SU787412A1 - Method of preparing cyclic arylchlorophosphites - Google Patents

Description

The invention relates to the chemistry of organophosphorus compounds, namely, to a new method of producing cyclic arylclorphosphites of the general formula .1 Hz R and R are hydrogen, alkyl, halo, oC-methylcyclohexyl or o (α, methylbenzyl; X is metizen, sulfur, 2- trichlo aegilidene or chlorobenzate, which can be used to synthesize the corresponding cyclic phosphorous acid esters, which are effective stabilizers of polymeric materials. A known method for producing cyclic aryl chlorophosphite with a five-membered pyrocatechin-chlorophosphite - by reacting pyrocatechin with trichloride phosphorus in the presence of catalytic amounts of heterocyclic bases, for example, pyridine, at 60-80 0. The target product is isolated in 91-95% l yield. The closest to the technical essence and achievable results of the invention is the method of obtaining cyclic aryl chlorophosphite of the formula (Yazy), which includes the production of sodium bisphenol and the interaction of finely dispersed sodium metal powder with bisphenol-2,2-methylene bis- (4-methyl37-6-tert.-butylphenol) in toluene ol and the interaction of sodium bisphenolate with phosphorus trichloride in benzene B medium for 60 hours with the formation of an eight-membered phosphorous acid chloride of formula 2. The disadvantage of this method is that it is laborious, as it is a two-stage process, it takes a long time to react . The purpose of the invention is to simplify the process. This goal is achieved by the method of obtaining cyclic aryl chlorophosphites of the formula I, which consists in the fact that the compound of the general formula) HON Ri-f Sx-XVi i CgKg where R, R and X have the above meanings, is reacted with phosphorus trichloride at a molar ratio of reagents 1: 1.05-1.3 in the environment of an organic solvent at 80-175 ° C. The proposed method makes it possible to simplify the process of obtaining cyclic ar | Ilchlorophosphites by using a more affordable starting bisphenol derivative of the formula C1 and carrying out the process in one stage, as well as reducing the time of the process to 3-5 hours. In addition, the use of excess trichloride from the stoichiometric ratio phosphorus allows you to increase the yield of the target product to 98-100%. Chlorotoluo, chlorobenzene, dichlorobenzene, isopropylbenzene or xylene are used as organic p. Solution in an amount of 2-8-8% of the weight of bisphenol, preferably 40-5O%. The temperature of the reaction mixture during the synthesis process is regulated in such a way that within 45-60 minutes from the start of the synthesis it reaches 75-8 ° C, and then the temperature is increased at a rate of 15 ° C / h to the temperature of solvent pegmirovaniya. In some cases, the input of trichloric phosphorus is rationally carried out already at 75-80. The final temperature of the reaction mixture, depending on the starting line of 2,2-bisphenol and the solvent, reaches 140-1 / 5 ° C. To fully complete the process, the reaction mixture is maintained at the specified elevated temperature for at least 60 minutes. To trap phosphorus trichloride carried away with abgas hydrogen chloride, a trap having a temperature of at least -15 ° C is connected to the system. Synthesized cyclic chlorophosphites are presented in the table. The structure of the synthesized compounds was proved by IR spectroscopy, elemental analysis, determination of molecular weights, as well as with the help of a number of chemical reactions. In the infrared Juppets of cyclic chlorine. hydrides there are no absorption bands of the 3350-3640 scG region corresponding to the stretching vibrations of the OH groups of isphenols, which on the one hand indicates the participation of both hydroxyl groups in the phosphorylation reaction, and the other characterizes the purity of the product, there is an absorption band in the region of 450 cm, it is typical communication R-Ce. The found values of elemental analysis and determination of molecular weights correspond to the calculated values (see table). When treating cyclic acid chlorides with some reagents (alcohols, phenols), the corresponding cyclic ethers were obtained, the characteristics of which coincided with the literature data. Example. Preparation of 2,2-methylenebis (4-4tetil-6-tert.-butypphenip) G chlorophosphite (compound 1). In a reactor equipped with a reflux condenser connected to a trap cooled by a mixture of dry ice with acetone and an acid vapor absorption system, a stirrer, an addition funnel, a thermometer, 2.2.2-methylenebis (4-methyl-b-tert.