The way to obtain 1,1-dichloro-4-methylpentadiene-1,4

 

(57) Abstract:

Usage: 1,1-dichloro-4-methylpentadiene-1,4-intermediate for the synthesis of the active insecticidal drug permethrin. The inventive target product is obtained by electroreduction 1,1,1-trichloro-2-hydroxy-4-methylpentene-4, the electrolysis is carried out with the use of two-phase Catolica containing 63,4-30.2% of water and 19,25-37,2% isopropanol, then separate the organic part of the emulsion is extracted from it by water, isopropanol and distilled with the separation of the target product in analytically pure form, and the aqueous layer was promelektroresurs the reaction mixture and the aqueous phase after extraction of the organic layer is subjected to processing, including extraction of the source reagent and distilled the mixture formed as a result of extraction of water-isopropanol solutions, allocate 20%(percent) commodity hydrochloric acid and water, which returns to the step of extraction with isopropanol from the organic layer. This increases the yield of the target product, simplifies the process, reduces its energy consumption, eliminates the wastewater generated in the allocation of 1,1-dichloro-4-methylpentadiene-1,4 lead the regeneration of the original Catolica and anolyte. table 1.

The invention OTC applied in the production of the intermediate product, necessary for the synthesis of insecticidal active substance of the drug permethrin.

Permethrin is one of the representatives of synthetic pyrethroids new generation of insecticides, the use of which is characterized by a high impact on crop pests, household insects and ectoparasites of cattle.

It is known [1,2,3] that the electrosynthesis of 1,1-dichloro-4-methylpentadiene-1,4 of 1,1,1-trichloro-2-hydroxy-4-methylpentene-4 outputs 80-83% carry on metals with high overvoltage of hydrogen in organic solvents. However, the latter circumstance makes it impossible to known methods to obtain the specified product on an industrial scale. There is also a way of electrosynthesis 1,1-dichloro-4-methylpentadiene-1.4 in water-ethanol solution using as electrolyte a mixture of hydrochloric and sulfuric acid, which is formed in accordance with the scheme:

CCl3-CHOH-CH2-C(CH3)= CH2CCl2= CH-CH2-C(CH3)=CH2(1)

A method of obtaining 1,1-dichloro-4-methylpentadiene-1,4 (output 87-90,5% ) electrochemical reduction dehydrochlorination 1,1,1-trichloro-2-hydroxy-4-methylpentene-4 electric is using as catolyte solution of hydrogen chloride (0.7 to 2.0 M) or a mixture of hydrogen chloride and H2SO4(0,6-1,3 about.) in a lower aliphatic alcohol (CH3OH; i-C3H7OH; the concentration of water in about 15-25.), and as the anolyte solution of an inorganic acid [4] In accordance with this method, the spent electrolyte is diluted with water, emit the target product in the organic layer; and forming at the same time water-alcohol layer is distilled alcohol is directed to the preparation of the original Catolica. The following should be highlighted the disadvantages of this method:

the low yield of the desired 1,1-dichloro-4-methylpentadiene-1,4 (87-90,5%);

significant energy consumption at the stage of obtaining the return of methanol from the aqueous methanol layer due to too much last (11-13 g of the water-methanol layer per 1 g of the target product), formed upon dilution of the reaction mass after electrolysis additional amount of water (dilute 50 ml of Catolica spend 100 ml of water);

the losses of the target product, unreacted source reagent and methanol when selecting the last of the water-methanol layer, due to the fact that in terms of the acceleration of the spent solution of 1,1-dichloro-4-methylpentadiene-1.4 and 1,1,1-trichloro-2-hydroxy-4-methylpentan-4 osmolyte, and alcohol is spent on aunola of the water-methanol layer of significant quantities of wastewater, containing hydrogen chloride, H2SO4and contaminated with organic substances;

the selection of the target product in the organic layer, which contains water, hydrogen chloride and alcohol, which affects the outputs of 1,1-dichloro-4-methylpentadiene-1,3 derived from 1,1-dichloro-4-methylpentadiene-1,4 next stage of synthesis of the active substance of the drug permethrin.

