CN114874095B - Preparation method of linalyl acetate - Google Patents
Preparation method of linalyl acetate Download PDFInfo
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- CN114874095B CN114874095B CN202110162993.2A CN202110162993A CN114874095B CN 114874095 B CN114874095 B CN 114874095B CN 202110162993 A CN202110162993 A CN 202110162993A CN 114874095 B CN114874095 B CN 114874095B
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- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
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Abstract
The invention discloses a preparation method of linalyl acetate, which takes linalool and 2-methoxypropene as raw materials and generates linalyl acetate through catalytic reaction in the presence of CO. The addition amount of the 2-methoxypropene is 100-300% of the molar amount of linalool, preferably 110-150%. The reaction of the invention adopts a non-acidic catalytic system, the reaction speed is high, the selectivity of the catalytic system is high, and the corrosion to equipment is reduced due to the non-acidic catalytic system, thereby avoiding the severe corrosion-resistant requirement of the traditional acidic catalyst to the reaction equipment.
Description
Technical Field
The invention relates to a preparation method, in particular to a preparation method of linalyl acetate, belonging to the technical field of organic synthesis.
Background
The main synthesis method of acetate is to directly esterify corresponding alcohols with acetic acid or acetic anhydride, and the catalyst is usually medium strong acid, such as concentrated sulfuric acid, p-toluenesulfonic acid, phosphoric acid and the like. The method for synthesizing the acetate compound under the acidic system is simpler, but has poorer catalytic effect on substances which cannot exist in an acidic medium stably or alcohols with high steric hindrance, and is more typical for the synthesis of linalyl acetate, wherein the reverse reaction rate constant of the esterification reaction of linalool and acetic anhydride is higher, and linalool is easy to isomerise under the acidic system to generate nerol, geraniol and the like, so that the synthesized linalyl acetate is accompanied with the generation of various byproducts such as neryl acetate and the like, and the selectivity of linalyl acetate is not high.
As an important essence raw material, linalyl acetate has very wide application in the fields of edible essence, soap essence and cosmetic essence, so how to solve the problems is important to provide a novel linalyl acetate preparation method. Patent CN1234391a reports that linalyl acetate is synthesized by using ketene as an acetylating reagent, the process has high atomic utilization rate and less side reaction, but ketene is extremely toxic, difficult to transport and prepare and difficult to store.
Disclosure of Invention
The invention aims to provide a preparation method of linalyl acetate of a non-acidic system, which aims to solve the problems of more byproducts and lower product selectivity in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of linalyl acetate uses linalool and 2-methoxypropene as raw materials, and the linalyl acetate is generated by catalytic reaction in the presence of CO. The reaction expression is as follows:
further, the 2-methoxypropene is added in an amount of 100 to 300% by mole, preferably 110 to 150% by mole, of linalool. The 2-methoxypropene can be added in any existing mode, such as continuous dripping mode or disposable feeding mode.
Further, the catalyst in the reaction is a non-acidic catalyst, and the non-acidic catalyst is preferably a combination of rhodium metal compound, organic phosphine ligand, methyl iodide and metal carbonyl compound in any proportion.
Further, the rhodium metal compound is one or more of halide, sulfate, nitrate, carbonyl compound and acetyl compound of rhodium, preferably RhCl 3 、Rh(CO) 2 acac、Rh 4 (CO) 12 Wherein acac is an acetylacetone ligand;
preferably, the addition amount of the rhodium metal compound in the reaction is 0.01-0.5 per mill of the molar amount of linalool based on the rhodium atomic substance.
Further, the organic phosphine ligand is one or more of triphenylphosphine, tri (p-methylphenyl) phosphorus, diphenylphosphine and tri-tert-butyl phosphorus, preferably triphenylphosphine;
preferably, the addition amount of the organic phosphine ligand in the reaction is 0.01-5% of the mole amount of linalool.
Further, the addition amount of the methyl iodide in the reaction is 0.01-1% of the mole amount of linalool.
Further, the metal carbonyl compound is selected from carbonyl compounds of metal iron, cobalt and nickel, preferably one or more of carbonyl iron, carbonyl cobalt and carbonyl nickel;
preferably, the addition amount of the metal carbonyl compound in the reaction is 0.01-0.5 per mill of the mole amount of linalool based on the amount of metal atomic substances. The addition of the metal carbonyl compound can inhibit the isomerization reaction of linalool, thereby achieving the purpose of improving the selectivity.
