CN103467287A - Preparation method for 4-acetoxyl-2-methyl-2-butenal - Google Patents

Preparation method for 4-acetoxyl-2-methyl-2-butenal Download PDF

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CN103467287A
CN103467287A CN201310449435XA CN201310449435A CN103467287A CN 103467287 A CN103467287 A CN 103467287A CN 201310449435X A CN201310449435X A CN 201310449435XA CN 201310449435 A CN201310449435 A CN 201310449435A CN 103467287 A CN103467287 A CN 103467287A
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acetoxyl
methyl
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olefine aldehydr
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CN103467287B (en
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田金金
甄剑飞
曾县明
单国红
管敏虾
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ZHEJIANG NHU PHARMACEUTICAL CO Ltd
ZHEJIANG XINHECHENG SPECIAL MATERIALS Co Ltd
SHANGYU XINHECHENG BIO-CHEMICAL Co Ltd
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ZHEJIANG XINHECHENG SPECIAL MATERIALS Co Ltd
SHANGYU XINHECHENG BIO-CHEMICAL Co Ltd
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Abstract

The invention discloses a preparation method for 4-acetoxyl-2-methyl-2-butenal. The method comprises the following steps that (1) in organic solvent, under the action of phosphine reagents, ethylene oxide and acraldehyde carry out a Morita-Baylis-Hillman reaction, and olefine aldehyde alcohol is obtained; (2) the olefine aldehyde alcohol obtained in the step (1) and an acetylation reagent carry out an acylation reaction, and olefine aldehyde alcohol ester is obtained; (3) under the action of double bond transposition catalysts and hydrogen, the olefine aldehyde alcohol ester obtained in the step (2) carries out a double bond transposition reaction, and the 4-acetoxyl-2-methyl-2-butenal is obtained. According to the preparation method, the ethylene oxide and the acraldehyde serve as raw materials to carry out three steps of reactions to obtain five-carbon aldehyde, the raw materials are common chemical raw materials, low in price, easy to obtain and low in cost, operation is simple, atom economy is extremely high, the three wastes are not produced, and the preparation method is an effective synthetic route.

Description

A kind of preparation method of 4-acetoxyl-2-methyl-2-butylenoic aldehyde
Technical field
The invention belongs to the chemical intermediate preparation field, be specifically related to a kind of preparation method of 4-acetoxyl-2-methyl-2-butylenoic aldehyde.
Background technology
The 4-acetoxyl-2-methyl-2-butylenoic aldehyde, referred to as five-carbon ring aldehydo, structure, as shown in formula I, is the key intermediate of synthesise vitamins A, current synthetic method mainly contains the dimethoxy acetone method, epoxyethane method, isoprene method and butylene glycol method etc.
Figure BDA0000388396800000011
U.S. Pat 5453547 discloses a kind of dimethoxy acetone method and has prepared five-carbon ring aldehydo, take dimethoxy acetone 1 as raw material, generate compound 2 with acetylene and hydrogen reaction, then react with acetic anhydride and obtain corresponding compound 3, under the effect of Cu series catalysts, double-bond isomerism obtains compound 4 again, and finally hydrolysis obtains five-carbon ring aldehydo.The subject matter of the method is: by compound 2 to 3, are acylation process of a tertiary alcohol, because the hydroxyl steric hindrance of the tertiary alcohol is larger, so yield is lower.Reaction formula is as follows:
Figure BDA0000388396800000012
U.S. Pat 4873362 discloses a kind of propylene oxide method and has prepared five-carbon ring aldehydo, this preparation method be take oxyethane 5 as starting raw material, obtain acetoxyl group ethanol 6 in acetic acid, then be oxidized to AOA 7 under the effect of catalyzer, then carry out aldol reaction with propionic aldehyde and obtain five-carbon ring aldehydo.The problem of this technique is that oxy-aldehyde is extremely unstable, is difficult to preserve, and the side reaction of final step aldol reaction is more, restive.Reaction formula is as follows:
Figure BDA0000388396800000021
U.S. Pat 5424478 discloses a kind of method that adopts the synthetic five-carbon ring aldehydo of isoprene method; the method be take isoprene 8 as raw material; obtain compound 9 and 10 with the clorox action-reaction, then by the aceticanhydride acidylate, obtain compound 11, last oxidation obtains five-carbon ring aldehydo.This reaction will produce a large amount of waste water.
