CN101092355A - Method for preparing antiform - 4 - acetoxy - 2 - methyl - butenoic aldehyde - Google Patents
Method for preparing antiform - 4 - acetoxy - 2 - methyl - butenoic aldehyde Download PDFInfo
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Abstract
This invention provides a method for preparing trans-4-acetoxy-2-methyl-2-crotonaldehyde. The method comprises: reacting isoprene and tert-butyl hypochlorite in acetic anhydride solution to obtain chlorine-containing ester, reacting with urotropine, and hydrolyzing to obtain trans-4-acetoxy-2-methyl-2-crotonaldehyde. The method has such advantages as few reaction procedures, easy operation, high isoprene conversion rate, high yield (40-56%), no need for DMSO during the oxidation process, no byproduct, low raw material cost, easy recovery of solvent, little environmental pollution and low cost, and is suitable for industrial production.
Description
Technical field
The present invention relates to organic chemistry filed, be specifically related to the preparation method of five rings unsaturated carbon skeleton compound, the preparation method of particularly trans-the 4-acetoxyl group-2-methyl-2-butene aldehyde.
Background technology
Trans 4-acetoxyl group-2-methyl-2-butene aldehyde is the key intermediate of synthetic vitamin A and derivative thereof, and its chemical structure is
The synthesis of trans 4-of domestic manufacturer acetoxyl group-2-methyl-2-butene aldehyde employing is the technology of starting raw material with the acetone dimethyl acetal at present, and this operational path is long, and yield is low, the raw material costliness, and cost is higher.
United States Patent (USP) " METHOD OF PREPARING E-4-ACETOXY-2-BUTENAL " (patent No. 4175204) discloses a kind of method for preparing trans 4-acetoxyl group-2-methyl-2-butene aldehyde, specifically be to utilize isoprene and sodium hypochlorite reaction to generate chloropharin, generate the chlorine ester with chloropharin and acetic acidreaction then, obtain trans 4-acetoxyl group-2-methyl-2-butene aldehyde with DMSO chlorine monoxide ester at last, yield is 40～50%.Though this method can obtain higher yield, can generate dimethyl sulfide with DMSO chlorine monoxide ester, if untimely removing, meeting and the reaction of chlorine ester, cause the yield of 4-acetoxyl group-2-methyl-2-butene aldehyde to descend, this brings very big trouble to actual production, and increases production cost.
" 4-acetoxyl group-2-methyl-2-butene aldehyde new synthetic process " literary composition disclose a kind of isoprene through with the novel process of the synthetic 4-acetoxyl group of hypochlorous acid addition, diacetyl oxide esterification and TEMPO catalyzed oxidation three-step reaction-2-methyl-2-butene aldehyde, total recovery reaches 65%, and concrete grammar is: (1) uses CO
2The pH value of control isoprene-alkaline chlorine dioxide solution system, temperature is carried out addition reaction 5～6h for 0～5 ℃, and the total recovery of 1-chloro-2-methyl-3-butene-2-pure and mild 4-chloro-3-methyl-2-butene-1-alcohol is 72%; (2) adopt load the ion exchange resin of Periodic acid make catalyzer, gained adduct and diacetyl oxide esterification: at first under 20～25 ℃, 1-chloro-2-methyl-3-butene-2-pure and mild 4-chloro-3-methyl-2-butene-1-alcohol is added drop-wise in the mixing solutions of diacetyl oxide and Periodic acid, be warming up to 50 ℃ of reaction 4.5h then, generate 1-acetoxyl group-4-chloro-3-methyl-2-butene, yield is 95%; (3) make catalyzer with TEMPO again; esterification products 1-acetoxyl group-4-chloro-3-methyl-2-butene is oxidized into 4-acetoxyl group-2-methyl-2-butene aldehyde: at ambient temperature 1-acetoxyl group-4-chloro-3-methyl-2-butene is added drop-wise to DMSO; TEMPO; the phosphoric acid hydrogen dimethylamino; in the mixing solutions of potassium primary phosphate; be warming up to 90 ℃ of reactions then and generate 4-acetoxyl group-2-methyl-2-butene aldehyde; yield reaches 97% (Yang Zehui; Yan Haiying; Xi Li; Chen