

34 cl, 19 ex

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EFFECT: high purity grade and high output.

4 ex

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1 tbl, 3 ex

FIELD: chemistry.

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EFFECT: production of new C-phosphorylated alkylamidines with high yield exceeding 78%.

1 cl, 9 ex

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