Figure BDA0000388396800000022
U.S. Pat 4124619 discloses a kind of method that adopts the standby five-carbon ring aldehydo of butylene glycol legal system; the method be take Isosorbide-5-Nitrae-butylene glycol 12 as raw material, at first by the aceticanhydride acidylate, obtains 1; 4-butylene diester 13 is then used reaction under high pressure and CO/H under precious metal Rh catalyst action 2the gas mixture effect obtains compound 14, and then under the protonic acid effect, decarboxylation acid obtains the olefine aldehydr alcohol ester, finally by double-bond isomerism, obtains final product five-carbon ring aldehydo.In general, the atom utilization of this technique is high, causes hardly by product, also emits no waste water, be one comparatively reasonable, the operational path of economy and environmental protection.But present method need to be used expensive rhodium series catalysts.
Figure BDA0000388396800000023
Summary of the invention
The invention provides a kind of preparation method of 4-acetoxyl-2-methyl-2-butylenoic aldehyde, this preparation method's raw material is cheap, operational path is short, yield is high and environmentally friendly.
A kind of preparation method of 4-acetoxyl-2-methyl-2-butylenoic aldehyde, comprise the steps:
(1), in organic solvent, under the effect of phosphonate reagent, the Morita-Baylis-Hillman reaction occurs in oxyethane and propenal, obtains olefine aldehydr alcohol;
The structural formula of described phosphonate reagent is PR 1r 2r 3, wherein, R 1, R 2and R 3independently selected from C 1~C 5alkyl and phenyl;
The structure of described olefine aldehydr alcohol is as shown in formula II:
Figure BDA0000388396800000031
(2) the olefine aldehydr alcohol and the acetylation reagent generation acylation reaction that step (1) are obtained, obtain described olefine aldehydr alcohol ester;
The structure of described olefine aldehydr alcohol ester is as shown in formula III:
Figure BDA0000388396800000032
(3), under the effect of two key position rotaring catalysts and hydrogen, two key translocation reactions occur in the olefine aldehydr alcohol ester that step (2) obtains, and obtain described 4-acetoxyl-2-methyl-2-butylenoic aldehyde.
Above-mentioned preparation method's reaction scheme is as follows:
The present invention has developed the route of new synthetic 4-acetoxyl-2-methyl-2-butylenoic aldehyde; wherein; step (1) adopts oxyethane and propenal as starting raw material; under the effect of phosphonate reagent; generation by the C-C key has obtained olefine aldehydr alcohol; complete constructing of product basic framework, and then obtained end product through acetylize and two key translocation reaction.This synthetic route has been avoided the use of valuable metal catalyst, and raw material and catalyzer used cheaply are easy to get, and route is shorter, and total recovery is higher, and the waste water produced in reaction is less, environmentally friendly.
In step (1), described organic solvent is the organic solvent that raw material fully can be dissolved, and as preferably, described organic solvent is aromatic hydrocarbon solvent; As further preferred, described organic solvent is at least one in benzene, toluene and p-Xylol, and while adopting these solvents, the yield that the Morita-Baylis-Hillman reaction occurs for oxyethane and propenal is high, and side reaction is few.Wherein, the consumption of described organic solvent, without strict especially requirement, can fully dissolve raw material to get final product.
In step (1), described phosphonate reagent is Phenylphosphine or low alkyl group phosphine, and as preferably, described phosphonate reagent is trimethyl-phosphine, tributylphosphine or triphenylphosphine, and now, the side reaction of reaction is less, and reaction yield is high.
In step (1), described propenal is under the effect of phosphonate reagent, the polyreaction of self can occur, reduce yield and the selectivity of product, as further preferred, described phosphonate reagent is trimethyl-phosphine, described organic solvent is toluene, while adopting preferred phosphonate reagent and organic solvent, can reduce to greatest extent the side reaction of the self-polymerization of propenal, improve yield and the selectivity of described olefine aldehydr alcohol.
As preferably, in step (1), the mol ratio of described propenal, oxyethane and phosphonate reagent is 1:0.9~1.2:0.9~1.2.
In step (1), the temperature of described Morita-Baylis-Hillman reaction is difficult for too high, and excess Temperature can cause the increasing of self-polymerization reaction of propenal, and as preferably, the temperature of described Morita-Baylis-Hillman reaction is 25~50 ℃.