The aim of the invention is to increase the yield of the target product, simplifying the process, reducing its energy intensity, othernote and exclusion of sewage in the allocation of 1,1-dichloro-4-methylpentadiene-1,4 and regeneration of the original Catolica and anolyte.

To obtain 1,1-dichloro-4-methylpentadiene-1,4 electrochemical vosstanovlenie,1,1-trichloro-2-hydroxy-4-methyl - pentene-4 in a cell, separated by ion exchange or filtration membrane with a cathode of lead or cadmium, and the anode of platinum or graphite, download two-phase catholyte containing 19,25-37,2 wt. isopropanol, 63,4 to 30.2 wt. water, a 2.9-10.5 wt. hydrogen chloride or p-toluenesulfonic acid and 10-30 wt. 1,1,1-trichloro-2-hydroxy-4-methylpentene-4. In the anode chamber of the electrolyzer is poured on 10% aqueous solution of sulfuric acid or 25-26% Sol is esta, equal 130-160% of theoretically required. The current density is 200 to 400 a/m2.

The choice of a two-phase source Catolica, as well as the specified ranges of concentrations of water (63,4 to 30.2 wt.) and isopropanol (19,25-37,2 wt.) in it are the necessary conditions that allow the synthesis of 1,1-dichloro-4-methylpentadiene-1,4 with high yield and to receive as a result of electrolysis emulsion that does not need to be diluted with additional water to highlight the target product and regeneration of the initial reaction mixtures. When using electrosynthesis homogeneous source Catolica as mixtures with concentrations of water and isopropanol outside these intervals 1,1-dichloro-4-methylpentadiene-1,4 formed with either low yields or to highlight in its pure form it is necessary to dilute the waste of the reaction mass with water. Namely, this operation causes the drawbacks of the known method of obtaining the target product.

After completion of the electrolysis cathode emulsion is poured into a separating funnel and separated into two layers: organic and water-isopropanol, each of which is analyzed by gas chromatography on the content of the target PCIe water, washing out a large part of isopropanol, and then redistilled. As a by-product distillation: distilled water, containing mainly isopropanol and 1,1-dichloro-4-methylpentadiene-1,4, 99,9% of the target product (yield at the stage of selection 90-92,5% d201,09 g/cm3; nD201,471) and high-boiling distillation sent for incineration. Part (24-47%) water-isopropanole layer is extracted with a new portion 1,1,1-trichloro-2-hydroxy-4-methylpentene-4, freeing in this way the mixture from isopropanol, unreacted source reagent and 1,1-dichloro-4-methylpentadiene-1,4. The aqueous layers from both extraction are mixed and distilled at atmospheric pressure, allocating 20% commodity hydrochloric acid, water-isopropanol and water fractions. The last two solutions, as well as unprocessed part (76-53%) piroelektricheskogo water-isopropanole layer, the distillate after distillation of the organic layer and the organic phase formed by the source extraction reagent of the first part (24-47%) water-isopropanole layer mix, getting a new source catholyte. The aqueous fraction after distillation of the mixture water-isopropanolic layers from the above extraction is used, furthermore, for the regeneration of the organic layer, on which islote the main product of the anode reaction is chlorine (not oxygen, as in the case of the anolyte 10% H2SO4), which is sent to the chlorination reactor ethanol to obtain by well-known methods of Chlorella starting compound in the synthesis of 1,1,1-trichloro-2-hydroxy-4-methylpentene-4:

C2H5OH + 4Cl2____ CCl3CHO + 5HCl (3)

The resultant hydrogen chloride absorb a mixture of 20% hydrochloric acid and parts of water fraction allocated after distillation waste water isopropanolic layers. This operation leads to regeneration of the original analyte 25-36% hydrochloric acid. This electrosynthesis 1,1-dichloro-4-methylpentadiene-1,4, whereby simultaneously with the restoration of 1,1,1-trichloro-2-hydroxy-4-methylpentene-4 in the cathode circuit carry out the synthesis of Chlorella using anode-generated chlorine, eliminates withdrawal from the process ottseplyayuschimsya HCl (scheme 1) in the form abgaznaya hydrochloric acid.

