RU1810350C - Method of arylhydrodichlorophosphonium tetrachloroaluminates synthesis - Google Patents

Abstract

Method for preparing aryl hydrodichlorophosphonium tetrachloroaluminates. Usage: as intermediates for the preparation of arylphosphonous acids and their derivatives. Summary of the Invention: The product tet.rahloralyuminat fenilgidrodihLOrfOSfONIYa p-ly SbN5R (H) S121A1S1 4D, BF SbNbA1S1bR, yield 96%, tetrachloroaluminate etilfenilgidrodihlorfbsfoni f-ly S2N5SbN4R (H) S121A1S | 4D, BFSbNyuA1S16R, 100% yield, cyclohexane tetrachloroaluminate silfenilgidrodihlorfosfoni uSbN11SbN4R (N) S121A S14G, BFS12N1bA1S1bR, 95% yield, tetrachloroaluminate toll hydrodichlorophosphonium SNsSbN4R (H) C12 A1s14G, BFS7N8A1S1b1O. Reagent 1:. Reagent 2: ArH, where Ar is phenyl or alkyl phenyl. Reagent 3:. Reaction conditions: at an equimolar ratio of reactants at 10-50 ° C. 1 tab

Description

The invention relates to organic chemistry and is devoted to the production of tetrachloroaluminates of aryl hydrodichlorophosphonium of the formula

GAG. 4-.C1

CHAH

n

 C1

AKV

(ABOUT

where Ar is phenyl or alkyl phenyl of interest as base materials for the preparation of arylphosphonous acids and their derivatives,

The complexes of aryldichlorophosphines and aluminum chloride (II) are currently known to be used for the preparation of arylphosphonates and their derivatives. These complexes are synthesized by prolonged boiling (80-100 ° С) of a mixture of phosphorus trichloride, aromatic hydrocarbon and aluminum chloride at a molar ratio of (3-5): 1: (1-1.2)

Coy rar (Oh

zoophobia s. yesi ri

PC1z + ArH +

fvPC A. feAr (ct) P-Pfri), An AC s. The disadvantages of this method are the need to use a large excess of toxic, volatile and corrosive phosphorus trichloride, low yields and, in some cases, the complete impossibility of producing complexes (I) based on alkylbenzenes.

Complexes (I) are still unknown.

To prepare them, a method is proposed which consists in reacting equimolar amounts of phosphorus trichloride, aromatic hydrocarbon and aluminum chloride at a temperature in the range of 10-50 ° C.

00

about

with

O1

about

H I

A1S1CH1

-J

In connection with the stated temperature range for carrying out the reaction of 10-50 ° C, it should be noted that although an increase in temperature accelerates the process, a complex mixture of products is obtained above 50 ° C. The value of the lower boundary of the claimed temperature range is due to a sharp slowdown in the reaction rate below 10 ° C due to an increase in the viscosity of the medium and an increase in the content of the products of oxidation and hydrolysis of complex (I) in the reaction mass. The reaction can be carried out both without a solvent and in an inert solvent, for example of the same or substantially less reactive aromatic hydrocarbon. To protect the product from oxidation and hydrolysis, it is advisable to carry out the reaction in an inert gas atmosphere. . :.

Complexes (I) are light yellow thick liquids that are not distillable and do not crystallize, soluble in polar aprotic solvents, vigorously oxidized and hydrolyzed in air. The preparation of complexes (I) and reactions that unambiguously confirm their structure and the possibility of preparative use are described in the examples.

Example 1. Preparation of phenylhydrodichlorophosphonium tetrachloroaluminate (I,), To a mixture of 1.0 mol (133.5 g) of granular anhydrous aluminum chloride and 1 mol (137.5 g) of freshly distilled phosphorus trichloride 1 mol (78 g) of absolute benzene and the reaction mixture are stirred under nitrogen at 18-20 ° C for 6 hours until the aluminum chloride is completely dissolved. After removal of volatile impurities at 30-50 ° C / 20-40 mmHg. 339.0 g (96%) of complex (i,) are obtained in the form of a light yellow oil with a strong odor of phosphine. Other complexes (I) are synthesized in a similar manner. The conditions of interaction, the yields of the complexes, their spectral and analytical characteristics are given in the table.

PRI me R 2. Obtaining phenyldichlorophosphine from complex (I,).

To a solution of 0.1 mol of complex (I,) in 20 ml of benzene was added dropwise with stirring and cooling with cold water 16 phosphorus oxychloride, the mixture was stirred until the evolution of

hydrogen chloride, the precipitate was filtered off, the filtrate was evaporated, and distillation of the residue gave 16.5. g (93%) of phenyldichlorphosphine, b.p. 120 ° C / 30 mmHg L r and me R 3. Obtaining cyclohexylpheg

nylphosphonous acid from the complex (I, Ar c SBNcSbN5.

A solution of 0.1 mol of the complex (I, Ag c SbNcSbN5), a mixture of o, m, n isomers) in 27 ml of benzene is poured with stirring into 100 ml of water, the organic layer is separated, washed with water, extracted with an aqueous solution of NaOH, the extract is filtered, the filtrate is acidified, the precipitate is filtered off, dried in

vacuum desiccator and get 9.9 g of a mixture of o, m, n isomers of cyclohexylphenylphosphonic acid, so pl. 162-163 ° C, the content of the basic substance according to potentiometric titration of 94%.

31P NMR spectrum: 5p 19.61 ppm relative to 85% NzROph JPH 552 Hz. . Found,%: C 64.50; H, 7.90. Ci2Hi702P. Calculated,%: C 64.25; H, 7.58.

f o r m ula invented and

The method of obtaining tetrachloroaluminates arylhydrodichlorophosphonium General formula

40

A1C1,

where Ar is phenyl or alkyl phenyl,

that phosphorus trichloride is reacted with an aromatic hydrocarbon and aluminum chloride at an aquimolar ratio of reactants and a temperature of 10-50 ° C;

Reaction parameters for the preparation of complexes (I), spectral and analytical properties of the latter