Xinzhi. colleges and universities' chemical engineering journal; 2004 04 phases .), prepare 4-acetoxyl group-2-methyl-2-butene aldehyde with this method and have the yield height; consuming time little; the advantage that cost is low.Use DMSO but remain during this method chlorine monoxide ester, the shortcoming of the method that United States Patent (USP) 4175204 is provided exists equally; This method has also been used TEMPO, the load expensive chemical reagent such as ion exchange resin of Periodic acid make the technology cost of this method increase greatly; Need two-step reaction from isoprene to synthetic chlorine ester, in the first step reaction, need to add excessive isoprene to suppress the addition production of by-products, the disposable utilization ratio of isoprene has only 33%, and total recovery has only 30% by the disposable yield that utilizes isoprene to calculate.The inventor has done repeatedly repeated authentication to the disclosed technological line of this article, and yield can not reach the described yield of this article.We press the described method of this article, react with 4 times of isoprene to the amount of substance of clorox, have only 10% to 15% chloropharin according to the isoprene calculated yield; Chlorine ester yield also has only about 80%, and wherein cis chlorine ester accounts for 15% to 20%; Final step is according to the condition of this article, the final product yield has only 50%, the by product of the reduzate dimethyl sulfide of DMSO and the reaction of chlorine ester is then near 40%, in order to reduce by product, must in reactor, feed nitrogen and drive dimethyl sulfide away, the yield of final product just can reach 80%, but operation is very loaded down with trivial details like this, and increases production cost.
Summary of the invention
The technical problem to be solved in the present invention is a production of by-products when reducing the chlorine monoxide ester, further improves the disposable utilization ratio of isoprene.
The technical scheme that the present invention solves the problems of the technologies described above is:
The preparation method of trans-the 4-acetoxyl group-2-methyl-2-butene aldehyde, this method is made up of following steps:
(1) in acetic anhydride solution, adds the isoprene of 0.5～1 times of acetic anhydride amount of substance, stir, be cooled to-10～0 ℃ and insulation, will in 1～2 hour, drip with the t-butyl hypochlorate of amount of substance such as isoprene; By the mol ratio of isoprene and catalyzer is to add catalyzer in 1: 0.01～1: 0.10, be warming up to 60～90 ℃, react the frozen water branch that adds 4～8 times after 6～10 hours and get organic phase, use elimination siccative after the siccative drying again, last under the pressure of 5mmHg, distill the chlorine ester;
(2) the resulting chlorine ester of step (1) is added in the organic solvent, the concentration that makes the amount of substance of chlorine ester in organic solvent is 2～3mol/L, add hexamethylenetetramine again with amount of substances such as chlorine ester, holding temperature is at 30～40 ℃, react after 6～10 hours, add and the isopyknic water of organic solvent, be warming up to 60～90 ℃, the glacial acetic acid of 1～2 times of chlorine ester amount of substance was dripped in 1～2 hour, continue to react to divide after 4～8 hours and get organic phase, use the siccative drying, under the pressure of 0.5mmHg, distill five-carbon ring aldehydo, promptly trans-the 4-acetoxyl group-2-methyl-2-butene aldehyde.
Catalyzer described in the inventive method can be a kind of in the mineral acids such as sulfuric acid, nitric acid, also can be a kind of in the organic acids such as Phenylsulfonic acid, tosic acid; Described siccative can be anhydrous sodium sulphate, Calcium Chloride Powder Anhydrous or Anhydrous potassium carbonate; Described organic solvent can be toluene, benzene, sherwood oil, chloroform, methylene dichloride, acetonitrile or 1,2-ethylene dichloride, preferably toluene or acetonitrile.
