CN108250042B - Preparation method of (S) - (-) -1,1, 2-triphenyl-1, 2-glycol - Google Patents
Preparation method of (S) - (-) -1,1, 2-triphenyl-1, 2-glycol Download PDFInfo
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- CN108250042B CN108250042B CN201810211017.XA CN201810211017A CN108250042B CN 108250042 B CN108250042 B CN 108250042B CN 201810211017 A CN201810211017 A CN 201810211017A CN 108250042 B CN108250042 B CN 108250042B
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
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Abstract
The invention relates to a preparation method of (S) - (-) -1,1, 2-triphenyl-1, 2-glycol, which is characterized in that methyl mandelate and phenyl magnesium bromide are respectively dissolved in a solvent to prepare a methyl mandelate solution and a phenyl magnesium bromide solution; respectively inputting the prepared methyl mandelate solution and phenyl magnesium bromide solution into a first microchannel reactor through a metering pump to carry out main reaction, directly flowing the reaction solution obtained after the reaction into a second microchannel reactor, inputting the acidic aqueous solution into the second microchannel reactor through a metering pump to carry out quenching reaction while the reaction solution flows into the second microchannel reactor, obtaining reaction liquid after the quenching reaction is finished, layering the reaction liquid to obtain an organic phase, drying the organic phase, carrying out reduced pressure concentration, and recrystallizing with toluene to obtain the finished product (S) - (-) -1,1, 2-triphenyl-1, 2-ethylene glycol. The invention has the advantages of high yield and quick reaction.
Description
Technical Field
The invention relates to a preparation method of (S) - (-) -1,1, 2-triphenyl-1, 2-glycol, in particular to a method for preparing (S) - (-) -1,1, 2-triphenyl-1, 2-glycol by using a microchannel reaction device.
Background
(S) - (-) -1,1, 2-triphenyl-1, 2-glycol is an important intermediate for preparing optically active medicines, pesticides and functional materials, and has a structural formula shown in the specification (A)
）：
The main synthesis method comprises the following steps: slowly dripping a solution of methyl mandelate into a solution of Grignard reagent phenyl magnesium bromide at a certain temperature, carrying out heat preservation reaction, and carrying out aftertreatment to obtain a product, wherein the reaction formula is as follows:
the main references are 1, Advanced Synthesis and Catalysis, vol.352, nb. 14-15, (2010), p.2611-2620: reacting for 50h at 0-20 ℃ in tetrahydrofuran solvent under the protection of inert gas, and performing post-treatment to obtain a product; 2. tetrahedron, vol.42, nb. 9, (1986), p.2421-2428, ether as solvent, heating and reacting for 2 hours, the yield is 80%; 3. journal of the American Chemical Society, vol.112, nb. 10, (1990), p.3949-; 4. organic Letters, vol.9, nb. 4, (2007), p.635-.
Most of the methods reported in the above documents adopt conventional reaction devices, most of the reaction time is long, some reaction time even reaches 50 hours, the yield is not high generally, the reason for analyzing the reaction is probably 1), and incomplete reaction is easy to generate due to the limited mixing effect of a reactor, so that the product contains a high proportion of impurities (S) -2-hydroxy-1, 2-diphenylethanone, and the structural formula of the product is shown as the following formula (II); 2) when hydrochloric acid is added for quenching after the reaction is finished, the local acid concentration is too high, dehydration side reaction is generated to generate impurity 1,2, 2-triphenyl vinyl alcohol, and the structural formula of the impurity is shown as the following formula (A)
）。
Disclosure of Invention
In view of the above disadvantages, the present invention provides a method for preparing (S) - (-) -1,1, 2-triphenyl-1, 2-glycol with high yield and fast reaction speed.
