CN1247504C - Process for preparing beta-halogen-alpha-phenyl ethyl alcohol compounds - Google Patents

Process for preparing beta-halogen-alpha-phenyl ethyl alcohol compounds Download PDF

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CN1247504C
CN1247504C CN 200410052975 CN200410052975A CN1247504C CN 1247504 C CN1247504 C CN 1247504C CN 200410052975 CN200410052975 CN 200410052975 CN 200410052975 A CN200410052975 A CN 200410052975A CN 1247504 C CN1247504 C CN 1247504C
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alpha
compounds
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methyl phenyl
halogen
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CN1587243A (en
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杨立荣
吴坚平
王明慧
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Zhejiang University ZJU
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Abstract

The present invention discloses a preparation method of beta-halogeno-alpha-phenylethyl alcohol compounds. Sodium borohydride or potassium borohydride is used as a reducing agent, under the existence of metal ions of stoichiometry or more than stoichiometry such as Ca<2+>, Mg<2+>, Sr<2+>, Ln<3+> (all the lanthanide trivalent ions such as La<3+>, Ce<3+>, etc.), Zn<2+> and Cu<2+>, alpha-halogeno-hypnone compounds are reduced to be the corresponding beta-halogeno-alpha-phenethyl alcohol compounds in methanol or ethanol media. Since the metal ions and the alpha-halogeno-hypnone compounds form stable compositions, halogen atoms on alpha-positions can not be substituted or reduced and the selectivity of reactions is greatly increased. The reactions have the advantages of wide temperature range, high selectivity and high yield, and can be carried out at normal temperature.

