CN103073392A - Method for preparing beta-methylene phenethyl alcohol - Google Patents
Method for preparing beta-methylene phenethyl alcohol Download PDFInfo
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- CN103073392A CN103073392A CN2013100439851A CN201310043985A CN103073392A CN 103073392 A CN103073392 A CN 103073392A CN 2013100439851 A CN2013100439851 A CN 2013100439851A CN 201310043985 A CN201310043985 A CN 201310043985A CN 103073392 A CN103073392 A CN 103073392A
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Abstract
The invention belongs to a synthesis technique for spice or midbody thereof in fine chemical engineering and particularly relates to a method for preparing beta-methylene phenethyl alcohol. The method comprises the following steps of: firstly, adding a diluting solvent under a nitrogen protection condition, then, adding a polymerization inhibitor and hyacinthin, then, adding organic amine salt-contained formaldehyde solution, and steaming off excess formaldehyde, diluting solvent and water under reduced pressure after a reaction is ended to obtain a beta-methylene hyacinthin crude product; adding isopropyl alcohol and aluminum isopropoxide to the beta-methylene hyacinthin crude product to perform a reduction reaction, and steaming off byproduct ketone and solvent under the reduced pressure after the reaction is ended to obtain respective crude products of products; and dissolving the crude product in water, and extracting by using an organic solvent to obtain the finished product beta-methylene phenethyl alcohol. The method has the advantages that the condition is mild; the operation is simple; raw materials and reagents can be easily got; the reaction is high in regioselectivity; the products can be easily separated and purified; and the yield is high. The method for preparing the beta-methylene phenethyl alcohol is suitable for industrial production.
Description
Technical field
The invention belongs to the synthetic technology of spices in the fine chemistry industry or its intermediate, specifically, relate to the preparation method of a kind of β-methylene-benzene ethanol.
Background technology
β-methylene-benzene ethanol (β-methylenephenethyl alcohol), for a kind of transparent colourless liquid, have strong fragrance, existing many as a kind of novel spices, its top is fragrant to have strong European cloves fragrance, and main note is soft rose fragrance.β-methylene-benzene ethanol also can be used as the raw material of synthetic other spices, is a kind of important intermediate in fine chemistry industry aspect.
β-methylene-benzene ethanol synthetic sees European patent report " preparation of the ester class of β-alkylene phenyl ethanol, ethers itself and analogue " the earliest.The synthetic method of existing β-methylene-benzene ethanol mainly contains three kinds, method one: by the method for Grignard reagent, and the difficult preparation of the Grignard reagent in the method, side reaction is more, and yield is undesirable.Method two: utilize the Heck reaction, with halogeno-benzene and the preparation of vinyl carbinol generation coupled reaction, used expensive palladium metal to be catalyzer in the Heck reaction, recovery is used and is difficult for, and needs complicated organophosphorus ligand.Method three: based on US Patent No. 4756840, be raw material with vinyl toluene, make through chloro, esterification and saponification reaction that this route is longer, yield is on the low side.
Summary of the invention
For overcoming deficiency of the prior art, the invention provides a kind of mild condition, simple to operate, the easy separated purifying of product, yield is high, and is suitable for the preparation method of the β of suitability for industrialized production-methylene-benzene ethanol.Aldol reaction occurs first in the method phenylacetic aldehyde and formaldehyde under the katalysis of organic amine salt, and rear elimination dehydration generates β-methylene-benzene acetaldehyde, makes β-methylene-benzene ethanol through selective reduction again.
Method of the present invention comprises the steps:
1) under the nitrogen protection condition, add first diluting solvent, add again stopper and phenylacetic aldehyde in the stirring, then add the formalin that is dissolved with organic amine salt, temperature of reaction 0-60 ℃, preferred 25-30 ℃, reaction times 12-16 hour, 15-35 ℃ of decompression steams excessive formaldehyde, and 40-75 ℃ of decompression steams diluting solvent and water, gets β-methylene-benzene acetaldehyde crude product;
2) get β-methylene-benzene acetaldehyde crude product, need not purifying, directly add Virahol and aluminum isopropylate and carry out reduction reaction, temperature of reaction 30-80 ℃, preferred 50-70 ℃, reaction times 6-8 hour, decompression steamed ketone and the solvent of by-product, obtained the crude product of product;
3) crude product is soluble in water, use organic solvent extraction, merge organic phase, drying is filtered, and decompression steams organic solvent, gets finished product β-methylene-benzene ethanol.