Comparative analysis of the proposed solutions with the prototype shows that the proposed method differs from the known application for the electrosynthesis of the target product of the two-phase Catolica containing 63,4 to 30.2 wt. water and 19,25-37,2 wt. isopropanol. Thanks 1,1-dichloro-4-methylpentadiene-1,4 able to get to the outputs ipanemas operation of waste water dilution of the reaction mixture, which results in a simplification of the process, the reduction of power consumption, othernote and exclusion of sewage.

Thus, the claimed method meets the criteria of the invention of "novelty."

Ways to obtain 1,1-dichloro-4-methylpentadiene-1.4 electroreduction 1,1,1-trichloro-2-hydroxy-4-methylpentene-4 known [1,2,3,4]. however, the distinctive features of the proposed method is unknown in similar decisions and provide a positive effect. This allows to make a conclusion on the conformity of the proposed method the criteria of the invention "significant differences".

P R I m e R 1. A. the Electrosynthesis of 1,1-dichloro-4-methylpentadiene-1,4.

In the cathode space filter presnogo electrolytic cell equipped with a cathode lead (74 cm2) and cation exchange diaphragm MT-SK, put 68,78 g 8.4% hydrochloric acid, 88 ml (35,8 wt.) isopropanol and 54,98 g (28,52 wt.) 1,1,1-trichloro-2-hydroxy-4-methylpentene-4 with a basic substance content of 92% To the anode (the anode is platinum) pour a 10% aqueous solution of sulfuric acid (265,5 g). The electrolysis is carried out at 20-25aboutC and stirring with the help of centrifugal pumps, the flowing amount of electricity, amounting to 130% of Teoreticheskaya, putting the last separation in a separating funnel at two layers: organic (39,37 g) and water isopropanolic (160,73 g). After unloading part (17.0 g 7,83% by weight of the entire cathodic emulsion) of the reaction mixture remains in the cathode circuit of the cell from which it is extracted by washing apparatus 250 ml of methanol. (In the case of the electrosynthesis of 1,1-dichloro-4-methylpentadiene-1,4 using returnable components specified operation is not carried out; remaining in the cell after unloading 17.0 g cathodic emulsion is used as an integral part of the newly prepared source Catolica (see example 1B)).

The obtained methanol solution, and the organic and aqueous-isopropanolic layers will be analyzed by the chromatograph LHM-80.

(Conditions: detector flame ionization, Tdet. 160aboutS, Tuse220aboutS; VNot25 ml/min, Vd. 300 ml/min; VH280 ml/min; lspeakers= 2 m; the carrier of N-AW-DM-chromatin (Csof 0.16-0.2 mm) impregnated with 5% silicone HEH-60; program from 50 to 170aboutWith speeds of 4aboutC/min Label dodecan). According to gas-liquid chromatography receive to 34.06 g of 1,1-dichloro-4-methylpentadiene-1,4 (exit through the material at 90.77%) and of 2.92 g of 1,1,1-trichloro-2-hydroxy-4-methylpentene is pererabotka with the aim of making a new source Catolica and selection of the target product in pure form.

B. Processing of the organic layer formed during the electroreduction 1,1,1-trichloro-2-hydroxy-4-methylpentene-4.

A mixture of (39,37 g) organic matter (12,85% isopropanol; 76,55% 1,1-dichloro-4-methylpentadiene-1,4; 4.95% of 1,1,1-trichloro-2-hydroxy-4-methylpentene-4; 2,0% water; 0,27% HCl and 3.4% other), selected after electrolysis (see example 1A), mixed with 46 ml of water, and then separated using a separating funnel on two layers: organic (34,175 g) and water (N 1) (50,64 g), representing 9%th solution of isopropanol in water. Proektirovanii the organic layer, from which is extracted in this way a large part of isopropanol, distilled in vacuum (40 mm Hg), receiving 1,365 g of distillate (TKip.30-60aboutC), 27,33 g

the main fraction (TKip.60-61,5about(C) with 99.9% content 1,1-Dehler-4-methylpentadiene-1,4 (exit at the stage of selection of 92.5%) and 4.6 g of high-boiling products (distillation) sent for destruction. The distillate, consisting of isopropanol (52,98% ), 1,1-dichloro-4-methylpentadiene-1,4 (40,66%), water (6,0%) and HCl (0,97%), used in the preparation of new source Catolica.

