CN109867601B - Preparation method of (R) -2- (4-hydroxyphenoxy) butyl propionate - Google Patents
Preparation method of (R) -2- (4-hydroxyphenoxy) butyl propionate Download PDFInfo
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Abstract
The invention discloses aR) The preparation method of (E) -2- (4-hydroxyphenoxy) butyl propionate adopts an immiscible binary organic solvent system and comprisesS) Preparing (2-butyl chloropropionate) and excessive hydroquinone through normal pressure reaction under the action of an acid binding agent and a catalystR) -butyl 2- (4-hydroxyphenoxy) propionate. The invention adopts a reaction extraction mode, reduces side reaction, has high product content and low pyrocatechol content, has the yield of more than 95.0 percent (calculated by hydroquinone), avoids generating a large amount of phenol-containing waste water, reduces the environmental protection pressure, and is suitable for industrial production.
Description
Technical Field
The invention relates to aR) Preparation method of (E) -2- (4-hydroxyphenoxy) butyl propionate, in particular to preparation of (E) by using binary organic solventR) -butyl 2- (4-hydroxyphenoxy) propionate.
Background
(R) Butyl-2- (4-hydroxyphenoxy) propionate (compound 1) is a key intermediate for synthesizing the efficient chiral herbicide cyhalofop-butyl, and the structural formula of the intermediate is as follows:
(R) The synthesis route of the butyl (4-hydroxyphenoxy) propionate is mainly a hydroquinone method, namely a method using hydroquinone and (C)S) Taking-2-butyl chloropropionate as a raw material, taking water, DMF (dimethyl formamide) or ethylene glycol monomethyl ether as a solvent, and carrying out etherification reaction under the action of an acid-binding agent to obtain a main byproduct (a)R) -butyl 2- (4-hydroxyphenoxy) propionate with (A)S) The etherification reaction of the (2-butyl chloropropionate) is continued to obtain a by-product of the double etherification, namely 2, 2' - (1, 4-phenyl (dioxy)) (2R, 2’R) Dibutyl dipropionate (2). The method is simple, but has the following common problems: the one-way conversion rate must be sacrificed to ensure the product selectivity, and the product quality is poor because the hydroquinone is easy to oxidize and difficult to separate from the product and the byproduct; the increase of the one-way conversion rate of byproducts increases, the cost is increased, and the economical efficiency is poor; when water is used as a solvent, a large amount of phenol-containing waste brine is generated, and great pressure is generated on environmental protection treatment. The reaction formula is as follows:
zhang Zujia et al (pesticide, No. 5 of 2010) uses hydroquinone and potassium hydroxide as raw materials, and firstly refluxes water in DMSO and toluene to obtain potassium salt, and then distills to remove toluene, and then dropwise adds 3, 4-difluorobenzonitrile in DMSO solution to perform etherification, so as to obtain a similar monoetherification product with the content of 94%. The method can not inhibit the bi-etherification by-products, the separation of the bi-ethers from the products is difficult, the product purity is low, and the quality of downstream products is influenced.
Hongxiang et al (CN 104803883) reacted butyl lactate and p-toluenesulfonyl chloride to produce a condensate, then reacted with hydroquinone in an alkaline condition using DMF as a solvent, and after the reaction was completed, the solvent was removed by washing with water and distilling the organic layer under reduced pressure, and there was no report on the yield and the product quality. The method can not inhibit the bi-etherification by-products, and the separation of the bi-ethers from the products is difficult.
In addition, although the conventional method adopting large excess of hydroquinone can reduce the diether byproduct 2, the residual hydroquinone in the reaction liquid is very much because of the hydroquinone and the product (A), (B), (C) and (D)R) The butyl-2- (4-hydroxyphenoxy) propionate contains phenolic hydroxyl, the content of hydroquinone in the product is controlled to be lower than 0.1 percent through complex post-treatment, a large amount of phenolic wastewater is generated, and great environmental protection pressure is caused.
