CN102304024B - Method for synthesizing difluoroethanol - Google Patents
Method for synthesizing difluoroethanol Download PDFInfo
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- CN102304024B CN102304024B CN201110203654.0A CN201110203654A CN102304024B CN 102304024 B CN102304024 B CN 102304024B CN 201110203654 A CN201110203654 A CN 201110203654A CN 102304024 B CN102304024 B CN 102304024B
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- VUYQBMXVCZBVHP-UHFFFAOYSA-N 1,1-difluoroethanol Chemical compound CC(O)(F)F VUYQBMXVCZBVHP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000007789 gas Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- JTLAIKFGRHDNQM-UHFFFAOYSA-N 1-bromo-2-fluoroethane Chemical compound FCCBr JTLAIKFGRHDNQM-UHFFFAOYSA-N 0.000 claims description 23
- 238000010992 reflux Methods 0.000 claims description 22
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 20
- 238000004821 distillation Methods 0.000 claims description 18
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 17
- 238000010189 synthetic method Methods 0.000 claims description 13
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 abstract description 2
- JVYROUWXXSWCMI-UHFFFAOYSA-N 2-bromo-1,1-difluoroethane Chemical compound FC(F)CBr JVYROUWXXSWCMI-UHFFFAOYSA-N 0.000 abstract 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 abstract 2
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000010471 Markovnikov's rule Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 2
- -1 acetyl halide Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 230000005477 standard model Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VOGSDFLJZPNWHY-UHFFFAOYSA-N 2,2-difluoroethanol Chemical compound OCC(F)F VOGSDFLJZPNWHY-UHFFFAOYSA-N 0.000 description 1
- AZPWOLJQERBBBM-UHFFFAOYSA-N 2-chloro-2,2-difluoroacetyl chloride Chemical compound FC(F)(Cl)C(Cl)=O AZPWOLJQERBBBM-UHFFFAOYSA-N 0.000 description 1
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical compound OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 description 1
- 241001137251 Corvidae Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CSSYKHYGURSRAZ-UHFFFAOYSA-N methyl 2,2-difluoroacetate Chemical compound COC(=O)C(F)F CSSYKHYGURSRAZ-UHFFFAOYSA-N 0.000 description 1
- PLFLRQISROSEIJ-UHFFFAOYSA-N methylborane Chemical compound CB PLFLRQISROSEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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Abstract
The invention discloses a method for synthesizing difluoroethanol. The method comprises the following steps of: (1), in a reaction kettle, adding polar or weak polar solvent and initiator in a mass ratio of (300: 1) to (30: 1); heating to 50-150 DEG C and continuously feeding vinylidene fluoride gas and hydrobromic acid gas in a mol ratio of (1: 1.05) to (1: 2.05); distilling to obtain 1,1-difluoro-2-bromoethane and absorbing tail gas by alkali solution; and (2), in the reaction kettle, adding 1,1-difluoro-2-bromoethane and sodium carbonate water solution with the mass concentration of 10-30% in a mol ratio of (2.5: 1) to (1.2: 1) and agitating under a backflow condition and reacting for 2-5 hours; cooling, adding methylbenzene, and distilling most water by co-boiling methylbenzene and water; then rectifying to obtain the difluoroethanol with the purity of more than 98%. The method provided by the invention has the advantages of high synthesis yield, less pollution, simple process, convenience in continuous operation of self-made vinylidene fluoride and hydrobromic acid gases, safety and reliability.
Description
Technical field
The present invention relates to the synthetic method of compound, relate in particular to a kind of synthetic method of difluoroethanol.
Background technology
The special construction that difluoroethanol contains difluoromethyl, therefore makes its different in kind in other alcohols, can participate in multiple organic synthesis, is particularly useful for synthetic fluorine-containing medicine, agricultural chemicals and dyestuff, is one of important intermediate of fluorine-containing fine chemicals.Under 2,2-difluoroethanol normal temperature, be colourless liquid, 96 ℃ of boiling points, fusing point-28.2 ℃, relative density 1.71, specific refractory power 1.338, acid suitable with phenol, water-soluble, sour, ethanol, ether equal solvent, poisonous, stable in properties.
