SU1331860A1 - Method of producing 1-chloro-1-phenylethane - Google Patents

Abstract

The invention relates to halogen-retarding hydrocarbons, in particular to 1-chloro-1-phenylethane (CPE), which. used as a semi-product in the ion exchange resins and high molecular weight substances. In order to increase the yield, the CPE process is carried out under certain conditions in the presence of another catalyst (QD). The preparation of HFE is carried out in ether, nitrile or lower aliphatic chlorohydrocarbon at (-70) - - (- 15) C in the presence of the CT-complex. CuCl with triphenylphosphine, and HC1 in an amount of 2–5 mol per 1 mol of styrene is preliminarily passed through a solution of styrene in an organic solvent. The yield of HFE rises to 98-99%. CO 00 00 Od

Description

The invention relates to methods for producing 1-chloro-1-phenylethane (HFE), used as an intermediate in the manufacture of ion exchange resins and high molecular weight substances.

The aim of the invention is to increase the yield of the target product.

The catalyst used is a complex of monovalent copper and copper with triphenylphosphine of the formula Cu (CgHj.). Jp C1 The reaction is carried out in ether, nitrile, or lower aliphatic chlorohydrochloride at 15, hydrogen chloride in an amount of 2-5 mol per 1 mol, styrene is passed through a solution of styrene in the appropriate solvent before introduction to the analyzer.

Triphenylphosphine complex of monovalent copper chloride was not previously used as a hydrochlorination catalyst. Attempts were made to apply it as a catalyst for the carbonylation of toluene and xylene, which proved to be unsuccessful.

The implementation parameters of the method are necessary and sufficient for achieving optimum results.

, Conducting the process at temperatures above -15 ° C is impractical because the yield of CPE falls (Example 9). The use of temperatures below -70 ° C is possible: for example, at -90 ° C, identical results are obtained, but with additional energy costs for creating a lower temperature, which does not improve the process performance.

The process with a preliminary transmission of less than 2 mol of hydrogen chloride per 1 mol of styrene is impractical because the yield of the target product decreases (Example 10). Preliminary transmission of more than 5 mol of HC1 to a mol of styrene does not lead to an increase in the yield of CPE and, therefore, also impractical.

In the course of the process, it is necessary to simultaneously use the entire set of techniques — the catalyst used, the solvents, and the preliminary passing of hydrogen chloride. The elimination of any of these techniques leads to a sharp drop out of HFE (examples 11-13). Use by nearest 40 45

thirty

50

f55

five

Our analogue of the proposed catalyst, monovalent copper chloride, also does not give the desired result (Example 14).

The catalyst was prepared as follows.

5.92 g of triphenylphosphine is dissolved in 40 ml of chloroform and 0.56 g of anhydrous monovalent copper chloride is added. The resulting suspension is stirred for 2 days with a magnetic stirrer at 200 ° C, then the solid residue is filtered on a Buchner funnel and recrystallized twice from diethyl ether. Obtain 4.6 g of triphenylphosphine complex of monovalent copper chloride, yield 92%, so pl. 167 С (according to literary data 166 С) ,. In the UV spectrum, bands at 232 and 262 nm are observed, coinciding with those given for the complex in the literature.

Calculated,%: C 7.18,

Cj H ClCuP

Found,%: C 7.29 ..

Example 1. 10.4 g (0.1 mol) of styrene is mixed with 10 ml of diethyl ether, cooled to -50 Siv for 30 min. 0.27 mol of HCl is passed through (molar ratio HCl to styrene is 2: 7). Then, without discontinuing hydrogen chloride, a catalytic complex is introduced: 10 ml of ethereal solution g of monovalent copper triphenylphosphine complex of copper containing 0.1 g (1.2-10: mol) of the complex. Within 30 minutes, another 0.3 mol of HC1 is passed through. The unreacted HC1 is condensed into a liquid nitrogen-cooled trap and used again. After cessation of the flow of HC1, the reaction mass is heated to room temperature and the solvent is distilled off under vacuum first, then HPE. Obtain 13.2 g (yield 94%) of HPE, BP. 68-70 ° / / 13.5 mm Hg The spectrum of the PNR is identical to the spectrum of an independently synthesized standard. There are no bands of polymers or styrene oligomers in the PMR spectrum. The residue containing the catalytic complex that remains after distillation is used, along with a fresh catalyst, in further experiments.

