CN102070446A - Method for producing acetic p-isopropyl phenyl methyl ester - Google Patents
Method for producing acetic p-isopropyl phenyl methyl ester Download PDFInfo
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- CN102070446A CN102070446A CN2010105903726A CN201010590372A CN102070446A CN 102070446 A CN102070446 A CN 102070446A CN 2010105903726 A CN2010105903726 A CN 2010105903726A CN 201010590372 A CN201010590372 A CN 201010590372A CN 102070446 A CN102070446 A CN 102070446A
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Abstract
The invention relates to a production process for organically synthesizing spices, in particular to a process for producing acetic p-isopropyl phenyl methyl ester used as organic spices, which belongs to the technical field of chemical engineering. The process disclosed by the invention comprises the following sequential steps: 1. preparing p-isopropyl phenyl methyl ester; and 2, preparing the acetic p-isopropyl phenyl methyl ester. The invention provides a process suitable for producing the acetic p-isopropyl phenyl methyl ester in industrialized production, the flow process is simple, safety and reliability are realized, the production cost is low, byproducts are few, the pollution is low, the total yield of products is higher than 90 percent, in addition, the product purity is high, the fragrance is pure, and the method disclosed by the invention has wide purpose in spice synthesis enterprises.
Description
Technical field
The present invention relates to a kind of production technique of organic synthesis spices, relate in particular to a kind of production technique of the acetate cumic aldehyde methyl esters as organic perfume; Belong to chemical technology field.
Technical background
Acetate cumic aldehyde methyl esters, popular name are cuminyl acetate, and English name is 4-Isopropylbenzyl acetate or Cuminyl acetate, and the CAS registration number is [59230-57-8].Chemical structural formula is:
Acetate cumic aldehyde methyl esters has the spice product of the fruital fragrance of Citrus bergamia sample, can use and prepares ancient dragon and Citrus bergamia type essence, is mainly used in the perfume formulation of daily chemical products.
With cumic aldehyde hydrogenation preparing isopropylbenzyl alcohol, use isopropylbenzyl alcohol and aceticanhydride or Glacial acetic acid prepared in reaction acetate cumic aldehyde methyl esters production technique again, do not see patent report both at home and abroad as yet.
External Giordano Claudio et al.[J.Org.Chem.1979; 44 (13): 2314-5] and Baciocchi Enrico et al.[J.Chem.Res.Synap.1984; (10): 334-5] and domestic Bi Liangwu, Liu Xianzhang [chemistry of forest product with industry, 2003,23 (2): 1-6] all reported and to have produced the method for acetate cumic aldehyde methyl esters behind the Paracymene catalyzed oxidation, the characteristics of these class methods are that the reaction times is short, but severe reaction conditions, productive rate is low, and the oxidized byproduct of generation is many, and be difficult to separate, therefore do not possess the potential quality of suitability for industrialized production.
Jia Chunhua, [chemistry world 1995 such as Shi Dachang; (1): 27-28] reported to be starting raw material with the cumene, itself and formaldehyde and hydrogenchloride chloromethylation in the presence of zinc chloride are obtained p-isopropylbenzyl chlorine, p-isopropylbenzyl chlorine with gained makes cuminyl acetate with the sodium-acetate reaction under the phase-transfer catalyst effect again, under optimum process condition, the overall yield of two-step reaction has only 63.2%, and productive rate is lower; Because hydrogen chloride gas participates in reaction as raw material, has safety and environment hidden danger, bring bigger pressure for safety in production and environment protection; Remaining chlorion also has certain influence to the fragrance of product in the cuminyl acetate in addition.Therefore this method also is unsuitable for industrial production.
Summary of the invention
The present invention mainly solves the deficiency that aforesaid method is produced acetate cumic aldehyde methyl esters, and a kind of new production technique is provided, and this technical process is simple, and is safe and reliable, and production cost is low, and by product is few, pollutes lowly, and the yield of product is more than 90%.
The present invention is implemented by the following technical programs: a kind of production technique of acetate cumic aldehyde methyl esters, and this technology comprises following sequential steps:
(1) preparation of isopropylbenzyl alcohol: in cumic aldehyde, add catalyzer, again material is added in the hydrogenation reaction kettle, after the logical nitrogen displacement, feed hydrogen, make isopropylbenzyl alcohol through after the hydrogenation reaction, catalyst system therefor is ruthenium, platinum, palladium, rhodium or the Raney's nickel catalyst of carbon load.
