CN111484407B - Preparation method of 1-halogenated-2-methyl-4-substituted carbonyloxy-2-butene - Google Patents
Preparation method of 1-halogenated-2-methyl-4-substituted carbonyloxy-2-butene Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/297—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
Abstract
The invention provides a preparation method of 1-halogenated-2-methyl-4-substituted carbonyloxy-2-butene, which comprises the steps of carrying out acylation reaction on 2-methyl-4-hydroxy-1-butene and an acylation reagent under the action of a catalyst to prepare 2-methyl-4-substituted carbonyloxy-1-butene, and then carrying out addition reaction and alkali elimination reaction on the 2-methyl-4-substituted carbonyloxy-2-butene with halogen to prepare the 1-halogenated-2-methyl-4-substituted carbonyloxy-2-butene. The method has the advantages of cheap and easily obtained raw materials and low product cost; the process flow is simple, the reaction condition is easy to realize, the operation is safe and simple, the waste water generation amount is small, and the method is green and environment-friendly; the reaction intermediate product is stable, the reaction activity is proper, the reaction selectivity is high, the side reaction is less, the yield and the purity of the target product are high, and the method is suitable for green industrial production.
Description
Technical Field
The invention relates to a preparation method of 1-halogenated-2-methyl-4-substituted carbonyloxy-2-butene, belonging to the technical field of medical chemistry.
Background
1-halo-2-methyl-4-substituted carbonyloxy-2-butene (I) is an important intermediate that can be used to prepare vitamin A acetate intermediates, vitamin A palmitate intermediates, wittig's reagent and various carotenoids, and has the following structural formula:
wherein, in the structural formula of the compound of the formula I, X is chlorine or bromine; r substitutionRadical being hydrogen, C n H 2n+1 A group (1 ≦ n ≦ 18), phenyl, or benzyl.
US patent documents US4175204 and US5424478 use isoprene as a raw material, and the isoprene is added with sodium hypochlorite to obtain a mixture of 3-methyl-3-hydroxy-4-chloro-1-butene and 1-chloro-2-methyl-4-hydroxy-2-butene, and then the mixture is esterified with acetic anhydride to prepare 1-chloro-2-methyl-4-acetoxy-2-butene (I) 1 ) The reaction sequence is depicted as scheme 1 below.
Synthesis scheme 1
Chinese patent document CN103012131A uses isoprene as a raw material, and reacts with tert-butyl hypochlorite and acetic acid to obtain a mixture of 3-methyl-3-acetoxy-4-chloro-1-butene and 1-chloro-2-methyl-4-hydroxy-2-butene, and then the mixture is esterified by acetic anhydride to prepare 1-chloro-2-methyl-4-acetoxy-2-butene (I) 1 ) The reaction sequence is depicted as scheme 2 below.
Synthesis scheme 2
The raw materials of isoprene and tert-butyl hypochlorite required by the method are high in price, and the waste water amount of the sodium hypochlorite method is large, so that the method is not beneficial to green and environment-friendly production.
In conclusion, the research and optimization of the low-cost green industrial preparation route of the 1-halo-2-methyl-4-acetoxyl-2-butene and other 1-halo-2-methyl-4-substituted carbonyloxy-2-butenes has important significance for green production of products such as vitamin A acetate, vitamin A palmitate, various carotenoids and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of 1-halogenated-2-methyl-4-substituted carbonyloxy-2-butene. The method has the advantages of cheap and easily available raw materials and low product cost; the process flow is simple, the reaction condition is easy to realize, the operation is safe and simple, the waste water generation amount is small, and the method is green and environment-friendly; the reaction intermediate product is stable, the reaction activity is proper, the reaction selectivity is high, the side reaction is less, the yield and the purity of the target product are high, and the method is suitable for green industrial production.
