CN101798267A - Production method of cyclohexyloxy allyl acetate - Google Patents
Production method of cyclohexyloxy allyl acetate Download PDFInfo
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- CN101798267A CN101798267A CN201010107002A CN201010107002A CN101798267A CN 101798267 A CN101798267 A CN 101798267A CN 201010107002 A CN201010107002 A CN 201010107002A CN 201010107002 A CN201010107002 A CN 201010107002A CN 101798267 A CN101798267 A CN 101798267A
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Abstract
The invention discloses a production technique of organic synthetic perfume, and more particularly relates to a new production method of cyclohexyloxy allyl acetate which is takes as organic perfume. The method comprises the following steps of: (1) preparation of cyclohexyloxy ethyl acetate, adding solvent into ethyl phenoxyacetate, adding catalyst after the mixture is dissolved, pumping into hydrogen, and obtaining the cyclohexyloxy ethyl acetate by hydrogenation reaction; and (2) preparation of the cyclohexyloxy allyl acetate, leading the prepared cyclohexyloxy ethyl acetate and allyl alcohol to have ester exchange reaction under the action of catalyst to synthesize the cyclohexyloxy allyl acetate. The invention provides the new production method of the cyclohexyloxy allyl acetate, which has simple process flow, safety and reliability, low production cost, less by-product and low pollution, and the yield and the purity of the product are more than 90%.
Description
Technical field
The present invention relates to a kind of production technique of organic synthesis spices, relate in particular to a kind of as the new production method of the cyclohexyloxy allyl acetate of organic perfume.
Technical background
Cyclohexyloxy allyl acetate claims ring lattice paulin ester again, and English name is Allyl cyclohexoyacetate, and the CAS registration number is [68901-15-5].Chemical structural formula is:
It is a kind of have very strong lattice fluffy like blue or green fragrance, and with the spice product of fruital note.This product can be used in the daily chemical essence prescription, is mainly used in soap compound, synthetic detergent with in the perfume formulation.
Prepare the cyclohexyloxy ethyl ester from phenoxy acetic acid ethyl ester shortening, under catalyst action, transesterification reaction takes place with cyclohexyloxy ethyl ester and vinyl carbinol again, generate the production method of cyclohexyloxy allyl acetate, there is no report both at home and abroad.
Deng Shuhua etc. (fine chemistry industry, 1999,16,14～17) have reported and have prepared the hexamethylene sodium alkoxide with hexalin and sodium hydroxide earlier, make cyclohexyloxy sodium with hexamethylene sodium alkoxide and sodium chloroacetate reaction again, make cyclohexyloxy with hydrochloric acid reaction again, and yield is 81%.With cyclohexyloxy and vinyl carbinol esterification takes place in the presence of catalyzer then, make cyclohexyloxy allyl acetate, the esterification yield is 87.1%.The sodium alkoxide yield is lower in this technology, and the reaction times is very long, and whole operational path step is more, and complex process is polluted greatlyyer, and product yield is lower.
Jin Xin etc. (modern chemical industry, 2007,27,1:42～45) have reported that with hexalin and ethyl diazoacetate be raw material, carry out O-H insertion reaction synthesizing cyclohexane 1 ethoxyacetic acid ethyl ester in the presence of catalyzer, and reaction yield is 83%.With cyclohexyloxy ethyl ester and vinyl carbinol transesterification reaction takes place in the presence of catalyzer again, make cyclohexyloxy allyl acetate, esterification yield is 85%～90%.This method used ethyl diazoacetate when preparation cyclohexyloxy ethyl ester very easily explodes, and have bigger potential safety hazard, and the yield of cyclohexyloxy ethyl ester is lower.
Summary of the invention
The present invention will solve the deficiency that aforesaid method is produced cyclohexyloxy allyl acetate, and a kind of new production method is provided, and flow 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 and purity are all more than 90%.
