CN102304024A - Method for synthesizing difluoroethanol - Google Patents
Method for synthesizing difluoroethanol Download PDFInfo
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- CN102304024A CN102304024A CN201110203654A CN201110203654A CN102304024A CN 102304024 A CN102304024 A CN 102304024A CN 201110203654 A CN201110203654 A CN 201110203654A CN 201110203654 A CN201110203654 A CN 201110203654A CN 102304024 A CN102304024 A CN 102304024A
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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 45
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000007789 gas Substances 0.000 claims abstract description 47
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 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 class FCCBr JTLAIKFGRHDNQM-UHFFFAOYSA-N 0.000 claims description 23
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 20
- 238000001308 synthesis method Methods 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
- 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
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 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
- 238000010992 reflux Methods 0.000 description 13
- 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 7
- 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
- 239000002253 acid Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 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
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 description 3
- 239000011737 fluorine Substances 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
- 238000007259 addition reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 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
- 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
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000004678 hydrides 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 class 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
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 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 synthesis method of compound, relate in particular to a kind of synthesis method of difluoroethanol.
Background technology
Difluoroethanol contains the special construction of 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.2,2-difluoroethanol normal temperature is down colourless liquid, 96 ℃ of boiling points, and 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 synthesis method of now existing difluoroethanol, as follows:
People such as W.G.Reifenrath [W.G.Reifenrath. J.Med Chem., 23 (9), (1980), 985-990], and people [Booth, Harold such as Booth Harold; Readshaw, Simon A. Tetrahedron, 1990, vol.46, #6p. 2097-2110] in the anhydrous diethyl ether solvent, realized reduction equally to difluoroacetic acid with the methyl boron mercaptide.
People [Schrems, 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 with difluoroacetic acid under the reflux state very smoothly in THF, the NaBH of stoichiometry such as a reaction needs
4With ZnCl
2[Mariappan Periasamy. Journal of Organometallic Chemistry2000, (609): 137 – 151]; With NaBH
4– I
2The reduction system difluoroacetic acid is a solvent with THF, can obtain difluoroethanol at ambient temperature.[Lv Hongfei, Bian Ming open favour. chemistry and bonding, 2007,29 (4): 284-288]; With NaBH
4– ZrCl
4System at room temperature also can be reduced to alcohol with acid, can obtain higher productive rate.[M..Lewis.?J?Chem?Res.,Miniprint,?2001,(8):844-856]。
The shortcoming of above synthesis method is that the market price of some reagent is higher in the reaction, causes its synthetic cost to improve; And the last handling process of difluoroethanol reaction is wanted the water cancellation, because difluoroethanol and water sepn difficulty cause its productive rate obviously to descend, makes it in suitability for industrialized production, can not obtain higher income, this method only be applicable to batch than hour preparation.
O is starting raw material than people [patent France200680047867] such as Xi Na, R Corvidaes with two fluoracyl chlorides; It is characterized in that catalyzer that this method is included in significant quantity exists hydrogenation down to meet the acetyl halide of following formula, this catalyzer comprises at least a periodictable VIII family element that is deposited on the electrodeless carrier of the solid with acid matter.In said formula, X representes the halogen atom except that fluorine atom.
The shortcoming of this synthesis method is that the market price of catalyzer is expensive, will consider synthetic cost aspect selection of catalysts and the consumption; And reaction will be carried out under certain pressure, and condition is comparatively harsh, and is not economic and practical in suitability for industrialized production.
Gloomy 4 to the 8 purpose gacs that just waited people [patent JP61268639] will be adsorbed with massfraction 0.5% with RfCOX are packed into the reaction tubes of one meter of internal diameter 1 cm long; Put in the reaction unit of 170 ℃ of thermostatically heating; Feed difluoro carboxylic acid halides and hydrogen to reactor; React 24 h, can obtain corresponding fluoroethanol.
The shortcoming of this synthesis method is, owing to be gas-phase reaction, makes its bad control in reaction process, and reaction treating processes in early stage and reaction unit are all comparatively complicated, and it is not economic and practical to take all factors into consideration this working method.