Further, in the reaction, the reaction temperature is 150-250 ℃, preferably 160-220 ℃; the reaction time is 2 to 12 hours, preferably 3 to 8 hours;
preferably, the CO gas reaction pressure is 1.0 to 10.0MPa absolute, preferably 3.0 to 5.0MPa absolute.
Further, the reaction system optionally uses a solvent or not; the solvent is preferably inert aliphatic alkane, aromatic hydrocarbon, ether and halogenated alkane which do not react with the raw materials, more preferably one or more of normal hexane, toluene, methylene dichloride and 1, 4-dioxane, and the dosage of the solvent is 50-500% of the mass of linalool;
preferably, the reaction system does not use a solvent.
Further, there are generally impurities containing S, P, N elements such as hydrogen sulfide, phosphine, etc. in the CO gas, and the total content of the above impurities in the CO gas is preferably less than 2ppm by volume; in addition, the water content of the reaction system is strictly limited, and an increase in the water content leads to an increase in the amount of 2-methoxypropene used, so that the water content of the reaction system is preferably less than 0.1%. To ensure a low water content, the feedstock may be pretreated by stripping or drying.
The invention has the positive effects that:
1) The reaction adopts a non-acidic catalytic system, the reaction speed is high, the acetic acid content is hardly detected in the reaction process, the selectivity of the catalytic system is high, the selectivity of linalyl acetate is more than or equal to 99.0%, and the linalool conversion rate can reach more than 99.0%; the catalyst is non-acidic catalytic system, so that the corrosion to equipment is reduced, and the severe corrosion-resistant requirement of the traditional acidic catalyst (p-toluenesulfonic acid, sulfuric acid and the like) to reaction equipment is avoided.
2) The catalytic system effectively inhibits the isomerization reaction of linalool by introducing metal carbonyl compounds, thereby achieving the purpose of improving selectivity. The products of the isomerization reaction of linalool such as geranyl acetate, neryl acetate and the like in the products are far lower than those of the traditional method, and the product performance is greatly optimized.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The analysis method comprises the following steps:
gas chromatograph: agilent7820A, column HP-5 (30 m×320 μm×0.25 μm), sample inlet temperature: 150 ℃; the split ratio is 50:1; carrier gas flow rate: 1.5ml/min; heating program: maintaining at 50deg.C for 1min, heating to 90deg.C at 10deg.C/min, maintaining for 0min, heating to 180deg.C at 5deg.C/min, maintaining for 0min, and heating to 280deg.C at 30deg.C/min, maintaining for 6min. Detector temperature: 280 ℃.
CO gas: from the smokestack torches gas stock, inc., with a total S, P, N content of less than 1ppm.
Linalool with purity of 99.05% and main impurity component of dihydro linalool; and soaking linalool in the dried 5A molecular sieve for 48 hours, and then distilling under reduced pressure to obtain the linalool for experiments, wherein the water content of the linalool after treatment is 0.01 percent.
Example 1
4.18mg of rhodium chloride, 1.31g of triphenylphosphine, 3.92mg of carbonyl iron, and 71.12mg of methyl iodide were dissolved in 154g of linalool (purity: 99.05%) under an inert gas atmosphere, and after 3 times of substitution with 3MPa of CO gas, CO was maintained at 3MPa. The reaction kettle is heated to 150 ℃ and 108g of 2-methoxypropene is added dropwise, the total time period for adding 2-methoxypropene dropwise is 2h, the temperature in the kettle is kept at 150 ℃ in the dripping process, and the temperature in the kettle is kept at 150 ℃ after the dripping is finished, and the reaction is continued for 6h. After the reaction was completed, the temperature was lowered to room temperature and the pressure was released. The composition was measured by sampling gas chromatography, and the composition of the reaction solution, the conversion of the raw materials and the selectivity of the product are shown in Table 1.
Example 2
2.58mg of rhodium acetylacetonate carbonyl, 2.62g of triphenylphosphine, 1.71mg of nickel carbonyl, and 14.21mg of methyl iodide were dissolved in 154g of linalool (purity: 99.05%) under an inert gas atmosphere, and after 3 times of substitution with CO gas of 5MPa, CO was kept at 5MPa. The reaction kettle is heated to 200 ℃ and dripping 86.4g of 2-methoxypropene is started, the total time for dripping the 2-methoxypropene is 2 hours, the temperature in the kettle is kept at 200 ℃ in the dripping process, and the temperature in the kettle is kept at 200 ℃ after dripping is finished, and the reaction is continued for 8 hours. After the reaction was completed, the temperature was lowered to room temperature and the pressure was released. The composition was measured by sampling gas chromatography, and the composition of the reaction solution, the conversion of the raw materials and the selectivity of the product are shown in Table 1.
