The method of obtaining unsaturated chlorohydrocarbons

 

(57) Abstract:

The invention relates to a method for producing unsaturated chlorohydrocarbons. Describes a method that involves dehydrochlorination di - and peliharakan 30-50% aqueous solution of hydroxide of alkali metal in the presence of 0.4-2 wt.% of the catalyst. The catalyst obtained by the interaction of polyethylenepolyamines and their alkyl derivatives with benzyl chloride when a molar ratio of 1 : 1-5. The technical result is to increase the yield of the target product, the reduction in the duration of the process. 1 C.p. f-crystals, 2 tab.

The invention relates to petrochemical synthesis, in particular to a method for producing unsaturated chlorohydrocarbons used to produce polymeric materials for various purposes.

A method of obtaining vinyl chloride by dehydrochlorination dichloroethane at a temperature of 70-75oC aqueous solution (10%) of alkali metal hydroxide in the presence as catalyst of Quaternary ammonium, fofanah compounds such as benzyldimethylamine (Ketamin AB), benzyltriphenylphosphonium and alkylpolyglycoside C18H37(CH2CH2O)is closer to the stated on the totality of symptoms is the way to obtain unsaturated chlorohydrocarbons (chloroethene), including vinyl chloride, by dehydrochlorinating di - and peliharakan aqueous solution of alkali metal hydroxide in the presence of a catalyst, class of Quaternary ammonium salts /2/ (SU 771081, class C 07 C 21/04, 1978).

The dehydrochlorination at the specified method is carried out at a temperature of 30-100oC water 24-30% solution of alkali metal hydroxide at a molar ratio of hydroxide and di - and peliharakan 1-3:1, in the presence of a catalyst is a Quaternary ammonium salt of the formula:

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where R1- CH3or CH2CH2OH, R2- C10-C18alkyl, taken in an amount of 1-10 wt.% in the calculation of the original di - and peliharakan. The yield of the target product is equal to 60-95%, the reaction time is 1-3 hours.

For reasons that impede the achievement of specified following technical result when using the known method, taken as a prototype, is that in the known method a narrow range of used catalysts, not a high yield of the target product and the duration of the process.

Object of the invention is the expansion of the range used in the process of obtaining unsaturated chlorohydrocarbons, catalysts of the class of Quaternary W time process.

This technical result in the implementation of the invention is achieved by the fact that in the proposed method, when receiving unsaturated chlorohydrocarbons by dehydrochlorination di - and peliharakan aqueous solution of alkali metal hydroxide in the presence of a catalyst of the class of Quaternary ammonium salts peculiarity lies in the fact that the dehydrochlorination spend 30-50% solution of alkali metal hydroxide and in the presence of 0.4-2 weight. % in terms of the initial di - and peliharakan catalyst obtained by the interaction of polyethylenepolyamines and their alkyl derivatives with benzyl chloride when a molar ratio of 1:1-5. In addition, the feature of the method lies in the fact that the use of polyethylenepolyamine obtained by vacuum distillation and containing Diethylenetriamine 30-45 wt.%, N-AMINOETHYLPIPERAZINE - 30-65 wt.%, Triethylenetetramine and higher polyamine - 20-35 wt.%.

Most simply to carry out the invention as follows: to a reactor, representing a three-neck flask equipped with a mechanical stirrer, thermometer, reflux condenser, Gasometer, employees and also for removal of the formed gas, upload di - or peliharakan (dichloroethane, 1,3-di the di - and peliharakan : caustic soda to 1: 1.1 to 1.2. The process is conducted at a constant temperature of 40-80oC, depending on the di - and peliharakan, with stirring, for about 1-1,5 hours. The amount of catalyst is 0.4-2% in terms of the initial peliharakan.

The products resulting from dehydrochlorination of peliharakan, isolated by known methods.

The method is illustrated by the following examples.

Example 1. Chloride N-(- benzylamino)-N-benzylpiperazine (1).