(2) preparation of acetate cumic aldehyde methyl esters: the isopropylbenzyl alcohol of above-mentioned preparation and aceticanhydride or Glacial acetic acid reaction are made acetate cumic aldehyde methyl esters, and used catalyzer is sulfuric acid or hydrochloric acid.
The reaction equation of the preparation of isopropylbenzyl alcohol is as follows in the step of the present invention (1):
This method has been simplified technical process greatly, has reduced production cost; Reaction obtains chromatogram content greater than 99% isopropylbenzyl alcohol.Because this technology do not use any solvent with respect to general hydrogenation reaction, and product purity reaches more than 99%, so need not to carry out rectifying, this method has been simplified technical process, has reduced product consumption and production cost.After reaction mass was told catalyzer after filtration, the gained isopropylbenzyl alcohol can be directly used in next step reaction, and productive rate reaches more than 98%.
The reaction equation of acetate cumic aldehyde methyl esters preparation is as follows in the step of the present invention (2):
It is catalyzer that this reaction process adopts sulfuric acid or hydrochloric acid commonly used, and after washing, rectifying gets acetate cumic aldehyde methyl esters, and yield reaches more than 90%.
In the production technique of above-mentioned acetate cumic aldehyde methyl esters, be 0.0001～0.5: 1 in the weight ratio of catalyzer described in the step (1) and cumic aldehyde; The temperature of described hydrogenation reaction is controlled at 40～200 ℃; The pressure-controlling of described hydrogenation reaction is at 0.1～10MPa; The time of described hydrogenation reaction was controlled at 1～60 hour.
As preferably, the weight ratio of described catalyzer and cumic aldehyde is 0.005～0.5: 1; The temperature of described hydrogenation reaction is controlled at 50～150 ℃; The pressure-controlling of described hydrogenation reaction is at 1.5～3MPa; The time of described hydrogenation reaction was controlled at 4～20 hours.
Adopt specific temperature and hydrogen pressure in the present invention, guaranteed the yield and the purity of product.
In the technology of step of the present invention (1) preparation isopropylbenzyl alcohol, the control of catalyzer and hydroconversion condition is crucial; The ruthenium of carbon load, platinum, palladium, rhodium catalyst adopt immersion process for preparing, gac be immersed in the solution of certain density ruthenium, platinum palladium or rhodium, and drying, roasting under the nitrogen protection, the hydrogen argon with 10% before using mixes the gas reduction activation; Raney's nickel catalyst adopts the method preparation of W-6 type, referring to the 9th page of China Light Industry Press's " Minute Organic Synthesis principle and technology ".
In the production technique of above-mentioned acetate cumic aldehyde methyl esters, be 1: 0.3～10 in the mol ratio of the isopropylbenzyl alcohol described in the step (2) and aceticanhydride or Glacial acetic acid; The temperature of reaction of described reaction is controlled at 40～240 ℃; The time of described reaction was controlled at 1～60 hour.
As preferably, the mol ratio of described isopropylbenzyl alcohol and aceticanhydride or Glacial acetic acid is 1: 0.5～6; The temperature of reaction of described reaction is controlled at 60～180 ℃; The time of described reaction was controlled at 4～24 hours.Prepare in the acetate cumic aldehyde methyl esters process in the present invention, aceticanhydride or Glacial acetic acid should be excessive, if aceticanhydride or Glacial acetic acid are few, then reaction is incomplete, and long reaction time.
In the production technique of above-mentioned acetate cumic aldehyde methyl esters, at catalyst sulfuric acid or hydrochloric acid described in the step (2), wherein the weight ratio of catalyzer and isopropylbenzyl alcohol is 0.0001～0.005: 1.
The detailed process of step of the present invention (2) is: add a certain amount of isopropylbenzyl alcohol and appropriate amount of catalysts earlier, after stirring intensification, drip an amount of aceticanhydride or Glacial acetic acid again, temperature rising reflux reaction 1～2 hour is controlled drop temperature then at 100～115 ℃; Reach more than 95% up to sampling stratographic analysis acetate cumic amide ester content, then once in water respectively, 10% yellow soda ash and each washing of water, atmospheric distillation reclaims excessive acetic acid then, and acetate cumic aldehyde methyl esters is collected in rectification under vacuum again, and productive rate reaches 90～95%.
The effect that the present invention is useful is: proposed a kind of acetate cumic aldehyde methyl esters production technique that is suitable for suitability for industrialized production, this technical process is simple, and is safe and reliable, reaction times is short, and by product is few, pollutes low, the total recovery of product is more than 90%, and the product purity height, and fragrance is pure.