Disclosure of Invention
The idea of the invention is as follows: according to the nature that hydroquinone is easily soluble in strongly polar solvents and poorly soluble in nonpolar solvents (R) The method is characterized in that butyl-2- (4-hydroxyphenoxy) propionate is easily soluble in a nonpolar solvent, and etherification reaction needs to be carried out in a strong polar solvent, starting from the stage of controlling etherification reaction to stay in a monoether, a polar solvent and a nonpolar solvent which are poor in mutual solubility are selected as reaction solvents, a mode of feeding excessive hydroquinone and 18-crown-6 are adopted as catalysts, and the products are extracted into a nonpolar solvent phase immediately after being generated through reaction and extraction, so that the concentration of the products in the polar solvent is always kept at a very low level and the concentration of the hydroquinone is kept at a high level, the etherification reaction selectivity is improved, the generation of a double-etherification byproduct is reduced, the purpose of selective monoetherification is realized, and the reaction process is shown in the attached drawing of the specification.
Description of the drawings: fig. 1 shows reaction scheme 1, fig. 2 shows reaction scheme 2, fig. 3 shows reaction scheme 3, and fig. 4 shows reaction scheme 4.
It has been found through prior studies that hydroquinone and (A), (B), (CR) The above inventive idea can be realized by the distribution rule of the mixture of butyl (4-hydroxyphenoxy) propionate in different binary solvent systems. Mixing 50% of hydroquinone and 50%, (R) Adding a mixture of butyl (E) -2- (4-hydroxyphenoxy) propionate into a polar solvent and a nonpolar solvent, wherein the ratio of the polar solvent to the nonpolar solvent is 1:1, stirring and standing the mixture at room temperature for layering, respectively sampling, and analyzing the composition in the two phases by using a gas spectrum.
The technical scheme of the invention is as follows: an immiscible binary organic solvent system as a reaction solvent, andS) Preparing (2-butyl chloropropionate) and excessive hydroquinone through normal pressure reaction under the action of an acid binding agent and a catalystR) -butyl 2- (4-hydroxyphenoxy) propionate. The immiscible binary solvent system is composed of a polar solvent and a non-polar solvent. Filtering and desalting the polar solvent phase after the reaction is finished, and directly recycling; the nonpolar solvent phase is directly recycled after simple distillation and recovery, and the mother liquor is obtained by vacuum rectificationR) -butyl 2- (4-hydroxyphenoxy) propionate. The technology adopts a reaction extraction scheme, so that the selectivity is high, and the yield is more than 95.0 percent (calculated by hydroquinone).
According to the invention, hydroquinone is adopted to react at first with molar excess of 50-100%, and a batch equimolar feeding method is adopted, wherein the polar solvent is one of ethylene glycol or glycerol, and the dosage of the polar solvent is 5-10 times of the mass of hydroquinone; the nonpolar solvent is one of petroleum ether, toluene, xylene or cumene, and the dosage of the nonpolar solvent is 5-10 times of the mass of hydroquinone.
The acid-binding agent is one of potassium hydroxide and sodium hydroxide, and the dosage of the acid-binding agent is 0.50-0.75 time of the molar weight of hydroquinone.
The reaction temperature is 90-120 ℃, and the reaction time is 3-8 h.
The catalyst is 18-crown ether-6, and the dosage of the catalyst is 0.1-0.3 percent of the mass of the hydroquinone.