Description of terms:
a compound of formula II: 2-methyl-4-hydroxy-1-butene (II);
a compound of formula III: 2-methyl-4-substituted carbonyloxy-1-butene (iii); wherein, in the structural formula of the compound in the formula III, the substituent R is hydrogen and has a general formula C n H 2n+1 A group (1 ≦ n ≦ 18), phenyl or benzyl;
a compound of formula IV: 1,2-dihalo-2-methyl-4-substituted carbonyloxybutane (iv); wherein, in the structural formula of the compound shown in the formula IV, a substituent X is chlorine or bromine, and a substituent R is the same as the substituent R in the structural formula of the compound shown in the formula III;
a compound of formula I: 1-halo-2-methyl-4-substituted carbonyloxy-2-butene (I); wherein, the substituent X and R in the structural formula of the compound shown in the formula I are the same as the substituent X and R in the structural formula of the compound shown in the formula III.
In the specification, the compound numbers are completely consistent with the structural formula numbers, have the same reference relationship, and are based on the structural formula of the compound.
The technical scheme of the invention is as follows:
a process for the preparation of 1-halo-2-methyl-4-substituted carbonyloxy-2-butene (I) comprising the steps of:
(1) Preparing a compound of formula III by subjecting a compound of formula II and an acylating agent to an acylation reaction;
wherein, in the structural formula of the compound in the formula III, the substituent R is hydrogen and has a general formula C n H 2n+1 A group (1 ≦ n ≦ 18), phenyl or benzyl;
(2) Preparing a compound of formula IV by subjecting a compound of formula III and a halogen to addition reaction, followed by elimination reaction to prepare 1-halo-2-methyl-4-substituted carbonyloxy-2-butene (I);
wherein, in the structural formula of the compound shown in the formula IV, a substituent X is chlorine or bromine, and a substituent R is the same as the substituent R in the structural formula of the compound shown in the formula III.
Preferably, in step (1), the acylation of the compound of formula II and the acylating agent is carried out in solvent A in the presence of a catalyst.
Preferably, the solvent A is one or the combination of more than two of toluene, xylene, benzene, n-hexane, cyclohexane, n-heptane, petroleum ether with the boiling range of 60-90 ℃ or chlorobenzene; the mass ratio of the solvent A to the compound shown in the formula II is (2-15) to 1; further preferably, the mass ratio of the solvent A to the compound of the formula II is (3-8): 1.
Preferably, the catalyst is one or the combination of more than two of benzene sulfonic acid, p-methyl benzene sulfonic acid, methyl sulfonic acid or concentrated sulfuric acid with the mass concentration of 70-98%; the mass of the catalyst is 0.02-2.0% of that of the compound shown in the formula II; further preferably, the mass of the catalyst is 0.1 to 1.0% of the mass of the compound of formula II.
Preferably, the acylating agent is formic acid, acetyl chloride, acetic anhydride, benzoic acid, benzoic anhydride, phenylacetic acid, phenylacetic anhydride or a compound having the formula HOOCC n H 2n+1 Carboxylic acid of the formula HOOCC n H 2n+1 In (1 ≦ n ≦ 18; further preferably, the acylating agent is acetic acid, acetic anhydride or palmitic acid; the molar ratio of the acylating agent to the compound of the formula II is (1.0-1.5) to 1; further preferably, the molar ratio of the acylating agent to the compound of formula II is (1.1-1.3): 1.
Preferably, the acylation reaction temperature is 40-140 ℃; further preferably, the acylation reaction temperature is 60-120 ℃. The acylation reaction time is 1-10 hours; further preferably, the acylation reaction time is 3 to 6 hours.
Preferably, according to the present invention, the preparation of 1-halo-2-methyl-4-substituted carbonyloxy-2-butene (I) in step (2) comprises the steps of: in a solvent B, carrying out addition reaction on a compound shown in a formula III and halogen to prepare a compound shown in a formula IV; then adding alkali to prepare 1-halogeno-2-methyl-4-substituted carbonyloxy-2-butene (I) through elimination reaction.
Preferably, the solvent B is one or the combination of more than two of dichloromethane, chloroform, 1,2-dichloroethane, trichloroethane, toluene, chlorobenzene, xylene, normal hexane, cyclohexane, normal heptane or petroleum ether with the boiling range of 60-90 ℃; the mass ratio of the solvent B to the compound shown in the formula III is (2-15): 1; further preferably, the mass ratio of the solvent B to the compound of the formula III is (3-10): 1.
