SU410019A1 - - Google Patents

Description

The invention relates to a process for the preparation of heterocyclic phosphorus derivatives, i.e., 2-alkox- (alkyl) -3-bis (dialkylamino) phosphino-4,5-benzo-1,3,2-oxazaphospholiums of the general formula

xPlNRo)

2g

Р-В

/

where R is alkoxy or alkyl;

R is alkyl,

which can be used as intermediates for the synthesis of biologically active substances.

The proposed method for the preparation of 2-alkoxy (alkyl) -3-bis- (dialkylamino) phosphino-4,5benzo-1, 3,2-oxaphospholanes, based on an analogy-free reaction, is that 2-alkoxy (alkyl) -4,5-benzo-1,3,2oxaphospholane of the general formula

P-r

where R is alkoxy or alkyl.

subjected to interaction with hexaalkyltriaminophosphine of General formula

/(.)

where R is alkyl.

The process is carried out with heating, preferably at 110 -150 ° C.

Dialknlamine is distilled off during the reaction.

Target products are isolated by known methods. Yield 45-75%.

In the NMR spectra of compounds in weak fields, there are two signals of equal intensity, which indicate the presence of nonequivalent atoms of trivalent phosphorus with a different chemical environment.

Example 1. 2-Isopropoxy-3-bis (diethylamino) phosphino-4,5-benzo-1,3,2-oxazaphospholane.

3 g of 2-isopropoxy-4,5, -benzo-1,3,2-oxazaphospholane and 3.9 g of hexaztiltriamipophosphip are heated in a flask with a descending cooler for 1.5 hours. 0.5 g (45%) of diethyl distillate is distilled off. During distillation

4.3 g (77%) are obtained

product, 1.5338,

t. klp

1.0774.

Paidono,%: N ll, 6h-P

Ci-H.iXaOaPo.

Calculated,%: N 11,32; P 16.73.

Example 2. 2-Isopropoxy-3-bis (dimethylamino) phosphino-4,5-benzo-1,3,2-oxazaphospholane.

6 g of 2 - isopropoxy - 4,5 - benzo - 1,3,2 - oxazaphospholane and 5 g of hexamethyltriaminophosphine are heated under reflux at 120-140 ° C for 1 hour. During the distillation receive 6.3 g (65%) of the target product, so Kip.

115 ° C / 0.04 mm Hg Art., 1.5548, 1.1201.

Found,%: N 13,17; R 19.51.

С1зН2гМзО2Р2.

Calculated,%: N 13.33; R 19.69.

Example 3. 2-Methoxy-3-bis (dimethylamino) phosphino-4,5-benzo-1,3,2-oxazaphospholane.

10 g of 2-methoxy-4,5-benzo-1,3,2-oxazaphospholane and 9.7 g of hexamethyltriaminophosphine are heated with a descending cooler at PO-130 ° C for 1.5-2 hours. The excreted dimethylamine is absorbed by water. Yield 1.3 g (50%). During the distillation receive 8 g (47%) of the target product, so Kip. 111 ° C / 0.007 mm Hg Art., 1.5610, 1.1577.

Found,%: N 14.52; R 21.83.

Ci.HigNsOaPa.

Calculated,%: N 14,64; R 22.30.

Example 4. 2-Ethyl-3-bis (diethylamino) phosphino-4, 5-benzo-1,3,2-oxazaphospholac.

8.3 g of 2-ethyl-4,5-benzo-1,3,2-oxazaphospholane and 12.4 hexaethyltriaminophosphine are heated with a descending cooler at 140 ° C for 1.5 hours. As a result of distillation, 9.6 g (56%) of the desired product are obtained, t. Bales. 133-135 ° C / 0.004 mm Hg. Art., at 1.5523, d4 1,0733.

Found,%: N 12.57; P 18.56.

CieHagNaOPz.

Calculated,%: N 12,32; P 18.20.

Subject invention

Claims (2)

1. The method of obtaining 2-alkoxy (alkyl) -Zbis (dialkylamino) phosphipo-4,5-benzo - 1,3, 2-oxazaphospholanes of the general formula / r (w;) 2 g Р-В where R is alkoxy or alkyl; R is alkyl, characterized in that 2-alkoxy (alkyl) -4,5-benzo-1,3,2-oxazaphospholane is reacted with hexaalkyltriaminophosphine by heating, followed by separation of the target product by known methods. 2. A method according to claim 1, characterized in that the process is carried out at 110-150 ° C.