Description

The preparation method of β-halo-methyl phenyl carbinol compounds
Technical field
The present invention relates to the preparation method of a kind of β-halo-methyl phenyl carbinol compounds.
Background technology
β-halo-methyl phenyl carbinol compounds is fine-chemical intermediates such as important medicine, dyestuff, can be by the corresponding alpha-halogen of reduction-acetophenone compounds preparation.The method that ketone is reduced to alcohol mainly contains: catalytic hydrogenation method, metal hydride hydrogenation aluminium lithium, sodium borohydride or POTASSIUM BOROHYDRIDE, borine and reduction methods such as their part hydrogen substituent such as trimethoxy lithium aluminum hydride, aluminum isopropylate reduction method.Catalytic hydrogenation method general requirement pressure-resistant equipment, the device structure complexity, cost an arm and a leg, catalyzer precious metal commonly used such as platinum, rhodium, rhenium etc., the catalyzer on also useful copper basis (is the method for CN 1205323A as patent publication No.) produces the by product phenylethane in reaction.The reducing activity height of lithium aluminum hydride requires anhydrous condition.Sodium borohydride or POTASSIUM BOROHYDRIDE are commonly used for the reductive agent that aldehyde, ketone is reduced into alcohol, and selectivity is good, and easy and simple to handle, safety does not need anhydrous requirement, and reaction is generally carried out in water or alcoholic solution.Someone is at ice-water bath; use solid POTASSIUM BOROHYDRIDE reductase 12-chloro-1-(2 ' in methyl alcohol or DMF under room temperature or the reflux; 4 '-dichlorophenyl)-ethyl ketone [Liu Shangzhong etc.; agricultural chemicals, 1995,34 (10); 13-14] [Jiang Cailing; Zhang Guohong, Chinese Journal of Pharmaceuticals, 1997; 28 (5); 231-232], [Ye Baohui etc., Chinese Journal of Pharmaceuticals; 1990; 21 (2), 56-57], thermal discharge is big in reaction process; there is intensive gas to produce; add the difficult control of solid borohydride operation, easily cause reaction solution being overflowed cause danger, follow the substitution reaction of α-halogen atom in the reaction simultaneously and produce a large amount of multiple by products such as phenyl ethylene oxide because of reacting; alpha-halogen-bata-phenethyl alcohol; methyl phenyl carbinol; bata-phenethyl alcohol; phenylethane etc.; reduce the selectivity and the productive rate of reaction, faced the difficulty of later separation purifying.It is low to reduce the reaction efficiency of alpha-halogen-methyl phenyl ketone with aluminum isopropylate.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of β-halo-methyl phenyl carbinol compounds.
The step of method is as follows:
1) with metal chloride or nitrate by metal ion and alpha-halogen-acetophenone compounds be in molar ratio 1.0～2.0 and Fatty Alcohol(C12-C14 and C12-C18) or ether compound reaction solvent join in the reactor, at room temperature stirred 15-40 minute;
2) taking by weighing the sodium borohydride that is equivalent to 1～1.5 times of alpha-halogen-acetophenone compounds molar weight or POTASSIUM BOROHYDRIDE is dissolved in 1%～2% the aqueous sodium hydroxide solution or water-alcohol solution, in ice bath or room temperature and under stirring, this sodium borohydride or solution of potassium borohydride are added dropwise in the reaction mixture;
3) dropwise after, continue under ice bath or room temperature or heating, to react 10～40 minutes, add dilute hydrochloric acid solution decomposition-reduction product;
4) most of solvent is removed in normal pressure or underpressure distillation, with organic product and the aqueous phase separation that generates, water is again with the ether organic solvent extraction and merge in the organic product adding Calcium Chloride Powder Anhydrous or anhydrous magnesium sulfate drying agent drying, organic solvent is removed in distillation, gets final product.
The present invention is by adding metal chloride such as calcium chloride, rare earth chloride or nitrate, under metal ion participates in, become corresponding β-halo-methyl phenyl carbinol compounds with sodium borohydride or solution of potassium borohydride reduction alpha-halogen-acetophenone compounds, range of reaction temperature is wide, can carry out at normal temperatures, reaction temperature and, easy to operate, equipment is simple.Because metal ion and reaction substrate alpha-halogen-acetophenone compounds have formed complex compound, avoided oxygen cyclization, α-chlorine by side reactions such as getting and reduction, thereby make the selectivity of reducing carbonyl high, obtain high yield and highly purified product β-halo-methyl phenyl carbinol compounds.
Embodiment
Fatty Alcohol(C12-C14 and C12-C18) of the present invention is methyl alcohol, ethanol, Virahol or the trimethyl carbinol.Ether compound is tetrahydrofuran (THF), dioxane or glycol dimethyl ether.The metal ion of metal chloride or nitrate is Ca 2+, Mg 2+, Sr 2+, Mn 2+, La 3+, Ce 3+... all lanthanon+3 valency ions, Cu 2+, Zn 2+The temperature of reaction of step 3) of the present invention is-5 ℃ of boiling temperatures to solvent for use, and at room temperature Fan Ying time is 20～30 minutes.Substituting group on the phenyl ring of alpha-halogen-acetophenone compounds is F, Cl, Br, OH, OCH 3, SCH 3, CH 2OH, NH 2, NO 2, CH 3, C 2H 5, t-Bu, CF 3, Ph, Benzyl.
With sodium borohydride or POTASSIUM BOROHYDRIDE is reductive agent, in stoichiometry or in the presence of more than stoichiometric metal ion, in pure media such as methyl alcohol or ethanol, alpha-halogen-acetophenone compounds is reduced into corresponding β-halo-methyl phenyl carbinol compounds, its chemical equation is as follows:
Figure C20041005297500041
M N+: Ca 2+, Mg 2+, Sr 2+, Mn 2+, Ln 3+(La 3+, Ce 3+... wait all lanthanon+3 valency ions), Zn 2+, Cu 2+Soluble chloride or nitrate.
In the compound ketone: X=Cl, Br, R 1, R 2, R 3, R 4=H, F, Cl, Br, OH, OCH 3, SCH 3, CH 2OH, NH 2, NO 2, CH 3, C 2H 5, t-Bu, CF 3, Ph, groups such as Benzyl.Some representational compounds are listed in the table below:
R 1 H X H F H Cl F H H H OH H H H
R 2 H H X H F Cl F H H OH OH H OH Ph
R 3 H H H H H H H X NO 2 CH 2OH H OH H F
R 4 H H H H H H H H H H H OH H H
R1 H Cl H CH 3 H H CH 3 CH 3 H OH H
R 2 NO 2 Cl NH 2 H CH 3 C 2H 5 CH 3 H t-Bu H Ph
R 3 H Cl Cl H H H H H H CH 3 NO 2
R 4 H H Cl H H H CH 3 H H H
R 1 OH H H OCH 3 OCH 3 NH 2 H H H
R 2 OCH 3 H OCH 3 OCH 3 H H NH2 H X
R 3 H OCH 3 OCH 3 H OCH 3 H H NH 2 NH 2
R 4 H H H H H H H H H
Key of the present invention is to add above-mentioned metal ion and reactant alpha-halogen-methyl phenyl ketone has formed a kind of more stable title complex, halogen atom on the alpha-position no longer is substituted or reduces, and has greatly improved the selectivity of reaction.
The reaction implementation process is as follows:
With ketone reactant and solvent methanol or ethanol (also can be other Fatty Alcohol(C12-C14 and C12-C18) such as Virahol, the trimethyl carbinol etc. or ether such as tetrahydrofuran (THF), dioxane, glycol dimethyl ether etc.) and above-mentioned metal chloride or nitrate such as calcium chloride, nitrocalcite, Manganous chloride tetrahydrate, Lanthanum trichloride, Cerium II Chlorides etc. make metal ion and ketone form title complex at room temperature or stirring reaction certain hour under the heat a little.The add-on of metal ion will guarantee to make itself and the abundant complexing of ketone.Under agitation drip sodium borohydride (or POTASSIUM BOROHYDRIDE) solution in reaction system.Sodium borohydride (or POTASSIUM BOROHYDRIDE) is 1.0-1.5 or lower with the mol ratio of reactant.The consumption of sodium borohydride (or POTASSIUM BOROHYDRIDE) is to guarantee abundant reduction.Sodium borohydride (or POTASSIUM BOROHYDRIDE) is mixed with the aqueous solution or the water-alcohol solution of 1% sodium hydroxide (or potassium hydroxide), can not decompose in solution to guarantee sodium borohydride (or POTASSIUM BOROHYDRIDE), and the alkalescence that is unlikely to solution again reduces reducing power too greatly.Too violent for preventing reaction, preferably reactor is placed ice-water bath.Adopt the liquid feed way among the present invention, than solid feed way more convenient operation, reaction more easy to control has prevented from reaction solution to be overflowed cause danger because of reacting.At room temperature reacted after dropwising 10 minutes to 30 minutes, the length in reaction times is relevant with the species of metal ion and the temperature of reaction of ketone reactant and adding again.Temperature of reaction at-5 ℃ to the boiling spread of solvent.Under reflux temperature, be reflected at 10 minutes and just can finish.At room temperature reaction is easy to operate, and therefore save energy selects reaction at room temperature more favourable again, and being reflected at 20-30 minute can finish.After the reactant total overall reaction is intact, add dilute hydrochloric acid solution in reactor.It is necessary adding diluted acid, and its objective is: (1) decomposes unreacted sodium borohydride; (2) reductive hydrolysis product.Mixture is moved in the water distilling apparatus, and most of solvent is removed in underpressure distillation.To be cooled after room temperature, if there is not the metal chloride precipitation to separate out, then mixed solution moved in the separating funnel organic layer is told.If there is precipitation to separate out, then add a certain amount of ether or other organic solvent that can dissolve organic product dissolves product, filter or suction filtration is removed precipitation, again mixed solution is moved in the separating funnel organic layer is told.The water extracted with diethyl ether merges in the organic phase.With dry this diethyl ether solution of siccative such as anhydrous magnesium sulfate or Calcium Chloride Powder Anhydrous.Ether is removed in distillation, promptly gets product β-halo-methyl phenyl carbinol.Crude product can be with suitable solvent recrystallization.Degree of purity of production can be used gas Chromatographic Determination.
Below with Ca 2+For example explanation metal ion and alpha-halogen-methyl phenyl ketone formation title complex by the mechanism of sodium borohydride reduction:
Figure C20041005297500061
The present invention emphasizes simultaneously, if do not add metal ion in reaction system, obtain highly selective reduzate β-halo-methyl phenyl carbinol, and reduction reaction temperature must be controlled at below 15 ℃.Temperature of reaction is high more, and the amount of by product is big more.
Embodiment is as follows:
Come the inventive method is described in detail by embodiment.
Embodiment 1: synthetic 1-(2,4 dichloro benzene base)-2-chloro-ethanol
With 0.2mol (22.2g) calcium chloride, 0.1mol (22.35g) 2,2 ', 4 '-Trichloroacetophenon, 90ml methyl alcohol join in the 250ml there-necked flask,, stirred 0.5 hour down at 25 ℃.. the sodium borohydride of 0.12mol (4.8g) 96% is dissolved in the solution that 10ml methyl alcohol+10ml 1% aqueous sodium hydroxide solution is made into. at ice bath and under stirring, drip sodium borohydride solution.After dropwising, at room temperature continued stirring reaction 20 minutes down. along with the adularescent solid that carries out that reacts produces.The hydrochloric acid soln that adds 50ml (1+2) decomposes.Most of methyl alcohol is removed in underpressure distillation.Be cooled to room temperature, separatory is told organic layer, and water extracts with ether (20ml * 2), and extraction liquid merges in the organic phase, uses anhydrous magnesium sulfate drying.Ether is removed in distillation, gets yellow oily liquid product 22g, places and separates out white crystal gas chromatographic analysis, product 1-(2,4 dichloro benzene base)-2-chloro-purity of alcohol nearly 100%.Get white needle-like crystals 20g with 20ml sherwood oil recrystallization, yield 88.7%.