Preferably, the halogen is chlorine or bromine; the molar ratio of halogen to compound of formula III is (1.0-1.4): 1; further preferably, the molar ratio of halogen to compound of formula III is (1.0-1.2): 1.
Preferably, the addition reaction temperature is-10-100 ℃; further preferably, the addition reaction temperature is 20 to 50 ℃. The addition reaction time is 1-10 hours; further preferably, the addition reaction time is 3 to 5 hours.
Preferably, the alkali is sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate or calcium carbonate, and the molar ratio of the alkali to the compound shown in the formula III is (0.5-2.0): 1; further preferably, the molar ratio of the base to the compound of formula III is (1.1-1.3): 1.
Preferably, the elimination reaction temperature is 0-100 ℃; further preferably, the elimination reaction temperature is 30 to 60 ℃. The elimination reaction time is 2-10 hours; further preferably, the elimination reaction time is 3 to 5 hours.
The reaction process of the present invention is depicted as the following synthetic scheme 3:
synthesis scheme 3
Wherein, in the structural formula of the compound in the formula III, the substituent R is hydrogen and has a general formulaFormula C n H 2n+1 A group (1 ≦ n ≦ 18), phenyl, or benzyl; in the structural formula of the compound shown in the formula IV, a substituent X is chlorine or bromine, and a substituent R is the same as the substituent R in the structural formula of the compound shown in the formula III; in the structural formula of the compound shown in the formula I, substituent groups R and X are the same as substituent groups X and R in the structural formula of the compound shown in the formula IV.
The invention has the technical characteristics and beneficial effects that:
1. the invention provides a preparation method of 1-halogenated-2-methyl-4-substituted carbonyloxy-2-butene, which comprises the steps of carrying out acylation reaction on 2-methyl-4-hydroxy-1-butene and an acylation reagent under the action of a catalyst to prepare 2-methyl-4-substituted carbonyloxy-1-butene, and then carrying out addition reaction and alkali elimination reaction on the 2-methyl-4-substituted carbonyloxy-2-butene with halogen to prepare the 1-halogenated-2-methyl-4-substituted carbonyloxy-2-butene.
2. The method does not use the raw materials with higher price such as isoprene, tert-butyl hypochlorite and the like, and the raw materials are cheap and easy to obtain and have low cost; the process flow is simple, the reaction is easy to realize and control, the operation is safe and simple, the waste water production amount is small, and the method is green and environment-friendly; the reaction intermediate product is stable, the reaction activity is proper, the reaction selectivity is high, the side reaction is less, the atom economy is high, the yield and the purity of the target product are high, the total yield can reach 90.1 percent, and the method is suitable for green industrial production.
3. The invention prepares the 2-methyl-4-substituted carbonyloxy-1-butene by acylation reaction of the 2-methyl-4-hydroxy-1-butene and the acylation reagent under the action of the catalyst, the carbon-carbon double bond keeps the reaction inertia, and the reaction selectivity and the conversion rate of the hydroxy and the acylation reagent are high. Then the addition reaction of the carbon-carbon double bond and halogen is specific, and then the high activity of the halogen connected with tertiary carbon is utilized to eliminate one molecule of hydrogen halide by alkali to obtain the 1-halogeno-2-methyl-4-substituted carbonyloxy-2-butylene.
Detailed Description
The present invention is described in detail below with reference to examples, but the present invention is not limited thereto.
The raw materials and reagents used in the examples are all commercially available products.
In the examples, "%" is a mass percentage unless otherwise specified.
The yields in the examples are all molar yields.
Example 1: 2-methyl-4-acetoxy-1-butene (III) 1 ) Preparation of
Into a 500 ml four-necked flask equipped with a stirrer, a thermometer, a water separator and a reflux condenser, 300 g of toluene, 86.0 g (1.0 mol) of 2-methyl-4-hydroxy-1-butene (II), 72.0 g (1.2 mol) of acetic acid, 0.5 g of p-toluenesulfonic acid were subjected to azeotropic dehydration at 100 to 105 ℃ and stirred for reaction for 4 hours. Cooling to 60-65 deg.C, distilling under reduced pressure to recover toluene and excessive acetic acid, and distilling under high vacuum (60-75 deg.C/1-2 mmHg) to obtain 124.6 g of 2-methyl-4-acetoxy-1-butene (III) 1 ) The yield was 97.3% and the gas phase purity was 99.8%.