Compared with other synthesis methods, the invention has the following advantages: 1) the process is simple, the reaction condition is mild, and the used solvent is suitable for the industrial requirement; 2) after the product layer is rectified, the content of hydroquinone is lower than 0.1 percent, the content of the product is higher than 99 percent through liquid spectrum analysis, the rectification difficulty is reduced, and the production period is shortened; 3) the selectivity is improved, and the yield is high; 4) does not generate a large amount of phenol-containing wastewater, greatly reduces the energy consumption and the three wastes, and has obvious energy-saving, emission-reducing and environmental-protection benefits.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
Example 133 g (0.3 mol) of Hydroquinone, 13.1g (0.21 mol) of 95% potassium hydroxide, 200mL of ethylene glycol, 300mL of Petroleum ether, and 0.005 g of catalyst 18-crown-6 were placed in a 1000 mL three-necked flask, and heated to 80 ℃ with stirringS) Adding 2-butyl chloropropionate in 4h, continuing to react for 4h after the addition is finished, cooling after the reaction is finished, performing suction filtration under negative pressure, taking potassium chloride as a filter cake, standing the filtrate, and then separating phases, wherein the upper phase is a nonpolar solvent phase, (b) adding 2-butyl chloropropionate into the filtrate, and then adding a solvent into the filtrate to obtain a filtrateR) The content of butyl-2- (4-hydroxyphenoxy) propionate was 97.3% (normalized by liquid area) and the content of hydroquinone was 1.7% (normalized by liquid area). Phase separation, high vacuum rectification to obtain 98.5%R) -butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content 0.42%; the lower phase is a polar solvent phase, the hydroquinone content is 85.7 percent (liquid spectrum area is normalized), (b)R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 14.4 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor for recycling. The content of the byproduct compound 2 in the reaction solution is less than 0.5 percent.
Recycling the mother liquor obtained above: 33g (0.3 mol) of hydroquinone, 12.4g (0.2 mol) of 95% potassium hydroxide, 0.005 g of 18-crown-6 as a catalyst, and about 200mL or 300mL of petroleum ether in the entire circulating mother liquor were put in a 1000 mL three-necked flask, and 33.2g (0.2 mol) of (petroleum ether was heated to 80 ℃ with stirringS) Adding 2-butyl chloropropionate in 4 hours, continuing to react for 4 hours after the addition is finished, cooling after the reaction is finished, performing suction filtration under negative pressure, taking potassium chloride as a filter cake, standing the filtrate, and then performing phase separation, wherein the upper phase is a nonpolar solvent phase, the content of monoether is 98.1% (liquid spectrum area normalization), and the content of hydroquinone is 1.2% (liquid spectrum area normalization). Phase separation, solvent recovery of the upper reaction solution, and high vacuum distillation to obtain 45.3g of 99.0% ((R))R) Butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content of 0.10 percent and reaction yield of 94.2 percent (calculated by hydroquinone); the lower phase is a polar solvent phase, the hydroquinone content is 92.5 percent (liquid spectrum area is normalized), (b)R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 7.0 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor to be continuously recycled.
Example 244 g (0.4 mol) of hydroquinone, 9.2g (0.22 mol) of 95% sodium hydroxide, 300mL of ethylene glycol, 200mL of toluene, 0.013 g of catalyst 18-crown-6 were placed in a 1000 mL three-necked flask, the temperature was raised to 100 ℃ with stirring, and 33.2g (0.2 mol) of (C.) (C. (0.2 mol)S) Adding 2-butyl chloropropionate in 3h, continuing to react for 3h after the addition is finished, cooling after the reaction is finished, performing suction filtration under negative pressure, taking sodium chloride as a filter cake, standing the filtrate, and then separating phases, wherein the upper phase is a nonpolar solvent phase, (b) adding 2-butyl chloropropionate into the filtrate, and then adding a solvent into the filtrate to obtain a filtrateR) The content of butyl-2- (4-hydroxyphenoxy) propionate is 98.7% (normalized by liquid area), and the content of hydroquinone is 0.4% (normalized by liquid area). Phase separation, high vacuum rectification to obtain 99.4%, (R) -butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content 0.07%; the lower phase is a polar solvent phase, the hydroquinone content is 91.0 percent (the liquid chromatogram area is normalized), (R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 7.3 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor for recycling. The content of the byproduct compound 2 in the reaction solution is less than 0.3 percent.