The present invention is achieved by following technology examination scheme:
A kind of production method of cyclohexyloxy allyl acetate, this technology comprises following sequential steps:
(1) preparation of ring agent ethoxyacetic acid ethyl ester: add solvent in the phenoxy acetic acid ethyl ester, dissolve the back and add catalyzer, feed hydrogen, through getting the cyclohexyloxy ethyl ester after the hydrogenation reaction, catalyst system therefor is ruthenium, platinum, palladium or the rhodium catalyst of carbon load;
(2) preparation of cyclohexyloxy allyl acetate: the cyclohexyloxy ethyl ester and the vinyl carbinol of above-mentioned preparation are carried out transesterification reaction synthesizing cyclohexane 1 ethoxyacetic acid allyl ester under the effect of catalyzer, catalyst system therefor is the carbonate of basic metal or alkaline-earth metal.
The reaction equation of the preparation of cyclohexyloxy ethyl ester is as follows in the step of the present invention (1):
Technical process has been simplified in this reaction greatly, has reduced to become to produce cost; Reaction obtains chromatogram content greater than 96% cyclohexyloxy ethyl ester crude product, after filtration, reclaim solvent after, rectifying obtains content greater than 99% cyclohexyloxy ethyl ester, yield reaches more than 90%.
The reaction equation of the preparation of cyclohexyloxy allyl acetate is as follows in the step of the present invention (2):
It is catalyzer that this reaction process adopts the carbonate of basic metal or alkaline-earth metal, reduces the corrosion to equipment, has simplified aftertreatment, convenient production, and the yield of cyclohexyloxy allyl acetate reaches more than 90%.
In the production method of above-mentioned cyclohexyloxy allyl acetate, at the catalyzer described in the step (1) and the weight ratio of phenoxy acetic acid ethyl ester be: 0.0001～0.5: 1; The temperature of described hydrogenation reaction is controlled at 40～280 ℃; The pressure-controlling of described hydrogenation reaction is at 0.1～18MPa; The time of described hydrogenation reaction was controlled at 1～60 hour; As preferably, the weight ratio of described catalyzer and phenoxy acetic acid ethyl ester is: 0.005～0.5: 1; The temperature of described hydrogenation reaction is controlled at 60～200 ℃; The pressure-controlling of described hydrogenation reaction is at 0.5～10MPa; The time of described hydrogenation reaction was controlled at 4～40 hours.
Adopt specific temperature and hydrogen pressure in the present invention, guaranteed the yield and the purity of product.
In the new production method of above-mentioned cyclohexyloxy allyl acetate, be a kind of in the alcoholic solvents such as methyl alcohol, ethanol, propyl alcohol or butanols at the solvent described in the step (1), wherein dehydrated alcohol, Virahol are preferred.
Prepare in the method for cyclohexyloxy ethyl ester in step of the present invention (1), the control of catalyzer and hydroconversion condition is crucial; Catalyzer adopts immersion process for preparing, gac is immersed in the solution of certain density ruthenium, platinum, palladium, rhodium, and drying, roasting under the nitrogen protection, the hydrogen argon with 10% before using mixes the gas reduction activation.
In the new production method of above-mentioned cyclohexyloxy allyl acetate, be 1: 0.1～5 in the weight ratio of cyclohexyloxy ethyl ester described in the step (2) and vinyl carbinol; The temperature of reaction of described transesterification reaction is controlled at 40～200 ℃; The time of described transesterification reaction was controlled at 1～40 hour; As preferably, the weight ratio of described cyclohexyloxy ethyl ester and vinyl carbinol is 1: 0.5～3; The temperature of reaction of described transesterification reaction is controlled at 50～150 ℃; The time of described transesterification reaction was controlled at 5～30 hours.Prepare in the cyclohexyloxy allyl acetate process in the present invention, vinyl carbinol is excessive, if vinyl carbinol is few, then transesterify is incomplete, and long reaction time.