C. Preparation of Catolica and anolyte from reflexive components.

Part (75,5 g) water-isopropanole layer, selected last is about substance 92%) to extract from the specified aqueous solution of such organic substances, as propanol, 1,1,1-trichloro-2-hydroxy-4-methylpentan-4 and 1,1-dichloro-4-methylpentadiene-1,4. The separation in a separating funnel will get:

the aqueous layer (N 2) (43,66 g; composition: 11,3% HCl; 6,6% isopropanol; 82,1% water; traces of organic substances);

the organic layer (N 2) (85,99 g; composition: 26,45% isopropanol; 4.7% of water; 1,6% HCl; 1,06% 1,1-dichloro-4-methylpentadiene-1,4; 58,73% 1,1,1-trichloro-2-oxymethylene-4 and 7.4% other), sent together with the remaining 85,23 g waste water isopropanole layer (from example 1A) in the preparation of the new Catolica.

Water layers N 1 (see example 1B) and N 2 mix (concentration of isopropanol in the mixture to 7.99% total concentration of the target product and the source reagent < 0.1%) and distilled under atmospheric pressure, highlighting:

Fraction 1 with TKip.79,5-83aboutWith (8,2 g) containing 87,45% isopropanol and 12.55% of the water.

Fraction 2 with TKip.90-102about(61,1 g) containing 99,1% water, 0,12% HCl and 0.78% isopropanol.

Fraction 3 with TKip.102-107,5about(To 24.66 g), which represents 20% of the commodity hydrochloric acid.

Then in the cathode space filter presnogo cell placed the organic layer N 2 (85,99 g), 85,23 g waste water isopropanole layer, francisconi organic layer (see example 1B) and 0.55 g of fresh isopropanol. In the anode chamber fill exhaust anolyte (236,63 g), part (6.75 g) fraction 2 after distillation of the mixture of water layers of the N 1 and N 2 and 22,17 g of water (fraction 2 (61,1 g) allocated during the distillation of a mixture of water layers of the N 1 and N 2, is directed to the preparation of the new Catolica (8.0 g), on the preparation of a new analyte (6.75 g), on extraction from isopropanol obtained after electrolysis of the organic layer (46,3 g) (see example 1A)).

Thus, the new source catholyte in number (see example 1A) 206,31 g, prepared using returnable components, contains 33.7% of isopropanol, 30,67% water, to 4.4% HCl, 2,17% 1,1-dichloro-4-methylpentadiene-1,4, 24,75% 1,1,1-trichloro-2-hydroxy-4-methylpentene-4, 4.3% of other substances, and again received the anolyte (265,55 g) 90% water and 10% H2SO4.

, The Electrosynthesis 1,1-dichloro-4-methylpentadiene-1,4 using Catolica and anolyte from reflexive components.

Under the conditions described in example 1A, conducting electrolysis using Catolica and anolyte, the composition of which is given in example 1B. After separation promelektroresurs emulsion in the organic (46,82 g) and water (166,8 g) layers receive, according to chromatographic analysis, 39,53 g of the target product, of which 4 1,1,1-trichloro-2-hydroxy-4-methylpentene-4 96,3%

P R I m m e R 2. In the cathode space filter presnogo electrolytic cell equipped with a cathode lead (74 cm2and filter fenelonov aperture, place of 78.47 g 7,38% hydrochloric acid, and 70.5 ml (32,3 wt.) isopropanol, 5.0 g (2,92 wt. ) p-toluenesulfonic acid and 32,58 g (19.01 in wt.) 1,1,1-trichloro-2-hydroxy-4-methylpentene-4 with the content of the basic substance 98,95% To the anode (the anode is platinum) pour a 10% aqueous solution of sulfuric acid. The electrolysis is carried out at 20-25aboutC and stirring, the flowing amount of electricity, amounting to 160% of theoretically required. The current density of 400 a/m2. At the end of the electrolysis carry out operations similar to those described in example 1A. According to gas-liquid chromatography gain of 21.7 g of 1,1-dichloro-4-methylpentadiene-1,4 (output 90,73%). Conversion of the source reagent is 95.2%

P R I m e R 3. A. the Electrosynthesis of 1,1-dichloro-4-methylpentadiene-1,4, combined with obtaining Chlorella from ethanol and androgynemichinaga chlorine.

