SU314757A1 - METHOD FOR OBTAINING DERIVATIVES OF PHOSPHOSE COMPOUNDS - Google Patents

Description

The invention relates to the preparation of new compounds that can be used as physiologically active substances and semi-products of organic synthesis.

The method of obtaining derivatives of phosphazo compounds of the general formula

/ R-C-N pfB (I)

Oh and

SM R- (AOZ R /

(AOZ

I

R is alkyl, phenyl, substituted alkyl

e

or phenyl; X - oxygen, alkylenimino group

or p-chlorophenylsulfonylmino; And - phenoxy-, phenylmercapto- or

O-oxime group; B and C are chlorine, A or amido;

RI - alkylene or halogen-substituted

chlorophosphazo compounds with compounds containing mobile hydrogen, and consists in the fact that the corresponding chlorine, dichloro - or bistrichlorphosphazo compound of the general formula

, /

R-C-N P C1

II

C-N PCU

or rj

C-N PCU

where R, Ri and X have the outlined values,

D-C1 or phenoxy group is treated with phenol, thiophenol, oxime or amine in the presence of an organic base in an organic solvent medium, preferably followed by boiling the reaction mixture and isolation of the target product by known methods. The process can be carried out with sodium phenolate or thiophenolate, and in the case of reaction with an amine, its excess can be used.

Example 1. A 0.03 or 0.06 g-mole of phenol and, respectively, 0.03 or 0.06 g-mole of trinethylamine in 50 ml of anhydrous benzene are placed in a 0.2-liter roundal flask with a capacity of 0.2 l.

With constant unmixed and cooling with ice water, a solution of 0.3 g-mol trhlorfoephaso-K-p-chlorophenylsulfonnliniminobenzoyl is added continuously. The reaction mixture was a knit of 30-40 ppm and left to stand at 20 ° C for 3-4 hours. The liberated triethylamine hydrochloride salt is filtered off. The benzene is distilled off in vacuo. In the residue, the corresponding aroxindichloro- or diaroxychlorophosphazo-; - /; - chlo1) fi1i1sul (|) (; nilimniobenzoyl P, in the form of a ryeToii liquid, which is a) och1; n), is repeated by the use of a nrososa / kdenneum from a benzene solution of non-trolley. h efnro.m.

Dimension 2. In a round-bottomed flask with a capacity of 0.2 l, supplying IlI10 with a reflux condenser, having a nominal volume of 0.03 nly 0.06 g-mol of sodium phenol, 50 ml of anhydrous solvent and standing HOMCiiHujaHHH and cooling the ice Noah water. A solution of 0.03: -.) L () t) iichlorophosphazo - - chlorofeshkesulfonyliminobenzoyl.

The reaction mixture is boiled for an hour and left to stand for 3-4 hours at 20 ° C. Br-1 divided chl) |) true and sodium are filtered off. The solvent is evaporated in vacuo. I ociaTke noluchlu corresponding (1) ariksidih.yurili diarox g; ki) 1) osp; i) -K - /; - chlorine (| kileyulphonyl. Minobenzoyl in the form of thick H11D1i) ci. Cleaning, as in example 1.

 E and r 3. 3. In a circle; 1 donuyu Ko; i6y with a capacity of 0.2 l. Put 0.03 or 0.06 g-mole amnna and COOTDCTCTBCIHIO 0.03 or 0.06 g-mole tr 1 ethylamine in 30 ml of benzene.

When the mixture is stirred unnaturated with ice water, a solution of 0.03 ml of 0.06 g-mol or diaroxychloro-yln-aroxy-IH-chlorophospho-N- / J chlorophenylsulfonyl-1-Ge1H; .oil in 30 ml of beizol. 1- part c: .iecb boiled 30-40M1SH n left to stand for 6 hours nr. Succinated; 1st triethylamine is aspirated. The benzene is distilled off in vacuo.

The residue is phenoxydiamino- or diphenoxy-aiyl endophosphazo - N- /; - Chlorine sulfonylnolbepzonone, a viscous liquid that is purified by repeated use of the eos / kdenneum from a benzene solution of petrols and ether.

EXAMPLE 4. A round bottom flask with a capacity of 0.2 liters is placed in a 0.06 or 0.12 g-mol a PP-Ia bottle in 30 ml of benzene.

With constant displacement and cooling with ice-water, an 11p1 solution was mixed with an unbroken solution of 0.03 or 0.06 gm-mol, corresponding to diaroxychloro- or hydroxy-chlorophosphazo-X - /; chlorophenylsulfoiylpmioeboisoyl in 30 ml of benzene. The reaction mixture was thrown for 30-40 minutes and left to stand for 6 hours at a time.

eat

-2

In the residue, phenoxydianilidoyl diphenoxyannylmdophosphazochlorofsylsulfonyliminobenzoyl is obtained as a viscous liquid. Cleaning as in nptmepe 3.

