CN105085213B - A kind of process for purification of the trans- α-methylcinnamaldehyde of high-purity - Google Patents
A kind of process for purification of the trans- α-methylcinnamaldehyde of high-purity Download PDFInfo
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- VLUMOWNVWOXZAU-VQHVLOKHSA-N (e)-2-methyl-3-phenylprop-2-enal Chemical compound O=CC(/C)=C/C1=CC=CC=C1 VLUMOWNVWOXZAU-VQHVLOKHSA-N 0.000 title claims abstract description 83
- 238000000746 purification Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 41
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012043 crude product Substances 0.000 claims abstract description 28
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims abstract description 18
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 16
- VLUMOWNVWOXZAU-CLFYSBASSA-N 2-Methyl-3-phenyl-2-propenal Chemical compound O=CC(/C)=C\C1=CC=CC=C1 VLUMOWNVWOXZAU-CLFYSBASSA-N 0.000 claims description 45
- 239000001496 (E)-2-methyl-3-phenylprop-2-enal Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 5
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims description 5
- 229930016911 cinnamic acid Natural products 0.000 claims description 5
- 235000013985 cinnamic acid Nutrition 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 3
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 claims description 3
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 3
- 235000013372 meat Nutrition 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 241000522254 Cassia Species 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000003444 phase transfer catalyst Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- 238000009835 boiling Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XNCRUNXWPDJHGV-BQYQJAHWSA-N (e)-2-methyl-3-phenylprop-2-enoic acid Chemical compound OC(=O)C(/C)=C/C1=CC=CC=C1 XNCRUNXWPDJHGV-BQYQJAHWSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen Potassium oxide Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of process for purification of the trans- α methyl cinnamic aldehydes of high-purity, with benzaldehyde and propionic aldehyde α methyl cinnamic aldehyde crude products are obtained to be condensed under the action of phase transfer catalyst in a solvent, using a rectifying, secondary rectifying, acidolysis, the technique of rectifying three times, obtains the trans- α methyl cinnamic aldehydes of high-purity of 99.0% or more content, while improving the yield of product.
Description
Technical field
The invention belongs to technical field of fine chemical synthesis, and in particular to a kind of process for purification of α-methylcinnamaldehyde.
Background technology
α-methylcinnamaldehyde is a kind of widely used fragrance, is usually used in the blending of cosmetics, perfumed soap, food etc., meanwhile,
α-methylcinnamaldehyde is also the important intermediate of diabetes medicament Yi Pasitan, and commodity are trans- α-methylcinnamaldehyde, with sugar
The increase of patient, the increase in demand to the drug are urinated, the demand to intermediate also increases, and therefore, it is necessary to improve it to synthesize work
Skill improves quality.
Currently, the synthesis of α-methylcinnamaldehyde is with benzaldehyde and positive propionic aldehyde in a solvent with the effect of phase transfer catalyst
Under be condensed, there are two kinds of cis and trans α-methylcinnamaldehyde in product obtained by the reaction, be for pharmaceutical intermediate
Trans- α-methylcinnamaldehyde, however, subtractive process only once rectifying in existing refined preparation process, trans- Alpha-Methyl in product
Cinnamic acid purity is 97%, and cis- α-methylcinnamaldehyde is 2% or more；The low boiling transition of rectifying also has more cis- Alpha-Methyl
Cinnamic acid is only detached by rectifying again, could obtain trans- α-methylcinnamaldehyde commodity.In this way, only through a rectifying
Cis- α-methylcinnamaldehyde is discarded as low component, in addition, being difficult to point along α-methylcinnamaldehyde and trans- α-methylcinnamaldehyde
From the high energy consumption of production, consumption is big, and cost is big.
Invention content
The purpose of the present invention is overcome to contain the cis- α-first of high level in existing trans- α-methylcinnamaldehyde synthesis technology
The problem of base cinnamic acid, hardly possible separation, discarded waste of resource.
