SU1735302A1 - Method of 3,3-dichloro-1-methylallylphosphonic acid dichloroanhydride synthesis - Google Patents

Abstract

The invention relates to the chemistry of organophosphorus compounds, in particular the production of 3,3-dichloro-1-methylallylphosphonic acid dichloride, which can be used as an intermediate for organophosphorus synthesis. The purpose is to create a new method for the preparation of a new substance of the specified class. Synthesis is carried out by the reaction of 2,2-dichloro-1-alkoxymethylcyclopropane with phosphorus trichloride and aluminum at their molar ratio of 1: 2: 1 at 25-30 ° C, followed by treatment of the resulting complex with water in methylene chloride at 5 -10 ° C. Yield 30%, bk. 96-98 ° C (4 mmHg), do 1.5107, 20 each 1,5 1,522, gross f la SzNzSMOR. C / 1 s

Description

This invention relates to the chemistry of phosphorus-organic compounds with a phosphorus-carbon bond, namely, to a new method for the preparation of 3,3-dichloro-1-methyl-methylphosphonic acid dichloride hydride

se, s -sn-ss-P (o) seg si

which is a new compound and can be widely used as an intermediate for organophosphorus synthesis, as well as a monomer for the synthesis of phosphorus-containing polymers, anti-pyrene, plasticizers and biologically active compounds.

A known method for producing 2-chloroalkenylphosphonic acid dichlorohydrides by reacting 1-alkyne with trichloride phosphorus in the presence of oxygen.

There is also known a process for the preparation of cyclopropylalkenylphosphonic or -thiophosphonic acid dichlorohydrides, which consists in the fact that 1,1-di (2,2-dichlorocyclopropyl) methoxy ethane is reacted with phosphorus pentachloride in an inert organic solvent at 20 -45 ° C followed by treatment of the intermediate adduct with acetone or hydrogen sulfide.

However, none of these methods can not get a new 3,3-dichloro-1-methylallylphosphonic acid dichloride.

The purpose of the invention is to develop an available general method for the synthesis of compounds

sg s

N

type 3,3-dichloro-1-methylzlilliphosphonic acid dichloride.

The goal is achieved by the fact that according to the method for producing a compound of the above formula, 2,2-dichloro-1-alkoxy-methylcyclopropane is reacted with phosphorus trichloride and anhydrous aluminum trichloride at a reagent ratio of 1: 2: 1 at 25-30 ° C, followed by treatment formed complex compound with water in methylene chloride at 5-10 ° C.

The target product is a colorless liquid that is stable when stored without moisture and air at room temperature. The data of the elemental analysis of the IR, NMR1H and 31P spectra correspond to the indicated formula.

Example 1. 3,3-dichloro-1-methylallylphosphonic acid dichloride.

To a suspension of 16 g (0.12 mol) of anhydrous aluminum trichloride in 33 g (0.24 mol) of phosphorus trichloride with vigorous stirring at 25 ° C, 20 g (0.12 mol) of 2.2-dichloro- 1-ethoxymethylcyclopropane at such a rate that the temperature in the mixture does not exceed 30 ° C. The reaction mixture is then kept at 25 ° C for 12 hours. The excess phosphorus trichloride is distilled off, the residue is dissolved in 120 ml of methylene chloride and 16.6 g (0.92 mol) of water are treated at 5-10 ° C. The precipitated trichloride aluminum hydrate is filtered off, washed with 2x20 ml of methylene chloride. The filtrate is distilled and 6.5 g (30%) of the desired product are obtained; bp 96-98 ° C (4 mm Hg); och

,20

1.5107; 1 47.99).

i 11

20

1.5222, MRo 48.79 (calculated

Found,%: C20,2; H 2.2; CI 59.1; R 12.4.

SdNbSmor

Calculated,%: C 19.9; H 2.1; CI 58.6; R 12.8. 5 NMR spectrum 31R: dp + 47 ppm

NMR1H spectrum d, ppm: 2.05 (doublet of doublets, 3J (HH) 7 Hz, 3J (PH) 26 Hz (CH3); 3.6 - 4.58 (multiplet (PCH); 6.32 ( doublet of doublets, 3J (HH) 8. Hz, 3J (PH) 10 Hz (CH 10 CCl2).

IR spectrum, 3050, 1615, 895 (); 1280 (); 730 (CCte); 575, 550 (PCI2).

Thus, the proposed method allows to obtain a previously undescribed compound, is simple and does not require complex processing, is based on available raw materials and, if necessary, can be implemented in production. The method allows to obtain a polyfunctional 20 compound, which is a valuable intermediate of organophosphorus synthesis. The presence of chlorine atoms in the allyl radical makes it possible to consider the target product as a starting compound for the synthesis of flame retardants, fire-resistant polymers and potential biologically active substances.

Claims (1)

Invention Formula The method of producing 3,3-dichloro-1-methyl-ethylphosphonic acid dichloride, 30 plots, is concluded in that 2,2-dichloro-1-al coxymethyl cyclopropane is reacted with phosphorus trichloride and aluminum at their molar ratio of 1: 2: 1, at 25–30 ° C, followed by treating the complex formed with water in methylene chloride at 5–10 ° C.