In step (2), described acetylation reagent is acetic acid, diacetyl oxide or Acetyl Chloride 98Min., is preferably diacetyl oxide, and using diacetyl oxide is that productive rate is the highest.
In step (2); as preferably; described acylation reaction is carried out under the effect of catalyzer; the ion exchange resin that described catalyzer is the load Periodic acid; by adding catalyzer can improve the yield of described acylation reaction; wherein, the ion exchange resin of load Periodic acid can improve the transformation efficiency of reaction effectively, can easily be reclaimed again.
In step (2), the mol ratio of described acetylation reagent and described olefine aldehydr alcohol is 1~2:1.
In step (2), the temperature of described acylation reaction is 70~90 ℃.
As preferably, in step (3), the described pair of key position rotaring catalyst be for containing the Pd catalyzer, the palladium-carbon catalyst that is more preferably 5% containing the palladium amount.
In step (3), the mass ratio of described pair of key position rotaring catalyst and described olefine aldehydr alcohol ester is 10 -4~10 -3: 1, described hydrogen adopts inert gas dilution, and concentration is 5~10%.
As preferably, in step (3), described pair of key translocation reaction carries out in toluene.
In step (3), the temperature of described pair of key translocation reaction is 90~110 ℃.
In step (1)~(3), the reaction times is monitored by GC.
Compared with the existing technology, beneficial effect of the present invention is embodied in: the raw material propylene aldehyde and the oxyethane that use are cheap and easy to get, have reduced preparation cost; The route of reaction is short, and yield is high; The three wastes that produce in reaction process are few, environmentally friendly.
Embodiment
Detail of the present invention is described in detail in embodiment below.But embodiment should not be construed as restriction protection scope of the present invention.
Embodiment 1
(1) preparation of olefine aldehydr alcohol
Under 0 ℃, 44g oxyethane is dissolved in 100ml toluene, be mixed with oxyethane toluene solution cryopreservation.Add the 56g propenal in reaction flask, and dissolve with appropriate toluene, add 76g trimethylammonium phosphorus to reaction flask while stirring, after 0.5h, dropwise add the oxyethane toluene solution prepared to reaction system, after 40 ± 5 ℃ of lower continuously stirring 24h, reaction finishes.Normal pressure steams solvent toluene, and rear decompression steams colourless aqueous product olefine aldehydr alcohol 87g, and content is 97.5%, and yield is 85%.
(2) preparation of olefine aldehydr alcohol ester
Add the 100g diacetyl oxide in reaction flask, (ion exchange resin used is Amberlyst15 to add at normal temperatures the ion exchange resin of 5g load Periodic acid, by the Periodic acid solution soaking of 0.1M 12 hours, after draining, obtain), be warming up to gradually 80 ℃ after 5min, start to drip olefine aldehydr alcohol 87g, 30min drips off, insulation reaction 3h.Through GC, analyze, when extremely residual without olefine aldehydr alcohol, reaction finishes.Be cooled to normal temperature, the elimination solid impurity, in system, add appropriate methylene dichloride to be extracted, and be washed till neutrality with 10% sodium hydroxide solution, separate organic phase, then use saturated common salt water washing secondary, obtain the colourless aqueous product olefine aldehydr alcohol ester of 115g after the reclaim under reduced pressure methylene dichloride, content 98%, yield 92.7%.
(3) preparation of five-carbon ring aldehydo
300g olefine aldehydr alcohol ester (product repeatedly merged) and the Pd-C catalyzer of 0.3g5% are dissolved in the 500ml toluene solvant, at N 2be heated to 100 ℃ under protection, with containing 6%H 2argon purge, GC follows the tracks of reaction, after 5~6h, reaction finishes, and except rectification under vacuum after desolventizing, obtains the 155g product.GC content is 98.5%, and retention time is consistent with standard substance, and yield is 51%.
Embodiment 2
(1) preparation of olefine aldehydr alcohol
Under 0 ℃, 44g oxyethane is dissolved in p-Xylol, be mixed with oxyethane toluene solution cryopreservation.Add the 56g propenal in reaction flask, and dissolve with appropriate p-Xylol, add 76g trimethylammonium phosphorus to reaction flask while stirring, after 0.5h, dropwise add the oxyethane toluene solution prepared to reaction system, after continuously stirring 24h, reaction finishes.Normal pressure steams solvent toluene, and rear decompression steams colourless aqueous product olefine aldehydr alcohol 82g, and content is 97.1%, and yield is 79.8%.