The inventive method is to be raw material with the isoprene, reacts in acetic anhydride solution with t-butyl hypochlorate, makes the chlorine ester, and by chlorine ester and hexamethylenetetramine (being urotropine) reaction, hydrolysis again makes five-carbon ring aldehydo, specifically reacts as follows then:
The inventive method prepares trans-4-acetoxyl group-2-methyl-2-butene aldehyde, step only from isoprene to the chlorine ester, reduced reactions steps, to utilize isoprene to calculate be 40～56% to yield by disposable; Avoided the use of DMSO, made byproduct of reaction significantly reduce, and employed cost of material is low, solvent is easy to recycle, and technical difficulty is little relatively, and environmental pollution is little, and Financial cost is lower, is applicable to industrial production.
Embodiment
Example 1
(1) in 2mol acetic anhydride solution, add the 1mol isoprene, stir, be cooled to-10 ℃～0 ℃, keep this temperature, then the 1mol t-butyl hypochlorate was dripped in 1.5 hours.After dripping, be warming up to 80 ℃, add 0.05mol tosic acid reaction 10 hours, reaction adds the 500ml frozen water after finishing, and divides and gets organic phase, with elimination siccative behind the 20g anhydrous sodium sulfate drying.Under 5mmHg, distill 0.8mol chlorine ester, content is 93%.
(2) 1mol chlorine ester is joined in the toluene of 500ml, add the 1mol hexamethylenetetramine again, holding temperature is about 40 ℃, reacted 8 hours, and added 500ml water then, be warming up to 80 ℃, then the 2mol glacial acetic acid was dripped in 2 hours, continue reaction 10 hours, divide after reaction finishes and get organic phase, use the 20g anhydrous sodium sulfate drying, under 0.5mmHg, distill five-carbon ring aldehydo 0.7mol, content is 90%, is 56% with respect to the yield of isoprene.
Example 2
(1) in the solution of 2mol acetic anhydride, add the 1mol isoprene, stir, be cooled to-10-0 ℃, keep this temperature, then the 1mol t-butyl hypochlorate was dripped in 1.5 hours.After dripping, be warming up to 80 ℃, added the 0.1mol sulfuric acid reaction 10 hours, reaction adds the 500ml frozen water after finishing, and divides and gets organic phase, with elimination siccative after the 20g Calcium Chloride Powder Anhydrous drying.Under 5mmHg, distill 0.81mol chlorine ester, content is 93%.
(2) 1mol chlorine ester is joined in the acetonitrile of 500ml, add the 1mol hexamethylenetetramine again, holding temperature is about 40 ℃, reacted 8 hours, and filtered then, filter cake adds water 500ml dissolving, add 500ml1 again, the 2-ethylene dichloride is warming up to 80 ℃, then the 2mol glacial acetic acid was dripped in 2 hours, continue reaction 6 hours, divide after reaction finishes and get organic phase, use the 20g anhydrous sodium sulfate drying, under 0.5mmHg, distill five-carbon ring aldehydo 0.81mol, content is 93%.
Example 3
(1) in 2mol acetic anhydride solution, add the 1mol isoprene, stir, be cooled to-10-0 ℃, keep this temperature, then the 1mol t-butyl hypochlorate was dripped in 1.5 hours.After dripping, be warming up to 80 ℃, added the 0.1mol nitric acid reaction 10 hours, reaction adds the 500ml frozen water after finishing, and divides and gets organic phase, with elimination siccative behind the 20g anhydrous sodium sulfate drying.Under 5mmHg, distill 0.78mol chlorine ester, content is 91%.
(2) 1mol chlorine ester is joined in the sherwood oil of 500ml, add the 1mol hexamethylenetetramine again, holding temperature is about 40 ℃, reacted 8 hours, add 500ml water then, be warming up to 90 ℃, then the 2mol glacial acetic acid was dripped in 2 hours, continue reaction 6 hours, divide after reaction finishes and get organic phase, use the 20g anhydrous sodium sulfate drying, under 0.5mmHg, distill five-carbon ring aldehydo 0.74mol, content is 94%.