People such as Lewis [Lewis. J Chem Res., Miniprint 8 (2001), 844-856] obtain difluoroethanol through the sodium borohydride reduction ethyl difluoro; People [Tamura, Kenji such as Tamura Kenji; Yamazaki; Takashi. Journal of Fluorine Chemistry; 2005; Vol.126; #6p.918-930] and [patent EP2298723A1; 2011], and equally ethyl difluoro is reduced into difluoroethanol with sodium methoxide respectively through in tetrahydrofuran solution, reacting with tetrahydrochysene lithium aluminium.[patent EP1820789A1,2007] feed H through with catalyst rhodium/carbon in autoclave
2The reduction of difluoroacetic acid methyl esters is obtained difluoroethanol.People such as Henne [JACS, 74 (1952), 1426-8] and [patent US221859A1,2009] prepare difluoroethanol with hydride reduction two fluoracyl chlorides and difluoro chloroacetyl chloride.
The shortcoming of this type of reduction reaction is that post-processing stages needs water to carry out cancellation, and then uses ether extration; Cause productive rate obviously to descend; And also contain a certain amount of moisture in the difluoroethanol extract, water and difluoroethanol azeotropic are difficult to obtain the lower product of water content.The gas phase reaction under high pressure, conversion unit is had relatively high expectations, and reaction treating processes in early stage and reaction unit are all comparatively complicated.
People [Smith, Peter such as Smith Peter; Donovan, William H. Magnetic Resonance in Chemistry, 1995, vol.33, #5p.395 – 405] through using the catalyzer titanium chloride, vinylidene is made difluoroethanol with hydroperoxidation.
The shortcoming of this type of reaction is, catalyzer market price is more expensive, and hydrogen peroxide agent is dangerous, and reactant is gas, and certain difficulty is arranged in the 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 the method more complicated is closed in some reaction; Or have the comparatively shortcoming of difficulty of difluoroethanol last handling process, and totally cause its productive rate obviously to descend, can not make high-quality product.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of synthesis method of difluoroethanol is provided.
The step of the synthesis method of difluoroethanol is following:
1) in reaction kettle; Adding mass ratio is polarity or weak polar solvent and the initiator of 300:1～30:1; Be heated to 50 ℃～150 ℃; Vinylidene gas and Hydrogen bromide gas that continuous feeding mol ratio is 1:1.05～1:2.05 react; Distillation; Obtain 1,1-two fluoro-2-monobromethanes, tail gas absorbs with alkali lye;
2) in reaction kettle; Adding mol ratio is 1 of 2.5:1～1.2:1; 1-two fluoro-2-monobromethanes and mass concentration are 10%～30% aqueous sodium carbonate; Stirring reaction 2 hr～5 hr under refluxad; Cooling adds toluene, removes most of water through toluene and water component distillation; Rectifying again obtains purity greater than 98% difluoroethanol.
Described polarity or weak polar solvent are N, dinethylformamide or acetonitrile.Used solvent property is stable, and is good to the vinylidene solvability, makes reacting balance and abundant, can reduce the generation of by product, and recyclable utilization.Described initiator is an azo-initiator, and azo-initiator is a 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 ℃.The mol ratio of described vinylidene gas and Hydrogen bromide gas is 1:1.1～1:1.2.Described aqueous sodium carbonate mass concentration is 20%～30%.Described 1, the mol ratio of 1-two fluoro-2-monobromethanes and alkali lye is 2:1～1.5:1.
The present invention relates to a kind of synthesis method of difluoroethanol; Reagent is simple and easy in the invention; Reaction process is polluted few; Technology is simple, need not complex apparatus, easy handling; Be convenient to the continuous production operation from preparing vinylidenefluoride and Hydrogen bromide gas; Safe and reliable, and synthesis yield is high, obtains the purity high product after making with extra care.
Description of drawings
Fig. 1 is the synthesis method schema of difluoroethanol;
Fig. 2 is the gas chromatogram of difluoroethanol standard model;
Fig. 3 be the present invention close or the difluoroethanol gas chromatogram.