Example 2: 2-methyl-4-acetoxy-1-butene (III) 1 ) Preparation of
Into a 500 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 300 g of n-hexane, 86.0 g (1.0 mol) of 2-methyl-4-hydroxy-1-butene (II), 112.0 g (1.1 mol) of acetic anhydride and 0.4 g of p-toluenesulfonic acid were charged and reacted with stirring at 65 to 70 ℃ for 5 hours. Cooling to 40-45 deg.C, distilling to recover n-hexane, acetic acid and excessive acetic anhydride, and vacuum distilling at 60-75 deg.C/1-2 mmHg to obtain 123.8 g 2-methyl-4-acetoxy-1-butene (III) 1 ) The yield was 96.7% and the gas phase purity was 99.6%.
Example 3: 1-chloro-2-methyl-4-acetoxy-2-butene (I) 1 ) Preparation of (2)
Into a 500 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a gas-guide tube and a 30wt% aqueous sodium hydroxide solution absorption device were charged 300 g of 1,2-dichloroethane, 64.0 g (0.5 mol) of 2-methyl-4-acetoxy-1-butene (III) obtained in example 1 1 ) Heating, keeping the temperature between 30 and 40 ℃, slowly introducing 42.5 g (0.6 mol) of chlorine, finishing the introduction for about 2 to 3 hours, then stirring and reacting for 3 hours at 40 to 45 ℃, cooling to 20 to 25 ℃, bubbling nitrogen to blow residual chlorine for 1 hour, adding 83.0 g (0.6 mol) of potassium carbonate, heating to 50 to 55 ℃, stirring and reacting for 4 hours, cooling to 20 to 25 ℃, filtering, and using 1,2-dichloroethane to filter cakesWashing 2 times, 50 g each time, combining the organic phases, recovering 1,2-dichloroethane by atmospheric distillation, then rectifying under reduced pressure (95-105 deg.C/1-2 mmHg) to obtain 75.2 g of 1-chloro-2-methyl-4-acetoxy-2-butene (I) 1 ) The yield was 92.6% and the gas phase purity was 99.6%.
The nuclear magnetic data of the product obtained are as follows:
1 HNMR(400MHz,CDCl 3 ):δppm
1.83(s,3H),2.06(s,3H),4.07(s,2H),4.64(d,2H),5.68(t,1H)。
example 4: 1-bromo-2-methyl-4-acetoxy-2-butene (I) 2 ) Preparation of
Into a 500 ml four port flask equipped with a stirrer, a thermometer, a reflux condenser, a constant pressure dropping funnel and a 30wt% aqueous sodium hydroxide solution absorption device were charged 200 g of methylene chloride, 64.0 g (0.5 mol) of 2-methyl-4-acetoxy-1-butene (III) obtained in example 2 1 ) Heating, keeping the temperature between 20 and 25 ℃, slowly dripping a mixture of 82.0 g (0.5 mol) of liquid bromine and 100 g of dichloromethane, finishing dripping after about 2 to 3 hours, stirring and reacting at 20 to 25 ℃ for 3 hours, adding 83.0 g (0.6 mol) of potassium carbonate, heating to 35 to 40 ℃, stirring and reacting for 4 hours, cooling to 20 to 25 ℃, filtering, washing a filter cake with dichloromethane for 2 times, 50 g each time, combining organic phases, distilling at normal pressure to recover dichloromethane, and then rectifying under reduced pressure (100 to 115 ℃/1 to 2 mmHg) to obtain 91.7 g of 1-bromo-2-methyl-4-acetoxyl-2-butene (I) 2 ) The yield was 88.6% and the gas phase purity was 99.3%.
