SU455967A1 - The method of obtaining -hydrazonphosphinates - Google Patents

Description

one

The invention relates to a process for the preparation of a previously unknown type of compounds containing phosphine and hydrazone centers, which may be referred to as α-hydrazone phosphinates.

These substances may have beneficial biological and complexing properties.

Dialkylphosphorous acids are known to be capable of bonding through a carbon-nitrogen double bond of ald- or ketazines to form aa-hydrazonin-phosphonates.

However, the acidic esters of the phosphonous acid were not introduced into this reaction.

The implementation of this reaction allowed us to obtain a new type of hydrazones containing an alkyl (aryl) phosphonic group in the hydrozine fragment, which may have properties of practical interest.

A method for the preparation of a-hydrozonophosphinates by the interaction of acid esters of phosphonous acids with ald or ketazines is proposed.

O O R; X

P + 0-N-N (

/

H

TO

to. with

- R

TO

/

R (; -Ш1-№ with

E

TO

R

great warming up. Leave for several days at room temperature.

After distilling off the ether, 4.9 g (65%) of crystalline precipitate are obtained. The product is filtered, washed with ether and dried in a vacuum desiccator.

T. pl. the resulting product 115-117 ° C; Rf 0.57 (benzene: acetone system 2: 1); Rf 0.86 (system hexane: dioxane: acetonitrile - 2: 2: 1).

Found,%: C 69.07; And 6.15; P 8.20.

C22H23N2O2P.

Calculated,% C 69.9; H 6.08; P 8.20.

Example 2. In a two-neck flask with reflux, 4.2 g (0.02 mol) of benzalazine and 3.3 g (0.03 mol) of methylphosphonic acid ethyl ester are heated in a stream of argon at 100-110 ° C for 4 hours.

The mixture was incubated for 3 days, after which the entire mass crystallized. The yield of the product is 3.4 g (53%). The product is filtered, washed with ether, dried in a vacuum desiccator. T. pl. 102-103 ° C; Rf 0.52 (benzene: acetone system 2: 1); Rf 0,80 (system hexane: dioxane: acetonitrile - 2:: 2: 1).

Found,%: C 64.20; 64.05; H 6.88; 6.77; N 8.81; 7.68; P 9.24; 9.47.

C, 7H2iN2O2P.

Calculated,%: C 64.60; H 6.65; N 8.85; R 9.80.

Example 3. In a two-neck flask with reflux in a stream of argon is heated 3.38 g of azine of cyclohexanone and 6.0 g of ethyl ester of phenylphosphonic acid at 90-100 ° C for 2.5 hours. After cooling, the reaction mixture gradually crystallizes. The yield of the product is 4.5 g (70%). The recrystallization is carried out from acetone. T. ll. product 124-125 ° C; Rf 0.73 (benzene system:: acetone 2: 1); Rf 0.91 (system hexane: dioxane: acetonitrile 2: 2: 1).

Found,%: C 66.04; 65.99; H 8.79; 8.94; P 8.64; 8.59.

C2H3lN2O2P.

Calculated,%: C, 66.3; H 8.56; R 8.56.

Example 4. To 5.25 g of molten cyclohexanone azine was added 3.2 g of methylphosphonic acid ethyl ester. The mixture is heated to 40 ° C. Leave overnight. The reaction mixture gradually crystallizes. Filtered, washed with hexane, dried in a vacuum desiccator. 4.9 g (60%) of crystalline product are obtained. T. pl. product 74-76 ° C, Rf 0.45 (system benzene: acetone 2: 1); Rf 0.77 (system hexane: dioxane: acetonitrile 2: 2: 1).

Found,%: C 59.95; 60.08; H 9.57; 9.65; P 10.45; 10.36.

C15H29 20zR.

Calculated,%: C 60.00; H 9.67; R 10.30. Subject invention

Claims (3)

1. A method for the preparation of cc-hydrazone phosphinates, characterized by the fact that the acidic esters of phosphonous acids are reacted with ald or ketazines, followed by isolation of the target product by known methods. 2. A method according to claim 1, in which it is carried out with heating, for example. to 90-110 ° C. 3. The method according to claim 1, wherein the process is carried out at room temperature in an organic inert solvent, for example, ether.