Embodiment
The step of the synthesis method of difluoroethanol is following:
1) in reaction kettle; Adding mass ratio is polarity or weak polar solvent and the initiator of 300:1～30:1; Be heated to 50 ℃～150 ℃; Vinylidene gas and Hydrogen bromide gas that continuous feeding mol ratio is 1:1.05～1:2.05 react; Distillation; Obtain 1,1-two fluoro-2-monobromethanes, tail gas absorbs with alkali lye;
2) in reaction kettle; Adding mol ratio is 1 of 2.5:1～1.2:1; 1-two fluoro-2-monobromethanes and mass concentration are 10%～30% aqueous sodium carbonate; Stirring reaction 2 hr～5 hr under refluxad; Cooling adds toluene, removes most of water through toluene and water component distillation; Rectifying again obtains purity greater than 98% difluoroethanol.
Described polarity or weak polar solvent are N, dinethylformamide or acetonitrile.Used solvent property is stable, and is good to the vinylidene solvability, makes reacting balance and abundant, can reduce the generation of by product, and recyclable utilization.
Described initiator is an azo-initiator, and azo-initiator is a Diisopropyl azodicarboxylate.Diisopropyl azodicarboxylate is the most frequently used a kind of azo-initiator, and its advantage is more steady when reacting, and stores and use and all compare safety, and its decomposition temperature of Diisopropyl azodicarboxylate belongs to the low activity initiator at 50～70 ℃.
The mass ratio of described polarity or weak polar solvent and initiator is 100:1～40:1.In this scope, the side reaction odds is relatively low, and the main reaction transformation efficiency is higher.
Described Heating temperature is 60 ℃～100 ℃.Temperature is low excessively, initiator efficiency of initiation variation, and temperature is too high, is prone to side reaction takes place, and in this temperature range, main reaction more is prone to carry out.
The mol ratio of described vinylidene gas and Hydrogen bromide gas is 1:1.1～1:1.2.At this moment, the olefin gas transformation efficiency increases, and product yield improves.
Described aqueous sodium carbonate mass concentration is 20%～30%.In this mass concentration scope, the nucleophilicity of alkali is preponderated, and helps nucleophilic substitution reaction, can effectively reduce 1, and 1-two fluoro-2-monobromethanes remove the elimination side reaction of hydrogen bromide.
Described 1, the mol ratio of 1-two fluoro-2-monobromethanes and alkali lye is 2:1～1.5:1.Reaction conversion ratio is high, and side reaction is less.
Following experimental example is for illustrating the present invention, and limiting examples.
In instance,,, can infer that product is a difluoroethanol, and draw product purity with the standard model contrast through gas chromatographic analysis.
Vinylidene gas is by containing 1-chloro-1 among the present invention, the acetonitrile solution of 1-C2H4F2 C2H4F2 (142b), and in the presence of the phase-transfer catalyst Tetrabutyl amonium bromide, being 40% the NaOH aqueous solution 55 ℃ the time with concentration, reaction obtains.Reaction conversion ratio is high, and speed is fast, does not have the 142b gas of conversion, and the acetonitrile solution that is absorbed still again absorbs, and reclaims and carries out the next batch reaction.
Hydrogen bromide gas is to be that 80% sulfuric acid reaction obtains by Sodium Bromide and concentration among the present invention.
Anti-markovnikov's rule addition reaction takes place in homemade vinylidene and Hydrogen bromide gas in the presence of Diisopropyl azodicarboxylate, generate 1,1-two fluoro-2-monobromethanes.The markovnikov's rule regulation: in the electrophilic addition reaction of alkene, the positively charged property 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).The orientation of electrophilic reagent such as unsymmetrical alkenes and hydrogen halide generation addition reaction with press orientation that markovnikov's rule predicts when inconsistent, be called anti-markovnikov's rule.
Embodiment 1
1) in the reaction kettle that gas introduction tube, reflux exchanger and thermometer are housed, adding mass ratio is solvent acetonitrile and the initiator Diisopropyl azodicarboxylate of 40:1, is heated to 70 ℃; Feeding mol ratio continuously is vinylidene gas and the bromize hydrogen gas of 1:1.2, reacts, and distillation obtains 1,1-two fluoro-2-monobromethanes, and tail gas absorbs with alkali lye.
