SU1067005A1 - Process for preparing j-ketophosphineoxides - Google Patents

Abstract

1. METHOD OF OBTAINING TP1ETHYL Y-KETOPHOSPHINOXES OF THE GENERAL ABOUT O AND J PCiH CiHClB tvI M H, where RJ- or,}) R3-CHj or CgHu or R and R together (S), implying that interaction with an equimolar amount of tertiary y-amino ketone hydrochloride of the general formula i HCQ, l where and have the indicated values; R. or CeHj or (CHi) 5, at 100-150 ° C. C. 2. The method according to claim 1, which consists in the fact that the process will be conducted in an organic solvent in an inert atmosphere.

Description

ate

This invention relates to the chemistry of phosphorus-organic compounds, namely, to a process for the preparation of new tertiary If-ketone phosphine oxides of the general formula

ABOUT

-

(I) in

where R - C is NOT or n-CH.

R

 n

b 5 1 - CHS or HS HS or

R and K together - (SC, which can be used as extractants, complexing agents and surfactants.

A known method of producing a yoke of phosphine oxides by reacting hydroxyalkyl ketone with dioorganochlorine phosphine oxide at -15 ° C in an atmosphere of carbon dioxide SP.

The disadvantage of this method is the low availability of chlorides of organophosphinic acids.

There is also known a method for producing tertiary y-ketophosphine oxides, which implies that diorganophosphinic acid is reacted with cd, jS-unsaturated ketone at 50-60 ° C in the presence of a basic catalyst CH.

The disadvantage of this method is the low availability of the starting unsaturated ketones with an unsubstituted vinyl group due to their tendency to polymerization, which in some cases also accompanies the preparation of J -keto phosphine oxides.

Tertiary J-ketophosphine oxides of the general formula (T) are new and the method for their preparation is not described in the literature.

The aim of the invention is to develop an accessible process for the preparation of compounds of general formula (I).

The goal is achieved according to the method for producing tertiary j-keto-phosphine oxides of general formula (G), which consists in reacting diorganophosphinic acid with an equimolar amount of tertiary y-amino ketone hydrochloride of the general formula

her . B $ NCH2.CH where H, R- CH ,, or nd. And R together - (CHg) y (- CHj and Liis Ns or R -CCHj), with lOO-lSO C.

The process is preferably carried out in an organic solvent medium in an inert atmosphere. In this case, it is likely that the tertiary a1C Mnoketone hydrochloride decomposes with the formation of vinyl ketone, which at the time of isolation reacts unequivocally with diorganophosphinic acid to form the target γ-keto phosphine oxide.

The proposed method makes it possible to use available starting materials, in particular, hydrochlorides of 5 tertiary y-amino ketones, which are easily obtained by the reaction of formaldehyde, secondary amine hydrochloride and various aliphatic ketones.

0 The secondary amine hydrochloride formed during the reaction is easily separated from the lf-keto phosphine oxide and can be used again to produce tertiary hydrochlorides.

5 y-aminoketones. The output of ketone phosphine oxides 60-90%, purity 95-98%.

Despite the widespread use of Mannich ketone hydrochlorides in organic synthesis, they

Q has not previously been reacted with PHH compounds (in this case with phosphinic acids) in order to obtain Jf -organophosphorophosphorus compounds.

With the interaction of y-aminoketone

With PH compounds, the most likely reaction of the latter is to add a carbonyl group – carbonyl compounds reaction to the carbonyl group, with a PH bond,

 therefore, the preparation of tertiary jf-keto phosphine oxides by the proposed method is not obvious.

Example 1. Getting 2-di. phenylphosphinyl ethylphenyl ketone.

5 A mixture of 10.7 g of 2-dimethylaminoethylphenyl ketone hydrochloride and 10.1 g of diphenylphosphinic acid is heated for 2.5 hours at 140-150 ° C in a nitrogen atmosphere. Then the reaction mass is cooled, treated with 50 ml of benzene and 50 ml of water, the organic layer is separated, washed with a solution of soda and water, dried with calcined sodium sulfate and the product is planted

5 by adding hexane. After drying, 13.4 g (80%) of the product is obtained, Tr, 132-131C.