(2) preparation of olefine aldehydr alcohol ester
Add the 94g diacetyl oxide in reaction flask, (ion exchange resin used is Amberlyst15 to add at normal temperatures the ion exchange resin of 4.7g load Periodic acid, by the Periodic acid solution soaking of 0.1M 12 hours, after draining, obtain), be warming up to gradually 80 ℃ after 5min, start to drip olefine aldehydr alcohol 82g, 30min drips off, insulation reaction 3h.Through GC, analyze, when extremely residual without olefine aldehydr alcohol, reaction finishes.Be cooled to normal temperature, the elimination solid impurity, in system, add appropriate methylene dichloride to be extracted, and be washed till neutrality with 10% sodium hydroxide solution, separate organic phase, then use saturated common salt water washing secondary, obtain the colourless aqueous product olefine aldehydr alcohol ester of 107g after the reclaim under reduced pressure methylene dichloride, content 97%, yield 91.8%.
(3) preparation of five-carbon ring aldehydo
The Pd-C catalyzer of 30g olefine aldehydr alcohol ester and 0.03g5% is dissolved in the 50ml toluene solvant, at N 2be heated to 100 ℃ under protection, with containing 6%H 2argon purge, GC follows the tracks of reaction, after 3~4h, reaction finishes, and except rectification under vacuum after desolventizing, obtains the 15g product.GC content is 98.2%, and retention time is consistent with standard substance, and yield is 50%.
Embodiment 3
(1) preparation of olefine aldehydr alcohol
Under 0 ℃, 44g oxyethane is dissolved in toluene, be mixed with oxyethane toluene solution cryopreservation.Add the 56g propenal in reaction flask, and dissolve with appropriate toluene, add the 250g triphenylphosphine to reaction flask while stirring, after 0.5h, dropwise add the oxyethane toluene solution prepared to reaction system, after continuously stirring 24h, reaction finishes.Normal pressure steams solvent toluene, and rear decompression steams colourless aqueous product olefine aldehydr alcohol 65g, and content is 95%, and yield is 62%.
(2) preparation of olefine aldehydr alcohol ester
Add the 75g diacetyl oxide in reaction flask, (ion exchange resin used is Amberlyst15 to add at normal temperatures the ion exchange resin of 4g load Periodic acid, by the Periodic acid solution soaking of 0.1M 12 hours, after draining, obtain), be warming up to gradually 80 ℃ after 5min, start to drip olefine aldehydr alcohol 65g, 30min drips off, insulation reaction 3h.Through GC, analyze, when extremely residual without olefine aldehydr alcohol, reaction finishes.Be cooled to normal temperature, the elimination solid impurity, in system, add appropriate methylene dichloride to be extracted, and be washed till neutrality with 10% sodium hydroxide solution, separate organic phase, then use saturated common salt water washing secondary, obtain the colourless aqueous product olefine aldehydr alcohol ester of 84g after the reclaim under reduced pressure methylene dichloride, content 97%, yield 90.9%.
(3) preparation of five-carbon ring aldehydo
The Pd-C catalyzer of 30g olefine aldehydr alcohol ester and 0.03g5% is dissolved in the 50ml toluene solvant, at N 2be heated to 100 ℃ under protection, with containing 6%H 2argon purge, GC follows the tracks of reaction, after 3~4h, reaction finishes, and except rectification under vacuum after desolventizing, obtains the 14.6g product.GC content is 97.9%, and retention time is consistent with standard substance, and yield is 48.6%.
Comparative Examples 1
(1) preparation of olefine aldehydr alcohol
Under 0 ℃, 44g oxyethane is dissolved in toluene, be mixed with oxyethane toluene solution cryopreservation.Add the 56g propenal in reaction flask, and dissolve with appropriate toluene, add the 106g Tetramethyl Ethylene Diamine to reaction flask while stirring, after 0.5h, dropwise add the oxyethane toluene solution prepared to reaction system, after continuously stirring 24h, reaction finishes.Normal pressure steams solvent toluene, and rear decompression steams colourless aqueous product olefine aldehydr alcohol 32g, and content is 90%, and yield is 29%.