The synthetic method of now existing difluoroethanol is as follows:
The people such as W.G.Reifenrath [W.G.Reifenrath. J.Med Chem., 23 (9), (1980), 985-990], and people [Booth, the Harold such as Booth Harold; Readshaw, Simon A. Tetrahedron, 1990, vol.46, #6p. 2097-2110] in anhydrous diethyl ether solvent, with methyl boron mercaptide, realized the reduction to difluoroacetic acid equally.
People [Schrems, the Otto such as Schrems Otto; Oberhoffer, Helmut M. Journal of Physical Chemistry, 1984, vol.88, #19p.4335-4342] with tetrahydrochysene lithium aluminium, difluoroacetic acid is reduced into difluoroethanol.
With NaBH
4– ZnCl
2system can be reduced to difluoroethanol by difluoroacetic acid very smoothly under reflux state in THF, and reaction only need to wait the NaBH of stoichiometry
4with ZnCl
2.[Mariappan Periasamy. Journal of Organometallic Chemistry2000, (609): 137 – 151]; With NaBH
4– I
2reduction system difluoroacetic acid, take THF as solvent, can obtain difluoroethanol at ambient temperature.[Lv Hongfei, Bian Ming, a favour. chemistry and bonding, 2007,29 (4): 284-288]; With NaBH
4– ZrCl
4system at room temperature also can be reduced to alcohol by acid, can obtain higher productive rate.[M..Lewis.?J?Chem?Res.,Miniprint,?2001,(8):844-856]。
The shortcoming of above synthetic method is that in reaction, the market price of some reagent is higher, causes its synthetic cost to improve; And the last handling process of difluoroethanol reaction is wanted water cancellation, due to difluoroethanol and water separation difficulty, causes its productive rate obviously to decline, and makes it can not obtain higher income in suitability for industrialized production, this method be only applicable to batch compared with hour preparation.
O be take two fluoracyl chlorides as starting raw material than people [patent France200680047867] such as Xi Na, R Corvidaes, it is characterized in that the catalyzer that the method is included in significant quantity exists lower hydrogenation to meet the acetyl halide of following formula, this catalyzer comprises at least one the periodictable Ⅷ family element being deposited on the electrodeless carrier of solid with Acidity.In described formula, X represents the halogen atom except fluorine atom.
The shortcoming of this synthetic method is, the market price of catalyzer is more expensive, aspect the selection of catalyzer and consumption, will consider synthetic cost; And reaction will be carried out under certain pressure, condition is comparatively harsh, not economic and practical in suitability for industrialized production.
Gloomy has just been waited people [patent JP61268639] to have 4 to 8 object gacs of massfraction 0.5% to be packed into the reaction tubes of one meter of internal diameter 1 cm long absorption with RfCOX, put in the reaction unit of 170 ℃ of thermostatically heating, to reactor, pass into difluoro carboxylic acid halides and hydrogen, react 24 h, can obtain corresponding fluoroethanol.
The shortcoming of this synthetic method is, owing to being gas-phase reaction, makes its bad control in reaction process, and reaction treating processes in early stage and reaction unit all comparatively complicated, consider this production method not economic and practical.
The people such as Lewis [Lewis. J Chem Res., Miniprint 8 (2001), 844-856] obtain difluoroethanol by sodium borohydride reduction ethyl difluoro; People [Tamura, the Kenji such as Tamura Kenji; Yamazaki, Takashi. Journal of Fluorine Chemistry, 2005, vol.126, #6p.918-930] and [patent EP2298723A1,2011] respectively by reacting in tetrahydrofuran solution with tetrahydrochysene lithium aluminium, and equally ethyl difluoro is reduced into difluoroethanol with sodium methoxide.[patent EP1820789A1,2007], by with catalyst rhodium/carbon, pass into H in autoclave
2methyl difluoroacetate reduction is obtained to difluoroethanol.Difluoroethanol is prepared with hydride reduction two fluoracyl chlorides and difluoro chloroacetyl chloride in the people such as Henne [JACS, 74 (1952), 1426-8] and [patent US221859A1,2009].