In the cathode space filter presnogo electrolytic cell equipped with a cathode lead (74 cm2) and cation exchange diaphragm, MT-SK, put 66.5 g 8,72% hydrochloric acid, 88 ml (37,22 wt.) isopropanol and 50,15 g (to 27.0 wt.) 1,1,1-trichloro-2-hydroxy-4-methylpentene-th acid. The electrolysis is carried out at 20-25aboutC and stirring with the help of centrifugal pumps, the flowing amount of electricity, amounting to 130% of theoretically required. The current density of 400 a/m2. Generated at the anode chlorine send at a speed of 2.5 g/h into the reactor chlorination of ethanol, in which the synthesis of Chlorella by well-known methods. At the end of the electrolysis free chloral separated from chlorates, mixing with an equal weight amount of sulfuric acid ( 1.84 g/cm3), and then turning the mixture from the flask vyurts. Fractions Chlorella taken at a temperature in pairs 95-97aboutC. Receive product with a basic substance content of 98.3% (nD201,456). The output Chlorella is 53% Dedicated chloral transferred to chloralhydrate (Tpl.52aboutC) analyze (Calculation, C 14,52; H 1,828; Cl 64,3. Found, C 14,72; H 2,09; Cl 63,23). Promelektrooborudovanie the anolyte and a cathode emulsion is drained, exposing the last separation in a separating funnel at two layers: organic (30.0 g) and water isopropanolic (151,61 g). After unloading part (13.3 g) of the reaction mixture remains in the cathode circuit of the cell, which is either extracted therefrom by washing apparatus 250 ml of methanol, or use the AC the hydrated solution, along with water-isopropanol and organic layer, to analyze the chromatograph LHM-80 (see example 1). According to gas-liquid chromatography receive 34,07 g of 1,1-dichloro-4-methylpentadiene-1,4 (yield of 91.6%) and 1.45 g 1,1,1-trichloro-2-hydroxy-4-methylpentene-4 (conversion to 97.1%). Then the spent water-isopropanol and organic layers are subjected to further processing in order to prepare a new source Catolica and selection of the target product in pure form.

B. Processing of the organic layer formed during the electroreduction 1,1,1-trichloro-2-hydroxy-4-methylpentene-4.

A mixture of 30.0 g) organic matter (to $ 7.91% isopropanol; 87,0% 1,1-dichloro-4-methylpentadiene-1,4; 2,16% 1,1,1-trichloro-2-hydroxy-4-methylpentene-4; 0.8% of water; 0,33% HCl and 0.94% area), selected after electrolysis in example 3A, mix from 22.4 ml of water, and then separated using a separating funnel on two layers: organic (27,52 g) and water (N 1) (24,81 g), representing 8.5%of th solution of isopropanol in water. Proektirovanii the organic layer is distilled under vacuum (40 mm Hg), receiving 2,22 g of distillate (TKip.25-60aboutC) and 23.4 g of the main fraction (TKip.60-62aboutC) of 99.98% content of 1,1-dichloro-4-methylpentadiene-1,4 (crisoprodol (23%), 1,1-dichloro-4-methylpentadiene-1,4 (72,9%), water (3.1%) and HCl (0,17%) are used in the preparation of a new source Catolica.