In the new production method of above-mentioned cyclohexyloxy allyl acetate, at the catalyzer described in the step (2) is one or more mixtures in yellow soda ash, salt of wormwood, lime carbonate, the magnesiumcarbonate etc., and wherein the weight ratio of catalyzer and cyclohexyloxy ethyl ester is 0.001～0.05: 1.The advantage of using this catalyzer is to have reduced side reaction, has improved the purity of product, simultaneously because catalytic erosion is lower, and the work-ing life of having improved equipment.
In the new production method of above-mentioned cyclohexyloxy allyl acetate, contain stopper in the transesterification reaction described in the step (2); Wherein the weight ratio of stopper and cyclohexyloxy ethyl ester is 0.001～0.04: 1.In the transesterify process, add stopper, reduce polymerization, reduce side reaction, obtain the product purity height, simplify aftertreatment, convenient for production; As preferably, described stopper is one or more mixtures in Resorcinol, para benzoquinone, MEHQ, the MEHQ hydroquinone monomethyl ether.
In the new production method of above-mentioned cyclohexyloxy allyl acetate, contain entrainer in the transesterification reaction described in the step (2); Wherein the weight ratio of entrainer and cyclohexyloxy ethyl ester is 0.05～0.5: 1.In the transesterify process, add entrainer, can remove the ethanol that generates in the reaction timely, help the carrying out of transesterification reaction, shortened the reaction times, improved product yield.As preferably, described entrainer is one or more mixing in hexanaphthene, benzene, the toluene.
The detailed process of step of the present invention (2) is: add the cyclohexyloxy ethyl ester and the vinyl carbinol of method for preparing earlier, wherein the weight ratio of cyclohexyloxy ethyl ester and vinyl carbinol is 1: 0.1～5; Stir down, add 1 ‰～5% catalyzer, 1 ‰～4% stopper and 5%～50% entrainer, temperature rising reflux reaction 1～40 hour.Reaction finishes the back and reclaims excessive vinyl carbinol, and required cut is collected in last rectification under vacuum.The cyclohexyloxy allyl acetate productive rate is more than 90%.
The effect that the present invention is useful is: proposed a kind of new cyclohexyloxy allyl acetate production technique, flow process is simple, and is safe and reliable, the reaction times section, and production cost is low, and by product is few, pollutes lowly, and the yield of product and purity are all more than 90%.
Embodiment
Below by specific examples, the present invention will be further described:
The used catalyzer immersion process for preparing of phenoxy acetic acid ethyl ester hydrogenation among the present invention, existing is that example is illustrated with the Ru/C catalyzer, detailed process is as follows:
It is the RuCl of 0.1g/ml that the 19g gac is added 20ml solubility
3In the aqueous solution, dipping stirred 24 hours, under the room temperature air-dry after again 120 ℃ of following vacuum-dryings 12 hours, make the Ru/C catalyzer, standby.Catalyzer needs before use under 300 ℃, is that 10% hydrogen argon mixes gas and reduces and activated in 5 hours with hydrogen content.Pd/C, Pt/C and Rh/C catalyzer are used with quadrat method and are prepared.
Embodiment 1
In the autoclave of 2L, add 400g phenoxy acetic acid ethyl ester, the 500ml dehydrated alcohol is heated to 40 ℃, make the dissolving of phenoxy acetic acid ethyl ester under stirring, add 10g again with the Ru/C catalyzer of method for preparing, with nitrogen replacement 3 times, use hydrogen exchange 3 times again after, feed hydrogen, slowly heat up, temperature is controlled at 60 ℃, and hydrogen pressure is controlled at 1MPa; After the hydrogenation reaction 30 hours, stop hydrogenation reaction, be cooled to room temperature, discharging, filter, reclaim after the catalyzer drying, filtrate is 97% through the chromatogram detection level, reclaims the solvent dehydrated alcohol, rectifying after finishing, (GC content: cyclohexyloxy ethyl ester 99%), productive rate are 95% to obtain 380g.