Recycling the mother liquor obtained above: 22 g (0.2 mol) of hydroquinone, 8.4g (0.2 mol) of 95% sodium hydroxide, 0.01g of 18-crown-6 as a catalyst, about 300mL of the total circulating mother liquor and 200mL of toluene were put in a 1000 mL three-necked flask, and 33.2g (0.2 mol) of (toluene was heated to 100 ℃ with stirringS) Adding 2-butyl chloropropionate in 3h, continuing to react for 3h after the addition is finished, and reactingCooling, vacuum filtering to obtain filter cake of sodium chloride, standing the filtrate, and separating phase to obtain upper phase of nonpolar solvent phase (step (b))R) The content of butyl-2- (4-hydroxyphenoxy) propionate is 98.4% (normalized by liquid area), and the content of hydroquinone is 0.5% (normalized by liquid area). Phase separation, solvent recovery of the upper reaction solution, high vacuum rectification to obtain 44.9g of 99.3% (R)R) Butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content of 0.03 percent and reaction yield of 93.6 percent (calculated by hydroquinone); the lower phase is a polar solvent phase, the hydroquinone content is 91.7 percent (the liquid chromatogram area is normalized), (b)R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 7.9 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor to be continuously recycled.
Example 344 g (0.4 mol) of Hydroquinone, 12.5g (0.3 mol) of 95% sodium hydroxide, 400mL of ethylene glycol, 300mL of xylene, and 0.01g of catalyst 18-crown-6 were placed in a 1000 mL three-necked flask, and the temperature was raised to 110 ℃ with stirring, and 33.2g (0.2 mol) of (C.) (C., (C.))S) Adding 2-butyl chloropropionate in 2h, continuing to react for 2h after the addition is finished, cooling after the reaction is finished, performing suction filtration under negative pressure, taking sodium chloride as a filter cake, standing the filtrate, and then separating phases, wherein the upper phase is a nonpolar solvent phase, (b) adding 2-butyl chloropropionate into the filtrate, and (d) adding a nonpolar solvent phase into the filtrateR) The content of butyl-2- (4-hydroxyphenoxy) propionate is 99.0% (normalized by liquid area), and the content of hydroquinone is 0.3% (normalized by liquid area). Phase separation, high vacuum rectification to obtain 99.5%R) -butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content 0.08%; the lower phase is a polar solvent phase, the hydroquinone content is 91.7 percent (the liquid chromatogram area is normalized), (b)R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 6.5 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor for recycling. The content of the byproduct compound 2 in the reaction solution is less than 0.3 percent.
Recycling the mother liquor obtained above: 22 g (0.2 mol) of hydroquinone, 8.4g (0.2 mol) of 95% sodium hydroxide, 0.01g of 18-crown-6 as a catalyst, about 400mL of the total circulating mother liquor and 300mL of xylene were put in a 1000 mL three-necked flask, and 33.2g (0.2 mol) of (xylene and (xylene) were heated to 110 ℃ with stirringS) Adding 2-butyl chloropropionate within 2h, continuing to react for 2h after the addition is finished, cooling after the reaction is finished, and pumping under negative pressureFiltering, the filter cake is sodium chloride, the filtrate is separated into phases after standing, the upper phase is a non-polar solvent phase (a)R) The content of butyl-2- (4-hydroxyphenoxy) propionate is 99.1% (normalized by liquid area) and the content of hydroquinone is 0.5% (normalized by liquid area). Phase separation, solvent recovery of the upper reaction solution, and high vacuum distillation to obtain 45.7g of 99.2% ((R))R) Butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content of 0.03 percent and reaction yield of 95.2 percent (calculated by hydroquinone); the lower phase is a polar solvent phase, the hydroquinone content is 92.8 percent (liquid chromatogram area is normalized), (b)R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 7.3 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor to be continuously recycled.
Example 444 g (0.4 mol) of Hydroquinone, 12.5g (0.3 mol) of 95% sodium hydroxide, 400mL of ethylene glycol, 400mL of cumene, and 0.01g of catalyst 18-crown-6 were placed in a 1000 mL three-necked flask, and the mixture was stirred to raise the temperature to 120 ℃ to add 33.2g (0.2 mol) of (0.2 mol)S) Adding 2-butyl chloropropionate in 2h, continuing to react for 1h after the addition is finished, cooling after the reaction is finished, performing suction filtration under negative pressure, taking sodium chloride as a filter cake, standing the filtrate, and then separating phases, wherein the upper phase is a nonpolar solvent phase, (b) adding 2-butyl chloropropionate into the filtrate, and (d) adding a nonpolar solvent phase into the filtrate, and then adding a solvent phase toR) The content of butyl-2- (4-hydroxyphenoxy) propionate is 99.1% (normalized by liquid area) and the content of hydroquinone is 0.2% (normalized by liquid area). Phase separation, high vacuum rectification to obtain 99.6%, (R) -butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content 0.05%; the lower phase is a polar solvent phase, the hydroquinone content is 92.0 percent (the liquid chromatogram area is normalized), (R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 5.8 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor for recycling. The content of the byproduct compound 2 in the reaction solution is less than 0.5 percent.
