The method of obtaining mono - and dibromopropanol or their chlorinated analogues
(57) Abstract:The invention relates to chemical technology perhalogenated, namely the method of production of mono - and dibromopropanol or their chlorinated analogues, which are used as intermediates in the synthesis of dyes, pharmaceuticals, monomers, etc. get Them by substitution of fluorine in hexaferrite on bromine or chlorine with the direct interaction of hexaferrite with non-ionic, halogen-containing substance and a catalyst - activated carbon, free from compounds of Halogens, at 300 - 500oC. as halogenated substances take halogenated alkanes, arenes, halogenated carbonyl compounds, Cl2, Br2. Significantly reduces the temperature of the process, simplified technology, reducing the amount of reactors. table 1. The invention relates to chemical technology of mono - and dibromopropanol or their chlorinated analogues, which have been used as intermediates in the synthesis of dyes, pharmaceuticals, monomers, etc.A known method of producing bromopentafluorobenzene by substitution of hydrogen in the ptx2">The output of bromopentafluorobenzene is 70-82% (J. Chem. Soc., 1959, 166).< / BR>The sign of a well-known method, coinciding with the essential features of the claimed invention is used as a feedstock molecular bromine.Barriers to getting in the known method the required technical result is that as the initial connection is inaccessible pentafluorobenzoyl; to obtain 1 mole of bromopentafluorobenzene requires 1 mol of bromine, in this case on 1 mol of bromopentafluorobenzene is formed as a waste of one mole of hydrogen bromide, in addition, it is necessary to use dry reagents and protection is required for the reaction medium from the access of moisture in the air.A method of obtaining mono - and di(bromo or chloro)performancenow substitution respectively bromine or chlorine in hexachlor or hexabromobenzene on fluoride fluorides of alkali metals (Izv. WITH an SSSR, ser. chem. 1963, S. 1524).< / BR>In the known method, there are no signs consistent with the essential features of the claimed invention, which consists in the substitution of fluorine bromine or chlorine in hexaferrite complex: non-ionic halogenated connection is th result is that the process is carried out at a temperature of 480-540oC and a pressure of 80-100 MPa. In addition, the process is characterized by low selectivity of the formation of mono - and disubstituted benzenes.A method of obtaining hexaferrite, mono - and dibromopropanol, which consists in heating tribromoethanol at a temperature of 700-850oC in a flow reactor (Bull. Soc., chem Belg., 1958. 676).CFBr3C6F5Br+C6F4Br2< / BR>In the known method, there are no signs consistent with the essential features of the claimed invention, which consists in the substitution of fluorine bromine or chlorine in hexaferrite complex non-ionic halogenated compounds with the catalyst.Barriers to getting in the known method the required technical result is that the reaction is characterized by low selectivity and propertiesa are byproducts and their output is not more than 10%.Also known is a method of obtaining bromine - or harperperennial, which is the closest to the claimed .This method consists in the reaction between geksaftorbenzola and halogen at a temperature of 300-1000oC in th net, coal tablets.The characteristics of the prototype, coinciding with the essential features of the invention consist in the substitution of a fluorine atom in the halogen in the benzene ring at an elevated temperature in a flow system.Barriers to getting in the prototype of the desired technical result are as follows:
the process inert nozzles, does not exhibit catalytic properties;
- carrying out substitution reactions of fluorine halogen at high temperatures (in the description above 500oC);
the necessity of application of solid reagents - halides of the metals on the carrier - charcoal;
the use of carbon as a carrier for solid reagent metal halide;
process limited stock of applied solid reagent in the coal tablets, so it is impossible to conduct the reaction in a continuous mode;
the substitution of fluorine halogen is carried out in more than three-fold excess of halogen;
- the formation of large quantities of byproduct hydrogen-containing compounds;