C. Preparation of Catolica and anolyte from reflexive components.

Part (36,4 g) water-isopropanole layer, selected after electrolysis (example 3A), is subjected to extraction with a new portion of the source reagent (50,52 g) with the content of the basic substance (100%) to extract from the specified aqueous solution of such organic substances as isopropanol, 1,1,1-trichloro-2-hydroxy-4-methylpentan-4 and 1,1-dichloro-4-methylpentadiene-1,4. The separation in a separating funnel will get:

the aqueous layer (N 2) (18,44 g; composition: 9,35% isopropanol; 74,65% water; 13,9% HCl; traces of organic substances);

the organic layer (N 2) (68,42 g; composition: of 19.72% isopropanol; 3,82% water; 0,91% HCl; 1,4% 1,1-dichloro-4-methylpentadiene-1,4; 74.1% of 1,1,1-trichloro-2-hydroxy-4-methylpentene-4), sent together with the remaining 115,22 g waste water isopropanole layer (example 3A) in the preparation of the new Catolica.

Water layers N 1 (example 3B) and N 2 mix (concentration of isopropanol in the mixture 8,84%) and distilled at 1 ATM: highlighting:

Fraction 1 with TKip79-83aboutWith (4.4 g), containing 87,22% isopropanol and 12,56% water.

Fraction 2 with Tabout(12.7 g), which represents 20% hydrochloric acid.

Then in the cathode circuit of the filter presnogo cell placed the organic layer N 2 (68,42 g), 115,22 g waste water isopropanole layer (see example 3A), fraction 1 (4.4 g) after distillation of the mixture of water layers of the N 1 and N 2 and the distillate (2,22 g), obtained after the pickup of the organic layer (see example 3B). In the anode chamber fill exhaust anolyte (275,67 g) and the mixture fraction 3 (12.7 g) and fraction 2 (the remainder of fraction 2 allocated during the distillation of a mixture of water layers of the N 1 and N 2, is directed to the extraction from isopropanol obtained after electrolysis of the organic layer). (0,41 g), which was previously used to absorb abgasnorm HCl generated during the synthesis of Chlorella (see example 3A).

Thus, the new source catholyte (see example 3A) (203,53 g) prepared using returnable components, contains 30.2% of water, 34.1% of isopropanol, 5,66% HCl, 4,58% 1,1-dichloro-4-methylpentadiene-1.4 and 25,21% 1,1,1-trichloro-2-hydroxy-4 - methylpentene-4, and again received the anolyte (303,64 g) 70,95% water, 28,24% HCl and 0.82% chlorine. The use of these mixtures for the electrosynthesis of 1,1-dichloro-4-methylpentadiene-1,4 produces a result similar to that what about the electrolyzer, equipped with a cathode lead (75 cm2and ceramic diaphragm, place of 67.1 g of 5% hydrochloric acid, 25 ml (19,52 wt.) isopropanol, 3 g (2.98 wt.) p-toluenesulfonic acid and 10.8 g (a 10.74 wt.) 1,1,1-trichloro-2-hydroxy-4-methylpentene-4. To the anode (the anode is platinum) pour a 10% aqueous solution of sulfuric acid. The electrolysis is carried out at 20-25aboutC and stirring with a mechanical stirrer for 3 h, the current Density 200 a/m2. At the end of the electrolysis cathode emulsion is poured into a separating funnel where they separate the organic layer from the water-isopropanole. Selected reaction solutions are examined for the content of 1,1-dichloro-4-methylpentadiene-1,4 by gas chromatography. Get 7,31 g of the target product (yield 91,24%) and 0,303 g of unreacted 1,1,1-trichloro-2-hydroxy-4-methylpentene-4 (conversion 97,2%).

P R I m e R 5. Under the conditions described in example 4, conducting electrolysis using as Catolica mixture consisting of of 23.6 ml (19,25 wt.) isopropanol, 67,54 g of 15% aqueous solution of p-toluenesulfonic acid and 10.2 g (10.6 wt. ) 1,1,1-trichloro-2-hydroxy-4-methylpentene-4. At the end of the experiment (time of electrolysis 2.5 h) get to 6.88 g of 1,1-dichloro-4-methylpentadiene-1,4 (output 90,92%) and 0,238 g source reagent (converse is SS="ptx2">

Thus, the proposed method allows to increase the yield of the target product and to improve the process from a technological and environmental points of view, as it simplifies the allocation of 1,1-dichloro-4-methylpentadiene-1,4, reduced losses, reduced water-isopropanole layer processed after electrolysis (1,27-2,77 g water-isopropanole layer of 1 g of 1,1-dichloro-4-methylpentadiene-1,4), which is re-used in electrosynthesis. Consequently, it is possible to eliminate wastewater generation, reduce the expenditure coefficients for raw materials, energy consumption at the stage of regeneration of the anolyte and catolyte, as well as the amount of organic waste sent for incineration.

