CN102285873A - Method for synthesizing hydroxyaldehyde intermediate - Google Patents
Method for synthesizing hydroxyaldehyde intermediate Download PDFInfo
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- CN102285873A CN102285873A CN201110186389XA CN201110186389A CN102285873A CN 102285873 A CN102285873 A CN 102285873A CN 201110186389X A CN201110186389X A CN 201110186389XA CN 201110186389 A CN201110186389 A CN 201110186389A CN 102285873 A CN102285873 A CN 102285873A
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Abstract
The invention relates to a method for synthesizing a hydroxyaldehyde intermediate, in particular to a new synthesis method for producing the hydroxyaldehyde intermediate of polybasic alcohol in an organic solvent-water double-phase reaction system by taking alpha-hydrogen atom-containing short-chain fatty aldehyde and formaldehyde as raw materials under the catalysis of organic tertiary amine through a hydrogenation method. In the method, the conversion rate of the raw materials can be adjusted through an organic solvent in the reaction system; and unreacted raw materials and byproducts are extracted by using the organic solvent in the system after the reaction is finished, so that the raw materials are separated from products before reduced pressure distillation, extract (namely organic phase) can be circularly applied, raw material distillation, condensation and recovery are not required, and the raw materials can be recycled through simpler operation. The water phase is subjected to the reduced pressure distillation to extract the hydroxyaldehyde intermediate, so that the method can be directly used for producing the polybasic alcohol through hydrogenation reaction.
Description
Technical field
The present invention relates to a kind of synthetic method of aldol class intermediate, be particularly related to the novel method that the shortening method is produced the aldol class intermediate of polyvalent alcohol in a kind of heterogeneous reaction system, be specifically related to a kind of in organic solvent-water biphasic reaction system, with the short-chain fat aldehyde and the formaldehyde that contain α-hydrogen atom is raw material, and hydrogenation method is used to produce the novel synthesis of the aldol class intermediate of polyvalent alcohol under trimethylamine catalysis.
Background technology
Polyvalent alcohols such as tetramethylolmethane, trimethylolethane, neopentyl glycol and TriMethylolPropane(TMP) have purposes widely aspect the fine chemicals such as production Synolac, senior lubricant, urethane resin.The traditional processing technology of above-mentioned polyvalent alcohol is the Connizzaro method, promptly utilize the alkanoic and the formaldehyde that contain α-hydrogen atom to be raw material, carry out aldol reaction and cannizzaro reaction under the mineral alkali catalytic condition, purifying through means such as underpressure distillation obtains target product.This method exists that equipment corrosion is serious, by product is many, environmental pollution is serious, product purification difficulty is big, product quality is subjected to operational condition to influence shortcomings such as fluctuation is bigger.The environmental type novel process of exploitation is the shortening method at present, promptly adopt trimethylamine as catalyzer, alkanoic and formaldehyde generation aldol reaction that catalysis contains α-hydrogen atom obtain intermediate--the aldol compound, after simple the purification, under metal catalyst catalysis, carry out hydrogenation reaction, obtain target product.This method has advantages such as by product is few, environmental pollution is little, yield is high, good product quality.
The committed step that the shortening method is produced polyvalent alcohol is to carry out aldol reaction with the aldehyde that organic base catalytic contains α-hydrogen atom with formaldehyde to synthesize the aldol compound intermediate.Under alkaline condition, contain in the aldehyde generation aldol reaction of α-hydrogen atom and as the aldehyde compound of raw material and aldol class product cannizzaro reaction to take place under base catalysis easily all and generate alcohol, the aldehyde that contains a plurality of α-hydrogen atoms simultaneously is with formaldehyde generation aldol reaction the time, exist the α-hydrogen atom of this aldehyde can not whole substituted situations, cause by product more, therefore in order to improve the selectivity of aldol reaction in the shortening method, generally adopt the transformation efficiency of control raw material aldehyde under mild conditions, the recycled reaction solution is through repeatedly reacting the method for synthetic aldol compound intermediate.