Example 3
Under an inert gas atmosphere, 25.8mg of rhodium acetylacetonate carbonyl, 13.11g of triphenylphosphine, 85.50mg of cobalt carbonyl, 710.12mg of methyl iodide were dissolved in 154g of linalool (purity: 99.05%) and replaced 3 times with 4MPa of CO gas, and then the CO was kept at 4MPa. The reaction kettle is heated to 220 ℃ and dripping of 79.86g of 2-methoxypropene is started, the total time for dripping the 2-methoxypropene is 2 hours, the temperature in the kettle is kept at 220 ℃ in the dripping process, and the temperature in the kettle is kept at 220 ℃ after the dripping is finished, and the reaction is continued for 3 hours. After the reaction was completed, the temperature was lowered to room temperature and the pressure was released. The composition was measured by sampling gas chromatography, and the composition of the reaction solution, the conversion of the raw materials and the selectivity of the product are shown in Table 1.
Example 4
37.39mg of tetrarhodium laurylcarbonyl, 5.24g of triphenylphosphine, 17.11mg of cobalt carbonyl and 236.66mg of methyl iodide were dissolved in 154g of linalool (purity: 99.05%) under an inert gas atmosphere, and after 3 times of substitution with CO gas of 4.5MPa, CO was kept at 4.5MPa. The reaction kettle is heated to 190 ℃ and begins to drip 93.68g of 2-methoxypropene, the total time for dripping the 2-methoxypropene is 2 hours, the temperature in the kettle is kept at 190 ℃ in the dripping process, and the temperature in the kettle is kept at 190 ℃ after dripping is finished, and the reaction is continued for 5 hours. After the reaction was completed, the temperature was lowered to room temperature and the pressure was released. The composition was measured by sampling gas chromatography, and the composition of the reaction solution, the conversion of the raw materials and the selectivity of the product are shown in Table 1.
Example 5
62.72mg of rhodium chloride, 0.026g of triphenylphosphine, 8.55mg of cobalt carbonyl and 1422.44mg of methyl iodide were dissolved in 154g of linalool (purity: 99.05%) under an inert gas atmosphere, and after 3 times of substitution with CO gas of 3.5MPa, CO was kept at 3.5MPa. The reaction kettle is heated to 180 ℃ and dropwise adding 100.89g of 2-methoxypropene is started, the total time for dropwise adding the 2-methoxypropene is 2 hours, the temperature in the kettle is kept at 180 ℃ in the dropwise adding process, and the temperature in the kettle is kept at 180 ℃ after the dropwise adding is finished, and the reaction is continued for 8 hours. After the reaction was completed, the temperature was lowered to room temperature and the pressure was released. The composition was measured by sampling gas chromatography, and the composition of the reaction solution, the conversion of the raw materials and the selectivity of the product are shown in Table 1.
Example 6
129.2mg of rhodium acetylacetonate carbonyl, 7.87g of triphenylphosphine, 7.94mg of iron carbonyl and 473.32mg of methyl iodide were dissolved in 154g of linalool (purity: 99.05%) under an inert gas atmosphere, and after 3 times of substitution with CO gas of 5.0MPa, CO was kept at 5.0MPa. The reaction kettle is heated to 170 ℃ and begins to drip 86.47g of 2-methoxypropene, the total time for dripping the 2-methoxypropene is 2 hours, the temperature in the kettle is kept at 170 ℃ in the dripping process, and the temperature in the kettle is kept at 170 ℃ after dripping is finished, and the reaction is continued for 5 hours. After the reaction was completed, the temperature was lowered to room temperature and the pressure was released. The composition was measured by sampling gas chromatography, and the composition of the reaction solution, the conversion of the raw materials and the selectivity of the product are shown in Table 1.
Comparative examples 1 to 6
Comparative examples 1-6 linalyl acetate was prepared according to the methods of examples 1-6, respectively, except that no metal carbonyl compound was added as a catalyst. The composition of the reaction solution prepared in each comparative example, the conversion rate of raw materials and the selectivity of products are shown in Table 1.