2) in the reaction kettle that agitator, reflux exchanger and thermometer are housed, adding mol ratio is 1 of 2.5:1, and 1-two fluoro-2-monobromethanes and mass concentration are 30% aqueous sodium carbonate, under refluxad stirring reaction 2 hr.Cooling adds toluene, removes most of water through toluene and water component distillation, and rectifying gets difluoroethanol again, and purity is 98%, and productive rate is 95%.
1) in the reaction kettle that gas introduction tube, reflux exchanger and thermometer are housed, adding mass ratio is the solvent N of 100:1, and dinethylformamide and initiator Diisopropyl azodicarboxylate are heated to 100 ℃; Feeding mol ratio continuously is vinylidene gas and the bromize hydrogen gas of 1:1.1, reacts, and distillation obtains 1,1-two fluoro-2-monobromethanes, and tail gas absorbs with alkali lye.
2) in the reaction kettle that agitator, reflux exchanger and thermometer are housed, adding mol ratio is 1 of 2:1, and 1-two fluoro-2-monobromethanes and mass concentration are 20% aqueous sodium carbonate, under refluxad stirring reaction 5 hr.Cooling adds toluene, removes most of water through toluene and water component distillation, and rectifying gets difluoroethanol again, and purity is 98.5%, and productive rate is 92%.
Embodiment 3
1) in the reaction kettle that gas introduction tube, reflux exchanger and thermometer are housed, adding mass ratio is the solvent N of 300:1, and dinethylformamide and initiator Diisopropyl azodicarboxylate are heated to 150 ℃; Feeding mol ratio continuously is vinylidene gas and the bromize hydrogen gas of 1:1.05, reacts, and distillation obtains 1,1-two fluoro-2-monobromethanes, and tail gas absorbs with alkali lye.
2) in the reaction kettle that agitator, reflux exchanger and thermometer are housed, adding mol ratio is 1 of 1.5:1, and 1-two fluoro-2-monobromethanes and mass concentration are 20% aqueous sodium carbonate, under refluxad stirring reaction 3 hr.Cooling adds toluene, removes most of water through toluene and water component distillation, and rectifying gets difluoroethanol again, and purity is 98.8%, and productive rate is 94%.
Embodiment 4
1) in the reaction kettle that gas introduction tube, reflux exchanger and thermometer are housed, adding mass ratio is solvent acetonitrile and the initiator Diisopropyl azodicarboxylate of 30:1, is heated to 50 ℃; Feeding mol ratio continuously is vinylidene gas and the bromize hydrogen gas of 1:2.05, reacts, and distillation obtains 1,1-two fluoro-2-monobromethanes, and tail gas absorbs with alkali lye.
2) in the reaction kettle that agitator, reflux exchanger and thermometer are housed, adding mol ratio is 1 of 1.2:1, and 1-two fluoro-2-monobromethanes and mass concentration are 10% aqueous sodium carbonate, under refluxad stirring reaction 4 hr.Cooling adds toluene, removes most of water through toluene and water component distillation, and rectifying gets difluoroethanol again, and purity is 99%, and productive rate is 88%.
Embodiment 5
1) in the reaction kettle that gas introduction tube, reflux exchanger and thermometer are housed, adding mass ratio is solvent acetonitrile and the initiator Diisopropyl azodicarboxylate of 30:1, is heated to 70 ℃; Feeding mol ratio continuously is vinylidene gas and the bromize hydrogen gas of 1:2.05, reacts, and distillation obtains 1,1-two fluoro-2-monobromethanes, and tail gas absorbs with alkali lye.
2) in the reaction kettle that agitator, reflux exchanger and thermometer are housed, adding mol ratio is 1 of 1.2:1, and 1-two fluoro-2-monobromethanes and mass concentration are 30% aqueous sodium carbonate, under refluxad stirring reaction 3 hr.Cooling adds toluene, removes most of water through toluene and water component distillation, and rectifying gets difluoroethanol again, and purity is 98.7%, and productive rate is 93%.
Embodiment 6
1) in the reaction kettle that gas introduction tube, reflux exchanger and thermometer are housed, adding mass ratio is the solvent N of 280:1, and dinethylformamide and initiator Diisopropyl azodicarboxylate are heated to 128 ℃; Feeding mol ratio continuously is vinylidene gas and the bromize hydrogen gas of 1:1.15, reacts, and distillation obtains 1,1-two fluoro-2-monobromethanes, and tail gas absorbs with alkali lye, and productive rate is 89%.