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In chetyrehosnuju flask (reactor) equipped with a stirrer, thermometer, reflux condenser and addition funnel, loads of 21.9 g (0.1 mol) N-(-benzylamino)piperazine in 15 ml of distilled water and 12.6 g (0.1 mole) of benzylchloride and stirred at a temperature of 50-60oC for 1 hour, then the temperature was raised up to 80-120oC for 3 hours. Then water is removed by vacuum distillation, the residue is crystallized from acetone and alcohol (1: 0.5 to 1). Received and 31.7 g (92%) of the product ("connection") 1. Compound 1 contains in its composition: N (nitrogen) - 11.7 wt.%, Cl (chlorine) - 9.8 wt.%, C20H283Cl.

Calculated: N - 12,5% (Found 12,3%). Calculated: Cl - 10,27% (Found - 10,4%). The melting point of the connection 1 - 280-282oC.

Example 2. PI is up to 21.9 g (0.2 mole) N-(-benzylamino)piperazine, of 12.6 g (0.1 mole) of benzylchloride in 50 ml of isopropyl alcohol. The reaction mixture is heated at 80-100oC for 6 hours, then cooled to 30-40oC, poured 4 g (0.1 mol) of caustic soda or sodium hydroxide in 20 ml of isopropyl alcohol, stirred for 0.5 hours at a temperature of 50-80oC, the reactor is cooled, the precipitate is filtered off and added to 12.6 g (0.1 mole) of benzylchloride, stirred at a temperature of 90-100oC for 4 hours, then the reactor is cooled, the alcohol is distilled off by distillation. Received or 37.4 g (86%) of compound 2. The melting point is amorphous. Found N - 9,20%, Cl - 7,78%, C27H343Cl. Calculated: N - For 9.64, Cl ~ 8,15.

Example 3. Dichloride, N-(1-benzyl-1-benzylamino)-4-dibenzylpiperazine (3).

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In the conditions of example 1 was charged to the reactor of 43.5 g (0.1 mole) of compound 2 in 50 ml of ethanol, poured 12,6 g benzylchloride, stirred at a temperature of 70-90oC for 4 hours. The end of the reaction is determined by the increase of the chlorine ion in the reaction mixture. The solvent is removed by distillation. Received and 42.7 g (76%) of compound 3. The melting point is amorphous. Found: N - 7,08%, Cl - 12,21%, C34H413Cl2. Calculated: N - 7,47%, Cl - 12,63%.

Example 4. Chloride (1-benzyl-1-dibenzylamino)-4-benserazide in 50 ml of ethanol, of 25.2 g (0.2 mole) of benzylchloride and stirred at a temperature of 80-120oC for 6 hours. Then add 8 g (0.2 mole) sodium hydroxide in 25 ml of ethanol. The mixture is stirred at a temperature of 100-110oC for 2 hours. The reactor is cooled, the precipitated NaCl is filtered off, the filtrate is an alcoholic solution of intermediate 1-dibenzylamino-4-benzylpiperazine loaded into the synthesis reactor, type of 12.6 g (0.1 mole) of benzylchloride and stirred at a temperature of 60-100oC for 4 hours, after which the reactor is cooled, the alcohols are removed by distillation. Received of 44.1 g (84%) of compound 4, the melting point is amorphous. Found: N - 7,45%, Cl - 6,38%, C34H403Cl.

Calculated: N - 7,99%, Cl To 6.75%.

Example 5. Dichloride (1-benzyl-1-dibenzylamino)-4-dibenzylpiperazine (5).

The reaction scheme:

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Charged to the reactor 52,5 g (0.1 mol) of compound 44 in 100 ml of isopropyl alcohol and 12.6 g of benzylchloride and stirred at a temperature of 80-90oC for 4 hours. Then the reactor is cooled, the solvent is removed by distillation. Received a 49.5 g (76%) of product 5. The melting point is amorphous. Found: N - 6,44%, Cl - 10,42%. C41H473Cl2.