For this purpose, the present invention provides a kind of process for purification of the trans- α-methylcinnamaldehyde of high-purity,
1) preparation of α-methylcinnamaldehyde crude product；By benzaldehyde and positive propionic aldehyde through α-first made from condensation, neutralization, desolventizing
Base cinnamic acid crude product, wherein α-methylcinnamaldehyde crude product includes benzaldehyde, benzyl alcohol, cis- α-methylcinnamaldehyde, trans- α-
- 3 benzenpropanal of methyl cinnamic aldehyde and 2- methyl -3- hydroxyls；
2) rectifying；α-methylcinnamaldehyde crude product made from step 1) is separated off benzene at vacuum -0.099MPa
Formaldehyde and benzyl alcohol, while -3 benzenpropanal of 2- methyl -3- hydroxyls is converted into Alpha-Methyl meat under the conditions of temperature is 100~160 DEG C
Cinnamic aldehyde；
3) secondary rectifying；Secondary rectifying will be carried out through step 2) treated α-methylcinnamaldehyde crude product, and isolate enrichment
The interim fraction of cis- α-methylcinnamaldehyde collects remaining finished product component；
4) acidolysis；By the interim fraction and concentration 2~3% of the cis- α-methylcinnamaldehyde of enrichment isolated in step 3)
Dilute sulfuric acid in mass ratio 1:0.2~1:1 is mixed reflux 8~10 hours, and reflux temperature is 100~103 DEG C, cis- Alpha-Methyl
Cinnamic acid is converted to trans- α-methylcinnamaldehyde, and the sodium hydroxide of refrigerated separation oil-yielding stratum, oil reservoir concentration 1% neutralizes；
5) rectifying three times；Oil reservoir after step 4) acidolysis is neutralized carries out rectification and purification three times, detaches and is enriched in oil-yielding stratum
The interim fraction of cis- α-methylcinnamaldehyde collects remaining finished product component；
6) step 3) and finished product component collected by step 5) are the trans- α-methylcinnamaldehyde of high-purity.
Above-mentioned steps 3) in secondary rectifying condition be in -0.099MPa vacuum under pressure rectifying, go out interim fraction time control
System reflux discharging is than being 5:1, go out finished product group Time-sharing control reflux discharging than being 1:1.
Above-mentioned steps 4) dilute sulfuric acid can use hydrochloric acid or phosphoric acid to substitute in acidolysis.
Above-mentioned steps 4) sodium hydroxide can use potassium hydroxide or soda ash to substitute in acidolysis.
Beneficial effects of the present invention：The process for purification of the trans- α-methylcinnamaldehyde of this high-purity provided by the invention will be smart
The cis- α-methylcinnamaldehyde being enriched in after evaporating in low boiling interim fraction is converted into trans- α-methylcinnamaldehyde product by acidolysis,
The load of rectifying is significantly reduced in this way, increases yield, improves product quality, avoids the useless of excessive cis- α-methylcinnamaldehyde
It abandons, it is cost-effective.
Specific implementation mode
Embodiment 1：
Contain the cis- α-methylcinnamaldehyde of high level in existing trans- α-methylcinnamaldehyde synthesis technology to overcome, it is difficult
The problem of separation, discarded waste of resource, a kind of process for purification of the trans- α-methylcinnamaldehyde of high-purity is present embodiments provided,
1) preparation of α-methylcinnamaldehyde crude product；By benzaldehyde and positive propionic aldehyde through α-first made from condensation, neutralization, desolventizing
Base cinnamic acid crude product, wherein α-methylcinnamaldehyde crude product includes benzaldehyde, benzyl alcohol, cis- α-methylcinnamaldehyde, trans- α-
- 3 benzenpropanal of methyl cinnamic aldehyde and 2- methyl -3- hydroxyls.
Wherein, the main reaction principle that benzaldehyde is reacted with positive propionic aldehyde is：
Side reaction in the reaction is：
2) rectifying；α-methylcinnamaldehyde crude product made from step 1) is separated off benzene at vacuum -0.099MPa
Formaldehyde and benzyl alcohol, while -3 benzenpropanal of 2- methyl -3- hydroxyls is converted into Alpha-Methyl meat under the conditions of temperature is 100~160 DEG C
Cinnamic aldehyde.
Wherein, the reaction principle that -3 benzenpropanal of 2- methyl -3- hydroxyls is converted into α-methylcinnamaldehyde is：
3) secondary rectifying；Secondary rectifying will be carried out through step 2) treated α-methylcinnamaldehyde crude product, and isolate enrichment
The interim fraction of cis- α-methylcinnamaldehyde collects remaining finished product component.