The invention has the technical content that the preparation method of (S) - (-) -1,1, 2-triphenyl-1, 2-glycol is characterized in that methyl mandelate and phenyl magnesium bromide are respectively dissolved in a solvent to prepare a methyl mandelate solution and a phenyl magnesium bromide solution, the molar concentration of the methyl mandelate solution is 0.1-3 mol/L, the molar concentration of the phenyl magnesium bromide solution is 0.1-2 mol/L, and the solvent is diethyl ether, tetrahydrofuran or 2-methyltetrahydrofuran; respectively inputting the prepared methyl mandelate solution and phenyl magnesium bromide solution into a first microchannel reactor through a metering pump to carry out main reaction, directly flowing the reaction solution obtained after the reaction into a second microchannel reactor, inputting an acidic aqueous solution into the second microchannel reactor through a metering pump to carry out quenching reaction while the reaction solution flows into the second microchannel reactor, obtaining reaction liquid after the quenching reaction is finished, layering the reaction liquid to obtain an organic phase, drying the organic phase, carrying out reduced pressure concentration, and recrystallizing with toluene to obtain a finished product (S) - (-) -1,1, 2-triphenyl-1, 2-ethylene glycol; wherein the main reaction residence time in the first microchannel reactor is 0.5-5 min, the reaction temperature is 10-50 ℃, and the input molar weight ratio of the methyl mandelate solution to the phenyl magnesium bromide solution is 1: 1-1: 3; the residence time of the quenching reaction in the second microchannel reactor is 0.5-1.5 min, the temperature of the quenching reaction is-10-30 ℃, the molar concentration of the acidic aqueous solution is 0.05-4 mol/L, and the molar input amount of the acid in the acidic aqueous solution is 1-2 times of that of the phenylmagnesium bromide.
In the preparation method of the (S) - (-) -1,1, 2-triphenyl-1, 2-glycol, the molar concentration of a methyl mandelate solution is 0.5-1 mol/L, the molar concentration of a phenylmagnesium bromide solution is 0.5-1 mol/L, and the solvent is 2-methyltetrahydrofuran; the main reaction residence time in the first microchannel reactor is 1-3 min, the reaction temperature is 20-30 ℃, the residence time in the first microchannel reactor is 0.5-5 min, and the input molar weight ratio of the methyl mandelate solution to the phenyl magnesium bromide solution is 1: 1.05-1: 1.5; the residence time of the quenching reaction in the second microchannel reactor is 0.8-1.2 min, the temperature of the quenching reaction is 0-10 ℃, the molar concentration of the acidic aqueous solution is 1-2 mol/L, and the molar input amount of the acid in the acidic aqueous solution is 1.05-1.2 times of that of the phenylmagnesium bromide.
Drying, vacuum concentration and toluene recrystallization are conventional processes in the preparation method of the (S) - (-) -1,1, 2-triphenyl-1, 2-ethanediol.
The microchannel reactor used in the invention is assembled by a plurality of modules, and the modules can be assembled in parallel or in series. The thermocouple is used for measuring the actual temperature of the heat exchange medium in the heat exchange passage or the external heat-conducting medium. The module can be made of silicon carbide, glass, stainless steel or metal alloy. The specific number of modules is determined by the scale of the reaction and the residence time of the reaction.
Compared with the prior art, the invention has the advantages that:
(1) the invention adopts the continuous flow reactor of the continuous flow of the micro-channel, the reaction time is shortened from the traditional hours or even dozens of hours to dozens of seconds to several minutes, and the reaction efficiency is obviously improved.
(2) And because the raw materials are mixed in the micro-channel very well, the temperature is controlled accurately, and the conversion rate of the raw materials and the selectivity of products are obviously improved.
(3) According to the invention, the whole process of the feeding mixing and reaction process is a continuous flow reaction, so that the influence of air and water gas on the reaction in the conventional batch reaction is avoided.