Example 4
(1) in 2mol acetic anhydride solution, add the 1mol isoprene, stir, be cooled to-10-0 ℃, keep this temperature, then the 1mol t-butyl hypochlorate was dripped in 1.5 hours.After dripping, be warming up to 80 ℃, add 0.05mol Phenylsulfonic acid reaction 10 hours, reaction adds the 500ml frozen water after finishing, and divides and gets organic phase, with elimination siccative after the 20g Anhydrous potassium carbonate drying.Under 5mmHg, distill 0.78mol chlorine ester, content is 93%.
(2) 1mol chlorine ester is joined in the chloroform of 500ml, add the 1mol hexamethylenetetramine again, holding temperature is about 40 ℃, reacted 8 hours, add 500ml water then, be warming up to 60 ℃, then the 2mol glacial acetic acid was dripped in 2 hours, continue reaction 6 hours, divide after reaction finishes and get organic phase, with 20g Anhydrous potassium carbonate drying, under 0.5mmHg, distill five-carbon ring aldehydo 0.6mol, content is 93%.
Example 5
(1) in the solution of 1mol acetic anhydride, add the 1mol isoprene, stir, be cooled to-10-0 ℃, keep this temperature, then the 1mol t-butyl hypochlorate was dripped in 1.5 hours.After dripping, be warming up to 80 ℃, add 0.05mol tosic acid reaction 8 hours, reaction adds the 500ml frozen water after finishing, and divides and gets organic phase, with elimination siccative behind the 20g anhydrous sodium sulfate drying.Under 5mmHg, distill 0.8mol chlorine ester, content is 96%.
(2) 1mol chlorine ester is joined 1 of 500ml, in the 2-ethylene dichloride, add the 1mol hexamethylenetetramine again, holding temperature was reacted 8 hours about 40 ℃, added 500ml water then, be warming up to 80 ℃, then the 2mol glacial acetic acid was dripped in 2 hours, continue reaction 6 hours, divide after reaction finishes and get organic phase, use the 20g anhydrous sodium sulfate drying, under 0.5mmHg, distill five-carbon ring aldehydo 0.76mol, content is 72%.
Example 6
(1) in the solution of 1mol acetic anhydride, add the 1mol isoprene, stir, be cooled to-10-0 ℃, keep this temperature, then the 1mol t-butyl hypochlorate was dripped in 1 hour; Be warming up to 60 ℃, add 0.05mol tosic acid reaction 10 hours, add the frozen water of 500ml after reaction finishes, divide and get organic phase, use anhydrous sodium sulfate drying then, the elimination anhydrous sodium sulphate, last under the pressure of 5mmHg, distill chlorine ester 0.75mol, content is 93%.
(2) in the 500ml toluene that 1.5mol chlorine ester is joined, add the 1.5mol hexamethylenetetramine again, holding temperature is at 30 ℃, reacted 10 hours, and added then and the isopyknic water of toluene, be warming up to 60 ℃, then the 3mol glacial acetic acid was dripped in 1 hour, continue reaction 8 hours, divide after reaction finishes and get organic phase, use anhydrous sodium sulfate drying, under the pressure of 0.5mmHg, distill five-carbon ring aldehydo, promptly trans-the 4-acetoxyl group-2-methyl-2-butene aldehyde 0.7mol, content is 95%.
Example 7
(1) in the solution of 1mol acetic anhydride, add the 1mol isoprene, stir, be cooled to-10-0 ℃, keep this temperature, then the 1mol t-butyl hypochlorate was dripped in 1 hour; Be warming up to 90 ℃, add 0.05mol tosic acid reaction 6 hours, add the frozen water of 500ml after reaction finishes, divide and get organic phase, use anhydrous sodium sulfate drying then, the elimination anhydrous sodium sulphate, last under the pressure of 5mmHg, distill chlorine ester 0.81mol, content is 0.96%.
