The way to obtain 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene
(57) Abstract:The invention relates to the field of chemistry of aromatic organochlorine compounds, and in particular to a method for producing 1,1-dichloro-2,2-(4-chlorophenyl)ethylene. Essence: 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane helps eliminate hydrogen chloride crystalline alkali at a molar ratio of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane : alkali as 1 : (1,5 - 1,75) and the process is conducted in the presence of the catalyst benzyltriethylammonium chloride. The invention relates to the field of chemistry organochlorine compounds, and in particular to a method for producing 1,1-dichloro-2,2-bis- (4-chlorophenyl)ethylene
< / BR>which can be used as an additive to polyester resins to improve the fire resistance.A method of obtaining 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene removal of hydrogen chloride alcohol alkali solution of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane [1,2] . The reaction is carried out with 3-fold excess of alkali boiling for 10 hours Using a diluted solution of alcohol alkali (~2%). The yield is 81%.Also known is a method of obtaining 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane as acceptor chloric organic solvents, preferably the reaction in ethyl cellosolve.< / BR>The closest is the way to obtain 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane using an alcoholic solution of alkali  . The process is carried out at the boiling temperature of the alcohol. For elimination of use threefold excess of alkali. The reaction mass consisting of 1,1,1-trichloro-2,2-bis-(4-chloro-phenyl)ethane, 3-fold excess of alkali and alcohol is boiled for 10 hours. Then spend the isolation and purification of the obtained 1,1-dichloro-2,2-bis-(4 - chlorophenyl)ethylene. To highlight a product of the pre-reaction mass is distilled alcohol.The disadvantage of this method is that elimination using a large excess of alkali (up to three times). The elimination process is within 10 h at the boiling temperature of the alcohol. Technology explosive, because it is used legkonastraivaemy solvent is ethyl or propyl alcohol.The invention is aimed at simplifying the technology for 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene.This is achieved by elimination of hydrogen chloride from 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane exercise crystalline seatstay catalyst benzyltriethylammonium.For implementing the method uses the following materials: 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane - so pl. to 108.5-109oC, NaOH - GOST 4328-77; benzyltriethylammonium chloride - TU 6-09-05-542-76.The method is as follows.To 0.5 mol of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane was added to 0.75 mol of alkali and 0.0005 mol of benzyltriethylammonium chloride. The mixture is heated at 90-100oC for 40-60 minutes the resulting mass is neutralized with an aqueous solution of hydrochloric acid. The precipitate is filtered off and dried. Output 93-97%, so pl. 88-89oC. Lit. T. pl. 88-89oC.The distinction of the proposed solutions from known is used as the eliminating agent of the crystalline alkali and catalyst. This avoids the use of organic solvents, a large excess of alkali (2 times), to reduce the reaction time (10 times), as well as to forgive the selection of the final product.The optimum amount of alkali is 1,5-1,75 mol per 1 mol of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane. Decreasing this number, the yield of the desired product decreases. To increase this number has no meaning, because the output is not increasing, not decreasing the duration of the reaction.Example 1. The mixture is and is heated under stirring for 40-60 min and a temperature of 90-100oC. Then the reaction mixture was neutralized with an aqueous solution of hydrochloric acid. The precipitate is filtered off and dried. The output 154 g (97%), so pl. 88-89oC. Lit. T. pl. 88-89oC.Example 2. Analogously to example 1. From a mixture containing 0.5 mol of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane, 1 mol of NaOH, of 0.0005 mol benzyltriethylammonium chloride, receive 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene with 96% yield. So pl. 88-89oC. Lit. T. pl. 88-89oC.Example 3. Analogously to example 1. From a mixture containing 0.5 mol to 1.1.1-trichloro-2,2-bis-(4-chlorophenyl)ethane, 0.5 mol of NaOH, of 0.0005 mole benzyldimethyl-ammonium chloride, receive 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene with 59% yield. So pl. 88-89oC. Lit.  T. pl. 88-89oC. The way to obtain 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene by treatment with 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane alkali at elevated temperature, characterized in that the alkali used crystalline alkali and the process is conducted at a molar ratio of 1,1,1-trichloro-2,2-bis - (4-chlorophenyl)ethane : lye, which is 1 : 1.5 to about 1.75, in the presence of a catalyst of benzyltriethylammonium chloride.
(R1)(I)where the residues R1and R2independently from each other mean a hydrogen/ halogen/ alkyl/ halogenated/ alkoxy/ halogenoalkane or unsubstituted or substituted aromatic residue and n and m mean 1/2 or 3
FIELD: organic synthesis catalysts.
SUBSTANCE: catalyst is prepared from allyl chloride production wastes comprising 30-50% 1,3-dichloropropenes, 30-60% 1,2-dichloropropane, and 3-5% 1,2,3-trichloropropane, which are treated at 5-10°C with 30-50% dimethylamine aqueous solution in such amount as to ensure stoichiometric ratio of dimethylamine with respect to 1,3-dichloropropenes. Resulting mixture is held at 20-25°C for 0.5-1.0 h and then 40-44 sodium hydroxide solution is added in stoichiometric amount regarding dimethylamine, after which clarified waste is added to dimethylamine at 60-70°C and stirring in amount ensuring stoichiometric ratio of dimethylamine to 1,3-dichloropropenes contained in clarified waste. Mixture is aged for 2-3 h, organic phase is separated, and remaining interaction phase is supplemented by C1-C4-alcohol or benzyl alcohol at alcohol-to-dimethylamine molar ratio 1:(1-3).
EFFECT: reduced expenses on starting materials.
2 cl, 3 ex
FIELD: chemical industry, in particular method for production of value monomer such as vinylchloride.
SUBSTANCE: claimed method includes passing of reaction mixture containing dichloroethane vapor trough catalytic layer providing dehydrochlorination of dichloroethane to vinylchloride. Catalyst has active centers having in IR-spectra of adsorbed ammonia absorption band with wave numbers in region of ν = 1410-1440 cm-1, and contains one platinum group metal as active component, and glass-fiber carrier. Carrier has in NMR29Si-specrum lines with chemical shifts of -100±3 ppm (Q3-line) and -110±3 ppm (Q4-line) in integral intensity ratio Q3/Q4 from 0.7 to 1.2; in IR-specrum it has absorption band of hydroxyls with wave number of ν = 3620-3650 cm-1 and half-width of 65-75 cm-1, and has density, measured by BET-method using argon thermal desorption, SAr = 0.5-30 m2/g, and specific surface, measured by alkali titration, SNa = 10-250 m2/g in ratio of SAr/SNa = 5-30.
EFFECT: method with high conversion ratio and selectivity.
3 cl, 2 ex
FIELD: industrial organic synthesis.
SUBSTANCE: gas-phase thermal dehydrochlorination of 1,2-dichloroethane is conducted in presence of hydrogen chloride as promoter dissolved in feed in concentration between 50 and 10000 ppm.
EFFECT: increased conversion of raw material and reduced yield of by-products.
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