Comparative example 7
7.7g of 85% phosphoric acid by mass are dissolved in 154g of linalool (purity 99.05%) under an inert gas atmosphere. Heating the reaction kettle to 70 ℃ and beginning to dropwise add 153g of acetic anhydride, wherein the total time period for dropwise adding the acetic anhydride is 2 hours, the temperature in the kettle is kept at 70 ℃ in the dropwise adding process, and the temperature in the kettle is kept at 70 ℃ after the dropwise adding is finished, and the reaction is continued for 4 hours. The composition was measured by sampling gas chromatography, and the composition of the reaction solution, the conversion of the raw materials and the selectivity of the product are shown in Table 1.
Table 1, reaction results in examples and comparative examples
Claims (21)
1. A preparation method of linalyl acetate is characterized in that linalool and 2-methoxypropene are used as raw materials, and linalyl acetate is generated by catalytic reaction in the presence of CO;
the catalyst in the reaction is a non-acidic catalyst, and the non-acidic catalyst is a combination of rhodium metal compound, organic phosphine ligand, methyl iodide and metal carbonyl compound in any proportion.
2. The method for preparing linalyl acetate according to claim 1, characterized in that the 2-methoxypropene is added in an amount of 100-300% of the molar amount of linalool.
3. The preparation method of linalyl acetate according to claim 2, characterized in that the 2-methoxypropene is added in an amount of 110-150% of the molar amount of linalool.
4. The method for preparing linalyl acetate according to claim 1, characterized in that the rhodium metal compound is one or more of halide, sulfate, nitrate, carbonyl compound and acetyl compound of rhodium.
5. The process for preparing linalyl acetate according to claim 4, wherein the rhodium metal compound is RhCl 3 、Rh(CO) 2 acac、Rh 4 (CO) 12 Wherein acac is an acetylacetone ligand.
6. The process for preparing linalyl acetate according to claim 4, wherein the rhodium metal compound is added in the amount of 0.01-0.5% by mole of linalool based on the amount of rhodium atomic substance.
7. The method for preparing linalyl acetate according to claim 1, characterized in that the organic phosphine ligand is one or more of triphenylphosphine, tri (p-methylphenyl) phosphorus, diphenylphosphine, tri-t-butylphosphine.
8. The method for preparing linalyl acetate according to claim 7, characterized in that the organic phosphine ligand is triphenylphosphine.
9. The method for preparing linalyl acetate according to claim 7, characterized in that the addition amount of the organic phosphine ligand in the reaction is 0.01-5% of the mole amount of linalool.
10. The method for preparing linalyl acetate according to claim 1, characterized in that the addition amount of methyl iodide in the reaction is 0.01-1% of the mole amount of linalool.
11. The method for preparing linalyl acetate according to claim 1, characterized in that the metal carbonyl compound is selected from carbonyl compounds of metallic iron, cobalt, nickel.
12. The method for preparing linalyl acetate according to claim 11, characterized in that the metal carbonyl compound is selected from one or more of iron carbonyl, cobalt carbonyl, nickel carbonyl.
13. The method for preparing linalyl acetate according to claim 11, characterized in that the metal carbonyl compound is added in the reaction in an amount of 0.01-0.5 per mill of the mole amount of linalool based on the amount of metal atomic substance.
14. The process for preparing linalyl acetate according to any one of claims 1-13, characterized in that in the reaction, the reaction temperature is 150-250 ℃; the reaction time is 2-12 h.
15. The method for preparing linalyl acetate according to claim 14, characterized in that in the reaction, the reaction temperature is 160-220 ℃; the reaction time is 3-8 h.
16. The method for preparing linalyl acetate according to claim 14, characterized in that the reaction pressure of CO gas is 1.0-10.0 MPa absolute.
17. The process for preparing linalyl acetate according to claim 16, characterized in that the reaction pressure of CO gas is 3.0-5.0 Mpa absolute.
18. The process for the preparation of linalyl acetate according to any one of claims 1 to 13, characterised in that the reaction system optionally uses a solvent or does not use a solvent.
19. The process for the preparation of linalyl acetate according to claim 18, characterized in that the solvent is an inert aliphatic alkane, aromatic hydrocarbon, ether, haloalkane which does not react with the raw material.
20. The preparation method of linalyl acetate according to claim 19, characterized in that the solvent is one or more of n-hexane, toluene, methylene dichloride and 1, 4-dioxane, and the solvent is 50-500% of linalool by mass.
21. The process for the preparation of linalyl acetate according to any one of claims 1 to 13, characterized in that the total content by volume of impurities S, P, N in the CO gas is lower than 2ppm; the mass content of water in the reaction system is lower than 0.1 percent.
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