(2) in the 500ml toluene that 1.5mol chlorine ester is joined, add the 1.5mol hexamethylenetetramine again, holding temperature is at 30 ℃, reacted 10 hours, and added then and the isopyknic water of toluene, be warming up to 90 ℃, then the 3mol glacial acetic acid was dripped in 1 hour, continue reaction 4 hours, divide after reaction finishes and get organic phase, use anhydrous sodium sulfate drying, under the pressure of 0.5mmHg, distill five-carbon ring aldehydo, promptly trans-the 4-acetoxyl group-2-methyl-2-butene aldehyde 0.72mol, content is 93%.
Claims (2)
1, the preparation method of trans-4-acetoxyl group-2-methyl-2-butene aldehyde, this method is made up of following steps:
(1) in acetic anhydride solution, adds the isoprene of 0.5～1 times of acetic anhydride amount of substance, stir, be cooled to-10～0 ℃ and insulation, will in 1～2 hour, drip with the t-butyl hypochlorate of amount of substance such as isoprene; By the mol ratio of isoprene and catalyzer is to add catalyzer in 1: 0.01～1: 0.10, be warming up to 60～90 ℃, react the frozen water branch that adds 4～8 times after 6～10 hours and get organic phase, use elimination siccative after the siccative drying again, last under the pressure of 5mmHg, distill the chlorine ester;
(2) the resulting chlorine ester of step (1) is added in the organic solvent, the concentration that makes the amount of substance of chlorine ester in organic solvent is 2～3mol/L, add hexamethylenetetramine again with amount of substances such as chlorine ester, holding temperature is at 30～40 ℃, react after 6～10 hours, add and the isopyknic water of organic solvent, be warming up to 60～90 ℃, the glacial acetic acid of 1～2 times of chlorine ester amount of substance was dripped in 1～2 hour, continue to react to divide after 4～8 hours and get organic phase, use the siccative drying, under the pressure of 0.5mmHg, distill five-carbon ring aldehydo, promptly trans-the 4-acetoxyl group-2-methyl-2-butene aldehyde;
Catalyzer described in the above-mentioned steps is sulfuric acid, nitric acid, Phenylsulfonic acid or tosic acid; Described siccative is anhydrous sodium sulphate, Calcium Chloride Powder Anhydrous or Anhydrous potassium carbonate; Described organic solvent is toluene, benzene, sherwood oil, chloroform, methylene dichloride acetonitrile or 1, the 2-ethylene dichloride.
2, according to claim 1 trans-preparation method of 4-acetoxyl group-2-methyl-2-butene aldehyde, it is characterized in that described organic solvent is toluene or acetonitrile.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794296A (en) * | 2017-05-05 | 2018-11-13 | 万华化学集团股份有限公司 | A kind of preparation method of 4- acetoxyl-2-methyl-2-butylenoic aldehydes |
| CN112321426A (en) * | 2020-09-29 | 2021-02-05 | 马鞍山科思化学有限公司 | Preparation of 4-acyloxy-2-methyl-2-butenal by catalytic oxidation method |
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2007
- 2007-07-09 CN CN 200710029071 patent/CN101092355A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794296A (en) * | 2017-05-05 | 2018-11-13 | 万华化学集团股份有限公司 | A kind of preparation method of 4- acetoxyl-2-methyl-2-butylenoic aldehydes |
| CN108794296B (en) * | 2017-05-05 | 2021-03-09 | 万华化学集团股份有限公司 | Preparation method of 4-acetoxyl-2-methyl-2-butenal |
| CN112321426A (en) * | 2020-09-29 | 2021-02-05 | 马鞍山科思化学有限公司 | Preparation of 4-acyloxy-2-methyl-2-butenal by catalytic oxidation method |
| CN112321426B (en) * | 2020-09-29 | 2024-01-23 | 马鞍山科思化学有限公司 | Catalytic oxidation process for preparing 4-acyloxy-2-methyl-2-butenal |
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