Recycling the mother liquor obtained above: 22 g (0.2 mol) of hydroquinone, 8.4g (0.2 mol) of 95% sodium hydroxide, 0.01g of 18-crown-6 as a catalyst, and 400mL of cumene and about 400mL of the total of the mother liquors were charged in a 1000 mL three-necked flask, and the temperature was raised to 120 ℃ with stirring, and 33.2g (0.2 mol) of (0.2 mol)S) Adding 2-butyl chloropropionate within 2h, continuing to react for 1h after the addition is finished, cooling after the reaction is finished, and performing suction filtration under negative pressure, wherein a filter cake is sodium chlorideThe filtrate is kept still and then phase separation is carried out, the upper phase is a non-polar solvent phase (1)R) The content of butyl-2- (4-hydroxyphenoxy) propionate is 99.4% (normalized by liquid area), and the content of hydroquinone is 0.2% (normalized by liquid area). Phase separation, solvent recovery of the upper reaction solution, and high vacuum distillation to obtain 45.9g of 99.6% ((R))R) Butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content of 0.03 percent and reaction yield of 96.0 percent (calculated by hydroquinone); the lower phase is a polar solvent phase, the hydroquinone content is 93.0 percent (the liquid chromatogram area is normalized), (R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 6.1 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor to be continuously recycled.
Example 544 g (0.4 mol) of Hydroquinone, 18.7g (0.3 mol) of 95% potassium hydroxide, 400mL of glycerol, 500mL of Petroleum ether, and 0.01g of catalyst 18-crown-6 were placed in a 1000 mL three-necked flask, and then heated to 80 ℃ with stirring, and 33.2g (0.2 mol) of (C.) (S) Adding 2-butyl chloropropionate in 4h, continuing to react for 4h after the addition is finished, cooling after the reaction is finished, performing suction filtration under negative pressure, taking potassium chloride as a filter cake, standing the filtrate, and then separating phases, wherein the upper phase is a nonpolar solvent phase, (b) adding 2-butyl chloropropionate into the filtrate, and then adding a solvent into the filtrate to obtain a filtrateR) The content of butyl-2- (4-hydroxyphenoxy) propionate is 98.3% (normalized by liquid area), and the content of hydroquinone is 0.9% (normalized by liquid area). Phase separation, high vacuum rectification to obtain 99.2%R) -butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content 0.1%; the lower phase is a polar solvent phase, the hydroquinone content is 90.6 percent (liquid spectrum area is normalized), (b)R) The content of butyl-2- (4-hydroxyphenoxy) propionate is 9.5% (normalized by liquid spectrum area), and can be directly used as mother liquor for recycling. The content of the byproduct compound 2 in the reaction solution is less than 0.6 percent.
Recycling the mother liquor obtained above: 22 g (0.2 mol) of hydroquinone, 12.4g (0.2 mol) of 95% potassium hydroxide, 0.01g of 18-crown-6 as a catalyst, about 400mL of the total of the mother liquors and 500mL of petroleum ether were put in a 1000 mL three-necked flask, and 33.2g (0.2 mol) of (petroleum ether was heated to 80 ℃ with stirringS) Adding 2-butyl chloropropionate in 4h, continuing to react for 4h after the addition is finished, cooling after the reaction is finished, performing suction filtration under negative pressure, taking potassium chloride as a filter cake, standing the filtrate, and then separating phases, wherein the upper phase isThe non-polar solvent phase had a monoether content of 98.8% (normalized by liquid area) and a hydroquinone content of 0.8% (normalized by liquid area). Phase separation, solvent recovery of the upper reaction solution, high vacuum distillation to obtain 45.0g of 98.9% (R)R) Butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content of 0.11 percent and reaction yield of 93.5 percent (calculated by hydroquinone); the lower phase is a polar solvent phase, the hydroquinone content is 92.7 percent (liquid spectrum area is normalized), (b)R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 6.6 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor to be continuously recycled.