Thermometer is being housed, in the there-necked flask of stirring and condensation reflux unit, is adding cyclohexyloxy ethyl ester 300g, vinyl carbinol 200; Stir and add 1g yellow soda ash and 2g down MEHQ hydroquinone monomethyl ether; Temperature is controlled at 70 ℃, back flow reaction 5 hours, and sampling reaches 95% through stratographic analysis cyclohexyloxy allyl acetate content, reclaims excessive vinyl carbinol, and rectification under vacuum obtains the 276g cyclohexyloxy allyl acetate, and (GC content: 99%) productive rate 92%.
Embodiment 2
In the autoclave of 2L, add 400g phenoxy acetic acid ethyl ester, the 500ml dehydrated alcohol is heated to 40 ℃, make the dissolving of phenoxy acetic acid ethyl ester under stirring, add 8g again with the Pd/C catalyzer of method for preparing, with nitrogen replacement 3 times, use hydrogen exchange 3 times again after, feed hydrogen, slowly heat up, temperature is controlled at 100 ℃, and hydrogen pressure is controlled at 10MPa; After the hydrogenation reaction 10 hours, stop hydrogenation reaction, be cooled to room temperature, discharging, filter, reclaim after the catalyzer drying, filtrate is 96% through the chromatogram detection level, reclaims the solvent dehydrated alcohol, rectifying after finishing, (GC content: cyclohexyloxy ethyl ester 99%), productive rate are 93% to obtain 372g.
Thermometer is being housed, in the there-necked flask of stirring and condensation reflux unit, is adding cyclohexyloxy ethyl ester 260g, vinyl carbinol 130; Stir and add 0.8g lime carbonate and 2.6g down para benzoquinone; Temperature is controlled at 80 ℃, back flow reaction 6 hours, and sampling reaches 94% through stratographic analysis cyclohexyloxy allyl acetate content, reclaims excessive vinyl carbinol, and rectification under vacuum obtains the 236.6g cyclohexyloxy allyl acetate, and (GC content: 99%) productive rate 91%.
Embodiment 3
In the autoclave of 2L, add 500g phenoxy acetic acid ethyl ester, the 600ml dehydrated alcohol is heated to 50 ℃, make the dissolving of phenoxy acetic acid ethyl ester under stirring, add 15g again with the Pt/C catalyzer of method for preparing, with nitrogen replacement 3 times, use hydrogen exchange 3 times again after, feed hydrogen, slowly heat up, temperature is controlled at 120 ℃, and hydrogen pressure is controlled at 0.5MPa; After the hydrogenation reaction 40 hours, stop hydrogenation reaction, be cooled to room temperature, discharging, filter, reclaim after the catalyzer drying, filtrate is 95% through the chromatogram detection level, reclaims the solvent dehydrated alcohol, rectifying after finishing, (GC content: cyclohexyloxy ethyl ester 99%), productive rate are 94% to obtain 470g.
Thermometer is being housed, in the there-necked flask of stirring and condensation reflux unit, is adding cyclohexyloxy ethyl ester 320g, vinyl carbinol 180; Stir and add 0.5g salt of wormwood and 3g MEHQ down; Temperature is controlled at 76 ℃, back flow reaction 8 hours, and sampling reaches 95% through stratographic analysis cyclohexyloxy allyl acetate content, reclaims excessive vinyl carbinol, and rectification under vacuum obtains the 294.4g cyclohexyloxy allyl acetate, and (GC content: 99%) productive rate 92%.
