SU975713A1 - Process for producing beta-iodoalkylphosphonic acids - Google Patents

Description

Union of Soviet Socialist Republics

USSR State Committee for Inventions and Discoveries

DESCRIPTION OF THE INVENTION

TO COPYRIGHT CERTIFICATE <11) 975713 (72) Authors of the invention (71) Applicant (61) Additional to author. certificate-wu - (22) Declared 05.02.81 (21) 3275764 / 23-04 with the addition of application No.- (23) Priority -

Published on 2311.82. Bulletin No. 43

Date of publication of the description 11.23.82 (51) M. Cl. ³

C 07 F 9/38 (53) UDC 547.341.

.07 (088.8)

S

G.K. Fedorova and L.G. Ananiev |

I: h, -. .

Institute of Organic Chemistry, Academy of Sciences of the Ukrainian SSR

(54) METHOD FOR PRODUCING β-IODALKYL PHOSPHONIC ACIDS relates to

The invention of organo-organic compounds is connected to a new method for the preparation of kilophosphonic acids of general phos chemistry, namely β-iodal formulas where R is hydrogen or alkyl, which can be used as plant growth regulators, as well as intermediates of organophosphorus synthesis.

A known method for producing p-iodoalkylphosphonic acids by reacting g-p-chloroalkylphosphonic acids with an excess of hydroiodic acid, by boiling the reaction mixture. The yield of the target products reaches 6070% [13.

The disadvantages of this method include the inaccessibility of p-chloroalkylphosphonic acids, associated with the multi-stage production of _M jHe-j [the need for purification, as well as the relatively low yield of target products. * • 'Λ. '' '’The aim of the invention is to simplify the process and increase the yield of target products.

The goal is achieved by the method of producing p-iodoalkylphosphonic acids, which consists in the fact that dichlorohydride B-chloroalkylphosphonic acid is reacted with hydroiodic acid at a molar ratio of reactants 1: 2-3.6 when the reaction mixture is boiled. The yield of target products is 80-93%.

The proposed method for producing p-iodoalkylphosphonic acids simplifies the process by using the more accessible dichlorohydrides of p-chloroalkylphosphonic acids, eliminating the need to obtain p-chloroalkylphosphonic acids and isolating them, and also increases the yield of target products by 20-30% compared to the known method. According to the proposed method, 57% hydroiodic acid is used, its excess after reaction is distilled off and the target product is purified by washing with sulfuric acid, followed by reprecipitation from sulfuric ether with petroleum ether or from benzene solution with decane. The method of obtaining p> -iodoalkylphosphonic acids allows you to simultaneously implement.

. -hydrolysis of acid chloride chlorine atoms and substitution of chlorine atoms with an iodine atom in a hydrocarbon radical.

EXAMPLE 1. A mixture of 0.2 mol of o-chlorhexylphosphonic acid dichloride and 100 ml of 57% hydroiodic acid was refluxed for 5 hours. The excess of hydroiodic acid was distilled off from the reaction mixture. The residue was dissolved in 50 ml of ether, the ethereal solution was washed with saturated sulfuric acid solution (.5x10 ml) until it bleached, dried with sodium sulfate and evaporated. The remainder of p-iodohexylphosphonic acid is purified by reprecipitation from an ether solution with petroleum ether and dried in an oil pump vacuum.

The output of p-iodhexylphosphonic acid 9 3%, so pl. 64-66 ° C. The melting point of the mixed sample ^with P ~ 20

-iodhexylphosphoic acid obtained by a known method, does not give depression.

Found,%: C 24.98, H 4.75, P10.43, '3 43.59.,

C ₆ H ₁₄ 1RO ₃

Calculated,%; C 24.65; H 4.79;

P 10.61; 3 43.49.

IR spectrum: 600 cm ~ ¹ (C-1) ^ 1265 cm ¹ (P = 0), 2700 cm ~ ¹ (P-OH).

Example 2. p-Iodheptylphosphonic acid 30 is obtained analogously to p-iodhexylphosphonic acid from d-chloroheptylphosphonic acid dichloride and 57% hydroiodic acid (ratio of 350 p-chloroheptylphosphonic acid dichloride and 3.5%) in moles of 90%: 1: , mp 66-67 ° C. The melting point of the mixed sample with p-iodheptylphosphonic acid 40 obtained by a known method, not.

gives depression.

Found,%: P 9.88; ³ 41.18.

with ₇ n ₁ ero ₃

Calculated,%: P 10.13, □ 41.50. 45

Example 3. p-Iodheptylphosphonic acid is prepared in the same manner as described in Example 2. The ratio of p-chloroheptylphosphonic acid dichloride and HO is 1: 2. The yield of p-iodoheptylphosphonic acid is 86%. Identified by the melting point of the mixed sample.