Example 2. The process is carried out as in example 1, but at -70 ° C and the molar ratio of previously passed HC1 to styrene is 2: 1. Reaction time 45 min. Output HFE according to GLC

0

0

five

31331860

and PMR 100%, after distillation, the isolated complex does not completely dissolve and is partially suspended. The reaction time is 2 h, (. HFE yield according to GLC and HMR 55%, no by-products were detected.

Example 13. The process is carried out as in Example 1, but without first passing HCl through a solution of 10 styrene. Catalytic solution

intense turbidity of the solution due to polymerization of styrene. Output HFE

HFE with a yield of 98%.

Example 3. The process is carried out as in example 1, but acetonitrile is used as the solvent. Reaction time 15 min. The yield of HFE according to GLC and PMR 100%, after distillation, obtained 13.9 g of HFE, which corresponds to a yield of 99%.

Example 4. The process is carried out as the complex is introduced immediately after in example 1, but as HC1 bubbling as a solvent. Inters are observed using methylene chloride and the process is carried out at - .. The yield of HFE after distillation is 97% .. 15 according to the PMR of 66%.

Example 5. The process is carried out as Example 14. The process is carried out in example 1, but as a solvent, as in example 1, but 1,2-dichloroethane, tem-, is used instead of the catalyst. Such a reaction complex is used at –15 ° С; the molar weight amount of chloride is the same as the ratio previously missed –20 valence copper. Pass for HC1 and styrene 5: 1. The reaction time of 2 h 1 mol HC1 does not lead to the formation of measurable amounts of CPE.

Claims (1)

Thus, the proposed method makes it possible to increase the yield of the target 25 product in comparison with the known one by 2–9% (or by 8–10%, taking into account the loss in allocation). An additional advantage of the process is the absence of by-products, which is charged as in Example 3, but propionitrile is used as the growing environment and requiring solvent. . recycling. Due to the possibility of a 100% yield, according to GLC and PMR, after the torus use of catalytic distillation, 99% of the complex, solvents and non-Example 8. The process is carried out, the HC1 reacted method is as in Example 1, but as a plant no waste scavenger USE methylchlorphenol. The yield after distillation is 96%, the formula of the invention Example 9. The process is conducted. as in Example 1, but at 0 ° C. Yield, Method for producing 1-chloro-1-phenyl-HFE according to PMR and GLC 92%. According to 40 ethane, by reacting with chlorine PMR, styrene oligomers are present in the reaction products. Example 10. The process is conducted as in example 1, but previously 90 min, yield after distillation 96%. Example 6. The process is carried out as in Example 1 but dibutyl ether is used as the solvent. The reaction temperature is -40 ° C, the reaction time is 45 min, the yield after distillation is 96%. Example 7. The process is conducted. hydrogen in an organic solvent in the presence of a catalyst, characterized in that, in order to increase the yield of the target only O 1 mol HC1 is passed. Corresponding g of product as catalyst wearing pre-skipped HC1 to styrene 1: 1. The output of HFE according to PMR data is 91%. Styrene oligomers are present in the reaction products. Example 11. The process is carried out as in Example 1, but instead of a solution of the catalytic complex, pure diethyl ether is introduced. The subsequent transmission for 3 h of 1 mol HC1 does not lead to the formation of measurable amounts of CPE. PRI and m. 12. 12. The process is carried out as in example 1, but hexane is used as the solvent. Catalys p and is partially in suspension. The reaction time is 2 h, the yield of HFE according to GLC and PMR is 55%, no by-products were detected. Example 13. The process is carried out as in Example 1, but without first passing HCl through a solution of styrene. Catalytic solution intense turbidity of the solution due to polymerization of styrene. Output HFE The complex is introduced immediately after the start of the HCl bubbling. 66% of the PID is observed.  The method of producing 1-chloro-1-phenyl-ethane by reacting with chlorine hydrogen in an organic solvent in the presence of a catalyst, characterized in that, in order to increase the yield of the target use of a complex of monovalent copper chloride with triphenylphosphine of the formula Cu (C, H5), P, C1, and, as a solvent, ether, nitrile or lower aliphatic chlorohydrocarbon, the process is carried out at (-70) ° С, and before catalyst introduction through a solution of styrene in organic the solvent is pre-passed with hydrogen chloride in the amount of 2-5 mol per 1 mol of styrene.