- the use of a diluent is nitrogen.The above reasons result in a low conversion hexaferrite and low proizvoditelnostt> Mono - and dibromopropanol or their chlorinated analogues derived from hexaferrite and the corresponding non-ionic halogenation reagent under heating in the temperature range varying between 250 and 600oC in a flow reactor in the presence of a catalyst, which is activated carbon not containing ionic compounds of Halogens.The problem to which the invention is directed, is to increase the productivity of the method, the reduced formation of by-products and the facilitation of technology for mono - and dibromopropanol or their chlorinated analogues.The technical result contributing to the solution of the stated problem is achieved by use as a halogenation agent complex of the catalyst with a halogen-containing non-ionic compound, which reduces the reaction temperature up to 350-500oC against 500-700oC prototype.The technical result is achieved that is used as the catalyst, activated carbon, free from ionic halides, capable of combining with non-ionic halogenated compounds stable complexes with charge transfer, the speakers when the high is as a source of halogen, in addition to molecular Br2and Cl2are non-ionic halogenated compounds:
- alkanes General formula CnHalgmF2n+2-mHkwhere n=1-4, m=0 to 2n+1; k=0 to 2n, Halg=Cl, Br;
arena C6HalgnF6-nwhere n=2-6; Halg=Cl, Br;
- halogenated carbonyl compounds RfCOHalg, where Rf=F, Cl, Br, CF3- C8F17; Halg=Cl, Br;
- mixtures of the above classes of compounds.The technical result is also achieved by the fact that the complex non-ionic halogenation of compounds with active charcoal can be continuously regenerated as positives when applying non-ionic halogenated substances in the flow reactor filled with catalyst, together with geksaftorbenzola. This allows you to make the process continuous, to achieve the most complete conversion hexaferrite (up to 98%).The technical result is also achieved by the fact that the process is carried out at a stoichiometric ratio of the reagents phenyl :halogenation compound and in the absence of a diluent.Information confirming the possibility of carrying out the invention are illustrated by the following examples.Examples.1. Preparation halogenide Bunny internal thermocouple and the outer heated, filled with activated charcoal, which is connected with the receiving tank, equipped with a reflux condenser, heated to a temperature of 400 to 500oC, then the dispenser is served in the reactor 180-200 ml non-ionic halogenated compounds, sostojavshegosa of 1 mol of hexaferrite and 0.5 g of bromine atoms containing halogenated compound. At the outlet of the reactor in the receiving tank collect phenyl remaining after adsorption, which returns for solution preparation.2. The process.In the halogenation reactor, heated to a temperature of 350-500oC, the dispenser serves a pre-prepared mixture of hexaferrite and halogenated compounds (see table) with a flow rate that provides a complete conversion of halogenated compounds. The reaction products are collected in the receiving tank, and then heated and sent to the lower part of the continuous tray type distillation column efficiency 15-20 theoretical plates and the performance of 150-200 ml/h With the top of the column select light by-products, and from the middle columns of unreacted phenyl, which returns to the preparation of a mixture with a halogen-containing compound.The results obtained in examples 1 to 9 shown in the table.Example 1.Getting bromopentafluorobenzene from hexaferrite and tetrabromomethane.Example 2.The mixture of bromopentafluorobenzene and dibromotetrafluoroethane from hexaferrite and tribromophenate.Example 3.Getting chloropentafluorobenzene and dichlorotetrafluoroethane from hexaferrite and tetrachlordibenzo.Example 4.Getting bromopentafluorobenzene from hexaferrite and bromohydrin performancewas acid.Example 5.The mixture of bromopentafluorobenzene and dibromotetrafluoroethane from hexaferrite and molecular bromine.Example 6.Getting bromopentafluorobenzene from hexaferrite and dibromotetrafluoroethane.Example 7.The mixture of chloropentafluorobenzene and dichlorotetrafluoroethane from hexaferrite and molecular chlorine.Example 8.The mixture of chloropentafluorobenzene and dichlorotetrafluoroethane from hexaferrite and dichlorohydrin carbonic acid.Example 9.Getting bromopentafluorobenzene of Gex the tx2">2. Vorozhtsov N. N. (ml), Platonov, C. E., Jacobson, G. - Izv. Sib. the CTD. Union RAS, ser. chem., 1963, S. 1524.3. Y. Desirant, Bull. Soc. chem. Belg., 676 (1958).4. High-temperature substitution reactions of hexaferrite. L. A. wall and other U.S. patent N 3429935, application N 393447 declared 31.08.1964, class C 17/20, 25/14; NCI 260-650 issued 25.02.69 (prototype). The method of obtaining mono - and dibromopropanol or their chlorinated analogues, which consists in the substitution of fluorine in the benzene ring hexaferrite on bromine or chlorine by passing the latter through the flow reactor at elevated temperature with a source of bromine or chlorine selected from the group of alkanes CBr4, CF3CBr3, CHBr3arena , C6HalnF6-nwhere n = 2 to 6, Hal = Cl, Br, a halogenated carbonyl compounds RFCOHal, where RF- CF3C6F13, Cl, Hal Is Cl, Br, halogen Cl2, Br2, characterized in that the substitution of lead in the presence of activated carbon, free from ionic compounds, halogen-free, 300 - 500oC.