PRI me R 4. A mixture of 0.03 mol of d, chlorohydride of p-iodoethylphosphonic acid and 15 ml of 57% hydroiodic acid (containing 0.11 mol HO) is refluxed for 20 hours. Excess hydroiodic acid it is distilled off, the crystalline product is filtered off, washed with petroleum ether and dried. The output of p-iodoethylphosphonic acid 80%, so pl. 115-117 ° C, identified by the melting point of the mixed sample, IR and PIR spectrum with the acid obtained previously.

Claims (2)

This invention relates to the chemistry of organophosphorus phosphoric compounds, namely, to a new method of producing / e-iodoalkylphosphonic acids of the general formula RtH3CH, PN R is hydrogen or alkyl, which can be used as plant growth regulators, as well as intermediates of organophosphorus synthesis. p -io alkylphosphonic acids by the interaction (L-chloroalkylphosphonic kslot with an excess of hydroiodic acid, etc.; boiling of the reaction mixture. The target products reaches 60 70% P. The disadvantages of this method include The availability of 5-chloroalkylphosphonic acids, associated with the multistage production of H jHe, the purification rate, as well as the relatively low yield of target products. The aim of the shading is to simplify the process and increase the yield of the Target products. α-iodoalkylphosphonic acids, which imply that dichlorohydrin, pi-chloroalkylphosphonic acid is reacted with hydroiodic acid at a molar ratio of reagents of 1: 2-3.6 at the boiling point of the reaction mixture. The yield of the target products 80-93%. The proposed method for producing b-iodoalkylphosphonic acids simplifies the process by using more available dichlorides (J-chloroalkylphosphonic acids, eliminating the need to obtain (i -chlorosylphosphonic acids and their isolation), and also increases the yield of the target products by 20-30% compared to the known method. According to the proposed method, 57% hydroiodic acid is used, its excess after the reaction is distilled off and the target product is purified by washing with sulfuric acid followed by reprecipitation A method for producing p-iodoalkylphosphonic acids can simultaneously be carried out and the hydrolysis of chlorohydride chlorine atoms and the substitution of chlorine atoms for an iodine atom in the hydrocarbon radical. p-chlorohexylphosphonic acid dichlorohydride and 100 ml of 57% hydroiodic acid are refluxed for 20 times. Excess of hydroiodic acid is distilled from the reaction mixture. The residue is dissolved in 50 ml of ether, the ethereal solution is washed with a saturated solution of sulfuric acid (5x10 decolorization, dried with sodium sulfate and evaporated. The residue is iodhexyl phosphonic acid, purified by precipitating from ether with petroleum ether and dried in an oil pump vacuum. Output - iodohexylphosphonic acid, 93%; mp. b4-bb ° C. The melting point of the mixed sample with (i-hedexylphosphonic acid, prepared by a known method, does not give depression. Found: C 24.98, H 4.75, R 10.43, 3 43.59. CbHi4 IPOj Calculated,%: C 24.65; H 4.79; P 10.61, -: 43.49. Spectrum: 600 (С-1), 1265 cm (), 2700 cm (Р-ОН). Example 2. p-Iodo-methylphosphonic acid is obtained analogously to P) -i-hexoxyphosphonic acid from dichloride / chloro-heptylphosphonic acid acid and 57% hydroiodic acid (the ratio of dichlorohydrin b - chloroeptylphosphonic acid and HD in mol x 1: 3, Yield 90%, mp. b6-67 ° C. Melting point of the mixed sample with | b - iodoheptylphosphonic acid, obtained by a known method, n gives depression. Found,%: P9.88; 341.18. С-, Н J РЗ Calculated,%: Р 10,13, 3 41,50. EXAMPLE 3. (I-Iodheptylphosphonic acid is obtained in the same way as described in example 2. The ratio of dihydro-phosphonic acid dichloride and BUT 1: 2. The yield of f-iodheptylphosphonic acid is 86%. Identified by the melting temperature of the mixed sample. Example 4. A mixture of 0.03 mol of d-hydrochloride, p-iodoethylphosphonic acid and 15 ml of 57% hydroiodic acid (containing 0.11 mol of HJ) was boiled under reflux for 20 hours. Excess the hydroiodic acid is distilled off, the crystalline product is filtered off, washed with petroleum ether and dried. The output of p, iodoethylphosphonic acid 80%, so pl. 115-117 ° C, identified by the melting point of the mixed sample, IR and PMR spectrum with the acid obtained earlier. DETAILED DESCRIPTION OF THE INVENTION A method for producing p, iodoalkylphosphonic acids by reacting an organophosphorus compound with an excess of hydroiodic acid at the boiling point of the reaction mixture, characterized in that, in order to simplify the process and increase the yield of the target products, the organophosphorus compound used is dichlorohydride (L-chloroalkylphosphonate) in the amount of 1 mole per 2-3.6 moles of hydroiodic acid.Sources of information taken into account during the examination 1. GK Fedorova et al. (L-iodalkylfdsfonov acid e. Journal of Organic Chemistry, 1979, p. 234 (prototype).