-butylphenol; a) 45 ml of a mixture of ortho-and para-chlorotoluenes and 45.4-g (0.33 g-mol) of phosphorus trichloride are poured. With stirring, the temperature of the reaction mixture is raised to 80 ° C in 1 hour and then at a rate of 25–30 ° C / h to. They are kept for 1 h with a weak reflux current. 4.2 g of phosphorus trichloride are taken from the trap and used in subsequent synthesis operations, and 79.6 g of 27.5% of hydrochloric acid are extracted in the system for absorption and gases. There is phosphorus in acid. 57 The reaction mass is cooled with simultaneous nitrogen gas generation to 100 and 100-120 (α-heptane is introduced into it with stirring. When it reaches 26, crystallization occurs. The crystals are filtered, washed with 50 ml of heptane, dried to a constant weight, and chlorophosphite is obtained with a yield of 103.2 g (85% with t. pl. 160-162C). Found%: C 68.01; H 7.68; CE 8.75; P 7.53. Oz. R. Calculated%: C 68.14; H 7.42; ce 8.77; P 7.66. The mother liquor is stripped in a rotary evaporator to a bath temperature of 175 ° C / 5 mm Hg, 18 g of melt are obtained, content,%: C &8.6; P - 7.8. Melting point, after recrystallization - 160-161 t. Total yield: 98.3%. Example 2. Preparation of 2,2-thio bis (4,6-dichlorophenyl) chlorine (|) osphite (compound 2). Suspension 71.3 g (0.2 g -Mol) 2,2-thiobis (4,6-dichlorophenol) and 28.8 g (0.21 g-mol) of phosphorus trichloride in 50 ml of paradichlorobenzene are heated, maintained and cooled under the conditions of example 1, 8O ml of tetrachloride is added carbon, cool to filter the precipitated crystals, wash with 10 ml of tetrachloride) carbon, dry under the conditions of example 1 to a constant weight and obtain 75.6 g (9O% 2,2-thiobis (4,6-aichlorophenyl)) of slorphhosphite — white crystalline powder with t. pl. . Found,%: C 34.63; H 1.11; Sat 42.99j p 7.60, 57.52. . Calculated,%: C 34.24; H Oh, 95; All 42.21; R 7.37; S7,60. Example 3. Getting $, bis (4-tert.-butylphenyl) klorfsufiga (compound 3). ZO ml of chlorobenzene is poured into 66 g of (0.2) 2,2-tHo6ac (4-tert.-butylphenol), heated to and added dropwise with 27.5 g (0.2 g-mol) of trach phosphorous for 1 hour. By the end of the dropping, the temperature of the reaction mixture is raised to 12 ° C. After 1 hour the temperature is raised to 14 ° C and under these conditions the reaction is completed within 1 hour. The solvent is distilled off and 66.8 (84.5) lightly colored straw color is obtained. abrasive to white powder with m. pl. 113 ° C. Found,%: C 6O, 00; H 6.37; Sat 8.71; P 7.31; S8,51. Oj, P5. Calculated,%: C 60.84; H 6.08; CB 8.99; R 7.86; 98.11. Example 4. Preparation of 2,2 -2-trichloroethyl-enbis (4-tert.-butylphenyl) chlorophosphite (compound 4). A suspension of 86 g (0.2 g- vlo) 2.2 -2-trichloroethylidenebis- (4-tert.-butylphenol) and 28.88 g (0.21 g-mol) of phosphorus trichloride in 40 ml of isopropylbenzene The mixture is heated as in Example 1 to 160 ° C, maintained at this temperature for 1 hour, and then the solvent is distilled off. Receive with exit. 98% white crystalline powder with mp, pl. Found,%: C 53.51; H 6.20; SS 28.40; P 6.13. 2 d 5 402Р В Calculated,%: C 53.44; H 5.06; Se28.74; R 6.27. Example 5. Preparation of 2,2-ortho-t-chlorobenzylidene-bis (4-tert.-butylphenyl) -chlorophosphite (compound 5). A suspension of 84.5 g (0.2 g-mol) 2,2-ortho-chlorobenzylidene-bis- (4-tert.-butylphenol) and 28.88 g (0.21 g-mol) of phosphorus trichloride in 5U ml of isopropyl benzene heated according to example 1 to 160 ° C, maintained at this temperature for 1 h and receive 95 g (97.5%) of a white crystalline powder with so pl. 163С, Found,%: С 66.7О; H 5.65; St 14.23 P 6.68. ,, p. Calculated,%: C, 66.53; H 5.95; Cei4.58; R 6.57. Example 6. Getting 2,2-2-. -trichLorethylidene-bis (4-methyl-6-chlorophenyl) -chlorophosphite (compound 6). . 41.46 g (OD g-mol) 2-trichloroethylidenebis (4-methyl-6-chlorophenol) is placed in a flask of a rotary evaporator, a solution of 16.5 g (0.13 g-mol phosphorus trichloride in 8 ml of an ortho- and parachlorotoluene. A rotor evaporator, connected through a} malt catcher with a receiver and a trap cooled with brine until connected to a water-jet pump (vacuum 740-745 mm Hg). During rotation of the cob suspension is heated 45 minutes to 80 C, then for 2 h The bath temperature is raised to 170 ° C to complete the reaction. A vacuum of 4–5 mm Hg is created in the system and held for 15 minutes at a temp. Treatment of the bath: 5 g of solvent are removed from the receiver and the trap, and a light yellow melt, 48 g (100% yield) is evaporated in the evaporator flask.