Embodiment
Below by specific examples, the present invention will be further described:
Embodiment 1
In the autoclave of 2L, add the 1400g cumic aldehyde, add the 5gPd/C catalyzer again, with nitrogen replacement 3 times, use hydrogen exchange 3 times again after, feed hydrogen, slowly heat up, temperature is controlled at 60 ℃, hydrogen pressure is controlled at 1.5MPa; After the hydrogenation reaction 10 hours, stop hydrogenation reaction, be cooled to room temperature, discharging is filtered, and reclaims catalyzer, and filtrate is detected through chromatogram, and isopropylbenzyl alcohol content is 98.64%.
In the there-necked flask that thermometer, stirring, dropping funnel and Webster fractional column are housed, add above-mentioned isopropylbenzyl alcohol 300g, sulfuric acid 2g; Stirring is warmed up to 80 ℃, drip aceticanhydride 300g, back flow reaction 8 hours, sampling reaches 97%, stopped reaction through stratographic analysis acetate cumic amide ester content, pour reaction mass into separating funnel after the cooling, successively use 100ml water, each washs the yellow soda ash of 100ml10% and 100ml water once, and acetate is reclaimed in air distillation again, rectification under vacuum obtains 360g acetate cumic aldehyde methyl esters (GC content: 99%), productive rate is 96% again.
Embodiment 2
In the autoclave of 2L, add the 1400g cumic aldehyde, add the 10g Raney's nickel catalyst again, with nitrogen replacement 3 times, use hydrogen exchange 3 times again after, feed hydrogen, slowly heat up, temperature is controlled at 80 ℃, hydrogen pressure is controlled at 2MPa; After the hydrogenation reaction 8 hours, stop hydrogenation reaction, be cooled to room temperature, discharging is filtered, and reclaims catalyzer, and filtrate is detected through chromatogram, and isopropylbenzyl alcohol content is 99.32%.
In the there-necked flask that thermometer, stirring, dropping funnel and Webster fractional column are housed, add above-mentioned isopropylbenzyl alcohol 300g, sulfuric acid 3g; Stirring is warmed up to 85 ℃, drip Glacial acetic acid 240g, back flow reaction 1 hour, control drop temperature then at 100～115 ℃, reach more than 95% up to sampling stratographic analysis acetate cumic amide ester content, stopped reaction, pour reaction mass into separating funnel after the cooling, successively use 100ml water, each washing of the yellow soda ash of 100ml10% and 100ml water once, excessive acetic acid is reclaimed in air distillation again, and rectification under vacuum obtains 347g acetate cumic aldehyde methyl esters (GC content: 99%), productive rate is 91.9% again.
Embodiment 3
In the autoclave of 2L, add the 1400g cumic aldehyde, add 4g Ru/C catalyzer again, with nitrogen replacement 3 times, use hydrogen exchange 3 times again after, feed hydrogen, slowly heat up, temperature is controlled at 100 ℃, hydrogen pressure is controlled at 2.3MPa; After the hydrogenation reaction 10 hours, stop hydrogenation reaction, be cooled to room temperature, discharging is filtered, and reclaims catalyzer, and filtrate is detected through chromatogram, and isopropylbenzyl alcohol content is 99.05%.
In the there-necked flask that thermometer, stirring, dropping funnel and Webster fractional column are housed, add above-mentioned isopropylbenzyl alcohol 300g, hydrochloric acid 8g; Stirring is warmed up to 80 ℃, drip Glacial acetic acid 200g, back flow reaction 1 hour, control drop temperature then at 100～115 ℃, reach more than 95% up to sampling stratographic analysis acetate cumic amide ester content, stopped reaction, pour reaction mass into separating funnel after the cooling, successively use 100ml water, each washing of the yellow soda ash of 100ml10% and 100ml water once, excessive acetic acid is reclaimed in air distillation again, and rectification under vacuum obtains 350g acetate cumic aldehyde methyl esters (GC content: 99%), productive rate is 92.95% again.
Embodiment 4
In the autoclave of 2L, add the 1400g cumic aldehyde, add the 50gPd/C catalyzer again, with nitrogen replacement 3 times, use hydrogen exchange 3 times again after, feed hydrogen, slowly heat up, temperature is controlled at 120 ℃, hydrogen pressure is controlled at 1.5MPa; After the hydrogenation reaction 12 hours, stop hydrogenation reaction, be cooled to room temperature, discharging is filtered, and reclaims catalyzer, and filtrate is detected through chromatogram, and isopropylbenzyl alcohol content is 98.22%.