Example 5. In a round-bottomed flask with a volume of 0.2 l, 0.03, 0.06, or 0.09 g-mole of oxpma, 0.03, 0.06, or 0.09 g-mole of triztilampa in 50 ml of benzene was placed. With constant stirring and o.cooled ice water, a solution of 0.03 g-mol of trichlorophosphase-α-alcpl (aryl) aminotri chloroacetyl is gradually added. The reaction mixture is boiled for 30-40 minutes and left to stand for 6 hours at 20 ° C. After extraction, the hydrochloric salt of triethylamine is sucked off, the solvent is distilled off in vacuo. Oxnmphosphazo-N-alkyl (aryl) -imorichloroacetyl is obtained in the form of crystals or a viscous liquid. The crystals are recrystallized from methanol, and the liquid is purified by repeated prescription from a benzene solution with a non-tethering refinery.

Example 6. In a 0.2 l round-bottomed flask equipped with a reflux condenser, 0.06 g-mol of tnophenol, 0.06 g-mol of triethylamine in 50 ml of benzene was placed. With constant stirring and cooling with ice water, a solution of 0.02 g-mol bstrichlorphosphazohaloacyl in 20 ml of benzene is gradually added.

The reaction mixture is boiled for 1 hour and left to stand at 20 ° C for 2-3 hours. The triethylamine hydrochloride released is filtered off with suction. The solvent is evaporated in vacuo. The residue, bis- (tritiotriaroksifosfazohalidatsil) - a thick liquid, which is cleaned by repeated re-precipitation from the benzene solution with petroleum ether.

Example 7. In a 0.2 L round bottom flask equipped with a reflux condenser, 0.06 gm-mol of sodium thiophenol and 50 ml of benzene was placed. With constant stirring and cooling with ice water, a solution of 0.01 g-mol of bis-trix; 10rphosphazohalo- acyl is gradually added. The reaction mixture was thrown for 1 hour and left to stand at 20 ° for 2-3 hours.

The sodium chloride that is precipitated is filtered off. The solvent is evaporated under vacuum to give bis-tritnotriaroxyphosphazohaloacyl, a thick liquid, which is purified by multiple precipitation of petroleum ether m from a benzene solution.

Example 8. In a 0.2 L round-bottom flask, fitted with a reciprocal of a refrigerator, put 203 g-mol of thiophenol, 0.03 g-mol of triethnlamp in 50 ml of benzene. With a constant blend and cooling with ice water, a solution of 0.0) g mol of trichlorophosphazotrichloroethyl in 20 ml of benzene is gradually added.

The reaction mixture is boiled for 4-0 minutes and left to stand for 3 hours at 20 ° C.

The triethylamine hydrochloride released is filtered off with suction. The benzene is distilled off in vacuo. In the residue, tritothiophenoxytrichloroacetyl is obtained as a thick liquid, which is purified by repeated reprecipitation of the benzene solution with petroleum ether. Yield 86%.

Paydeno,%: C1 21.16; N 2.59; S 18.43.

CanHi.CbNOPSs.

Calculated,%: C 20.60; N 2.70; S 18.60.

.- Taxes are obtained from phosphate compounds listed in Table. -four.

Table 3

Table 4

 Thick liquids. Found,%: S 15.78; 15.51. Calculated 96: S 15.40

Subject invention

Claims (3)

1. A process for the preparation of derivatives of phosphazo compounds of the general formula / R - C - B II (AOZ or R / C-N: z.P (A03 II o e R is alkyl, phenyl, substituted alkyl or phenyl; X - oxygen, alkylenimino group or p-chlorophenylsulfonylmino; And - phenoxy-, phenylmercapto- or O-oxime group; B and C are chlorine, A or amido; RI - alkylene or halogen-substituted alkylene; AI is a phenylmercapto group. characterized in that the corresponding chloro, dichloro, or bis trichlorophosphazo compound of the general formula 25 ./ R-C-N: P C1 II R. / or C-N PC1, 35 where R, RI and X have the above values, D-C1 or fenoxaprop, process phenol, thiophenol, oxime or amine in the presence of an organic base in the medium organic solvent followed by the selection of the target product known tricks. 2. A method according to claim 1, characterized in that the process is carried out with phenol or thiophenol on three . 3. Method according to paragraphs. 1 and 2, characterized in that the process is carried out with an excess of amine.