Found,%: C 39.47; H 2, O1; Се44, Г; P 6.13.

ClbH CGfeO P.

Calculated,%: C 40, O8; H 2.29; t ce 44.46; P 6.47,

Example 7. Preparation of 2,2-methylenebis {4-methyl-6-o-methyl-cyclohexylphenyl) chlorophosphite (compound 7)

A mixture of 21 g (0.05 g-mol) of 2,2-methylenebis (4-methyl-6-ob-methyl-cyclohexylphenol) and 11 ml of isopropylbenzene is heated to 80 ° C. and added dropwise. to a suspension of 8.93 g (0.065 g-mol) of phosphorus trichloride. After the dropping, the temperature of the reaction mixture is raised to 25-OOC for each hour, brought up and maintained at this temperature for 2.5 hours. The solvent is distilled off under vacuum, 13 ml of Heptane are poured over the residue, the precipitated crystals are filtered and recrystallized from octane. 19.4 g (8O%) of chlorophosphite are obtained with a Tg of 1.143-145 C,

Found,%: C 71.30; H 7.43; All 7.11; R 6, OO.

 .

. Calculated,%: C 71.67; H 7.82; . every 7.31; R 6.38.

Example 8. Preparation of 2,2-thio-bis (4-methyl-6-tert-butylphenyl) chlorophosphite.

A mixture of 89.6 g (0.25 g-mol), 2,2-thiobis (4-methyl-6-tert.-bougilf8Nola), 36.1 g (0.263 g-mol) of three phosphorus chloride and 40 ml of dry O- xylene is heated under conditions of example 1 to 166 ° C, incubated for 1.5 hours, cooled under a stream of nitrogen to 100 ° C, 50 ml of heptane are poured, cooled to room temperature, the precipitate is filtered off, washed with 50-70 ml of cooled heptane, dried, obtained. 90 g (85%) of white crystalline powder with Tj 16817О С; Of. An additional 11 g of the acid chloride is recovered from the mother liquor after evaporation of the solvents and crystallization from heptane. Total yield 95.2%. .

Found,%: C 62.4; H 6.71; Cr 8.36; P 7.3.3; S 7.52.

 ceops.

without,%: C 62.3; H 6.61; every 8.37; P 7.32; 97.56.

Example 9. Preparation of 2,2-thiobis (4-methyl-6-c1-methylbenzylphenyl) chlorophosphite.

A mixture of 45.26 g (0.1 gm) 2.2-thiobis (4-methyl-6-s.-methylbenzylphenol), 14.45 g (0.105 g-mol) of phosphorus trichloride in 25 ml of xylene is heated - under the conditions of example 1, 165 ° C, incubated for 1.5 hours, then proceed as indicated in example 8. Obtain 47 g (90.5%) of the acid chloride powder (Tc4b "C).

Found: C 57.2; H 6.62; Sat 7.8; P 6.80; S7.02.

.S- N. ceqps.

Claims (2)

. Calculated,%: C 57.1; H 6.6; Ce 7,8} P 6,82; $ 7, OZ. . 117 The invention The method of obtaining cyclic aryl chlorophosphites of the general formula </ BR> where R; | and R is hydrogen, alkyl C-C, halo, oJ-megylcyclohexyl or oi-methylbenzyl; ) (. - methylene, sulfur, 2-grichloro-hegilidene, or chlorobenzylidene; by reacting a bisphenol derivative with phosphorus trichloride in an organic solvent medium, about 1 ml and 2, because, in order to simplify the process, a bisphenol derivative is used the compound of the general formula ONOH in R, and R2 and X are as defined above, and the process is carried out with a molar ratio of bisphenol and phosphorus sinach equal to 1: 1.05-1.3, and 80-1 ... Sources of Information into account during the examination 1. USSR author's certificate No. 250139, class C 07 F 9 / 15, 1967. 2. US patent hfe 3297.631, cl. 260-45. 95, published in 1967 (prototype),.