In the there-necked flask that thermometer, stirring, dropping funnel and Webster fractional column are housed, add above-mentioned isopropylbenzyl alcohol 300g, sulfuric acid 3g; Stirring is warmed up to 130 ℃, drip aceticanhydride 80g, back flow reaction 12 hours, sampling reaches 96%, stopped reaction through stratographic analysis acetate cumic amide ester content, pour reaction mass into separating funnel after the cooling, successively use 100ml water, each washs the yellow soda ash of 100ml 10% and 100ml water once, and acetate is reclaimed in air distillation again, rectification under vacuum obtains 350g acetate cumic aldehyde methyl esters (GC content: 99%), productive rate is 95.6% again.
Embodiment 5
In the autoclave of 2L, add the 1400g cumic aldehyde, add the 100g Raney's nickel catalyst again, with nitrogen replacement 3 times, use hydrogen exchange 3 times again after, feed hydrogen, slowly heat up, temperature is controlled at 150 ℃, hydrogen pressure is controlled at 2MPa; After the hydrogenation reaction 8 hours, stop hydrogenation reaction, be cooled to room temperature, discharging is filtered, and reclaims catalyzer, and filtrate is detected through chromatogram, and isopropylbenzyl alcohol content is 98.92%.
In the there-necked flask that thermometer, stirring, dropping funnel and Webster fractional column are housed, add above-mentioned isopropylbenzyl alcohol 300g, sulfuric acid 3g; Stirring is warmed up to 85 ℃, drip Glacial acetic acid 240g, back flow reaction 6 hours, control drop temperature then at 100～115 ℃, reach more than 95% up to sampling stratographic analysis acetate cumic amide ester content, stopped reaction, pour reaction mass into separating funnel after the cooling, successively use 100ml water, each washing of the yellow soda ash of 100ml10% and 100ml water once, excessive acetic acid is reclaimed in air distillation again, and rectification under vacuum obtains 353g acetate cumic aldehyde methyl esters (GC content: 99%), productive rate is 92.9% again.
Embodiment 6
In the autoclave of 2L, add the 1400g cumic aldehyde, add 4g Ru/C catalyzer again, with nitrogen replacement 3 times, use hydrogen exchange 3 times again after, feed hydrogen, slowly heat up, temperature is controlled at 50 ℃, hydrogen pressure is controlled at 1.3MPa; After the hydrogenation reaction 10 hours, stop hydrogenation reaction, be cooled to room temperature, discharging is filtered, and reclaims catalyzer, and filtrate is detected through chromatogram, and isopropylbenzyl alcohol content is 99.05%.
In the there-necked flask that thermometer, stirring, dropping funnel and Webster fractional column are housed, add above-mentioned isopropylbenzyl alcohol 300g, hydrochloric acid 8g; Stirring is warmed up to 90 ℃, drip Glacial acetic acid 200g, back flow reaction 1 hour, control drop temperature then at 100～115 ℃, reach more than 95% up to sampling stratographic analysis acetate cumic amide ester content, stopped reaction, pour reaction mass into separating funnel after the cooling, successively use 100ml water, each washing of the yellow soda ash of 100ml10% and 100ml water once, excessive acetic acid is reclaimed in air distillation again, and rectification under vacuum obtains 350g acetate cumic aldehyde methyl esters (GC content: 99%), productive rate is 93.85% again.
Specific embodiment described in the invention only is that the present invention's spirit is illustrated.Those skilled in the art in the invention can make various modifications or replenish or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Claims (8)
1. the production method of an acetate cumic aldehyde methyl esters is characterized in that comprising following sequential steps:
(1) preparation of isopropylbenzyl alcohol: in cumic aldehyde, add catalyzer, again material is added in the hydrogenation reaction kettle, after the logical nitrogen displacement, feed hydrogen, make isopropylbenzyl alcohol through after the hydrogenation reaction, catalyst system therefor is ruthenium, platinum, palladium or the rhodium of carbon load, or Raney's nickel catalyst;
(2) preparation of acetate cumic aldehyde methyl esters: the isopropylbenzyl alcohol of above-mentioned preparation and aceticanhydride or Glacial acetic acid reaction are made acetate cumic aldehyde methyl esters, and used catalyzer is sulfuric acid or hydrochloric acid, and drop temperature is at 100～115 ℃.