(2) preparation of olefine aldehydr alcohol ester
Add the 40g diacetyl oxide in reaction flask, (ion exchange resin used is Amberlyst15 to add at normal temperatures the ion exchange resin of 2g load Periodic acid, by the Periodic acid solution soaking of 0.1M 12 hours, after draining, obtain), be warming up to gradually 80 ℃ after 5min, start to drip olefine aldehydr alcohol 32g, 30min drips off, insulation reaction 3h.Through GC, analyze, when extremely residual without olefine aldehydr alcohol, reaction finishes.Be cooled to normal temperature, the elimination solid impurity, in system, add appropriate methylene dichloride to be extracted, and be washed till neutrality with 10% sodium hydroxide solution, separate organic phase, then use saturated common salt water washing secondary, obtain the colourless aqueous product olefine aldehydr alcohol ester of 40g after the reclaim under reduced pressure methylene dichloride, content 91%, yield 87.9%.
(3) preparation of five-carbon ring aldehydo
The Pd-C catalyzer of 30g olefine aldehydr alcohol ester and 0.03g5% is dissolved in the 50ml toluene solvant, at N 2be heated to 100 ℃ under protection, with containing 6%H 2argon purge, GC follows the tracks of reaction, after 3~4h, reaction finishes, and except rectification under vacuum after desolventizing, obtains the 14.4g product.GC content is 97.7%, and retention time is consistent with standard substance, and yield is 48.0%.

Claims (10)

1. the preparation method of a 4-acetoxyl-2-methyl-2-butylenoic aldehyde, is characterized in that, comprises the steps:
(1), in organic solvent, under the effect of phosphonate reagent, the Morita-Baylis-Hillman reaction occurs in oxyethane and propenal, obtains olefine aldehydr alcohol;
The structural formula of described phosphonate reagent is PR 1r 2r 3, wherein, R 1, R 2and R 3independently selected from C 1~C 5alkyl and phenyl;
The structure of described olefine aldehydr alcohol is as shown in formula II:
Figure FDA0000388396790000011
(2) the olefine aldehydr alcohol and the acetylation reagent generation acylation reaction that step (1) are obtained, obtain described olefine aldehydr alcohol ester;
The structure of described olefine aldehydr alcohol ester is as shown in formula III:
Figure FDA0000388396790000012
(3), under the effect of two key position rotaring catalysts and hydrogen, two key translocation reactions occur in the olefine aldehydr alcohol ester that step (2) obtains, and obtain described 4-acetoxyl-2-methyl-2-butylenoic aldehyde.
2. the preparation method of 4-acetoxyl-2-methyl-2-butylenoic aldehyde according to claim 1, is characterized in that, in step (1), described organic solvent is at least one in benzene, toluene and p-Xylol.
3. the preparation method of 4-acetoxyl-2-methyl-2-butylenoic aldehyde according to claim 1 and 2, is characterized in that, in step (1), described phosphonate reagent is trimethyl-phosphine, tributylphosphine or triphenylphosphine.
4. the preparation method of 4-acetoxyl-2-methyl-2-butylenoic aldehyde according to claim 1 and 2, is characterized in that, in step (1), described phosphonate reagent is trimethyl-phosphine, and described organic solvent is toluene.
5. the preparation method of 4-acetoxyl-2-methyl-2-butylenoic aldehyde according to claim 1, is characterized in that, in step (1), the mol ratio of described propenal, oxyethane and phosphonate reagent is 1:0.9~1.2:0.9~1.2.
6. the preparation method of 4-acetoxyl-2-methyl-2-butylenoic aldehyde according to claim 1, is characterized in that, in step (1), the temperature of described Morita-Baylis-Hillman reaction is 25~50 ℃.
7. the preparation method of 4-acetoxyl-2-methyl-2-butylenoic aldehyde according to claim 1, is characterized in that, in step (2), described acetylation reagent is acetic acid, diacetyl oxide or Acetyl Chloride 98Min..
8. the preparation method of 4-acetoxyl-2-methyl-2-butylenoic aldehyde according to claim 1, is characterized in that, in step (2), described acylation reaction is carried out under the effect of catalyzer, the ion exchange resin that described catalyzer is the load Periodic acid.
9. the preparation method of 4-acetoxyl-2-methyl-2-butylenoic aldehyde according to claim 1, is characterized in that, in step (3), described pair of key position rotaring catalyst is for containing the Pd catalyzer.
10. the preparation method of 4-acetoxyl-2-methyl-2-butylenoic aldehyde according to claim 1, is characterized in that, in step (3), described pair of key translocation reaction carries out in toluene.