The top no calcium chloride that is reflected at participates in down ,-1-5 ℃ reduction down, product 1-(2,4 dichloro benzene base)-2-chloro-purity of alcohol reaches more than 99.8% with gas chromatographic analysis.
Embodiment 2: synthetic 1-(2,4 dichloro benzene base)-2-chloro-ethanol
With 0.20mol (39.58g) manganous chloride (MnCl 24H2O), 0.10mol (22.35g) 2,2 ', 4 '-Trichloroacetophenon, the ethanol of 100ml95% joins in the 250ml there-necked flask,, stirred 0.5 hour down at 25 ℃.The sodium borohydride of 0.15mol (5.70g) 96% is dissolved in 10ml 1% aqueous sodium hydroxide solution. slowly drip sodium borohydride solution in room temperature and under stirring.After dropwising, under 70 ℃ of heating in water bath, continuing stirring reaction 30 minutes. following processing is with embodiment 1.Get yellow oily liquid product 22g, place and separate out white crystal. use gas chromatographic analysis, product 1-(2,4 dichloro benzene base)-2-chloro-purity of alcohol 99.8%.Get white needle-like crystals 20g with 20ml sherwood oil recrystallization, yield 88.7%.
Embodiment 3: synthetic 1-(2,4 dichloro benzene base)-2-chloro-ethanol
With 0.1mol zinc chloride (13.63g) or 0.1mol zinc nitrate (29.75g), 0.05mol (11.175g) 2,2 ', 4 '-Trichloroacetophenon, 50ml methyl alcohol joins in the 250ml there-necked flask,, stirred 0.5 hour down at 25 ℃.The sodium borohydride of 0.075mol (2.85g) 96% is dissolved in 5ml methyl alcohol+8ml 1% aqueous sodium hydroxide solution. slowly drip sodium borohydride solution at ice-water bath and under stirring.After dropwising, under 50 ℃ of heating in water bath, continuing stirring reaction 30 minutes. following processing is with embodiment 1.Get yellow oily liquid product 12g, place and separate out white crystal. use gas chromatographic analysis, product 1-(2,4 dichloro benzene base)-2-chloro-purity of alcohol 98.5%.
Embodiment 4: synthetic 1-(2,4 difluorobenzene base)-2-chloro-ethanol
With 0.15mol (36.82g) lanthanum trichloride, 2-chloro-1-(2 ', 4 '-difluorophenyl)-ethyl ketone 0.1mol (19.05g), 90ml methyl alcohol joins in the 250ml there-necked flask, stirs 0.5 hour down at 25 ℃.. 0.10mol (3.96g) sodium borohydride (content 96%) is dissolved in the solution that 10ml methyl alcohol+the 10ml1% aqueous sodium hydroxide solution is made into. at ice bath and under stirring, drip sodium borohydride solution.After dropwising, at room temperature continued stirring reaction 30 minutes. along with the adularescent solid that carries out that reacts produces.The hydrochloric acid soln that adds 50ml (1+2) decomposes.Most of methyl alcohol is removed in underpressure distillation.Be cooled to room temperature, separatory is told organic layer, and water extracts with ether (20ml * 2), and extraction liquid merges in the organic phase, uses anhydrous magnesium sulfate drying.Ether is removed in distillation, gets yellow oily liquid product 18.8g, productive rate 97.7%.Gas chromatographic detection product 1-(2,4 difluorobenzene base)-2-chloro-ethanol content is greater than 99%.
Embodiment 5: Synthetic 2-chloro-1-phenylethyl alcohol
With 0.1mol (11.1g) calcium chloride, 0.05mol (7.725g) 2-chloro-acetophenone, 40ml methyl alcohol joins in the 250ml there-necked flask, and at room temperature (20-25 ℃) stirred 0.5 hour down.The 2.85g sodium borohydride is dissolved in the solvent of 10ml methyl alcohol+5ml 1%NaOH aqueous solution composition.Drip sodium borohydride solution in reactant at ice bath and under stirring.After dropwising, reacted 10 minutes down for 70 ℃ with heating in water bath.Add 25ml hydrochloric acid soln (1+2) acidolysis.Most of methyl alcohol is removed in underpressure distillation.Be cooled to room temperature, separatory is told organic layer, and water extracts with ether (20ml * 2), and extraction liquid merges in the organic phase, uses anhydrous magnesium sulfate drying.Ether is removed in distillation, gets yellow oily liquid product 7.32g, productive rate 93.5%.The content of gas chromatographic detection product 2-chloro-1-phenylethyl alcohol is 97.2%.
Embodiment 6: synthetic 1-(2, the 4-3,5-dimethylphenyl)-2-chloro-ethanol
With 0.10mol (11.10g) calcium chloride, 0.05mol (9.125g) 2-chloro-1-(2 ', 4 '-3,5-dimethylphenyl)-ethyl ketone, 50ml methyl alcohol join in the 250ml there-necked flask, and at room temperature (20-25 ℃) stirred 0.5 hour down.The 2.85g sodium borohydride is dissolved in the solvent of 5ml methyl alcohol+5ml 1%NaOH aqueous solution composition.Drip sodium borohydride solution in reactant at ice bath and under stirring.After dropwising, reacted 30 minutes down for 40 ℃ with heating in water bath.Add 50ml hydrochloric acid soln (1+2) acidolysis.Most of methyl alcohol is removed in underpressure distillation.Be cooled to room temperature, separatory is told organic layer, and water extracts with ether (20ml * 2), and extraction liquid merges in the organic phase, uses anhydrous magnesium sulfate drying.Ether is removed in distillation, gets yellow oily liquid product 9.00g, productive rate 97.56%.Gas chromatographic detection product 1-(2, the 4-3,5-dimethylphenyl)-2-chloro-alcoholic acid content is 95%.