The nuclear magnetic data of the product obtained are as follows:
1 HNMR(400MHz,CDCl 3 ):δppm
1.81(s,3H),2.05(s,3H),4.01(s,2H),4.61(d,2H),5.67(t,1H)。
example 5: 2-methyl-4-palmitoyloxy-1-butene (III) 2 ) Preparation of
Into a 1000 ml four-necked flask equipped with a stirrer, a thermometer, a water separator and a reflux condenser, 300 g of toluene, 86.0 g (1.0 mol) of 2-methyl-4-hydroxy-1-butene (II), 270.0 g (1.05 mol) of palmitic acid, 0.5 g of p-toluenesulfonic acid were added and azeotropic removal was carried out at 100 to 105 ℃The reaction was stirred with water for 5 hours. Cooling to 60-65 deg.C, changing into vacuum distillation system, distilling to recover toluene, and then changing into high vacuum distillation (130-145 deg.C/1-2 mmHg) to obtain 307.3 g 2-methyl-4-palmitoyloxy-1-butene (III) 2 ) The yield was 94.7% and the gas phase purity was 99.2%.
Example 6: 1-bromo-2-methyl-4-palmitoyloxy-2-butene (I) 3 ) Preparation of
Into a 500 ml four port flask equipped with a stirrer, a thermometer, a reflux condenser, a constant pressure dropping funnel and a 30wt% aqueous sodium hydroxide solution absorption device were charged 300 g of methylene chloride, 32.5 g (0.1 mol) of 2-methyl-4-palmitoyloxy-1-butene (III) obtained in example 5 2 ) Heating, keeping the temperature between 20 and 25 ℃, slowly dripping a mixture of 16.5 g (0.1 mol) of liquid bromine and 20 g of dichloromethane, finishing dripping within 1 hour, stirring and reacting at 20 to 25 ℃ for 3 hours, adding 16.5 g (0.12 mol) of potassium carbonate, heating to 35 to 40 ℃, stirring and reacting for 4 hours, cooling to 20 to 25 ℃, filtering, washing a filter cake with dichloromethane for 2 times, 50 g each time, combining organic phases, distilling at normal pressure to recover dichloromethane to obtain 40.1 g of 1-bromine-2-methyl-4-palmitoyloxy-2-butene (I) 3 ) The yield was 99.4% and the gas phase purity 98.2%.
The nuclear magnetic data of the product obtained are as follows:
1 HNMR(400MHz,CDCl 3 ):δppm
0.88(t,3H),1.22(m,26H),1.81(s,3H),2.22(t,2H),4.04(s,2H),4.62(d,2H),5.66(t,1H)。
comparative example: 1-chloro-2-methyl-4-acetoxy-2-butene (I) 1 ) Preparation of
Into a 500 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a gas-guide tube and a 30wt% aqueous sodium hydroxide absorption device were charged 300 g of 1,2-dichloroethane, 64.0 g (0.5 mol) of 2-methyl-4-acetoxy-1-butene (III) obtained by the method of example 1 1 ) Heating, keeping the temperature between 30 and 40 ℃, slowly introducing 32.0 g (0.45 mol) of chlorine for about 2 to 3 hours, then stirring and reacting at 40 to 45 ℃ for 3 hours, cooling to 20 to 25 ℃, bubbling nitrogen to blow residual chlorine for 1 hour, and adding 83.0 g (0).6 mol) of potassium carbonate, heating to 50-55 ℃, stirring for reaction for 4 hours, cooling to 20-25 ℃, filtering, washing a filter cake with 1,2-dichloroethane for 2 times, each time 50 g, combining organic phases, distilling at normal pressure to recover 1,2-dichloroethane, and then rectifying under reduced pressure (95-105 ℃/1-2 mmHg) to obtain 62.6 g of 1-chloro-2-methyl-4-acetoxyl-2-butene (I) 1 ) The yield was 77.0% and the gas phase purity 98.2%.
Comparative example shows that the halogen is used in an amount sufficient to make 2-methyl-4-acetoxy-1-butene (III) 1 ) The reaction is complete, e.g. 2-methyl-4-acetoxy-1-butene (III) 1 ) If the reaction is incomplete, the subsequent elimination reaction cannot be performed to obtain the target product, and the reaction yield is low. Residual 2-methyl-4-acetoxy-1-butene (III) 1 ) And products (I) 1 ) The boiling point is relatively close, the product is not easy to be completely rectified and removed, and the product purity is low.