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Cited By (10)

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CN106674012A (en) * 2016-12-28 2017-05-17 万华化学集团股份有限公司 Method for separating 4-acetoxy-2-methylene-butyraldehyde from hydrogenated product thereof
CN110143875A (en) * 2019-05-21 2019-08-20 万华化学集团股份有限公司 A kind of preparation method of 4- acetoxyl-2-methyl-2-butylenoic aldehyde
CN110734376A (en) * 2018-07-20 2020-01-31 新发药业有限公司 Preparation method of 2-methyl-4-acetoxyl-2-butenal
CN110734374A (en) * 2018-07-20 2020-01-31 新发药业有限公司 preparation method of 2-methyl-4-acetoxyl-2-butenal with high yield
CN113024367A (en) * 2021-03-22 2021-06-25 万华化学集团股份有限公司 Method for preparing alpha-hexyl cinnamaldehyde
CN113233979A (en) * 2021-04-29 2021-08-10 上虞新和成生物化工有限公司 Preparation method of 4-acetoxyl-2-methyl-2-butenal
CN113603592A (en) * 2021-06-29 2021-11-05 万华化学集团股份有限公司 Preparation method of 2-methyl-4-acetoxyl-2-butenal with thermal stability
CN113603587A (en) * 2021-06-29 2021-11-05 万华化学集团股份有限公司 Preparation method of 2-methyl-4-acetoxyl-2-butenal with stable chromaticity
CN114835577A (en) * 2022-06-07 2022-08-02 安徽智新生化有限公司 Method for synthesizing aldehyde
WO2024042131A1 (en) 2022-08-24 2024-02-29 Basf Se Method for preparing 4-hydroxy-2-methylene-butanal, 4-hydroxy-2-methyl-but-2-enal and esters thereof

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CN106674012A (en) * 2016-12-28 2017-05-17 万华化学集团股份有限公司 Method for separating 4-acetoxy-2-methylene-butyraldehyde from hydrogenated product thereof
CN106674012B (en) * 2016-12-28 2019-06-14 万华化学集团股份有限公司 A kind of 4- acetoxyl group -2- methylene-butyraldehyde and its hydrogenation products separation method
CN110734374B (en) * 2018-07-20 2022-07-01 新发药业有限公司 Preparation method of high-yield 2-methyl-4-acetoxyl-2-butenal
CN110734376A (en) * 2018-07-20 2020-01-31 新发药业有限公司 Preparation method of 2-methyl-4-acetoxyl-2-butenal
CN110734374A (en) * 2018-07-20 2020-01-31 新发药业有限公司 preparation method of 2-methyl-4-acetoxyl-2-butenal with high yield
CN110143875B (en) * 2019-05-21 2022-04-22 万华化学集团股份有限公司 Preparation method of 4-acetoxyl-2-methyl-2-butenal
CN110143875A (en) * 2019-05-21 2019-08-20 万华化学集团股份有限公司 A kind of preparation method of 4- acetoxyl-2-methyl-2-butylenoic aldehyde
CN113024367A (en) * 2021-03-22 2021-06-25 万华化学集团股份有限公司 Method for preparing alpha-hexyl cinnamaldehyde
CN113233979A (en) * 2021-04-29 2021-08-10 上虞新和成生物化工有限公司 Preparation method of 4-acetoxyl-2-methyl-2-butenal
CN113603592A (en) * 2021-06-29 2021-11-05 万华化学集团股份有限公司 Preparation method of 2-methyl-4-acetoxyl-2-butenal with thermal stability
CN113603587A (en) * 2021-06-29 2021-11-05 万华化学集团股份有限公司 Preparation method of 2-methyl-4-acetoxyl-2-butenal with stable chromaticity
CN114835577A (en) * 2022-06-07 2022-08-02 安徽智新生化有限公司 Method for synthesizing aldehyde
CN114835577B (en) * 2022-06-07 2024-04-19 安徽智新生化有限公司 Aldehyde synthesis method
WO2024042131A1 (en) 2022-08-24 2024-02-29 Basf Se Method for preparing 4-hydroxy-2-methylene-butanal, 4-hydroxy-2-methyl-but-2-enal and esters thereof
WO2024042132A1 (en) 2022-08-24 2024-02-29 Basf Se Method for preparing 4-hydroxy-2-methylene-butanal, 4-hydroxy-2-methyl-but-2-enal and esters thereof

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