Embodiment 4
In the autoclave of 2L, add 500g phenoxy acetic acid ethyl ester, the 600ml dehydrated alcohol is heated to 50 ℃, make the dissolving of phenoxy acetic acid ethyl ester under stirring, add 10g again with the Rh/C catalyzer of method for preparing, with nitrogen replacement 3 times, use hydrogen exchange 3 times again after, feed hydrogen, slowly heat up, temperature is controlled at 140 ℃, and hydrogen pressure is controlled at 12MPa; After the hydrogenation reaction 10 hours, stop hydrogenation reaction, be cooled to room temperature, discharging, filter, reclaim after the catalyzer drying, filtrate is 96% through the chromatogram detection level, reclaims the solvent dehydrated alcohol, rectifying after finishing, (GC content: cyclohexyloxy ethyl ester 99%), productive rate are 95% to obtain 475g.
Thermometer is being housed, in the there-necked flask of stirring and condensation reflux unit, is adding cyclohexyloxy ethyl ester 300g, vinyl carbinol 160; Stir and add 2g salt of wormwood and 2g para benzoquinone down; Temperature is controlled at 90 ℃, back flow reaction 7 hours, and sampling reaches 96% through stratographic analysis cyclohexyloxy allyl acetate content, reclaims excessive vinyl carbinol, and rectification under vacuum obtains the 285g cyclohexyloxy allyl acetate, and (GC content: 99%) productive rate 95%.
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 (6)
1. the production method of a cyclohexyloxy allyl acetate, this technology comprises following sequential steps:
(1) preparation of cyclohexyloxy ethyl ester: the phenoxy acetic acid ethyl ester is added solvent, the dissolving back adds catalyzer, feed hydrogen, through getting the cyclohexyloxy ethyl ester after the hydrogenation reaction, described solvent is a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol or the butanols, and catalyst system therefor is ruthenium, platinum, palladium or the rhodium catalyst of carbon load; The weight ratio of described catalyzer and phenoxy acetic acid ethyl ester is 0.0001～0.5: 1; The temperature of described hydrogenation reaction is controlled at 40～280 ℃; The pressure-controlling of described hydrogenation reaction is at 0.1～18MPa; The time of described hydrogenation reaction was controlled at 1～60 hour;
(2) preparation of cyclohexyloxy allyl acetate: the cyclohexyloxy ethyl ester and the vinyl carbinol of above-mentioned preparation are carried out transesterification reaction under the effect of catalyzer, synthesizing cyclohexane 1 ethoxyacetic acid allyl ester, catalyst system therefor are the carbonate of basic metal or alkaline-earth metal.
2. production method according to claim 1 is characterized in that the weight ratio at catalyzer described in the step (1) and phenoxy acetic acid ethyl ester is 0.005～0.5: 1; The temperature of described hydrogenation reaction is controlled at 60～200 ℃; The pressure-controlling of described hydrogenation reaction is at 0.5～10MPa; The time of described hydrogenation reaction was controlled at 4～40 hours.
3. production method according to claim 2 is characterized in that the solvent described in the step (1) is dehydrated alcohol, propyl alcohol, Virahol or butanols.
4. production method according to claim 1, the weight ratio that it is characterized in that cyclohexyloxy ethyl ester described in the step (2) and vinyl carbinol is 1: 0.1～5; The temperature of reaction of described transesterification reaction is controlled at 40～200 ℃; The time of described transesterification reaction was controlled at 1～40 hour.
5. production method according to claim 4, the weight ratio that it is characterized in that cyclohexyloxy ethyl ester described in the step (2) and vinyl carbinol is 1: 0.5～3; The temperature of reaction of described transesterification reaction is controlled at 50～150 ℃; The time of described transesterification reaction was controlled at 5～30 hours.
6. production method according to claim 1, the carbonate that it is characterized in that basic metal described in the step (2) or alkaline-earth metal is one or more mixtures in yellow soda ash, salt of wormwood, lime carbonate, the magnesiumcarbonate, and wherein the weight ratio of catalyzer and cyclohexyloxy ethyl ester is 0.001～0.05: 1.
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| CN104230705A (en) * | 2013-06-08 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method for pentaerythritol tetracarboxylate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104230705A (en) * | 2013-06-08 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method for pentaerythritol tetracarboxylate |
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Application publication date: 20100811 |