Example 644 g (0.4 mol) Hydroquinone, 9.2g (0.22 mol) 95% sodium hydroxide, 400mL glycerol, 400mL toluene, 0.01g catalyst 18-crown-6 were placed in a 1000 mL three-necked flask, the temperature was raised to 100 ℃ with stirring, and 33.2g (0.2 mol) of (C.) (0.2 mol)S) Adding 2-butyl chloropropionate in 3h, continuing to react for 3h after the addition is finished, cooling after the reaction is finished, performing suction filtration under negative pressure, taking sodium chloride as a filter cake, standing the filtrate, and then separating phases, wherein the upper phase is a nonpolar solvent phase, (b) adding 2-butyl chloropropionate into the filtrate, and then adding a solvent into the filtrate to obtain a filtrateR) The content of butyl-2- (4-hydroxyphenoxy) propionate is 99.0% (normalized by liquid area), and the content of hydroquinone is 0.2% (normalized by liquid area). Phase separation, high vacuum rectification to obtain 99.5%R) -butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content 0.05%; the lower phase is a polar solvent phase, the hydroquinone content is 91.9 percent (the liquid chromatogram area is normalized), (b)R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 7.4 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor for recycling. The content of the byproduct compound 2 in the reaction solution is less than 0.2 percent.
Recycling the mother liquor obtained above: 22 g (0.2 mol) of hydroquinone, 8.4g (0.2 mol) of 95% sodium hydroxide, 0.01g of 18-crown-6 as a catalyst, and 400mL of toluene and 400mL of the total amount of the mother liquor to be circulated were put in a 1000 mL three-necked flask, and 33.2g (0.2 mol) of (toluene was heated to 100 ℃ with stirringS) Adding 2-butyl chloropropionate in 3h, continuing to react for 3h after the addition is finished, cooling after the reaction is finished, performing suction filtration under negative pressure, taking sodium chloride as a filter cake, standing the filtrate, and then separating phases, wherein the upper phase is a nonpolar solvent phase, (b) adding 2-butyl chloropropionate into the filtrate, and then adding a solvent into the filtrate to obtain a filtrateR) A content of butyl (4-hydroxyphenoxy) 2-propionate of99.0 percent (liquid spectrum area normalization) and 0.33 percent of hydroquinone (liquid spectrum area normalization). Phase separation, solvent recovery of the upper reaction solution, and high vacuum distillation to obtain 45.4g of 99.5% ((R))R) Butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content of 0.02% and reaction yield of 94.9% (calculated by hydroquinone); the lower phase is a polar solvent phase, the hydroquinone content is 92.9 percent (liquid chromatogram area is normalized), (b)R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 6.7 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor to be continuously recycled.
Example 7
44g (0.4 mol) of hydroquinone, 9.2g (0.22 mol) of 95% sodium hydroxide, 300mL of glycerol, 400mL of xylene, and 0.01g of catalyst 18-crown-6 were placed in a 1000 mL three-necked flask, and the mixture was heated to 110 ℃ with stirring, and 33.2g (0.2 mol) of (C.)S) Adding 2-butyl chloropropionate in 2h, continuing to react for 2h after the addition is finished, cooling after the reaction is finished, performing suction filtration under negative pressure, taking sodium chloride as a filter cake, standing the filtrate, and then separating phases, wherein the upper phase is a nonpolar solvent phase, (b) adding 2-butyl chloropropionate into the filtrate, and (d) adding a nonpolar solvent phase into the filtrateR) The content of butyl-2- (4-hydroxyphenoxy) propionate is 99.1% (normalized by liquid area) and the content of hydroquinone is 0.3% (normalized by liquid area). Phase separation, high vacuum rectification to obtain 99.2%R) -butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content 0.08%; the lower phase is a polar solvent phase, the hydroquinone content is 91.6 percent (the liquid chromatogram area is normalized), (b)R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 7.7 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor for recycling. The content of the byproduct compound 2 in the reaction solution is less than 0.4 percent.