Calculated: N - 6,44%, Cl - 10,88%.

Example 6. Chloride N ethyl alcohol and 12.6 g (0.1 mole) of benzylchloride. The reaction mixture is stirred at the boiling temperature of the alcohol for 2 hours. The control end of the reaction are the number formed of the chloride ion. Then the solvent is removed by distillation. Obtained 22 g (92%) of amorphous product 6. Found: N - 11.25 per cent, Cl - 14,39%, C13H212Cl.

Calculated: N - 11,64%, Cl - Of 14.76%.

Note: N, N-dimethylpiperazine was obtained by methylation of piperazine formaldehyde and formic acid under the conditions of example 4.

Example 7. Dichloride N,N-di(benzylmethyl)piperazine (7).

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In the conditions of example 6 of 11.1 g (0.1 mol) of 1-methyl-4-dimethylaminopyridine in 50 ml of methanol 25.2 g benzylchloride received of 3.64 g (83%) of compound 7. Amorphous.

Found: N - 7,24%, Cl - 18,47%, C20H282Cl2. Calculated: N - 7,62%, Cl - 19,34%.

Example 8. Chloride, N-benzyl, N-dimethylaminoethyl-N-methylpiperazine (8)

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In the conditions of example 6 of 17.1 g (0.1 mol) of 1-methyl-4-dimethylaminopyridine in 50 ml of isopropyl alcohol and 12.6 g (0.1 mole) of benzylchloride received 28.8 g (97%) of compound 8. Amorphous.

Found: N - 13,78%, Cl - to 12.28%, C6H283Cl. Calculated: N - 14,11%, Cl - 11,93%.

Example 9. Dichloride, N-benzyl, N-dimethylaminoethyl-N-benzylaminopurine (1A and 25.3 g (0.2 mole) of benzylchloride received 24.5 g (82%) of compound (9). Amorphous. Found: N - 9,52%, Cl - 16,36%. C23H353Cl2. Calculated: N - 9,90%, Cl - 16,74%.

Example 10. Chloride N-(-allylamine)-N-benzylpiperazine (10).

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In the reactor load of 16.9 g (0.1 mole) N-(-allylamine)piperazine in 20 ml of allyl alcohol type of 12.6 g (0.1 mole) of benzylchloride. The reaction mixture is stirred at the boiling temperature of the alcohol for 4 hours, after which the alcohol is distilled off by distillation.

Received of 27.2 g (92%) of amorphous product connection 10.

Found: N - 13,91%, Cl - 12,34%, C16H253Cl.

Calculated: N - 14,26%, Cl - 12,05%.

Example 11. Chloride N-(-metalimnetic)-N-benzylpiperazine (11).

In the conditions of example 10 out of 12.9 g (0.1 mol) N-(-amino-ethyl)piperazine in 20 ml of ethyl alcohol and 9 g of metallicgold received 27.8 g (90%) of amorphous compound (11). Found: N - 13,98%, Cl - 11,19%. C17H283Cl.

Calculated: N - 13,57%, Cl - 11,47%.

Example 12. Quaternary ammonium chloride from a mixture of N-(aminoethyl)piperazine and DETA (Diethylenetriamine). Charged to the reactor of 11.6 g (0.1 mol) of a mixture of composition: N-(- amino-ethyl)piperazine - 50%, DETA - 50% (average molecular weight of 116) in the form of a 70% aqueous solution of 25.3 g (0.2 mole) of benzylchloride, stirred at a temperature of 80-100the round 20-40oC for 0.5 hours, then water and boiling components are removed by vacuum distillation, the precipitated sodium chloride is filtered off. Benzylamine process 12,65 g (0.1 mole) of benzylchloride in 25 ml of ethyl alcohol at a temperature of 60-80oC for 3 hours. Received of 37.7 g (88%) of product connection 12. Found: N - 9,94%, Cl - 8,07. C26H333Cl. Calculated: N - 9,94%, Cl - 8,40%.

