CN101654404A - Method for producing 2-alkylidene cyclopentanone - Google Patents
Method for producing 2-alkylidene cyclopentanone Download PDFInfo
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- CN101654404A CN101654404A CN200910070690A CN200910070690A CN101654404A CN 101654404 A CN101654404 A CN 101654404A CN 200910070690 A CN200910070690 A CN 200910070690A CN 200910070690 A CN200910070690 A CN 200910070690A CN 101654404 A CN101654404 A CN 101654404A
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Abstract
The invention discloses an environment-friendly method for producing 2-alkylidene cyclopentanone, which uses cyclopentanone and fatty aldehyde as raw materials and uses amine type weak-base ion-exchange resin for reaction under the condition of existence of fatty acid to produce 2-alkylidene cyclopentanone. The resin and the fatty acid which are separated can be recycled. The 2-alkylidene cyclopentanone is a key intermediate for synthesizing many spices (such as methyl dihydrojasmonate and delta-lactone). The traditional technology of the 2-alkylidene cyclopentanone has the outstanding problems that the acid-base solution catalytic system is adopted, which causes that the catalyst is very difficult to be recycled, the product yield is low, many by-products with high boiling points are generated, the reaction selectivity is poor, and a large amount of waste water is generated, thereby wasting resources and polluting environment. The method of the invention uses a catalytic system whichcan be recycled to replace the traditional solution catalytic system which can not be recycled, uses the cleaning production technology to improve the original technology, and simultaneously achievesthe purposes of saving and fully utilizing resources and protecting the environment.
Description
[technical field]
The present invention relates to the fine chemicals field of chemical engineering---the preparation of spices intermediate; replace original technology with clearer production technology; realize the saving of resource simultaneously and make full use of, and environment protection, particularly a kind of method of environmentally friendly production 2-alkylidene group cyclopentanone.
[background technology]
The condensation reaction of aldehydes and ketone is the reaction commonly used that increases carbochain, can form many new compounds, is the very important organic synthesis of a class.Synthetic many spices (for example methyl dihydrojasmonate, delta-lactone) important intermediate---2-alkylidene group cyclopentanone is that raw material obtains through condensation reaction with alkanoic and cyclopentanone:
2-alkylidene group cyclopentanone is in its traditional synthesis technique, and the condensation reaction of alkanoic and cyclopentanone is to carry out in the presence of liquid acid or alkaline catalysts.This catalyst system can cause many side reactions simultaneously in reaction process, produce many high boiling point by-products produced of utility value that almost do not have, cause the reduction of reaction preference, and owing to adopted the acid-base solution catalyzer, reaction later needs neutralization operation, can produce a large amount of waste water, and catalyzer can not recycling use, in postprocessing working procedures, cause raw material and product losses and waste, and the waste of the energy that causes indirectly.
Based on this, the present invention intends utilizing recyclable round-robin catalyst system to come the condensation of catalysis aldehyde ketone, substitutes traditional restored acid alkaline solution catalyzer that is difficult to, improve the selectivity of reaction simultaneously, reduce discharging of waste liquid, reduce the consumption of the resource and the energy, realize saving and efficiently utilize resource and utilize again.
[summary of the invention]
Purpose of the present invention is intended to overcome the problem that traditional technology exists, and a kind of method of environmentally friendly production 2-alkylidene group cyclopentanone is provided.The environmentally friendly catalyst system that this method is used have recyclablely recycle, highly selective and free of contamination advantage, thereby avoided the resource waste and pollution environment.
For achieving the above object, the invention discloses a kind of method of environmentally friendly production 2-alkylidene group cyclopentanone, it is characterized in that may further comprise the steps:
(1) cyclopentanone, alkanoic, weak-base ion-exchange resin, lipid acid and water are mixed in reactor, under 25～90 ℃ of temperature, react, complete until the alkanoic primitive reaction; The mol ratio of described cyclopentanone and alkanoic is 1～15: 1, the proportioning of described weak-base ion-exchange resin and alkanoic is: the wet heap of 0.1～50mL volume weak-base ion-exchange resin/every gram alkanoic, the mol ratio of described lipid acid and alkanoic is 0.01～2: 1, and the volume ratio of described water and weak-base ion-exchange resin is 0.1～3: 1;
(2) isolate resin phase, water and organic phase from the reaction mixture that step (1) obtains, resin can be recycled mutually and through spissated water (removing the water that dereaction generates);
(3) organic phase (oil phase) that step (2) is obtained adopts rectification under vacuum to slough the light constituent that contains unreacted cyclopentanone and fatty acid catalyst etc., and this light constituent can be recycled;
(4) send to according to the index of desired product to remove the product that obtains behind the light constituent through step (3) that to carry out further rectification under vacuum refining, obtain qualified 2-alkylidene group cyclopentanone.