The recycled pattern that adopts all is to adopt distillation under vacuum at present, considers the at high temperature easy and unreacting material generation side reaction of aldol intermediate, so the vacuum tightness of underpressure distillation is had relatively high expectations, has improved the withstand voltage properties requirement to production unit; Raw material is the lower boiling volatile substances in addition, when high-level efficiency reclaims the condensing works of production unit is had relatively high expectations, and will increase the equipment input in the production process through the multistage distillation, also has certain risk simultaneously in operation.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of synthetic method of simple and practical aldol class intermediate, this compound is mainly used in hydrogenation method and produces polyvalent alcohol, promptly in organic solvent-water biphasic reaction system, the hydrogeneration processes method is produced polyvalent alcohol under trimethylamine catalysis.
Technical conceive of the present invention is such: with the short-chain fat aldehyde and the formaldehyde that contain 1～3 α-hydrogen atom is raw material, in organic solvent-water biphasic reaction system, with the trimethylamine is catalyzer, feed intake according to certain mol proportion, under the certain temperature, reaction for some time, leave standstill cooling, separatory, water is concentrated through distilling, and promptly obtains target product aldol class intermediate.
The concrete technical scheme of the synthetic method of aldol class intermediate of the present invention is as follows:
The short-chain fat aldehyde that will contain α-hydrogen atom is dissolved in the organic solvent, this mixture and catalyzer trimethylamine are added drop-wise to respectively in the formalin that concentration is 5wt%～95wt%, be warming up to 20～100 ℃, reaction 0.5～6h, leave standstill cooling, separatory is told organic phase, water is concentrated through distilling, and promptly obtains target product aldol class intermediate.
The short-chain fat aldehyde carbonatoms of the described α of containing-hydrogen atom is C2～C6, preferred butyraldehyde-n.
Described organic solvent is selected from: benzene, toluene, m-xylene, o-Xylol, ethyl acetate, propyl acetate, butylacetate, 30～60 ℃ of sherwood oils, 60～90 ℃ of sherwood oils, 90～120 ℃ of sherwood oils, ether, or their mixture.
Described organic solvent input amount is the 5wt%～75wt% of reaction-ure mixture.
Described catalyzer trimethylamine is selected from: Trimethylamine 99, triethylamine, tripropyl amine.
The short-chain fat aldehyde of the described α of containing-hydrogen atom and the mole proportioning of formaldehyde are 1: 2～1: 6.
Described organic phase is as the solvent of next still reaction, and recycled contains unreacted raw material, organic solvent and a small amount of condensation product and by product in the organic phase.
The structural formula of aldol class intermediate of the present invention is as follows:
Wherein, R
1Be CH
2OH, C
1～C
4Alkyl is as CH
3, C
2H
5, C
3H
7Deng, R
2Be CH
2OH, C
1～C
4Alkyl is as CH
3, C
2H
5Or C
3H
7Deng.
The present invention proposes a kind ofly in organic solvent-water biphasic reaction system, is raw material with short-chain fat aldehyde and the formaldehyde that contains α-hydrogen atom, and the hydrogeneration processes method is produced the novel method of the aldol class intermediate of polyvalent alcohol under trimethylamine catalysis.This method can be regulated conversion of raw material by the organic solvent in the reaction system, after finishing, reaction utilize the organic solvent extracting in the system to take out unreacted raw material and by product, raw material is separated before underpressure distillation with product, capable of circulation the applying mechanically of extraction liquid (being organic phase), need not to carry out raw material distillation condensation and reclaim, under better simply operation, can finish the recycling of raw material.Water extracts aldol class intermediate through underpressure distillation can be directly used in hydrogenation reaction production polyvalent alcohol.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described in further detail, but described embodiment does not limit protection scope of the present invention.
Embodiment 1
In having the 1L reactor of cooling, stirring, thermometer, reflux condensate device, add 178.5g (2.2mol) 37% formalin under the agitation condition in order respectively, 121.5g water, 120g toluene, 72g (1.0mol) butyraldehyde-n, be warming up to 40 ℃, 0.5h drip 10.1g (0.1mol) triethylamine, continue reaction 0.5h, stop to stir, leave standstill cooling, separatory, tell organic phase 147g (wherein containing butyraldehyde-n 20.5g (GC)) altogether, water obtains the 94.4g condensation product through underpressure distillation, yield 71.5%.