Example 13. In the conditions of example 12 out of 11.2 g (0.1 mol, the average molecular weight of 112) of a mixture consisting of 35% N-(- amino-ethyl) piperazine and 65% DETA, 25,3 g (0.2 mole) of benzylchloride, 8 g of NaOH and 12,65 g benzylchloride received of 36.3 g (87%) (average molecular weight 418,6) viscous product connection 13. Found: N - 10,27%, Cl - 8,48%.

Example 14. In the conditions of example 12 (12.5 g (0.1 mol, the average molecular weight of 122.5) a mixture consisting of 75% N-(- amino-ethyl)piperazine and 25% DETA, 25,3 g (0.2 mole) of benzylchloride, 8 g (0.2 mol) of NaOH and 12,65 g (0.1 mole) of benzylchloride received of 35.4 g (90%) of a viscous product connection 14. Found: N For 9.47%, Cl - 8,18%.

Example 15. In the conditions of example 12 (12.5 g (0.1 mol, the average molecular weight of 125) of a mixture of DETA - 40%, N-(- amino-ethyl)piperazine - 36%, THETA and higher polyethylenepolyamines - 24%, to 25.3 g (0.2 mole) of benzylchloride, 8 g (0.2 mol) of NaOH and 12,65 g (0.1 mole) of benzylchloride, OYe dichloroethane. The 4-necked flask equipped with a mechanical stirrer, reflux condenser, thermometer and addition funnel, was added a 49.5 g (0.5 mole) of ethylene dichloride and catalyst connection 1-15 in the amount of 1-2% by weight of dichloroethane in the form of 25-50%-aqueous solution of water or alcohol. Then was added 40-50% solution of NaOH in a molar ratio of EDC: NaOH is 1: 1.1 to 1.2. The temperature was raised to 55-60oC, the formed gas - chloride was collected in a Gasometer, were analyzed. Chlorodrol absorbed distilled water before Gasometer. The results dehydrochlorinating shown in the table. The synthesis was completed at the termination of the allocation of chloride.

Example 17. In the conditions of example 16 in the reactor was loaded with 0.5 mole of limiting chloropetalum - 1,3-dichloropropan or 3,4-dichlorobutene, 1,2,2,3-tetrachloropropane or 1,1,2,2,3-pentachloropropane etc. and catalyst connection 1, 2, 4, 8, 9, 12, 14, 15 in the amount of 0.4-1.3% of the weight limit chloropetalum as 20-50% alcohol solution, and then was added 30-50% aqueous sodium hydroxide solution in a molar ratio of marginal chloropetalum : NaOH = 1: 1.1 to 1.4, at a temperature of 40-80oC. the results are shown in table. 1, 2.

The use of the proposed method will allow to expand the range used in Procom JSC "caustic", to increase the yield of the target product (98,6-and 99.8 wt.%) and to reduce the process time (30-50 min).

Bibliography

1. Armenian chem. journal, 1980, 33, 57.

2. A. S., 771081, class C 07 C 21/04, 1978

1. The method of obtaining unsaturated chlorohydrocarbons by dehydrochlorination di - and peliharakan aqueous solution of alkali metal hydroxide in the presence of catalysts of the class of Quaternary ammonium salts, characterized in that the dehydrochlorination spend 30 - 50%-s ' solution of alkali metal hydroxide and in the presence of 0.4 - 2 wt.% in terms of the initial di - and peliharakan, catalyst, obtained by the interaction of polyethylenepolyamines and their alkyl derivatives with benzyl chloride when a molar ratio of 1 : 1 - 5.

2. The method according to p. 1, characterized in that use polyethylenepolyamine obtained by vacuum distillation and containing Diethylenetriamine - 30 to 45 weight. %, N--AMINOETHYLPIPERAZINE - 30 to 65 wt.%, Triethylenetetramine and higher polyamine - 20 - 35%.

 

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