Detailed Description
Example 1, separately dissolving methyl mandelate and phenylmagnesium bromide in 2-methyltetrahydrofuran to obtain a methyl mandelate solution with a molar concentration of 0.5mol/L and a phenylmagnesium bromide solution with a molar concentration of 0.5 mol/L; respectively inputting the prepared methyl mandelate solution and phenyl magnesium bromide solution into a first microchannel reactor through a metering pump to carry out main reaction, directly flowing the reaction solution obtained after reaction into a second microchannel reactor, inputting hydrochloric acid aqueous solution into the second microchannel reactor through a metering pump to carry out quenching reaction while the reaction solution flows into the second microchannel reactor, obtaining reaction liquid after the quenching reaction is finished, flowing the reaction liquid into a receiver in a high dispersion phase continuous flow state, layering the reaction liquid in the receiver to obtain an organic phase, drying the organic phase by using anhydrous magnesium sulfate, then carrying out reduced pressure concentration, and recrystallizing by using toluene to obtain a finished product (S) - (-) -1,1, 2-triphenyl-1, 2-ethylene glycol; wherein the main reaction residence time in the first microchannel reactor is 3min, the reaction temperature is 20 ℃, and the input molar weight ratio of the methyl mandelate solution to the phenyl magnesium bromide solution is 1: 1.1; the residence time of the quenching reaction in the second microchannel reactor is 1min, the temperature of the quenching reaction is 5 ℃, the molar concentration of the hydrochloric acid aqueous solution is 1mol/L, and the molar input amount of the hydrochloric acid is 1.09 times of that of the phenylmagnesium bromide; the total conversion rate is 99.8 percent, and the yield of the product (S) - (-) -1,1, 2-triphenyl-1, 2-glycol is 92 percent.
Example 2, separately dissolving methyl mandelate and phenylmagnesium bromide in 2-methyltetrahydrofuran to obtain a methyl mandelate solution with a molar concentration of 0.5mol/L and a phenylmagnesium bromide solution with a molar concentration of 0.5 mol/L; respectively inputting the prepared methyl mandelate solution and phenyl magnesium bromide solution into a first microchannel reactor through a metering pump to carry out main reaction, directly flowing the reaction solution obtained after reaction into a second microchannel reactor, inputting a sulfuric acid aqueous solution into the second microchannel reactor through a metering pump to carry out quenching reaction while the reaction solution flows into the second microchannel reactor, obtaining reaction liquid after the quenching reaction is finished, flowing the reaction liquid into a receiver in a high dispersion phase continuous flow state, layering the reaction liquid in the receiver to obtain an organic phase, drying the organic phase by using anhydrous magnesium sulfate, then carrying out reduced pressure concentration, and recrystallizing by using toluene to obtain a finished product (S) - (-) -1,1, 2-triphenyl-1, 2-ethylene glycol; wherein the main reaction residence time in the first microchannel reactor is 1.5min, the reaction temperature is 25 ℃, and the input molar weight ratio of the methyl mandelate solution to the phenyl magnesium bromide solution is 1: 1.2; the residence time of the quenching reaction in the second microchannel reactor is 1min, the temperature of the quenching reaction is 5 ℃, the molar concentration of the sulfuric acid aqueous solution is 1mol/L, and the molar input amount of the sulfuric acid is 1.16 times of that of the phenylmagnesium bromide; the total conversion rate is 99.5 percent, and the yield of the product (S) - (-) -1,1, 2-triphenyl-1, 2-glycol is 91 percent.