Stopper described in the step 1) is one or more in Resorcinol, benzoquinones, p methoxy phenol, cuprous chloride, iron trichloride, antioxidant 1076, irgasfos 168, oxidation inhibitor 701, oxidation inhibitor B.H.T, TopanolA, antioxidant 3114, antioxidant 1010, anti-oxidant DLTP, the antioxidant TNP.
Diluting solvent described in the step 1) is methyl alcohol, ethanol or Virahol, preferred alcohol.
Organic amine salt described in the step 1) is hydrochloride, acetate or the propionic salt of secondary amine.
Described secondary amine is one or more in dimethylamine, diethylamine, Pyrrolidine, hexahydropyridine, morpholine, the piperidines.
The mol ratio of phenylacetic aldehyde and formaldehyde is 1:(1.05-1.3 in the step 1)), preferred 1:(1.05-1.1); The mol ratio of phenylacetic aldehyde and organic amine salt is 1:(0.02-0.2), preferred 1:(0.05-0.15); The mass ratio of phenylacetic aldehyde and diluting solvent is 1:(1-6); The consumption of stopper is the 0.2-2% of phenylacetic aldehyde quality; The mass content of formaldehyde is 37-40% in the formalin.
The molar ratio of β step 2)-methylene-benzene acetaldehyde crude product, Virahol, aluminum isopropylate is β-methylene-benzene acetaldehyde crude product: Virahol: aluminum isopropylate=1:(3-10): (0.05-0.3), preferred 1:(3-5): (0.1-0.2).
Step 2) reduction reaction described in is the reaction of homogeneous phase hydrogen transfer reduction.
Organic solvent described in the step 3) is methylene dichloride, 1, a kind of in 2-ethylene dichloride, ethyl acetate and the chloroform.
The present invention realizes the alpha-methylene of phenylacetic aldehyde and the selective reduction of aldehyde radical under the condition of gentleness, make β-methylene-benzene ethanol, compare with existing preparation technology, preparation method of the present invention, mild condition, simple to operate, product is easy to separate and purifying, yield is high, is fit to suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment preparation method of the present invention is described further, but protection scope of the present invention is not limited to this.
Embodiment 1:
N
2Protection is lower, in 1000 milliliters there-necked flask, pours the methyl alcohol of 480ml into, adds successively 1.8 gram Resorcinol and 120 gram phenylacetic aldehydes, stirs; 16.3 gram dimethylamine hydrochlorides are dissolved in the 89 gram formalins, wherein contain formaldehyde 33.8 grams, at room temperature be added drop-wise in the previous reaction liquid, incubated overnight to phenylacetic aldehyde has reacted; The decompression of reaction mixture normal temperature steams excessive formaldehyde, and 50 ℃ of decompressions steam the first alcohol and water, get a faint yellow dope; Add 240 gram Virahols and 20.4 gram aluminum isopropylates, heat up 60 degrees centigrade and reacted to aldehyde radical, decompression steams acetone and Virahol, after reaction solution is poured in the water of 650ml, divide three extractions with the ethyl acetate of 600ml, merge organic phase, anhydrous sodium sulfate drying filters, filtrate decompression steams ethyl acetate, get faint yellow transparent oily matter 115.2 grams, yield 86.0%, purity 98.7%(HPLC).
1HNMR（CDCl
3）δppm：2.2（s，1H），4.35（d，2H），5.31（m，1H），5.38（s，1H），7.10-7.34（m，5H）；
MS(m/z)：134（M
+）。
Embodiment 2:
N
2Protection is lower, in 1000 milliliters there-necked flask, pours the ethanol of 480ml into, adds successively 1.8 gram benzoquinones and 120 gram phenylacetic aldehydes, stirs; 8.77 gram diethylamine hydrochlorides are dissolved in the 89 gram formalins, wherein contain formaldehyde 33.8 grams, at room temperature be added drop-wise in the previous reaction liquid, incubated overnight to phenylacetic aldehyde has reacted; The decompression of reaction mixture normal temperature steams excessive formaldehyde, and 50 ℃ of decompressions steam the second alcohol and water, get an oily matter; Add 240 gram Virahols and 20.4 gram aluminum isopropylates, heat up 60 degrees centigrade and reacted to aldehyde radical, decompression steams acetone and Virahol, after reaction solution is poured in the water of 650ml, divide three extractions with the ethyl acetate of 600ml, merge organic phase, anhydrous sodium sulfate drying filters, filtrate decompression steams ethyl acetate, get faint yellow transparent oily matter 122.2 grams, yield 91.2%, purity 99.3%(HPLC).