Wherein, the condition of secondary rectifying is to control and flow back out when going out interim fraction in -0.099MPa vacuum under pressure rectifying
Material is than being 5:1, go out finished product group Time-sharing control reflux discharging than being 1:1.
4) acidolysis；By the interim fraction and concentration 2~3% of the cis- α-methylcinnamaldehyde of enrichment isolated in step 3)
Dilute sulfuric acid in mass ratio 1:0.2~1:1 is mixed reflux 8~10 hours, and reflux temperature is 100~103 DEG C, cis- Alpha-Methyl
Cinnamic acid is converted to trans- α-methylcinnamaldehyde, and the sodium hydroxide of refrigerated separation oil-yielding stratum, oil reservoir concentration 1% neutralizes.
Wherein, dilute sulfuric acid used in acidolysis can use hydrochloric acid or phosphoric acid to substitute；Sodium hydroxide used in acidolysis can use hydrogen
Potassium oxide or soda ash substitute.
5) rectifying three times；Oil reservoir after step 4) acidolysis is neutralized carries out rectification and purification three times, detaches and is enriched in oil-yielding stratum
The interim fraction of cis- α-methylcinnamaldehyde collects remaining finished product component；
6) step 3) and finished product component collected by step 5) are the trans- α-methylcinnamaldehyde of high-purity.
The process for purification of the trans- α-methylcinnamaldehyde of this high-purity provided by the invention will be enriched in low boiling mistake after rectifying
The cis- α-methylcinnamaldehyde crossed in fraction is converted into trans- α-methylcinnamaldehyde product by acidolysis, significantly reduces essence in this way
The load evaporated increases yield, improves product quality, avoids the discarded of excessive cis- α-methylcinnamaldehyde, cost-effective.
Embodiment 2：
On the basis of embodiment 1, the present embodiment specifically provides a kind of refining for trans- α-methylcinnamaldehyde of high-purity
Method：
First, by 500 grams of the dehydration crude product of benzaldehyde and positive propionic aldehyde condensation α-methylcinnamaldehyde crude product obtained in vacuum-
Rectification and purification under 0.099MPa, wherein the dehydration crude product group of α-methylcinnamaldehyde crude product becomes trans- α-methylcinnamaldehyde 75%,
Cis- α-methylcinnamaldehyde 2.5%, benzaldehyde 18%, benzyl alcohol 1.5% obtain 95 grams of low boiling component, 50 grams of interim fraction, at
330 grams of product, 20 grams of height boiling；Wherein, interim fraction group is divided into cis- α-methylcinnamaldehyde 10.5%, trans- α-methylcinnamaldehyde
87%；Finished product group is divided into cis- α-methylcinnamaldehyde 3.5%, trans- α-methylcinnamaldehyde 96.2%.
Then, by 300 grams of rectification and purifications at vacuum -0.099MPa of finished product obtained above, 50 grams of interim fraction is obtained,
245 grams of finished product；Wherein, interim fraction group is divided into cis- α-methylcinnamaldehyde 29%, trans- α-methylcinnamaldehyde 69%, finished product group
It is divided into cis- α-methylcinnamaldehyde 0.8%, trans- α-methylcinnamaldehyde 99.1%.
Finally, by above-mentioned all 100 grams of (components of interim fraction：Cis- α-methylcinnamaldehyde 19.8%, trans- Alpha-Methyl
Cinnamic acid 78%), 50 gram 2.5% of dilute sulfuric acid is added in the three-necked flask of 500ml, is stirred at reflux 10 hours, sampling analysis
Group is divided into cis- α-methylcinnamaldehyde 3.5%, trans- α-methylcinnamaldehyde 94%.In the sodium hydroxide for using concentration 1% later
The rectification and purification again with after, obtains 20 grams of interim fraction, 78 grams of finished product；Wherein, interim fraction group is divided into cis- Alpha-Methyl Chinese cassia tree
Aldehyde 15%, trans- α-methylcinnamaldehyde 82%, finished product group are divided into cis- α-methylcinnamaldehyde 0.7%, trans- α-methylcinnamaldehyde
99.2%.