Claims (6)

1. the preparation method of β-halo-methyl phenyl carbinol compounds is characterized in that the step of method is as follows:
1) be 1.0～2.0 with metal chloride or nitrate in molar ratio by metal ion and alpha-halogen-acetophenone compounds, join in the reactor with Fatty Alcohol(C12-C14 and C12-C18) or ether compound reaction solvent, at room temperature stirred 15-40 minute, metal chloride is calcium chloride, manganous chloride, zinc chloride, lanthanum trichloride;
2) taking by weighing the sodium borohydride that is equivalent to 1～1.5 times of alpha-halogen-acetophenone compounds molar weight or POTASSIUM BOROHYDRIDE is dissolved in 1%～2% the aqueous sodium hydroxide solution or water-alcohol solution, in ice bath or room temperature and under stirring, this sodium borohydride or solution of potassium borohydride are added dropwise in the reaction mixture;
3) dropwise after, continue under ice bath or room temperature or heating, to react 10～40 minutes, add dilute hydrochloric acid solution decomposition-reduction product;
4) most of solvent is removed in normal pressure or underpressure distillation, with organic product and the aqueous phase separation that generates, water adds Calcium Chloride Powder Anhydrous or anhydrous magnesium sulfate drying agent drying again with the ether organic solvent extraction and merge in the organic product, and distillation is removed organic solvent and got final product.
2. the preparation method of a kind of β-halo according to claim 1-methyl phenyl carbinol compounds is characterized in that, said Fatty Alcohol(C12-C14 and C12-C18) is methyl alcohol, ethanol, Virahol or the trimethyl carbinol.
3. the preparation method of a kind of β-halo according to claim 1-methyl phenyl carbinol compounds is characterized in that, said ether compound is tetrahydrofuran (THF), dioxane or glycol dimethyl ether.
4. the preparation method of a kind of β-halo according to claim 1-methyl phenyl carbinol compounds is characterized in that, the metal ion of said metal chloride or nitrate is Ca 2+, Mn 2+, Zn 2+, La 3+
5. the preparation method of a kind of β-halo according to claim 1-methyl phenyl carbinol compounds is characterized in that, the temperature of reaction of said step 3) is-5 ℃ of boiling temperatures to solvent for use, and at room temperature Fan Ying time is 20～30 minutes.
6. the preparation method of a kind of β-halo according to claim 1-methyl phenyl carbinol compounds is characterized in that, the substituting group on the phenyl ring of said alpha-halogen-acetophenone compounds is F, Cl, Br, OH, OCH 3, SCH 3, CH 2OH, NH 2, NO 2, CH 3, C 2H 5, t-Bu, CF 3, Ph, phenmethyl.
CN 200410052975 2004-07-15 2004-07-15 Process for preparing beta-halogen-alpha-phenyl ethyl alcohol compounds Expired - Fee Related CN1247504C (en)

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CN109553511B (en) * 2018-12-28 2021-08-10 江南大学 Method for preparing p-hydroxystyrene by coupling hydrogenation reaction and dehydration reaction with p-hydroxyacetophenone one-step method
CN111943806A (en) * 2020-09-03 2020-11-17 中国林业科学研究院资源昆虫研究所 Method for preparing higher alkanol by reducing white wax through sodium borohydride system under normal pressure

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