Recycling the mother liquor obtained above: 22 g (0.2 mol) of hydroquinone, 8.4g (0.2 mol) of 95% sodium hydroxide, 0.01g of 18-crown-6 as a catalyst, about 300mL of the total circulating mother liquor and 400mL of xylene were put in a 1000 mL three-neck flask, and 33.2g (0.2 mol) of (xylene and (xylene) were heated to 110 ℃ with stirringS) Adding 2-butyl chloropropionate in 2h, continuing to react for 2h after the addition is finished, cooling after the reaction is finished, performing suction filtration under negative pressure, taking sodium chloride as a filter cake, standing the filtrate, and then separating phases, wherein the upper phase is a nonpolar solvent phase, (b) adding 2-butyl chloropropionate into the filtrate, and (d) adding a nonpolar solvent phase into the filtrateR) -2- (4-Hydroxyphenoxy) propionic acid butyl esterThe content is 99.2 percent (normalized by liquid spectrum area) and the content of hydroquinone is 0.2 percent (normalized by liquid spectrum area). Phase separation, solvent recovery of the upper reaction solution, and high vacuum rectification to obtain 46.0g of 99.4% ((R))R) Butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content of 0.04 percent and reaction yield of 96.0 percent (calculated by hydroquinone); the lower phase is a polar solvent phase, the hydroquinone content is 92.7 percent (liquid chromatogram area is normalized), (b)R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 7.0 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor to be continuously recycled.
Example 844 g (0.4 mol) of Hydroquinone, 12.5g (0.3 mol) of 95% sodium hydroxide, 300mL of glycerin, 400mL of cumene, and 0.013 g of catalyst 18-crown-6 were put in a 1000 mL three-necked flask, and the mixture was stirred to raise the temperature to 120 ℃ to obtain 33.2g (0.2 mol) of (C.) (0.2 mol)S) Adding 2-butyl chloropropionate in 2h, continuing to react for 2h after the addition is finished, cooling after the reaction is finished, performing suction filtration under negative pressure, taking sodium chloride as a filter cake, standing the filtrate, and then separating phases, wherein the upper phase is a nonpolar solvent phase, (b) adding 2-butyl chloropropionate into the filtrate, and (d) adding a nonpolar solvent phase into the filtrateR) The content of butyl-2- (4-hydroxyphenoxy) propionate is 99.4% (normalized by liquid area), and the content of hydroquinone is 0.2% (normalized by liquid area). Phase separation, high vacuum rectification to obtain 99.6%, (R) -butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content 0.03%; the lower phase is a polar solvent phase, the hydroquinone content is 94.0 percent (the liquid chromatogram area is normalized), (R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 5.7 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor for recycling. The content of the byproduct compound 2 in the reaction solution is less than 0.2 percent.