Embodiment 3：
The present embodiment specifically provides a kind of process for purification of the trans- α-methylcinnamaldehyde of high-purity：
First, by 500 grams of the dehydration crude product of benzaldehyde and positive propionic aldehyde condensation α-methylcinnamaldehyde crude product obtained in vacuum-
Rectification and purification under 0.099MPa, wherein the dehydration crude product group of α-methylcinnamaldehyde crude product becomes trans- α-methylcinnamaldehyde 75%,
Cis- α-methylcinnamaldehyde 2.5%, benzaldehyde 18%, benzyl alcohol 1.5% obtain 95 grams of low boiling component, 50 grams of interim fraction, at
330 grams of product, 20 grams of height boiling；Wherein, interim fraction group is divided into cis- α-methylcinnamaldehyde 10.5%, trans- α-methylcinnamaldehyde
87%；Finished product group is divided into cis- α-methylcinnamaldehyde 3.5%, trans- α-methylcinnamaldehyde 96.2%.
Then, by 300 grams of rectification and purifications at vacuum -0.099MPa of finished product obtained above, 50 grams of interim fraction is obtained,
245 grams of finished product；Wherein, interim fraction group is divided into cis- α-methylcinnamaldehyde 29%, trans- α-methylcinnamaldehyde 69%, finished product group
It is divided into cis- α-methylcinnamaldehyde 0.8%, trans- α-methylcinnamaldehyde 99.1%.
Finally, by above-mentioned all 100 grams of (components of interim fraction：Cis- α-methylcinnamaldehyde 19.8%, trans- Alpha-Methyl
Cinnamic acid 78%), 20 gram 3% of hydrochloric acid is added in the three-necked flask of 500ml, is stirred at reflux 9 hours, sampling analysis group is divided into
Cis- α-methylcinnamaldehyde 4%, trans- α-methylcinnamaldehyde 93.5%.After using the potassium hydroxide of concentration 1% to neutralize later again
Secondary rectification and purification obtains 22 grams of interim fraction, 77 grams of finished product；Wherein, interim fraction group is divided into cis- α-methylcinnamaldehyde 16%,
Trans- α-methylcinnamaldehyde 82%, finished product group are divided into cis- α-methylcinnamaldehyde 0.8%, trans- α-methylcinnamaldehyde 99.1%.
Embodiment 4：
The present embodiment specifically provides a kind of process for purification of the trans- α-methylcinnamaldehyde of high-purity：
First, by 500 grams of the dehydration crude product of benzaldehyde and positive propionic aldehyde condensation α-methylcinnamaldehyde crude product obtained in vacuum-
Rectification and purification under 0.099MPa, wherein the dehydration crude product group of α-methylcinnamaldehyde crude product becomes trans- α-methylcinnamaldehyde 75%,
Cis- α-methylcinnamaldehyde 2.5%, benzaldehyde 18%, benzyl alcohol 1.5% obtain 95 grams of low boiling component, 50 grams of interim fraction, at
330 grams of product, 20 grams of height boiling；Wherein, interim fraction group is divided into cis- α-methylcinnamaldehyde 10.5%, trans- α-methylcinnamaldehyde
87%；Finished product group is divided into cis- α-methylcinnamaldehyde 3.5%, trans- α-methylcinnamaldehyde 96.2%.
Then, by 300 grams of rectification and purifications at vacuum -0.099MPa of finished product obtained above, 50 grams of interim fraction is obtained,
245 grams of finished product；Wherein, interim fraction group is divided into cis- α-methylcinnamaldehyde 29%, trans- α-methylcinnamaldehyde 69%, finished product group
It is divided into cis- α-methylcinnamaldehyde 0.8%, trans- α-methylcinnamaldehyde 99.1%.
Finally, by above-mentioned all 100 grams of (components of interim fraction：Cis- α-methylcinnamaldehyde 19.8%, trans- Alpha-Methyl
Cinnamic acid 78%), 100 gram 2% of phosphoric acid is added in the three-necked flask of 500ml, is stirred at reflux 8 hours, sampling analysis component
For cis- α-methylcinnamaldehyde 3%, trans- α-methylcinnamaldehyde 95%.It is smart again after using the soda ash of concentration 1% to neutralize later
Purification is evaporated, 18 grams of interim fraction, 80 grams of finished product are obtained；Wherein, interim fraction group is divided into cis- α-methylcinnamaldehyde 14%, trans-
α-methylcinnamaldehyde 84%, finished product group are divided into cis- α-methylcinnamaldehyde 0.6%, trans- α-methylcinnamaldehyde 99.3%.