The WAY to OBTAIN 1,1-DICHLORO-4-METHYLPENTADIENE-1,4 electrochemical recovery of 1,1,1-trichloro-2-hydroxy-4-methylpentene-4 in the cell, separated by ion exchange or filtration membrane with a cathode of lead or cadmium, and the anode of platinum or graphite, using as Catolica emulsion consisting of a source of reagent and water-isopropanolic solution of hydrogen chloride, and the anolyte solution of inorganic acid, characterized in that the electrolysis is carried out at a current density of 200 to 400 a/mis panola, then separate the organic part of the emulsion is extracted from it by water, isopropanol and distilled with the separation of the target product in analytically pure form, and the aqueous layer of the reaction mixture and the aqueous phase after extraction of the organic layer is subjected to processing, including extraction of isopropanol new portion of the source reagent and the rectification of mixtures resulting from all extraction of water-isopropanol solutions, allocate 20% commodity hydrochloric acid and water, which returns to the step of extraction with isopropanol from the organic layer.

 

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4 cl, 1 tbl, 8 ex

FIELD: chemistry of organochlorine compounds, chemical technology.

SUBSTANCE: method involves treatment of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane with solid calcium hydroxide or a mixture of solid calcium hydroxide and solid sodium hydroxide with the content of sodium hydroxide in mixture 30%, not above, in the molar ratio 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane to alkali = 1:(1.5-1.75) at heating in the presence of catalyst. As catalysts method involves benzyltrialkyl ammonium halides, preferably, benzyltriethyl ammonium chloride or benzyltrimethyl ammonium bromide, tetraalkyl ammonium halides, preferably, tetrabutyl ammonium bromide taken in the amount 0.0005-0.005 mole. Invention provides the development of a new method for preparing 1,1-dichloro-2,2-bis-(4-chlorophenyl)-ethylene allowing to enhance ecological safety of technological process and to improve quality of the end product.

EFFECT: improved method preparing.

2 cl, 15 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer and to a catalyst sued in catalytic preparing vinyl chloride monomer from flows comprising ethylene. Method for preparing vinyl chloride from ethylene is carried out by the oxidehydrochlorination reaction. Method involves combining reagents including ethylene, the source of oxygen and chlorine in the catalyst-containing reactor at temperature 350-500°C and under pressure from atmosphere to 3.5 MPa, i. e. under conditions providing preparing the product flow comprising vinyl chloride and ethylene. Catalyst comprises one or some rare-earth elements under condition that the atomic ratio between rare-earth metal and oxidative-reductive metal (iron and copper) is above 10 in the catalyst and under the following condition: when cerium presents then the catalyst comprises additionally at least one rare-earth element distinctive from cerium. Ethylene is recirculated from the product flow inversely for using at stage for combining reagents. Invention proposes a variant for a method for preparing vinyl chloride. Also, invention proposes variants of a method for catalytic dehydrochlorination of raw comprising one or some components taken among ethyl chloride, 1,2-dichloroethane and 1,1,2-trichloroethane in the presence of catalyst. Catalyst represents the composition of the formula MOCl or MCl3 wherein M represents a rare-earth element or mixture of rare-earth elements taken among lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium. The catalytic composition has the surface area BET value from 12 m2/g to 200 m2/g. Invention provides simplifying technology and enhanced selectivity of the method.

EFFECT: improved conversion method.