The present invention is a kind of method of environmentally friendly production 2-alkylidene group cyclopentanone, can be used for the important intermediate of synthetic many spices (for example methyl dihydrojasmonate, delta-lactone).
The invention has the beneficial effects as follows: developed a kind of method that adopts clearer production technology to produce 2-alkylidene group cyclopentanone, this method is taken into account resources conservation and environment protection simultaneously.
The present invention and catalyzer be difficult to recycling use, produce and morely almost do not have the high boiling point by-products produced and a large amount of waste water of utility value, cause the traditional method of the wasting of resources and environmental pollution to compare, have that catalyst system is renewable to be recycled, produce the high boiling point by-products produced and waste water of no utility value hardly, compliance with environmental protection requirements is a kind of environmentally friendly production technique.
This technology also can be applicable in the production of cyclopentanone and acetaldehyde, propionic aldehyde reaction Synthetic 2-ethylidene cyclopentanone (claim not only 2-ethene (base) cyclopentanone), 2-propylidene cyclopentanone (but also claiming 2-propylene (base) cyclopentanone).In addition, the reaction of pimelinketone and alkanoic also can be adopted the inventive method.
[description of drawings]
The mass spectrum of the 2-pentylidene cyclopentanone that Fig. 1 makes for the present invention.
[embodiment]
The method of environmentally friendly production 2-alkylidene group cyclopentanone of the present invention.Mainly may further comprise the steps:
(1) a certain amount of cyclopentanone, alkanoic, weak-base ion-exchange resin, lipid acid and water are mixed in reactor, react at a certain temperature, complete until the alkanoic primitive reaction.In this specialty, " reacting completely " is a theoretical boundary, refers to raw material 100% complete reaction.And in actual Chemical Manufacture, in order to save unnecessary time waste, it is generally acknowledged if raw material at least 99% reacts away and just can think that primitive reaction is complete;
(2) from the reaction mixture that step (1) obtains, isolate resin, water layer (phase) and oil phase (organic phase), resin can be recycled mutually and through spissated water (removing the water that dereaction generates), be to adopt conventional phase detachment technique so-called the separation, for example filter, centrifugation goes out the resin phase, and water and organic phase are separated for two-phase up and down because of natural layering;
(3) oil phase (organic phase) that step (2) is obtained adopts underpressure distillation to slough the light constituent that contains unreacted cyclopentanone and lipid acid, and this light constituent can be recycled;
(4) remove the product that obtains behind the light constituent through step (3) and send to according to the index of desired product that to carry out further underpressure distillation refining, to obtain qualified 2-alkylidene group cyclopentanone.
Hybrid mode in the described step (1) in reactor can be: will cyclopentanone under the room temperature, alkanoic, weak-base ion-exchange resin, lipid acid and water drops in the reactor and mix, be warming up to temperature of reaction then after, progressively add alkanoic again.Or:
Earlier cyclopentanone, weak-base ion-exchange resin, lipid acid and water are put into reactor, be warming up to temperature of reaction after, drip alkanoic.Or:
Earlier cyclopentanone, alkanoic are dropped into reactor, be warming up to the mixture that adds weak-base ion-exchange resin, lipid acid and water after the temperature of reaction.Or:
Earlier weak-base ion-exchange resin, lipid acid and water are put into reactor, be warming up to temperature of reaction then after, add the mixture of cyclopentanone and alkanoic simultaneously.Or:
Earlier weak-base ion-exchange resin, lipid acid and water are put into reactor, be warming up to temperature of reaction then after, add cyclopentanone successively, alkanoic.Or:
Earlier cyclopentanone is put into reactor, be warming up to temperature of reaction after, add the mixture of weak-base ion-exchange resin, lipid acid and water more successively, add alkanoic at last in batches.
Weak-base ion-exchange resin in the described step (1) is meant primary amine type ion exchange resin, secondary amine type ion exchange resin, tertiary amine-type ion exchange resin or their two or more mixtures.