In conclusion it is up to 99% or more by the trans- α-methylcinnamaldehyde purity that above-mentioned process for purification obtains, relative to
For existing primary rectified purified method, trans- α-methylcinnamaldehyde purity has a large increase in product, while will be compared with
More cis- α-methylcinnamaldehydes are converted into trans- α-methylcinnamaldehyde, avoid the waste of cis- α-methylcinnamaldehyde, save
Cost.
The foregoing examples are only illustrative of the present invention, does not constitute the limitation to protection scope of the present invention, all
Be with the present invention it is same or analogous design all belong to the scope of protection of the present invention within.
Claims (2)
1. a kind of process for purification of trans- α-methylcinnamaldehyde, it is characterised in that：Include the following steps：
1) preparation of α-methylcinnamaldehyde crude product；By benzaldehyde and positive propionic aldehyde through Alpha-Methyl meat made from condensation, neutralization, desolventizing
Cinnamic aldehyde crude product, wherein α-methylcinnamaldehyde crude product includes benzaldehyde, benzyl alcohol, cis- α-methylcinnamaldehyde, trans- Alpha-Methyl
- 3 benzenpropanal of cinnamic acid and 2- methyl -3- hydroxyls；
2) rectifying；α-methylcinnamaldehyde crude product made from step 1) is separated off benzaldehyde at vacuum -0.099MPa
And benzyl alcohol, while -3 benzenpropanal of 2- methyl -3- hydroxyls is converted into α-methylcinnamaldehyde under the conditions of temperature is 100~160 DEG C；
3) secondary rectifying；Secondary rectifying will be carried out through step 2) treated α-methylcinnamaldehyde crude product, it is cis- to isolate enrichment
The interim fraction of α-methylcinnamaldehyde collects remaining finished product component；
4) acidolysis；By dilute sulphur of the interim fraction and concentration 2~3% of the cis- α-methylcinnamaldehyde of enrichment isolated in step 3)
Acid in mass ratio 1:0.2~1:1 is mixed reflux 8~10 hours, and reflux temperature is 100~103 DEG C, cis- Alpha-Methyl Chinese cassia tree
Aldehyde is converted to trans- α-methylcinnamaldehyde, and the sodium hydroxide of refrigerated separation oil-yielding stratum, oil reservoir concentration 1% neutralizes；
5) rectifying three times；Oil reservoir after step 4) acidolysis is neutralized carries out rectification and purification three times, is enriched in separation oil-yielding stratum cis-
The interim fraction of α-methylcinnamaldehyde collects remaining finished product component；
6) step 3) and finished product component collected by step 5) are the trans- α-methylcinnamaldehyde of high-purity.
2. the process for purification of trans- α-methylcinnamaldehyde as described in claim 1, it is characterised in that：It is secondary in the step 3)
The condition of rectifying is in -0.099MPa vacuum under pressure rectifying, and control reflux discharging is than being 5 when going out interim fraction:1, go out finished product
Group Time-sharing control reflux discharging is than being 1:1, dilute sulfuric acid can use hydrochloric acid or phosphoric acid to substitute in the step 4) acidolysis, the step 4)
Sodium hydroxide can use potassium hydroxide or soda ash to substitute in acidolysis.
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| US20070032402A1 (en) * | 2004-05-18 | 2007-02-08 | Womack Gary B | Process for producing indenol esters or ethers |
| CN101265167A (en) * | 2008-04-30 | 2008-09-17 | 武汉市合中生化制造有限公司 | Process for preparing a-methyl cinnamaldehyde |
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| US20070032402A1 (en) * | 2004-05-18 | 2007-02-08 | Womack Gary B | Process for producing indenol esters or ethers |
| US7250528B2 (en) * | 2004-05-18 | 2007-07-31 | Firmenich Sa | Process for producing indenol esters or ethers |
| CN101265167A (en) * | 2008-04-30 | 2008-09-17 | 武汉市合中生化制造有限公司 | Process for preparing a-methyl cinnamaldehyde |
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