Example 3, separately dissolving methyl mandelate and phenylmagnesium bromide in 2-methyltetrahydrofuran to obtain a methyl mandelate solution with a molar concentration of 1mol/L and a phenylmagnesium bromide solution with a molar concentration of 1 mol/L; respectively inputting the prepared methyl mandelate solution and phenyl magnesium bromide solution into a first microchannel reactor through a metering pump to carry out main reaction, directly flowing the reaction solution obtained after reaction into a second microchannel reactor, inputting a nitric acid aqueous solution into the second microchannel reactor through a metering pump to carry out quenching reaction while the reaction solution flows into the second microchannel reactor, obtaining reaction liquid after the quenching reaction is finished, flowing the reaction liquid into a receiver in a high dispersion phase continuous flow state, layering the reaction liquid in the receiver to obtain an organic phase, drying the organic phase by using anhydrous magnesium sulfate, then carrying out reduced pressure concentration, and recrystallizing by using toluene to obtain a finished product (S) - (-) -1,1, 2-triphenyl-1, 2-ethylene glycol; wherein the main reaction residence time in the first microchannel reactor is 2.8min, the reaction temperature is 30 ℃, and the input molar weight ratio of the methyl mandelate solution to the phenyl magnesium bromide solution is 1: 1.2; the quenching reaction residence time in the second microchannel reactor is 1min, the quenching reaction temperature is 5 ℃, the molar concentration of the nitric acid aqueous solution is 1mol/L, and the molar input amount of the nitric acid is 1.16 times of that of the phenylmagnesium bromide; the total conversion rate is 100 percent, and the yield of the product (S) - (-) -1,1, 2-triphenyl-1, 2-glycol is 93 percent.
Example 4, separately dissolving methyl mandelate and phenylmagnesium bromide in 2-methyltetrahydrofuran to obtain a methyl mandelate solution with a molar concentration of 1mol/L and a phenylmagnesium bromide solution with a molar concentration of 0.5 mol/L; respectively inputting the prepared methyl mandelate solution and phenyl magnesium bromide solution into a first microchannel reactor through a metering pump to carry out main reaction, directly flowing the reaction solution obtained after reaction into a second microchannel reactor, inputting hydrochloric acid aqueous solution into the second microchannel reactor through a metering pump to carry out quenching reaction while the reaction solution flows into the second microchannel reactor, obtaining reaction liquid after the quenching reaction is finished, flowing the reaction liquid into a receiver in a high dispersion phase continuous flow state, layering the reaction liquid in the receiver to obtain an organic phase, drying the organic phase by using anhydrous magnesium sulfate, then carrying out reduced pressure concentration, and recrystallizing by using toluene to obtain a finished product (S) - (-) -1,1, 2-triphenyl-1, 2-ethylene glycol; wherein the main reaction residence time in the first microchannel reactor is 2.1min, the reaction temperature is 30 ℃, and the input molar weight ratio of the methyl mandelate solution to the phenyl magnesium bromide solution is 1: 1.1; the residence time of the quenching reaction in the second microchannel reactor is 1min, the temperature of the quenching reaction is 5 ℃, the molar concentration of the hydrochloric acid aqueous solution is 1mol/L, and the molar input amount of the hydrochloric acid is 1.18 times of that of the phenylmagnesium bromide; the total conversion rate is 99.6%, and the yield of the product (S) - (-) -1,1, 2-triphenyl-1, 2-glycol is 91.5%.
Example 5, separately dissolving methyl mandelate and phenylmagnesium bromide in 2-methyltetrahydrofuran to obtain a methyl mandelate solution with a molar concentration of 0.5mol/L and a phenylmagnesium bromide solution with a molar concentration of 1 mol/L; respectively inputting the prepared methyl mandelate solution and phenyl magnesium bromide solution into a first microchannel reactor through a metering pump to carry out main reaction, directly flowing the reaction solution obtained after reaction into a second microchannel reactor, inputting hydrochloric acid aqueous solution into the second microchannel reactor through a metering pump to carry out quenching reaction while the reaction solution flows into the second microchannel reactor, obtaining reaction liquid after the quenching reaction is finished, flowing the reaction liquid into a receiver in a high dispersion phase continuous flow state, layering the reaction liquid in the receiver to obtain an organic phase, drying the organic phase by using anhydrous magnesium sulfate, then carrying out reduced pressure concentration, and recrystallizing by using toluene to obtain a finished product (S) - (-) -1,1, 2-triphenyl-1, 2-ethylene glycol; wherein the main reaction residence time in the first microchannel reactor is 4min, the reaction temperature is 30 ℃, and the input molar weight ratio of the methyl mandelate solution to the phenyl magnesium bromide solution is 1: 1.3; the residence time of the quenching reaction in the second microchannel reactor is 1min, the temperature of the quenching reaction is 5 ℃, the molar concentration of the hydrochloric acid aqueous solution is 1mol/L, and the molar input amount of the hydrochloric acid is 1.2 times of that of the phenylmagnesium bromide; the total conversion rate is 100 percent, and the yield of the product (S) - (-) -1,1, 2-triphenyl-1, 2-glycol is 92 percent.