The shortcoming of this type of reduction reaction is, post-processing stages needs water to carry out cancellation, and then with ether extration, cause productive rate obviously to decline, and in difluoroethanol extract, also contain a certain amount of moisture, water and difluoroethanol azeotropic, be difficult to obtain the lower product of water content.Gas-phase high pressure reaction, conversion unit is had relatively high expectations, and reaction treating processes in early stage and reaction unit are all comparatively complicated.
People [Smith, the Peter such as Smith Peter; Donovan, William H. Magnetic Resonance in Chemistry, 1995, vol.33, #5p.395 – 405] by using catalyzer titanium chloride, vinylidene is made to difluoroethanol with hydroperoxidation.
The shortcoming of this type of reaction is, catalyzer market price is more expensive, and hydrogen peroxide agent is more dangerous, and reactant is gas, has certain difficulty in operation, and productive rate is undesirable.
In sum, these reactions or some cocatalyst, solvent market price are higher, cause its synthetic cost to improve; Or method more complicated is closed in some reaction; Or there is the comparatively shortcoming of difficulty of difluoroethanol last handling process, and totally cause its productive rate obviously to decline, can not make high-quality product.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of synthetic method of difluoroethanol is provided.
The step of the synthetic method of difluoroethanol is as follows:
1) in reactor, adding mass ratio is polarity or weak polar solvent and the initiator of 300:1～30:1, be heated to 50 ℃～150 ℃, the vinylidene gas and the Hydrogen bromide gas that pass into continuously mol ratio and be 1:1.05～1:2.05 react, distillation, obtain the fluoro-2-monobromethane of 1,1-bis-, tail gas alkali liquor absorption;
2) in reactor, adding mol ratio is 1 of 2.5:1～1.2:1, the fluoro-2-monobromethane of 1-bis-and mass concentration are 10%～30% aqueous sodium carbonate, stirring reaction 2 hr～5 hr under reflux conditions, cooling, add toluene, by toluene and water component distillation, remove most of water, rectifying again, obtains the difluoroethanol that purity is greater than 98%.
Described polarity or weak polar solvent are DMF or acetonitrile.Solvent property used is stable, good to vinylidene solvability, makes reacting balance and abundant, can reduce the generation of by product, and recoverable.Described initiator is azo-initiator, and azo-initiator is Diisopropyl azodicarboxylate.The mass ratio of described polarity or weak polar solvent and initiator is 100:1～40:1.Described Heating temperature is 60 ℃～100 ℃.Described vinylidene gas and the mol ratio of Hydrogen bromide gas are 1:1.1～1:1.2.Described aqueous sodium carbonate mass concentration is 20%～30%.Described 1, the mol ratio of the fluoro-2-monobromethane of 1-bis-and alkali lye is 2:1～1.5:1.
The present invention relates to a kind of synthetic method of difluoroethanol, in invention, reagent is simple and easy to get, reaction process is polluted few, technique is simple, without complex apparatus, and easy handling, from preparing vinylidenefluoride and Hydrogen bromide gas, be convenient to continuous production operation, safe and reliable, and synthesis yield is high, after refining, obtains the product that purity is higher.
Accompanying drawing explanation
Fig. 1 is the synthetic method schema of difluoroethanol;
Fig. 2 is the gas chromatogram of difluoroethanol standard model;
Fig. 3 be the present invention close or difluoroethanol gas chromatogram.
