SU436823A1 - Method for preparing dialkyl- or diaryl- / 1-acyloxy-1-methyl-2,2,2-trichloroethyl / phosphonates - Google Patents

Description

one

The invention relates to the production of new biologically active organophosphorus compounds of the general formula

SNZ Oh

C-0-CR I CC1

where R is alkyl or aryl;

R alkyl, which can be used as medicinal substances.

A known method for producing dialkyl (1-acyl-hydroxy-2,2,2-trichloroethyl) phosphonates by acylation of dialkyl (1-oxo-2,2,2-tri-chloroethyl) phosphonate with carboxylic acid anhydrides.

The purpose of the invention is to prepare dialkyllyl diaryl- (1-acyloxy-1-methyl-2,2,2-trichloroethyl) phosphonates. For this, dialkyl or diaryl (1-hydroxy-1-methyl-2,2,2-trichloroethyl) phosphonates are reacted with carboxylic acid anhydrides in the presence of catalytic amounts of strong mineral acids, for example sulfuric, followed by isolation of the desired product by known methods. The process is conducted by heating, for example, to 100 ° C.

Example 1. To 10 g of diethyl- (1-hydroxy-1-methyl-2,2,2-trichloroethyl) phosphonag is added

7 g of acetic anhydride, in which 3 drops of concentrated sulfuric acid are dissolved. The mixture is stirred for 6 hours at 100 ° C, then the unreacted acetic anhydride and the acetic acid formed are distilled off. The residue is distilled under vacuum twice. 8.9 g (78%) of diethyl (1-acetoxy-1-methyl-2,2,2-trichloroethyl) phosphonate are obtained with a bale. 102-103 ° / 0.01 mm Hg Art., ng 1.4770; rff 1.3535. MR: found 71.30; calculated 70.88.

Found,%: P 8.68; C1 31.01.

CgHieOgPCb.

Calculated,%: P 9.07, C1 31.18.

Example 2. To 20 g of diisopropyl- (1-hydroxymethyl-2, 2,2-trichloroethyl) phosphonate was added 12.2 g of acetic anhydride in which 5 drops of concentrated sulfuric acid were dissolved. The mixture is stirred for 6 hours at 100 ° C, then unreacted acetic anhydride and the acetic acid formed are distilled off, and the residue is distilled twice in vacuo. 13 g (57.5%) of di - isopropyl - (acetoxy - 1 - methyl-2,2,2-trichloroethyl) phosphonate are obtained with a bale. 103- 104 ° C / 0.03 mm Hg. Art., 1.4727; df 1.2848 M, R: found 80.62; calculated; 80.12.

Found,%: P 8.13; C1 28.53.

Scs.

Calculated,%: R 8.36; C1 28.82.

Example 3. To 18.7 g of dimethyl- (1-hydroxy-1methyl-2,2,2-trichloroethyl) phosphonate was added 13.8 g of propionic anhydride, in which 7 drops of concentrated sulfuric acid were dissolved. The mixture is stirred for 12 hours at 60 ° C, then the unreacted propioic anhydride and the resulting propionic acid are distilled off. The residue is distilled twice in vacuo. 10.5 g (46.5%) of dimethyl- (1-propionyl-1-methyl2, 2,2-trichloroethyl) phosphonate are obtained with m kip. 86-87 ° C / 0.02 mm Hg. Art., 1.4765; df 1,3990. MR: found 66.09; calculated 66.25.

Found,%: P 10.07; C1 32.44.

CgHuOsPCls.

Calculated,%: P 9,67; C1 32.52.

Example 4. To 10 g of diphenyl- (1-hydroxy-1 methyl-2,2,2-trichloroethyl) phosphonate was added 5 g of acetic anhydride, in which 4 drops of concentrated sulfuric acid were dissolved. The mixture is stirred for 6 hours at 100 ° C, then the unreacted acetic anhydride is distilled off and the resulting

acetic acid; and the residue twice distilled in vacuo. 6.4 g (58%) of diphenyl- (1-acetoxy - 1-methyl-2,2,2-trichloroethyl) f osfonate are obtained with a bale. 150 ° C / 0.001 mm Hg st ..

,20

1.5561,

nQi, oui, a thick liquid, which after some time completely crystallized, t. pl. 68-69 ° C.

Found,%: P 6.81, 6.97; C1 23.28, 23.35. Calculated,%: P 6,89; C1 23.69.

Subject invention

Claims (2)

1. A process for the preparation of dialkyl or diaryl (1-acyloxy-1-methyl-2,2,2-trichloroethyl) phosphonates, characterized in that dialkyl or diaryl (1-oxy-1-methyl-2.2.2 - trichloroethyl) phosphonates are reacted with carboxylic acid anhydrides in the presence of catalytic amounts of strong mineral acids, for example sulfuric, followed by isolation of the target product by known methods. 2. A method according to claim 1, characterized in that the process is carried out by heating to 100 ° C.