R=Me(a), Et(b), H-VI(in)
Closest to the technical essence and the achieved result is a method of producing compound (Ia)  consists in the consecutive action on m-differenza equivalent of sodium amide in liquid ammonia (8% solution of m-diferente) at -33aboutC for 0.5 h and iodotope bromide (1.3 equivalent) for 2 h
A method of obtaining 1,1-differetn and winifrida by fluorination of vinyl chloride hydrogen fluoride at elevated temperatures in the presence of a catalyst, followed by separation of the target product by known methods, wherein in order to intensify the process as a catalyst used aluminum fluoride with the addition of chromium oxide.with
FIELD: industrial organic synthesis.
SUBSTANCE: invention relates to preparation of alkylaromatic intermediates including perfluorinated carbon atom utilized in production of agrochemically important active compounds. Intermediates simultaneously containing aniline function are obtained from homocyclic arylcarbamoyl fluoride including at least one perhalogenated carbon atom preferably bearing at least two halogen atoms capable of being replaced by fluorine atoms when in liquid-phase contact with hydrofluoric acid and water. During this reaction, molar ratio of hydrofluoric acid to arylcarbamoyl fluoride is maintained equal to 4, preferably to 5 and not higher than 11. Water is added to reaction mixture (at 10 to 90°C) when only one exchangeable halogen atom remains unreplaced. Arylcarbamoyl fluoride is obtained in situ by adding corresponding isocyanate to liquid hydrofluoric acid at temperature not exceeding 10°C. Process is carried out continuously in two reactors, the first one serving for halogen exchange reaction and the second for addition of water. Temperature 40°C is maintained until only one exchangeable halogen atom remains unreplaced.
EFFECT: increased yield and improved quality of desired product and economical characteristics.
9 cl, 4 ex
FIELD: organic chemistry, in particular difluorochloromethane useful as cooling agent, propellant, blowing agent, as well as in fluoromonomers production.
SUBSTANCE: chloroform is treated with hydrogen fluoride in presence of catalyst predissolved in chloroform with concentration of 20-30 mol.% and chlorine, at temperature of 60-110°C and pressure of 7013 atm. As catalyst mixture of antimony pentachloride, fluorotetrachloride and trichloride in ratio of 1:(0.03-0.15):(0.03-0.15), respectively is used. Process is carried out under continuous controlling reaction mass electrical resistance which is maintained in limits of 600-1600 Om. Chlorine is introduced in amount of 0.01-0.3 mass % with respect to chloroform. Method of present invention makes it possible to control synthesis parameters in dependence of reaction mass electrical resistance.
EFFECT: increased process selectivity; new catalyst.
5 cl, 4 ex
FIELD: organic chemistry.
SUBSTANCE: claimed method includes interaction of mixture C3-C6-hydrofluoroalkane/hydrogen fluoride in absence of catalyst with at least one chloro-containing or cloro- and fluoro-containing organic compound reactive towards hydrogen fluoride in liquid phase. Hydrofluoroalkane is obtained by interaction of at least one chloro-containing or cloro- and fluoro-containing precursor with hydrogen fluoride in the first step. In one of the next steps at least part of products from the first step is made to react with hydrogen fluoride, wherein one step includes separation method. Also disclosed are azeotrope or pseudo-azeotrope composition applicable for 1,1,1,3,3-pentafluorobutane purification. Claimed composition contains as main components 1.5-27.5 mol.% of 1,1,1,3,3-pentafluorobutane and 72.5-98.5 mol.% of hydrogen fluoride.
EFFECT: method with optimized parameters.
16 cl, 4 dwg, 1 tbl, 5 ex