Embodiment
The step of the synthetic method of difluoroethanol is as follows:
1) in reactor, adding mass ratio is polarity or weak polar solvent and the initiator of 300:1～30:1, be heated to 50 ℃～150 ℃, the vinylidene gas and the Hydrogen bromide gas that pass into continuously mol ratio and be 1:1.05～1:2.05 react, distillation, obtain the fluoro-2-monobromethane of 1,1-bis-, tail gas alkali liquor absorption;
2) in reactor, adding mol ratio is 1 of 2.5:1～1.2:1, the fluoro-2-monobromethane of 1-bis-and mass concentration are 10%～30% aqueous sodium carbonate, stirring reaction 2 hr～5 hr under reflux conditions, cooling, add toluene, by toluene and water component distillation, remove most of water, rectifying again, obtains the difluoroethanol that purity is greater than 98%.
Described polarity or weak polar solvent are DMF or acetonitrile.Solvent property used is stable, good to vinylidene solvability, makes reacting balance and abundant, can reduce the generation of by product, and recoverable.
Described initiator is azo-initiator, and azo-initiator is Diisopropyl azodicarboxylate.Diisopropyl azodicarboxylate is the most frequently used a kind of azo-initiator, and its advantage is more steady while reacting, and stores and use all safelyr, and its decomposition temperature of Diisopropyl azodicarboxylate, at 50～70 ℃, belongs to low activity initiator.
The mass ratio of described polarity or weak polar solvent and initiator is 100:1～40:1.Within the scope of this, side reaction odds is relatively low, and main reaction transformation efficiency is higher.
Described Heating temperature is 60 ℃～100 ℃.Temperature is too low, initiator efficiency of initiation variation, and, easily there is side reaction in excess Temperature, and in this temperature range, main reaction is more easily carried out.
Described vinylidene gas and the mol ratio of Hydrogen bromide gas are 1:1.1～1:1.2.Now, olefin gas transformation efficiency increases, and product yield improves.
Described aqueous sodium carbonate mass concentration is 20%～30%.Within the scope of this mass concentration, the nucleophilicity of alkali is preponderated, and is conducive to nucleophilic substitution reaction, can effectively reduce the elimination side reaction that the fluoro-2-monobromethane of 1,1-bis-removes hydrogen bromide.
Described 1, the mol ratio of the fluoro-2-monobromethane of 1-bis-and alkali lye is 2:1～1.5:1.Reaction conversion ratio is high, and side reaction is less.
Experimental example is for illustrating the present invention below, and limiting examples.
In example, by gas chromatographic analysis, contrast with standard model, can infer that product is difluoroethanol, and draw product purity.
In the present invention, vinylidene gas is by the acetonitrile solution that contains 1-chlorine-1,1-difluoroethane (142b), and under the existence of phase-transfer catalyst Tetrabutyl amonium bromide, the NaOH aqueous solution that is 40% with concentration reacts and to obtain in the time of 55 ℃.Reaction conversion ratio is high, and speed is fast, there is no the 142b gas of conversion, then is absorbed the acetonitrile solution absorption of still, reclaims and carries out next batch reaction.
In the present invention, Hydrogen bromide gas is by Sodium Bromide and concentration, to be 80% sulfuric acid reaction obtains.
Under Diisopropyl azodicarboxylate exists, there is anti-markovnikov's rule addition reaction in homemade vinylidene and Hydrogen bromide gas, generates the fluoro-2-monobromethane of 1,1-bis-.Markovnikov's rule regulation: in the electrophilic addition reaction of alkene, the positively charged group of addition reagent will be added on the carbon atom of olefinic double bonds (or three key) band substituting group less (or hydrogeneous more).When the orientation of the electrophilic reagent such as unsymmetrical alkenes and hydrogen halide generation addition reaction is inconsistent with the orientation of pressing markovnikov's rule prediction, be called anti-markovnikov's rule.
Embodiment 1
1), in the reactor of gas introduction tube, reflux exchanger and thermometer is housed, adding mass ratio is solvent acetonitrile and the initiator Diisopropyl azodicarboxylate of 40:1, is heated to 70 ℃; Passing into continuously mol ratio is vinylidene gas and the bromize hydrogen gas of 1:1.2, reacts, and distillation, obtains the fluoro-2-monobromethane of 1,1-bis-, tail gas alkali liquor absorption.
