SU583136A1 - Method of preparing dichloranhydrides of b-choralkylphosphonous acids - Google Patents

Description

one

The invention relates to the chemistry of organophosphorus compounds with a C-P bond, which is a new method for the preparation of the dihydrahedhenes of the halogen phosphylphosphonic acids of the general formula

ECli- (H2-R (Jl

L i

where R is alkyl or phenyl, which can be used as a solid product. to obtain monomers or physiopogic. active compounds.

A known method for producing dichlorangs; reads alkenylphosphonic acids by the interaction of olefins. pichloride phospho. rum in a benzene medium followed by reduction of the resulting complex with white phosphorus in the presence of iodine.

There is also known a method of producing jij-chloroalkylphosphonic acid dichlorides by reacting olefins with phosphorus trichloride in an inert gas atmosphere when heated to a temperature of 85 ° C and a pressure of 1.2 atm in the presence of free radical initiators 2.

The yield of products is 9-10%. The disadvantages of this method include the need to use free radical initiators, heating, as well as the ambiguity of the process, resulting in a mixture of products of undeveloped structure and the target product with low speed.

The purpose of the invention is to simplify the process and increase the yield of 6-chloroalkyl phosphonic acid dichlorohydrides.

This is achieved by the described method for the preparation of Jb-chloroalkylphosphonic acid dichlorides, which is that the olefin is reacted with phosphorus phosphorus in an inert gas atmosphere in benzene at 1520 ° C, followed by reduction of the resulting complex with phosphorous hydrogen at room temperature. It is desirable to use 1-2 mol of phosphorus tetrachloride per 1 mole of olefin. The yield of products 5O-90%.