Embodiment 3:
N
2Protection is lower, in 1000 milliliters there-necked flask, pours the Virahol of 480ml into, is weighed into 1.8 gram cuprous chlorides and 120 gram phenylacetic aldehydes, stirs; 14.7 gram diethylamine propionic salts are dissolved in the 89 gram formalins, wherein contain formaldehyde 33.8 grams, be added drop-wise under the room temperature in the previous reaction liquid, incubated overnight to phenylacetic aldehyde has reacted; The reaction mixture decompression steams excessive formaldehyde, isopropyl alcohol and water, gets a faint yellow dope; Add 240 gram Virahols and 20.4 gram aluminum isopropylates, heat up 60 degrees centigrade and reacted to aldehyde radical, decompression steams acetone and Virahol, after reaction solution is poured in the water of 650ml, divide three extractions with the ethyl acetate of 600ml, merge organic phase, drying is filtered, filtrate decompression is concentrated, get oily matter 121.7 grams of a yellow transparent, yield 90.8%, purity 99%(HPLC).
Embodiment 4:
N
2Protection is lower, in 1000 milliliters there-necked flask, pours the ethanol of 480ml into, is weighed into 1.8 gram irgasfos 168s and 120 gram phenylacetic aldehydes, stirs; 11.6 gram Pyrrolidine propionic salts are dissolved in the 89 gram formalins, wherein contain formaldehyde 33.8 grams, be added drop-wise under the room temperature in the previous reaction liquid, incubated overnight to phenylacetic aldehyde has reacted; The reaction mixture decompression steams excessive formaldehyde, second alcohol and water, gets a yellow dope; Add 240 gram Virahols and 20.4 gram aluminum isopropylates, heat up 60 degrees centigrade and reacted to aldehyde radical, decompression steams acetone and Virahol, after reaction solution is poured in the water of 650ml, divide three extractions with the ethyl acetate of 600ml, merge organic phase, drying is filtered, filtrate decompression is concentrated, get the transparent oily matter of a dark yellow 110.6 grams, yield 82.5%, purity 98.5%(HPLC).
Embodiment 5:
N
2Protection is lower, in 1000 milliliters there-necked flask, pours the ethanol of 480ml into, is weighed into 1.8 gram Topanol A and 120 gram phenylacetic aldehydes, stirs; 20.3 gram hexahydropyridine acetates are dissolved in the 89 gram formalins, wherein contain formaldehyde 33.8 grams, be added drop-wise under the room temperature in the previous reaction liquid, incubated overnight to phenylacetic aldehyde has reacted; The reaction mixture decompression steams excessive formaldehyde, second alcohol and water, gets a dark yellow oily thing; Add 240 gram Virahols and 20.4 gram aluminum isopropylates, heat up 60 degrees centigrade and reacted to aldehyde radical, decompression steams acetone and Virahol, after reaction solution is poured in the water of 650ml, divide three extractions with the ethyl acetate of 600ml, merge organic phase, drying is filtered, filtrate decompression is concentrated, get light yellow transparent oily matter 116.6 grams, yield 87%, purity 98.8%(HPLC).
Embodiment 6:
N
2Protection is lower, in 1000 milliliters there-necked flask, pours the ethanol of 480ml into, is weighed into 1.8 gram anti-oxidant DLTPs and 120 gram phenylacetic aldehydes, stirs; 12.4 gram morpholine hydrochlorides are dissolved in the 89 gram formalins, wherein contain formaldehyde 33.8 grams, be added drop-wise under the room temperature in the previous reaction liquid, incubated overnight to phenylacetic aldehyde has reacted; The reaction mixture decompression steams excessive formaldehyde, second alcohol and water, gets a yellow dope; Add 240 gram Virahols and 20.4 gram aluminum isopropylates, heat up 60 degrees centigrade and reacted to aldehyde radical, decompression steams acetone and Virahol, after reaction solution is poured in the water of 650ml, divide three extractions with the ethyl acetate of 600ml, merge organic phase, drying is filtered, filtrate decompression is concentrated, get the transparent oily matter of a dark yellow 114.7 grams, yield 85.6%, purity 98.1%(HPLC).
Claims (9)
1. the preparation method of β-methylene-benzene ethanol is characterized in that, described method comprises the steps:
1) under the nitrogen protection condition, add first diluting solvent, add again stopper and phenylacetic aldehyde in the stirring, then add the formalin that is dissolved with organic amine salt, temperature of reaction 0-60 ℃, preferred 25-30 ℃, reaction times 12-16 hour, 15-35 ℃ of decompression steams excessive formaldehyde, and 40-75 ℃ of decompression steams diluting solvent and water, gets β-methylene-benzene acetaldehyde crude product;
2) get β-methylene-benzene acetaldehyde crude product, need not purifying, directly add Virahol and aluminum isopropylate and carry out reduction reaction, temperature of reaction 30-80 ℃, preferred 50-70 ℃, reaction times 6-8 hour, decompression steamed ketone and the solvent of by-product, obtained the crude product of product;
3) crude product is soluble in water, use organic solvent extraction, merge organic phase, drying is filtered, and decompression steams organic solvent, gets finished product β-methylene-benzene ethanol.