2) in the reaction kettle that agitator, reflux exchanger and thermometer are housed, adding mol ratio is 1 of 1.5:1, and 1-two fluoro-2-monobromethanes and mass concentration are 20% aqueous sodium carbonate, under refluxad stirring reaction 4 hr.Cooling adds toluene, removes most of water through toluene and water component distillation, and rectifying gets difluoroethanol again, and purity is 99%, and productive rate is 92%.
Claims (8)
1. the synthesis method of a difluoroethanol is characterized in that its step is following:
1) in reaction kettle; Adding mass ratio is polarity or weak polar solvent and the initiator of 300:1～30:1; Be heated to 50 ℃～150 ℃; Vinylidene gas and Hydrogen bromide gas that continuous feeding mol ratio is 1:1.05～1:2.05 react; Distillation; Obtain 1,1-two fluoro-2-monobromethanes, tail gas absorbs with alkali lye;
2) in reaction kettle; Adding mol ratio is 1 of 2.5:1～1.2:1; 1-two fluoro-2-monobromethanes and mass concentration are 10%～30% aqueous sodium carbonate; Stirring reaction 2 hr～5 hr under refluxad; Cooling adds toluene, removes most of water through toluene and water component distillation; Rectifying again obtains purity greater than 98% difluoroethanol.
2. the synthesis method of a kind of difluoroethanol according to claim 1 is characterized in that described polarity or weak polar solvent are N, dinethylformamide or acetonitrile.
3. the synthesis method of a kind of difluoroethanol according to claim 1 is characterized in that described initiator is an azo-initiator, and azo-initiator is a Diisopropyl azodicarboxylate.
4. the synthesis method of a kind of difluoroethanol according to claim 1, the mass ratio that it is characterized in that described polarity or weak polar solvent and initiator is 100:1～40:1.
5. the synthesis method of a kind of difluoroethanol according to claim 1 is characterized in that described Heating temperature is 70 ℃～100 ℃.
6. the synthesis method of a kind of difluoroethanol according to claim 1, the mol ratio that it is characterized in that described vinylidene gas and Hydrogen bromide gas is 1:1.1～1:1.2.
7. the synthesis method of a kind of difluoroethanol according to claim 1 is characterized in that described aqueous sodium carbonate mass concentration is 20%～30%.
8. the synthesis method of a kind of difluoroethanol according to claim 1 is characterized in that describedly 1, and the mol ratio of 1-two fluoro-2-monobromethanes and alkali lye is 2:1～1.5:1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102766024A (en) * | 2012-08-09 | 2012-11-07 | 西安近代化学研究所 | Method for preparing difluoroethanol |
| CN104030886A (en) * | 2014-06-04 | 2014-09-10 | 湖北海之杰化工有限公司 | Method for preparing 2,2-difluoroethanol from 2,2-difluoro-1-halogenated ethane |
| 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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| CN1429799A (en) * | 2003-01-04 | 2003-07-16 | 大连理工大学 | Synthesis method of 1-bromoane |
| WO2009040367A1 (en) * | 2007-09-28 | 2009-04-02 | Solvay (Société Anonyme) | Process for the preparation of fluorine containing organic compound |
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| CN1429799A (en) * | 2003-01-04 | 2003-07-16 | 大连理工大学 | Synthesis method of 1-bromoane |
| WO2009040367A1 (en) * | 2007-09-28 | 2009-04-02 | Solvay (Société Anonyme) | Process for the preparation of fluorine containing organic compound |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766024A (en) * | 2012-08-09 | 2012-11-07 | 西安近代化学研究所 | Method for preparing difluoroethanol |
| CN102766024B (en) * | 2012-08-09 | 2015-08-12 | 西安近代化学研究所 | The preparation method of difluoroethanol |
| CN104030886A (en) * | 2014-06-04 | 2014-09-10 | 湖北海之杰化工有限公司 | Method for preparing 2,2-difluoroethanol from 2,2-difluoro-1-halogenated ethane |
| 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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