Embodiment 2
In having the 2L reactor of cooling, stirring, thermometer, reflux condensate device, add organic phase, 178.5g (2.2mol) 37% formalin that 147g embodiment 1 reclaims under the agitation condition in order respectively, 121.5g water, 72g (1.0mol) butyraldehyde-n, be warming up to 40 ℃, 0.5h Dropwise 5 .1g (0.05mol) triethylamine, continue reaction 0.5h, stop to stir, leave standstill cooling, separatory is told organic phase 168.5g (wherein containing butyraldehyde-n 34.3g (GC)) altogether, water obtains the 106.7g condensation product through underpressure distillation, yield 80.8%.
Embodiment 3
In having the 2L reactor of cooling, stirring, thermometer, reflux condensate device, add the organic phase that 168.5g embodiment 2 reclaims under the agitation condition in order respectively, 178.5g (2.2mol) 37% formalin, 121.5g water, 72g (1.0mol) butyraldehyde-n, be warming up to 40 ℃, 0.5h drip 3.0g (0.03mol) triethylamine, continue reaction 0.5h, stop to stir, leave standstill cooling, separatory, tell organic phase 186.1g (wherein containing butyraldehyde-n 44.9g (GC)) altogether, water obtains the 112.6g condensation product through underpressure distillation, yield 85.3%.
Embodiment 4
In having the 2L reactor of cooling, stirring, thermometer, reflux condensate device, add the organic phase that 186.1g embodiment 3 reclaims under the agitation condition in order respectively, 178.5g (2.2mol) 37% formalin, 121.5g water, 72g (1.0mol) butyraldehyde-n, be warming up to 40 ℃, 0.5h drip 3.0g (0.03mol) triethylamine, continue reaction 0.5h, stop to stir, leave standstill cooling, separatory, tell organic phase 192.7g (wherein containing butyraldehyde-n 41.6g (GC)) altogether, water obtains the 118.5g condensation product through underpressure distillation, yield 89.8%.
Embodiment 5
In having the 2L reactor of cooling, stirring, thermometer, reflux condensate device, add the organic phase that 192.7g embodiment 4 reclaims under the agitation condition in order respectively, 178.5g (2.2mol) 37% formalin, 121.5g water, 72g (1.0mol) butyraldehyde-n, be warming up to 40 ℃, 0.5h drip 3.0g (0.03mol) triethylamine, continue reaction 0.5h, stop to stir, leave standstill cooling, separatory, tell organic phase 200.4g (wherein containing butyraldehyde-n 40.4g (GC)) altogether, water obtains the 120.9g condensation product through underpressure distillation, yield 91.5%.
Embodiment 6
In having the 500ml reactor of cooling, stirring, thermometer, reflux condensate device, add 89.2g (1.1mol) 37% formalin under the agitation condition in order respectively, 42.8g water, 39.6g m-xylene, 72g (1.0mol) butyraldehyde-n, be warming up to 40 ℃, 0.5h drip 10.1g (0.1mol) triethylamine, continue reaction 0.5h, stop to stir, leave standstill cooling, separatory, tell organic phase 61.7g (wherein containing butyraldehyde-n 15.7g (GC)) altogether, water obtains the 80.0g condensation product through underpressure distillation, yield 78.5%.
Embodiment 7
In having the 500ml reactor of cooling, stirring, thermometer, reflux condensate device, add organic phase, 89.2g (1.1mol) 37% formalin that 61.7g embodiment 6 reclaims under the agitation condition in order respectively, 42.8g water, 72g (1.0mol) butyraldehyde-n, be warming up to 40 ℃, 0.5h Dropwise 5 .1g (0.05mol) triethylamine, continue reaction 0.5h, stop to stir, leave standstill cooling, separatory is told organic phase 116.6g (wherein containing butyraldehyde-n 22.3g (GC)) altogether, water obtains the 89.2g condensation product through underpressure distillation, yield 87.4%.
Embodiment 8
In having the 500ml reactor of cooling, stirring, thermometer, reflux condensate device, add the organic phase that 116.6g embodiment 8 reclaims under the agitation condition in order respectively, 89.2g (1.1mol) 37% formalin, 42.8g water, 72g (1.0mol) butyraldehyde-n, be warming up to 40 ℃, 0.5h drips 3.0g (0.03mol) triethylamine, continues reaction 0.5h, stop to stir, leave standstill cooling, separatory is told organic phase 157.1g (wherein containing butyraldehyde-n 23.8g (GC)) altogether, water obtains the 98.6g condensation product through underpressure distillation, yield 96.7%.
