SU395372A1 - METHOD OF OBTAINING O-ALKYL-8-ORGANOCHLORANTIOPHOSPHATES - Google Patents

Description

one

A method is proposed for the preparation of the acid chloride. Of acids of thiafoxoric acids, a .ie "Ho" a new method for the preparation of O-alyl-3-organochlorophosphates of the general formula

R0

PCI RS /

II Oh

where R is alkyl, chloro- or diloalkyl; R - and l kil-or aril.

These compounds are of great interest in one of the half-preparations for the synthesis of various physiologically active organo-phosphorus compounds.

The known method (Preparation of O-alkyl-3-organo-chlorophosphates (by the interaction of dialkyl chlorophosphites iC sulfenic chlorides. This method allows to obtain | Healed products with a rather high yield, however dialkyl chlorophosphites are difficult to access.

The purpose of the invention is to simplify the process by utilizing more available starting materials (alkyld chlorophosphites). According to the proposed method, adducts dichlorophosphite is subjected to the interaction of 1ModeyByu with acetic acid and sulfibnil.chlorokam.

It is desirable to conduct the process in an inert organic medium (solvent, for example, chloroform, iri 1m-20 ° C.

In many cases, it is advisable to use as a sulfonyl chloride a freshly prepared reaction mass obtained by Bree – Ia and M on the action of gkvillirnyh quantities of organic tiyl or disulfide l chlorine or sulfuryl chloride.

The desired products are obtained in good yields (60-94 ° / o) and are isolated by known methods.

PRI m e ip 1. | P about lu ch e and O O -1,3 - d and 0 X l about r and 3 O in p about P And l - S - 1M et and l X l about r t and about phosphate.

To a solution of 0.25 g mol of dimethyl sulfide in 20 ml of chloroform three. Minus 50 - minus 40 ° С 0.05 g mol of chloride is added

5 sulfuryl or chlorine. The temperature of the mixture is brought to room temperature and a solution A is obtained. To a solution of O, 095 g of mol of 1,3-dichloroisopropyl of dichlorophosphite in 30 ml of chloroform, 0.095 g of mol of glacial acetic acid is heated at a temperature of 15 ml and cooled. minus 45 - minus 40 ° C - solution A. The tbMd mixture of the mixture is brought to room temperature, the volatile and the solvent is removed in

5 vacuum and distillation separated (product bp 136-138 ° C / 1.5 mm Hg; Art .;

,20

1.5220; df 1.4971; MRo found

52.46, calculated 52.85; 1 OUTPUT 92Vo.

Found, J / o: C 41.12; R

12.43; S 12.16.

С4Н8С1з02Р5

Calculated, o / o: C1 41.36; P 12.03; S 12.42.

Under the conditions of Llimer 1, each other is obtained, the substances whose yield and properties are given in this person.

Example 2. Getting O - and z o b ut And l - S - f le n and l X l o r t and o f o c f a t a.

To ipacT-Bopy of 0.05 g mol of thiophenol IB, 10 ml of chloroform and 0 ° C are added 0.05 g of mol of sulfuryl chloride. The mixture of qul t t 3Q min and get p, solution .4.

To a solution of 0.05 g mol of isobutyldichlorophosphite in 20 l (l of chloroform and 20 ° C) 0.05 g of glacial acetic acid, and then DI, mi nus 20 - miius 15 ° C - solution A. Temperature of the reaction mass t to room temperature, the solvent and volatile are removed in a van gum by distillation, the product is isolated, t, bp 144-146 ° C 3 mmHg, p 1.5420; 1 2396; MR 67 found 67.15, calculated 67, 22; yield 66%.

Found, o / o; C1 13.12; R 11.49; S 12.38.

Sums

Calculated, O / o: C1 13.41; P 11.72; S 12,10.

Priller 3. Obtaining O-butyL - 2,5 - d and X l o r f e and l l l r t and o f o c f at a.

To a mixture of 0.05 g mol of butyl dichlorophosphite, i 0.05 g of mol of glacial acetic acid in 20 ml of chloroform, while cooling to minus 30 - minus 20 ° C, add a solution of 0.05 g of mol of 2.5-dichlorophenylsulfonylchloro | Ida in 20 ml of chloroform. The temperature of the reaction mass is brought to room temperature, the solvent is removed in vacuo and the residue is obtained in a yield of 94%, p I, 5763; d2 ° 1.4197; , found 77.6, calculated 76.9.

Found, o / o; C1 31.52; P 9.46; S 9.18.

CioHpClsOsPS

Calculated, "/ o: C1 31,93; P 9.29; S 9.60.

Prevent Invention

Claims (3)

1. The method of obtaining 0-al (total-chloro-5-organo-chlorothiophosphate (formula RO PCI RS / 11 o R is alzhyl, chloro- or dichloroalkyl; where R is alkyl or aryl. on the basis of chlorophosphites and sulfenyl chlorides, characterized in that, in order to simplify the process, alkyl dichlorophosphite is subjected to interaction with acetic acid and sulfate and chloro: m. 2.Cnoico6 on 1P. 1, characterized in that the process is carried out with IB medium and} a synthetic orginal solvent, nano; 3. The method according to claim 1, characterized in that the process is at minus 50 - plus 20 ° C.