2. the preparation method of β according to claim 1-methylene-benzene ethanol, it is characterized in that the stopper described in the step 1) is one or more in Resorcinol, benzoquinones, p methoxy phenol, cuprous chloride, iron trichloride, antioxidant 1076, irgasfos 168, oxidation inhibitor 701, oxidation inhibitor B.H.T, Topanol A, antioxidant 3114, antioxidant 1010, anti-oxidant DLTP, the antioxidant TNP.
3. the preparation method of β according to claim 1-methylene-benzene ethanol is characterized in that, the diluting solvent described in the step 1) is methyl alcohol, ethanol or Virahol, preferred alcohol.
4. the preparation method of β according to claim 1-methylene-benzene ethanol is characterized in that, the organic amine salt described in the step 1) is hydrochloride, acetate or the propionic salt of secondary amine.
5. the preparation method of β according to claim 4-methylene-benzene ethanol is characterized in that, described secondary amine is one or more in dimethylamine, diethylamine, Pyrrolidine, hexahydropyridine, morpholine, the piperidines.
6. the preparation method of arbitrary described β-methylene-benzene ethanol is characterized in that according to claim 2-5, and the mol ratio of phenylacetic aldehyde and formaldehyde is 1:(1.05-1.3 in the step 1)), preferred 1:(1.05-1.1); The mol ratio of phenylacetic aldehyde and organic amine salt is 1:(0.02-0.2), preferred 1:(0.05-0.15); The mass ratio of phenylacetic aldehyde and diluting solvent is 1:(1-6); The consumption of stopper is the 0.2-2% of phenylacetic aldehyde quality; The mass content of formaldehyde is 37-40% in the formalin.
7. the preparation method of β according to claim 6-methylene-benzene ethanol, it is characterized in that, the molar ratio of β step 2)-methylene-benzene acetaldehyde crude product, Virahol, aluminum isopropylate is β-methylene-benzene acetaldehyde crude product: Virahol: aluminum isopropylate=1:(3-10): (0.05-0.3), preferred 1:(3-5): (0.1-0.2).
8. the preparation method of β according to claim 7-methylene-benzene ethanol is characterized in that step 2) described in reduction reaction be homogeneous phase hydrogen transfer reduction reaction.
9. the preparation method of β according to claim 8-methylene-benzene ethanol is characterized in that, the organic solvent described in the step 3) is methylene dichloride, 1, a kind of in 2-ethylene dichloride, ethyl acetate and the chloroform.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003856A (en) * | 2014-05-29 | 2014-08-27 | 中国科学院过程工程研究所 | Method for preparing methylacrolein by taking formaldehyde and propionaldehyde as raw materials |
| CN108752166A (en) * | 2018-05-22 | 2018-11-06 | 江苏馨瑞香料有限公司 | A kind of preparation method of Ebanol |
| CN114634414A (en) * | 2021-10-29 | 2022-06-17 | 山东德瑞高分子材料股份有限公司 | Efficient synthesis method of hydroxypropyl methacrylate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003856A (en) * | 2014-05-29 | 2014-08-27 | 中国科学院过程工程研究所 | Method for preparing methylacrolein by taking formaldehyde and propionaldehyde as raw materials |
| CN104003856B (en) * | 2014-05-29 | 2016-02-24 | 中国科学院过程工程研究所 | A kind of with formaldehyde and propionic aldehyde for the method for Methylacrylaldehyde prepared by raw material |
| CN108752166A (en) * | 2018-05-22 | 2018-11-06 | 江苏馨瑞香料有限公司 | A kind of preparation method of Ebanol |
| CN108752166B (en) * | 2018-05-22 | 2021-03-12 | 江苏馨瑞香料有限公司 | Preparation method of ebony alcohol |
| CN114634414A (en) * | 2021-10-29 | 2022-06-17 | 山东德瑞高分子材料股份有限公司 | Efficient synthesis method of hydroxypropyl methacrylate |
| CN114634414B (en) * | 2021-10-29 | 2023-01-03 | 山东德瑞高分子材料股份有限公司 | Efficient synthesis method of hydroxypropyl methacrylate |
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