Recycling the mother liquor obtained above: 22 g (0.2 mol) of hydroquinone, 8.4g (0.2 mol) of 95% sodium hydroxide, 0.01g of 18-crown-6 as a catalyst, about 300mL of the total circulating mother liquor, and 400mL of cumene were put in a 1000 mL three-necked flask, and 33.2g (0.2 mol) of (isopropyl benzene were heated to 120 ℃ with stirringS) Adding 2-butyl chloropropionate in 2h, continuing to react for 2h after the addition is finished, cooling after the reaction is finished, performing suction filtration under negative pressure, taking sodium chloride as a filter cake, standing the filtrate, and then separating phases, wherein the upper phase is a nonpolar solvent phase, (b) adding 2-butyl chloropropionate into the filtrate, and (d) adding a nonpolar solvent phase into the filtrateR) The content of butyl (4-hydroxyphenoxy) 2-propionate is 99.0% (liquid chromatography)Area normalized), hydroquinone content 0.2% (liquid spectrum area normalized). Phase separation, solvent recovery of the upper reaction solution, and high vacuum distillation to obtain 46.2g of 99.4% ((R))R) Butyl 2- (4-hydroxyphenoxy) propionate (liquid chromatography external standard method), hydroquinone content of 0.02% and reaction yield of 96.4% (calculated by hydroquinone); the lower phase is a polar solvent phase, the hydroquinone content is 95.1 percent (the liquid chromatogram area is normalized), (b)R) The content of the butyl-2- (4-hydroxyphenoxy) propionate is 4.3 percent (normalized by the liquid spectrum area), and the butyl-2- (4-hydroxyphenoxy) propionate can be directly used as mother liquor to be continuously recycled.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (7)
1. A preparation method of (R) -2- (4-hydroxyphenoxy) butyl propionate is characterized in that an immiscible binary organic solvent system is used as a reaction solvent, wherein a polar organic solvent is ethylene glycol or glycerol, and a nonpolar organic solvent is one of petroleum ether, toluene, xylene or cumene; adding (S) -2-butyl chloropropionate into excessive hydroquinone, an acid binding agent and a catalyst system at a certain temperature and for a certain time, and carrying out heat preservation reaction to obtain (R) -2- (4-hydroxyphenoxy) butyl propionate; and (2) filtering and desalting the polar solvent phase after the reaction is finished, directly recycling, simply distilling the non-polar solvent phase to recover the solvent, directly recycling the solvent, and carrying out vacuum rectification on the mother liquor to obtain the (R) -2- (4-hydroxyphenoxy) butyl propionate.
2. The method for preparing (R) -butyl 2- (4-hydroxyphenoxy) propionate according to claim 1, wherein the polar solvent is 5-10 times of hydroquinone, and the nonpolar solvent is 5-10 times of hydroquinone.
3. A composition according to claim 1R) The preparation method of the (E) -2- (4-hydroxyphenoxy) butyl propionate is characterized in that the acid-binding agent is one of potassium hydroxide and sodium hydroxide, and the dosage of the acid-binding agent is 0.5-0.75 time of the molar weight of hydroquinone.
4. A composition according to claim 1R) The preparation method of the (E) -2- (4-hydroxyphenoxy) butyl propionate is characterized in that the catalyst is 18-crown ether-6, and the dosage of the catalyst is 0.1-0.3 percent of the mass of hydroquinone.
5. A composition according to claim 1R) The preparation method of the (E) -2- (4-hydroxyphenoxy) butyl propionate is characterized in that the molar ratio of the first batch of reaction raw materials is hydroquinone: (S) -2-butyl chloropropionate = 1.5-2: 1, and the molar ratio of the raw materials in the applied batch is hydroquinone: (S) -2-chloropropionic acid butyl ester =1: 1.
6. A composition according to claim 1R) The preparation method of the (E) -2- (4-hydroxyphenoxy) butyl propionate is characterized in that the dropping temperature and the heat preservation temperature are 90-120 ℃.
7. A composition according to claim 1R) The preparation method of the butyl (4-hydroxyphenoxy) propionate is characterized in that the reaction time is 3-8 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4489207A (en) * | 1981-12-18 | 1984-12-18 | Basf Aktiengesellschaft | Preparation of 2-(hydroxyphenoxy)-carboxylates |
| CN1340497A (en) * | 2000-08-30 | 2002-03-20 | 中国科学院大连化学物理研究所 | Process for synthesizing 2-(4-hydroxylphenoxyl) butyl propionate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4489207A (en) * | 1981-12-18 | 1984-12-18 | Basf Aktiengesellschaft | Preparation of 2-(hydroxyphenoxy)-carboxylates |
| CN1340497A (en) * | 2000-08-30 | 2002-03-20 | 中国科学院大连化学物理研究所 | Process for synthesizing 2-(4-hydroxylphenoxyl) butyl propionate |
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