Should be noted that at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement the technical scheme of invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the claim scope of the present invention.
Claims (9)
1. the synthetic method of an aldol class intermediate is characterized in that, may further comprise the steps:
The short-chain fat aldehyde that will contain α-hydrogen atom is dissolved in the organic solvent, this mixture and catalyzer trimethylamine are added drop-wise to respectively in the formalin that concentration is 5wt%～95wt%, be warming up to 20～100 ℃, reaction 0.5～6h, leave standstill cooling, separatory is told organic phase, water is concentrated through distilling, and promptly obtains target product aldol class intermediate.
2. synthetic method according to claim 1 is characterized in that, described short-chain fat aldehyde contains 1～3 α-hydrogen atom.
3. synthetic method according to claim 1 is characterized in that, the carbonatoms of the short-chain fat aldehyde of the described α of containing-hydrogen atom is C2～C6.
4. synthetic method according to claim 1, it is characterized in that, described organic solvent is selected from: benzene, toluene, m-xylene, o-Xylol, ethyl acetate, propyl acetate, butylacetate, 30～60 ℃ of sherwood oils, 60～90 ℃ of sherwood oils, 90～120 ℃ of sherwood oils, ether, or their mixture.
5. synthetic method according to claim 1 is characterized in that, described organic solvent input amount is the 5wt%～75wt% of reaction-ure mixture.
6. synthetic method according to claim 1 is characterized in that, described catalyzer trimethylamine is selected from Trimethylamine 99, triethylamine, tripropyl amine.
7. synthetic method according to claim 1 is characterized in that, the short-chain fat aldehyde of the described α of containing-hydrogen atom and the mole proportioning of formaldehyde are 1: 2～1: 6.
8. synthetic method according to claim 1 is characterized in that described organic phase is applied mechanically as the solvent cycle of next still.
9. according to each described synthetic method of claim 1～8, it is characterized in that the structural formula of described aldol class intermediate is as follows:
Wherein, R
1Be CH
2OH, C
1～C
4Alkyl, R
2Be CH
2OH, C
1～C
4Alkyl.
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| CN201110186389XA CN102285873A (en) | 2011-07-05 | 2011-07-05 | Method for synthesizing hydroxyaldehyde intermediate |
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|---|---|---|---|
| CN201110186389XA CN102285873A (en) | 2011-07-05 | 2011-07-05 | Method for synthesizing hydroxyaldehyde intermediate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115677466A (en) * | 2022-11-11 | 2023-02-03 | 宁夏百川科技有限公司 | Preparation method of dimethylolbutyraldehyde |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5072058A (en) * | 1989-12-23 | 1991-12-10 | Hoechst Aktiengesellschaft | Process for the preparation of 2,2-dimethylpropane-1,3-diol |
| CN101219939A (en) * | 2008-01-17 | 2008-07-16 | 上海华谊丙烯酸有限公司 | Method for synthesizing hydroxyl radical pivalic aldehyde with alkalescence ion liquid catalysis |
| CN101381299A (en) * | 2008-10-14 | 2009-03-11 | 山东轻工业学院 | Method for synthesizing 2,2-bis(hydroxymenthyl)butyric acid |
| TW201031626A (en) * | 2009-01-12 | 2010-09-01 | Basf Se | Process for preparing polymethylols |
-
2011
- 2011-07-05 CN CN201110186389XA patent/CN102285873A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5072058A (en) * | 1989-12-23 | 1991-12-10 | Hoechst Aktiengesellschaft | Process for the preparation of 2,2-dimethylpropane-1,3-diol |
| CN101219939A (en) * | 2008-01-17 | 2008-07-16 | 上海华谊丙烯酸有限公司 | Method for synthesizing hydroxyl radical pivalic aldehyde with alkalescence ion liquid catalysis |
| CN101381299A (en) * | 2008-10-14 | 2009-03-11 | 山东轻工业学院 | Method for synthesizing 2,2-bis(hydroxymenthyl)butyric acid |
| TW201031626A (en) * | 2009-01-12 | 2010-09-01 | Basf Se | Process for preparing polymethylols |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115677466A (en) * | 2022-11-11 | 2023-02-03 | 宁夏百川科技有限公司 | Preparation method of dimethylolbutyraldehyde |
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Application publication date: 20111221 |