2) in the reactor of agitator, reflux exchanger and thermometer is housed, adding mol ratio is 1 of 2.5:1, the aqueous sodium carbonate that the fluoro-2-monobromethane of 1-bis-and mass concentration are 30%, under reflux conditions stirring reaction 2 hr.Cooling, add toluene, by toluene and water component distillation, remove most of water, then rectifying obtains difluoroethanol, purity is 98%, productive rate is 95%.
1), in the reactor of gas introduction tube, reflux exchanger and thermometer is housed, adding mass ratio is solvent DMF and the initiator Diisopropyl azodicarboxylate of 100:1, is heated to 100 ℃; Passing into continuously mol ratio is vinylidene gas and the bromize hydrogen gas of 1:1.1, reacts, and distillation, obtains the fluoro-2-monobromethane of 1,1-bis-, tail gas alkali liquor absorption.
2) in the reactor of agitator, reflux exchanger and thermometer is housed, adding mol ratio is 1 of 2:1, the aqueous sodium carbonate that the fluoro-2-monobromethane of 1-bis-and mass concentration are 20%, under reflux conditions stirring reaction 5 hr.Cooling, add toluene, by toluene and water component distillation, remove most of water, then rectifying obtains difluoroethanol, purity is 98.5%, productive rate is 92%.
Embodiment 3
1), in the reactor of gas introduction tube, reflux exchanger and thermometer is housed, adding mass ratio is solvent DMF and the initiator Diisopropyl azodicarboxylate of 300:1, is heated to 150 ℃; Passing into continuously mol ratio is vinylidene gas and the bromize hydrogen gas of 1:1.05, reacts, and distillation, obtains the fluoro-2-monobromethane of 1,1-bis-, tail gas alkali liquor absorption.
2) in the reactor of agitator, reflux exchanger and thermometer is housed, adding mol ratio is 1 of 1.5:1, the aqueous sodium carbonate that the fluoro-2-monobromethane of 1-bis-and mass concentration are 20%, under reflux conditions stirring reaction 3 hr.Cooling, add toluene, by toluene and water component distillation, remove most of water, then rectifying obtains difluoroethanol, purity is 98.8%, productive rate is 94%.
Embodiment 4
1), in the reactor of gas introduction tube, reflux exchanger and thermometer is housed, adding mass ratio is solvent acetonitrile and the initiator Diisopropyl azodicarboxylate of 30:1, is heated to 50 ℃; Passing into continuously mol ratio is vinylidene gas and the bromize hydrogen gas of 1:2.05, reacts, and distillation, obtains the fluoro-2-monobromethane of 1,1-bis-, tail gas alkali liquor absorption.
2) in the reactor of agitator, reflux exchanger and thermometer is housed, adding mol ratio is 1 of 1.2:1, the aqueous sodium carbonate that the fluoro-2-monobromethane of 1-bis-and mass concentration are 10%, under reflux conditions stirring reaction 4 hr.Cooling, add toluene, by toluene and water component distillation, remove most of water, then rectifying obtains difluoroethanol, purity is 99%, productive rate is 88%.
Embodiment 5
1), in the reactor of gas introduction tube, reflux exchanger and thermometer is housed, adding mass ratio is solvent acetonitrile and the initiator Diisopropyl azodicarboxylate of 30:1, is heated to 70 ℃; Passing into continuously mol ratio is vinylidene gas and the bromize hydrogen gas of 1:2.05, reacts, and distillation, obtains the fluoro-2-monobromethane of 1,1-bis-, tail gas alkali liquor absorption.
2) in the reactor of agitator, reflux exchanger and thermometer is housed, adding mol ratio is 1 of 1.2:1, the aqueous sodium carbonate that the fluoro-2-monobromethane of 1-bis-and mass concentration are 30%, under reflux conditions stirring reaction 3 hr.Cooling, add toluene, by toluene and water component distillation, remove most of water, then rectifying obtains difluoroethanol, purity is 98.7%, productive rate is 93%.