Claims (2)
1. A preparation method of (S) - (-) -1,1, 2-triphenyl-1, 2-glycol is characterized in that methyl mandelate and phenyl magnesium bromide are respectively dissolved in a solvent to prepare a methyl mandelate solution and a phenyl magnesium bromide solution, wherein the molar concentration of the methyl mandelate solution is 0.1-3 mol/L, the molar concentration of the phenyl magnesium bromide solution is 0.1-2 mol/L, and the solvent is diethyl ether, tetrahydrofuran or 2-methyltetrahydrofuran; respectively inputting the prepared methyl mandelate solution and phenyl magnesium bromide solution into a first microchannel reactor through a metering pump to carry out main reaction, directly flowing the reaction solution obtained after the reaction into a second microchannel reactor, inputting an acidic aqueous solution into the second microchannel reactor through a metering pump to carry out quenching reaction while the reaction solution flows into the second microchannel reactor, obtaining reaction liquid after the quenching reaction is finished, layering the reaction liquid to obtain an organic phase, drying the organic phase, carrying out reduced pressure concentration, and recrystallizing with toluene to obtain a finished product (S) - (-) -1,1, 2-triphenyl-1, 2-ethylene glycol; wherein the main reaction residence time in the first microchannel reactor is 0.5-5 min, the reaction temperature is 10-50 ℃, and the input molar weight ratio of the methyl mandelate solution to the phenyl magnesium bromide solution is 1: 1-1: 3; the residence time of the quenching reaction in the second microchannel reactor is 0.5-1.5 min, the temperature of the quenching reaction is-10-30 ℃, the molar concentration of the acidic aqueous solution is 0.05-4 mol/L, and the molar input amount of the acid in the acidic aqueous solution is 1-2 times of that of the phenylmagnesium bromide.
2. The process according to claim 1, wherein the molar concentration of the methyl mandelate solution is 0.5 to 1mol/L, the molar concentration of the phenylmagnesium bromide solution is 0.5 to 1mol/L, and the solvent is 2-methyltetrahydrofuran; the main reaction residence time in the first microchannel reactor is 1-3 min, the reaction temperature is 20-30 ℃, the residence time in the first microchannel reactor is 0.5-5 min, and the input molar weight ratio of the methyl mandelate solution to the phenyl magnesium bromide solution is 1: 1.05-1: 1.5; the residence time of the quenching reaction in the second microchannel reactor is 0.8-1.2 min, the temperature of the quenching reaction is 0-10 ℃, the molar concentration of the acidic aqueous solution is 1-2 mol/L, and the molar input amount of the acid in the acidic aqueous solution is 1.05-1.2 times of that of the phenylmagnesium bromide.
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| CN105753835A (en) * | 2016-04-11 | 2016-07-13 | 黑龙江鑫创生物科技开发有限公司 | Method for synthesizing 2-(4-fluorophenyl) thiophene |
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| CN105753835A (en) * | 2016-04-11 | 2016-07-13 | 黑龙江鑫创生物科技开发有限公司 | Method for synthesizing 2-(4-fluorophenyl) thiophene |
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| SYNTHETIC STUDIES OF THE DETOXIN COMPLEX. I. TOTAL SYNTHESIS OF (-) DETOXININE.;W. R. Ewing等;《Tcwahcdron》;19861231;第42卷(第9期);2421-2428 * |
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