Claims (6)
1. A process for the preparation of 1-halo-2-methyl-4-substituted carbonyloxy-2-butene (I) comprising the steps of:
(1) Preparing a compound of formula III by subjecting a compound of formula II and an acylating agent to an acylation reaction;
wherein, in the structural formula of the compound in the formula III, the substituent R is hydrogen and has a general formula C n H 2n+1 N is more than or equal to 1 and less than or equal to 18, phenyl or benzyl;
(2) Preparing a compound of formula IV by subjecting a compound of formula III and a halogen to addition reaction, and then subjecting to elimination reaction to prepare 1-halo-2-methyl-4-substituted carbonyloxy-2-butene (I);
the preparation of 1-halo-2-methyl-4-substituted carbonyloxy-2-butene (I) comprises the steps of: in a solvent B, a compound shown in the formula III and halogen are subjected to addition reaction to prepare a compound shown in the formula IV; then adding alkali to prepare 1-halogeno-2-methyl-4-substituted carbonyloxy-2-butene (I) through elimination reaction;
wherein, in the structural formula of the compound shown in the formula IV, a substituent X is chlorine or bromine, and a substituent R is the same as the substituent R in the structural formula of the compound shown in the formula III;
the solvent B is one or the combination of more than two of dichloromethane, chloroform, 1,2-dichloroethane, trichloroethane, toluene, chlorobenzene, xylene, normal hexane, cyclohexane, normal heptane or petroleum ether with the boiling range of 60-90 ℃; the mass ratio of the solvent B to the compound shown in the formula III is 2-15;
the molar ratio of the halogen to the compound of formula III is 1.0 to 1.2;
the temperature of the addition reaction is 20-50 ℃;
the alkali is sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate or calcium carbonate, and the molar ratio of the alkali to the compound shown in the formula III is 1.1-1.3;
the elimination reaction temperature is 30-60 ℃.
2. The process for the preparation of 1-halo-2-methyl-4-substituted carbonyloxy-2-butene (I) as claimed in claim 1, wherein the acylation of the compound of formula II with the acylating agent in step (1) is carried out in solvent A in the presence of a catalyst.
3. A process for the preparation of 1-halo-2-methyl-4-substituted carbonyloxy-2-butene (i) as claimed in claim 2, comprising one or more of the following conditions:
a. the solvent A is one or the combination of more than two of toluene, xylene, benzene, normal hexane, cyclohexane, normal heptane, petroleum ether with the boiling range of 60-90 ℃ or chlorobenzene; the mass ratio of the solvent A to the compound of the formula II is 2-15;
b. the catalyst is one or the combination of more than two of benzene sulfonic acid, p-methyl benzene sulfonic acid, methyl sulfonic acid or concentrated sulfuric acid with the mass concentration of 70-98 percent, and the mass of the catalyst is 0.02-2.0 percent of that of the compound shown in the formula II;
c. the acylating agent is formic acid, acetyl chloride, acetic anhydride, benzoic acid, benzoic anhydride, phenylacetic acid, phenylacetic anhydride or has a general formula of HOOCC n H 2n+1 Carboxylic acid of the formula HOOCC n H 2n+1 In (1 ≦ n ≦ 18; the molar ratio of the acylating agent to the compound of formula II is 1.0-1.5.
4. A process for the preparation of 1-halo-2-methyl-4-substituted carbonyloxy-2-butene (i) as claimed in claim 3, comprising one or more of the following conditions:
a. the mass of the catalyst is 0.1-1.0% of that of the compound shown in the formula II;
b. the acylating agent is acetic acid, acetic anhydride or palmitic acid; the molar ratio of the acylating agent to the compound of formula II is 1.1-1.3;
c. the molar ratio of the acylating agent to the compound of formula II is 1.1-1.3.
5. The process for producing 1-halo-2-methyl-4-substituted carbonyloxy-2-butene (I) according to claim 1, wherein the acylation reaction temperature in the step (1) is 40 to 140 ℃.
6. The process for producing 1-halo-2-methyl-4-substituted carbonyloxy-2-butene (I) according to claim 5, wherein the acylation reaction temperature is 60 to 120 ℃.
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