Embodiment 6
1), in the reactor of gas introduction tube, reflux exchanger and thermometer is housed, adding mass ratio is solvent DMF and the initiator Diisopropyl azodicarboxylate of 280:1, is heated to 128 ℃; Passing into continuously mol ratio is vinylidene gas and the bromize hydrogen gas of 1:1.15, reacts, and distillation, obtains the fluoro-2-monobromethane of 1,1-bis-, tail gas alkali liquor absorption, and productive rate is 89%.
2) in the reactor of agitator, reflux exchanger and thermometer is housed, adding mol ratio is 1 of 1.5:1, the aqueous sodium carbonate that the fluoro-2-monobromethane of 1-bis-and mass concentration are 20%, under reflux conditions stirring reaction 4 hr.Cooling, add toluene, by toluene and water component distillation, remove most of water, then rectifying obtains difluoroethanol, purity is 99%, productive rate is 92%.
Claims (1)
1. a synthetic method for difluoroethanol, is characterized in that its step is as follows:
1) in reactor, adding mass ratio is polarity or weak polar solvent and the initiator of 300:1～30:1, be heated to 50 ℃～150 ℃, the vinylidene gas and the Hydrogen bromide gas that pass into continuously mol ratio and be 1:1.05～1:2.05 react, distillation, obtain the fluoro-2-monobromethane of 1,1-bis-, tail gas alkali liquor absorption;
2) in reactor, adding mol ratio is 1 of 2.5:1～1.2:1, the aqueous sodium carbonate that the fluoro-2-monobromethane of 1-bis-and mass concentration are 10%～30%, stirring reaction 2 hr～5 hr under reflux conditions, cooling, add toluene, by toluene and water component distillation, remove most of water, rectifying again, obtains the difluoroethanol that purity is greater than 98%;
Described polarity or weak polar solvent are DMF or acetonitrile;
Described initiator is azo-initiator, and azo-initiator is Diisopropyl azodicarboxylate;
The mass ratio of described polarity or weak polar solvent and initiator is 100:1～40:1;
Described Heating temperature is 70 ℃～100 ℃;
Described vinylidene gas and the mol ratio of Hydrogen bromide gas are 1:1.1～1:1.2;
Described aqueous sodium carbonate mass concentration is 20%～30%;
Described 1, the mol ratio of the fluoro-2-monobromethane of 1-bis-and alkali lye is 2:1～1.5:1.
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| CN102766024B (en) * | 2012-08-09 | 2015-08-12 | 西安近代化学研究所 | The preparation method of difluoroethanol |
| CN104030886B (en) * | 2014-06-04 | 2016-01-13 | 湖北海之杰化工有限公司 | Be the method that 2,2-difluoroethanol prepared by raw material with the fluoro-1-halothane of 2,2-bis- |
| CN106187679A (en) * | 2016-06-29 | 2016-12-07 | 山东聊城中盛蓝瑞化工有限公司 | The recycling system and method for carbon dioxide in a kind of chlorinated hydrocabon hydrolysis tail gas |
| CN106810421A (en) * | 2016-12-19 | 2017-06-09 | 西安近代化学研究所 | A kind of separation method of difluoroethanol and water azeotropic mixture |
| CN107353179A (en) * | 2017-06-17 | 2017-11-17 | 南通宝凯化工有限公司 | A kind of preparation technology of difluoroethanol |
| CN111499492A (en) * | 2019-01-31 | 2020-08-07 | 中化近代环保化工(西安)有限公司 | Preparation method of 2, 2-difluoroethanol |
| CN112898121A (en) * | 2021-01-23 | 2021-06-04 | 四川上氟科技有限公司 | Preparation method of perfluoroalkyl alcohol |
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| WO2009040367A1 (en) * | 2007-09-28 | 2009-04-02 | Solvay (Société Anonyme) | Process for the preparation of fluorine containing organic compound |
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