2. the production method of acetate cumic aldehyde methyl esters according to claim 1 is characterized in that the weight ratio at catalyzer described in the step (1) and cumic aldehyde is 0.0001～0.5: 1; The temperature of described hydrogenation reaction is controlled at 40～200 ℃; The pressure-controlling of described hydrogenation reaction is at 0.1～10MPa; The time of described hydrogenation reaction was controlled at 1～60 hour.
3. the production method of acetate cumic aldehyde methyl esters according to claim 2 is characterized in that the weight ratio at catalyzer described in the step (1) and cumic aldehyde is 0.005～0.05: 1; The temperature of described hydrogenation reaction is controlled at 50～150 ℃; The pressure-controlling of described hydrogenation reaction is at 1.5～3MPa; The time of described hydrogenation reaction was controlled at 4～20 hours.
4. according to the production method of claim 1,2 or 3 described acetate cumic aldehyde methyl esters, it is characterized in that not using solvent in reaction process described in the step (1).
5. the production method of acetate cumic aldehyde methyl esters according to claim 1, ruthenium, platinum, palladium or the rhodium catalyst that it is characterized in that the carbon load in the step (1) are to adopt the immersion process for preparing gained, and the hydrogen argon with 10% before using mixes the gas reduction activation.
6. the production method of acetate cumic aldehyde methyl esters according to claim 1 is characterized in that the mol ratio at the isopropylbenzyl alcohol described in the step (2) and aceticanhydride or Glacial acetic acid is 1: 0.3～10; The temperature of reaction of described reaction is controlled at 40～240 ℃; The time of described reaction was controlled at 1～60 hour.
7. the production method of acetate cumic aldehyde methyl esters according to claim 6 is characterized in that the mol ratio at the isopropylbenzyl alcohol described in the step (2) and aceticanhydride or Glacial acetic acid is 1: 0.5～6; The temperature of reaction of described reaction is controlled at 60～180 ℃; The time of described reaction was controlled at 4～24 hours.
8. the production method of acetate cumic aldehyde methyl esters according to claim 7 is characterized in that the mol ratio at the isopropylbenzyl alcohol described in the step (2) and aceticanhydride or Glacial acetic acid is 1: 1.5～3; The temperature of reaction of described reaction is controlled at 80～100 ℃; The time of described reaction was controlled at 4～6 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557878A (en) * | 2011-12-29 | 2012-07-11 | 湖南科技学院 | Synthesis of cuminol by catalytic dehydrogenation with perilla alcohol as raw material |
| RU2658019C1 (en) * | 2017-03-31 | 2018-06-19 | Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) | Method of preparation of carbonyl compound and carboxylic acid esters |
Citations (1)
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| WO2010079035A2 (en) * | 2008-12-17 | 2010-07-15 | Basf Se | Continuous method for producing substituted cyclohexylmethanols |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010079035A2 (en) * | 2008-12-17 | 2010-07-15 | Basf Se | Continuous method for producing substituted cyclohexylmethanols |
Non-Patent Citations (2)
| Title |
|---|
| ROBERT L. ET AL: "Benzyl acetates as attractants for the male oriental fruit fly,Dacus dorsalis,and the male melon fly,Dacus cucurbitae", 《PROC.NATL.ACAD.SCI.》, vol. 83, March 1986 (1986-03-01), pages 1549 - 1553, XP002925825, DOI: doi:10.1073/pnas.83.6.1549 * |
| SAEID FARHADI ET AL: "Mixed-addenda 10-molybdo-2-vanadophosphoric heteropolyacid (H5PV2Mo10O40):An efficient catalyst under solvent-free conditions for rapid acylation of alcohols", 《CATALYSIS COMMUNICATIONS》, vol. 9, no. 5, 2008, pages 703 - 708, XP022453426, DOI: doi:10.1016/j.catcom.2007.08.006 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557878A (en) * | 2011-12-29 | 2012-07-11 | 湖南科技学院 | Synthesis of cuminol by catalytic dehydrogenation with perilla alcohol as raw material |
| CN102557878B (en) * | 2011-12-29 | 2016-02-17 | 湖南科技学院 | Take perillalcohol as catalytic material dehydrogenation synthesis cuminyl alcohol |
| RU2658019C1 (en) * | 2017-03-31 | 2018-06-19 | Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) | Method of preparation of carbonyl compound and carboxylic acid esters |
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Application publication date: 20110525 |