Distinctive features of the method are the use of low-purity phosphorus as a chloride and carrying out the process of benzene at a temperature of 1–15–20 ° C with subsequent reduction of the resulting complex with phosphorous hydrogen: at room temperature Cpx; products in high quality soft solids. All operations are carried out in the absence of moisture in an inert atmosphere. Example 1. Preparation of dichlorohydrin and da L-chloro-ji-phenylethylphosphonic acid; To a suspension of 80.2 g (0.385 g / mol) (a spot of phosphorus chloride in 4O ml of absolute bepzol, 20 g (0.193 g) are slowly added After 1 hour of stirring at this temperature, the reaction mixture is left overnight. The resulting white crystalline complex of Ipaa is passed through a sparger of dry, hydrogen phosphorus until the disappearance of the crystalline complex. Benzene and t-chlorophosphorus phosphorus are distilled off, the residue is removed in vacuum, 42 g (9O%) are separated. Substances t-jUA v.xiJtv m, l l I - V4rf l С at 9 mm Hg-4; 4 ° 1, 5b7 with -1-40-141 df 1.3410; MR- 61.33} calc. 6O, 72. ) .. MR 61.33: Cal. 66.72. Found,%: C 4, O2; H 3.45; UK 43.91; R 12.61. C H CEjP Calcined,%: C 39.8 O; H 3.31; , 05 P 12.82.31 Chemical. | shift Ph-i83 m, d. with respect to HjPD Example 2, Preparation of dichlorohydrin and f-chlorohexyl phono-phonic acid. Analogously to the example of Guys 99g (0.481 g / my phosphorus pentachloride and 2O g (O, 24 g / mi hexene -1 in 5O ml of absolute benzene) after the complex was reduced by phosphorous. 41 g (78%) of the substance was extracted with C, 1OZ-1O5 C at 2O .mmHg, P2p 1.4952; dj ° 1.1423; MR 56.51; deduction, 55.09; Found,%: C 32.55; H 5.42; P IC, CE 48 , 3. Calculated,%: C 32.40; H 5.31; R 14, O 48, O9. Chemical shift Hp -162 ppm relative to Hj PO. Example 3. Preparation of dichlorohydrin-chloro- | j -Phenylethylchlorophosphine. To a suspension of 40 g (0.192 g / mol) of phosphorus pentachloride in 4O to dry dry benzene, 20 g (0.192 g / mol) of styrene in molar molar is added. After 1 hour of stirring, at this temperature, the reaction mixture is left overnight, the white white crystal of the A complex is decomposed by passing dry phosphorous hydrogen through a sparger to a crystal of a small lump, -. - - - - .. d ... Ca at room temperature (18-25 C). Benzene and phosphorus trichloride. It is distilled off, the residue is fractionated in vacuo, fractionated in vacuo, isolated (74%) with 140–14 ° C and 32.3 g of 1 m.ph, l; 1.5968, 1.3413. at 9 mm Example 4, Preparation of dichlorohydride. If is chloroheptylphosphorous -acid. To a suspension of 84.8 g (0.40 x mol) of phosphorus pentachloride in 50 ml of dry benzene at 15–20 ° C, 20 g (O, 2O. G / mop) of 1-heptene in molar COOTHD- are slowly added, respectively 2; After stirring for 1 hour at this temperature, the reaction mixture is left overnight. The white crystalline complex formed is decomposed at room temperature (18-25 "C) by passing through a dry phosphorous hydrogen sparger until the crystalline complex disappears, Benzene and phosphorus trichloride are distilled off, residue 4 is co-evaporated in a vacuum, you. “G (63%) f of a substance with T 85-87 at 7 mm, Hg, Art .; df 1.1185; 10th 1.4G4y y -.4 MRj, 59.25; Calc., 5.72; Found,%: C 35.41; H 5.9O; CE 44.9O; 1 ° 12.87. Calculated,%: C35,69L. H 5.99; Sat 45.15; P 13.15 Example 5, Preparation of L-chloroctyl phosphonous acid dichlorohydrin. Analogously to Example 4, out of 37.1 g (0.178 g / mol) of phosphorus pentachloride and 1 (7g (O, O89 g / mol) of 1-octene in 5O ml of dry benzene, the molar ratio is 2: 1 after the decomposition of the formed m ". 1J. t.,, ftni li-tLfi i / v / | jci4: ii: 3CiDLUT :: 4 1 Lxl of the crystalline complex of phosphorous water op at one temperature, (1825 ° C), 12, O g (54% ) substances with T 97-99 at 7 mm of mercury, st; n | l, 4612j 1.07O6; MRj 63.98; deduction, 63.34;, Paideno,%: C 38.68; H 6.52; CC 42.41; P 12.20, C8 16 "zR Calculated,%: C 38.50; H 6.46; Sat 42.62; 12.41. Example 6, Preparation of | 1-styryl dichlorophosphine, K 20 g (0 , О82 g / mop) j - chlorine ft phenylethyldine. Chlorophosphine in 50 ml of benzene with stirring and cooling, maintaining the temperature in the mixture of 10-15C, 8.4 g (0.082 g / mol) of triethylamine is added dropwise. The reaction mixture is heated for 1 hour in a water bath, after which the precipitate the triethylamine batch is filtered off, the solvent is distilled off, and the residue is distilled in vacuo to give 12 g (71%) of the solution with L l47-138 C (io mm), l. Tt (- v V wadi;, dj® l, 27ftOi; MKg 57.44 "1.6362; calc. 55.81. Found,% {Ct 34.38. Ct 34.58. Literary Calculated,% data: ftS 1, 6355; 2 1.2790. Institutions 1, Method for the production of duchoranhydride-chloroacphosphoric acids by means of odefins with phosphorus chloride in an inert gas atmosphere, with a circuit, as a way, it is in the case, it is in the case, it is in the case, it is in the case, it is in the case, it is in the case, it is in the case, it is in the case, it is in the case, it is in the case, it is in the case, it is the case, it is the case, it is in the case, it is the case, it is in the case, it is in the world, it is in the atmosphere of gas, and the phosphorus chloride is in the atmosphere of inert gas, in a gas atmosphere, in the atmosphere of gas inert gas, in the atmosphere of gas inert gas, in the atmosphere of inert gas, in the atmosphere of gas inert gas, in the atmosphere of gas inert gas, in the atmosphere of gas and gas) Phosphorus chloride is spilled with p chlorine phosphorus and the process is carried out in a 6ein aopa prn medium at a temperature of 15–2 ° C / C with the subsequent reduction of the resulting complex of phosphorus phosphate. hydrogen, at room temperature, 2, The method according to claim 1, characterized in that 1-2 mol in 1 mol are sprinkled in 1 pt chlorophyll phosphorus. WcTOHHHKH information taken in an in-house examination: 1. Alkenyl dichlorophosphines. Academy of Sciences of the USSR, sulfur chemical 1976, N 1, p. 181-183 2. Heat “e e.Vj, Uf44 | WH The first of the piio pHof4J ttii € fi o“ 4de to oCft line.- .Am.Chetn. Soci945, p,.