Found,%: C 75.40; H 5.77; P 9.30.

0С;

Calculated,%: C, 75.44; H 5.73; P 9.26.,

IR spectrum (tablet s, cm): 1685 (); 1595, 1490 (benzene ring); 1440 (); 1180 (Р «0).

With a similar yield, this compound is obtained using 2-diethylamino-ethylphenyl ketone hydrochloride or piperidine ethylphenyl ketone hydrochloride instead of 2-dimethylamino-i ethylphenyl ketone equivalent, in use.

Example 2. Preparation of 2-di5 phenylphosphinyl ethyl methyl ketone.

A mixture of 3.0 g of 2-dimethylaminoethyl methyl ketone hydrochloride, 4.9 g of diphenylphosphonic acid and 20 mp of toluene is heated for 3 hours at 100-1 ° C. Then the reaction mixture is cooled, washed with water, soda solution, again with water and dried with anhydrous sodium sulfate. The solvent is distilled off and the residue is recrystallized from hexane, dried in a vacuum desiccator. 3.3 g are obtained (60% of the product, Tdd 104-105C.

Found,%: C 70.38; I am 6.27; R 11.36.

C, 4 OjP

. You, in number,%: C, 70.58; H 6.29; R 11.37. .

IR spectrum (tablet with KBG, cm) 1710 (); 1590, 1490 (benzene ring); 1440 (P-C); 1185 ().

Example 3. Preparation of 2-diphenylphosphine-methylcyclohexanone.

A mixture of 17.0 g of 2-dimethyl hydrochloride l amine ltsi kl ore KS anone, 17.9 g of diphenylphosphinic acid and -50 MP m-xylene is heated for 4 hours at 130-140 ° C under nitrogen atmosphere, after which the reaction mixture is cooled, washed with water, soda solution and again with water. The organic layer was separated, dried with calcined sodium sulfate, the solvent was distilled off, and the residue was recrystallized from hexane. After drying in a vacuum desiccator, half of 18.5 g (67%) of the product, m.p. 90-91 C.

Found,%: C 72.88; H 6.77; R 9.90.

.

Calculated,%: from 73.06; H 6.78; R 9.92.

IR spectrum (tablet with KBG,): 1715 (); , 1485 (benzene ring): 1440 (); 1195 ().

Example 4. Preparation of 2-diQ hexylphosphinyl ethyl phenyl ketone.

A mixture of 2.2 g of 2-dimethylaminoethylphenyl ketone hydrochloride, 2.2 g of dihexylphosphinic acid and 20 mp of toluene is heated for 5 hours at 100-110 C. Then the reaction mixture is washed

5 with water, soda solution and again with water, the organic layer is dried with anhydrous sodium sulfate. The solvent is distilled off and the residue is kept in a vacuum of 10-15 mm Hg. at 90-100 ° C 0 for an hour. 3.2 g (90%) of the product are obtained.

Found,%: C 71.95; H 10.01; P 8, -71.

. Calculated,%: C, 71.97; H 10.66; 5 8.84.

IR (thin layer, cm): 1695 (); 1585, 1495 (benzene. 0 ring) 1160 ().

The proposed method allows to obtain the target products with a yield of 60-90% and a purity of 95-98% in a simple manner using the readily available starting reagents.

Claims (2)

1. METHOD FOR PRODUCING Tertiary y-KETOPHOSPHINOXIDES of the general formula, R * O0 R ¹ R where R * - C _in H ₅ or n-C ₄ Shch _a ; R ^ft - H, R * is CH ₅ or C _in Well or R ^ and R ⁴ together - (CHa) ^, consisting in the fact that diorganophosphinic acid is reacted with an equimolar amount of tertiary y-aminoketone hydrochloride of the general formula HC & -R ^ NCHjCHR ^ COR ⁵ , where R. ² · and R * have the indicated meanings; R5-CH ₃ or C ^ Hj or d.2- (CH _g ) ₅ , at 100-150 ° C. 2. The method according to π. 1, consisting in the fact that the process is conducted in an organic solvent medium in an inert atmosphere.