61 cl, 8 tbl, 32 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to perfluoroolefins production technology, notably to heaxafluorobutadiene CF2=CF-CF=CF2. Process comprises reaction of 1,2,3,4-tetrachlorohexafluorobutane with zinc in aqueous medium at 30 to 90°C. Reaction is carried out by metering 1,2,3,4-tetrachlorohexafluorobutane into reaction vessel containing zinc and water, while simultaneously desired product formed is recovered. Advantageously, process is conducted in presence of promoter selected from acids such as sulfuric acid and hydrochloric acid, soluble weak base salts such as zinc and ammonium halides, interphase transfer catalysts such as quaternary ammonium salts, quaternary phosphonium salts, tetrakis(dialkylamino)phosphonium salts, and N,N',N"-hexaalkyl-substituted guanidinium salts, or mixtures of indicated substances.

EFFECT: increased purity of heaxafluorobutadiene and simplified technology.

4 cl, 7 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to oxidative halogenation processes to obtain halogenated products, in particular allyl chloride and optionally propylene. Process comprises interaction of hydrocarbon having between 3 and 10 carbon atoms or halogenated derivative thereof with halogen source and optionally oxygen source in presence of catalyst at temperature above 100°C and below 600°C and pressure above 97 kPa and below 1034 kPa. Resulting olefin containing at least 3 carbon atoms and halogenated hydrocarbon containing at least 3 carbon atoms and larger number of halogen atoms than in reactant. Catalyst contains essentially iron and copper-free rare-earth metal halide or oxyhalide. Atomic ratio of rare-earth metal to iron or copper is superior to 10:1. In case of cerium-containing catalyst, catalyst has at least one more rare-earth element, amount of cerium present being less than 10 atomic % of the total amount of rare-earth elements. Advantageously, process is conducted at volumetric alkane, halogen, and oxygen supply rate above 0.1 and below 1.0 h-1, while diluent selected from group including nitrogen, helium, argon, carbon monoxide or dioxide or mixture thereof is additionally used. Halogenated product is recycled while being converted into supplementary olefin product and olefin product is recycled in order to be converted into halogenated hydrocarbon product. Optionally, allyl chloride and ethylene are obtained via interaction of propane with chlorine source in presence of catalyst.

EFFECT: increased productivity of process and improved economical characteristics.

26 cl, 1 tbl

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of chlorinated ethylene derivatives, in particular, vinyl chloride, vinylidene chloride, trichloroethylene by the dehydrochlorination reaction of corresponding chlorinated ethane derivatives. The process is carried out in the presence of sodium hydroxide aqueous solution, catalyst of interphase transfer relating to polyglycols and an extractant-promoter representing mixture of chlorinated hydrocarbons of the general formula: CnH2n +2-xClx wherein n = 10-30; x = 1-7 with molecular mass 250-305 Da and the chlorine content is 24-43% followed by isolation of end substances by the known procedures. As a catalyst of interfase transfer the method uses polyethylene glycols in the amount 0.0001-1% of the mass of the parent chlorinated ethane derivative. Extractant-promoter is used in the amount 1-10% of the mass of the parent ethane derivative. The mole ratio of chlorinated ethane derivative to sodium hydroxide = 1:(1.15-5) at the concentration of sodium hydroxide aqueous solution 5-35 wt.-%. Invention provides the development of the complex method for synthesis of chlorinated ethylene derivatives from chlorinated ethane derivatives, among them, from depleted reagents of the method or waste of corresponding industry, and increasing yield of end products.

EFFECT: improved method of synthesis.

7 cl, 1 tbl, 12 ex

FIELD: chemical industry; methods of production of vinylidene chloride.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of vinylidene chloride by the dehydrochlorination of 1,1,2- trichloroethane with formation of the target product and the quaternary ammonium salts. As the reactant of the dehydrochlorination they use the water-alcoholic solutions of hydroxides - dimethyl-β or γ- chlorodipropenyl of ammonium gained by the electrolysis of the solutions of dimethyl-β or γ- chlorodipropenyl of ammonium chloride in the water at presence of methyl, ethyl or butyl alcohols in the electrolyzers with the ion-exchange membranes. At that the gained hydroxides are sent to the dehydrochlorination. The technical result of the invention is creation of the waste-free, highly-efficient and pollution-free process of production of vinylidene chloride.

EFFECT: the invention ensures creation of the waste-free, highly-efficient and pollution-free process of production of vinylidene chloride.

3 cl, 3 ex, 1 dwg

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