Lipid acid in the described step (1) is meant acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid or their two or more mixtures.
Alkanoic in the described step (1) is meant butyraldehyde, valeral, hexanal, enanthaldehyde, octanal or their two or more mixtures.
The mol ratio of cyclopentanone of the present invention and alkanoic is preferably 1～5: 1 (mol/mol).The proportioning of weak-base ion-exchange resin and alkanoic is preferably: every gram alkanoic needs 0.1～50mL (wet heap volume) resin.The mol ratio of described lipid acid and alkanoic is preferably: lipid acid: alkanoic=0.05～1: 1 (mol/mol).The volume ratio of described water and weak-base ion-exchange resin is preferably 0.1～2: 1.
Reactor used in the present invention can be a batch reactor, also can be flow reactor.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylidene group cyclopentanone may further comprise the steps for 1 one kinds:
(1) under the room temperature with mixing in the disposable input reactor of a certain amount of cyclopentanone, alkanoic, weak-base ion-exchange resin, lipid acid and water, be warming up to 30 ℃ then, under this temperature, continue reaction, complete until the alkanoic primitive reaction;
(2) isolate resin, water layer (phase) and oil phase (organic phase) from the reaction mixture that step (1) obtains, for the resin that still has reactive behavior, can be used for down, batch reaction uses deactivated resin sent for regeneration; Water then can be recycled;
(3) oil phase (organic phase) that step (2) is obtained adopts underpressure distillation to slough the light constituent that contains unreacted cyclopentanone and lipid acid, and this light constituent can be recycled;
(4) remove the product that obtains behind the light constituent through step (3) and send to according to the index of desired product that to carry out further underpressure distillation refining, to obtain qualified 2-alkylidene group cyclopentanone.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylidene group cyclopentanone may further comprise the steps for 2 one kinds:
(1) earlier with the disposable reactor of putting into of cyclopentanone, weak-base ion-exchange resin, lipid acid and water, be warming up to 50 ℃ after, under agitation drip alkanoic, maintain then and continue reaction under this temperature, complete until the alkanoic primitive reaction;
(2) isolate resin, water layer (phase) and oil phase (organic phase) from the reaction mixture that step (1) obtains, for the resin that still has reactive behavior, can be used for down, batch reaction uses deactivated resin sent for regeneration; Water then can be recycled;
(3) oil phase (organic phase) that step (2) is obtained adopts underpressure distillation to slough the light constituent that contains unreacted cyclopentanone and lipid acid, and this light constituent can be recycled;
(4) remove the product that obtains behind the light constituent through step (3) and send to according to the index of desired product that to carry out further underpressure distillation refining, to obtain qualified 2-alkylidene group cyclopentanone.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylidene group cyclopentanone may further comprise the steps for 3 one kinds:
(1) earlier a certain amount of cyclopentanone, alkanoic are dropped into reactor, be warming up to the mixture that drops into weak-base ion-exchange resin, lipid acid and water after 70 ℃, maintain then and continue reaction under this temperature, complete until the alkanoic primitive reaction;
(2) isolate resin, water layer (phase) and oil phase (organic phase) from the reaction mixture that step (1) obtains, for the resin that still has reactive behavior, can be used for down, batch reaction uses deactivated resin sent for regeneration; Water then can be recycled;
(3) oil phase (organic phase) that step (2) is obtained adopts underpressure distillation to slough the light constituent that contains unreacted cyclopentanone and lipid acid, and this light constituent can be recycled;
(4) remove the product that obtains behind the light constituent through step (3) and send to according to the index of desired product that to carry out further underpressure distillation refining, to obtain qualified 2-alkylidene group cyclopentanone.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylidene group cyclopentanone may further comprise the steps for 4 one kinds:
(1) earlier with the disposable reactor of putting into of weak-base ion-exchange resin, lipid acid and water, be warming up to 80 ℃ then after, add the mixture of cyclopentanone and alkanoic, maintain and continue reaction under this temperature, complete until the alkanoic primitive reaction;
(2) isolate resin, water layer (phase) and oil phase (organic phase) from the reaction mixture that step (1) obtains, for the resin that still has reactive behavior, can be used for down, batch reaction uses deactivated resin sent for regeneration; Water then can be recycled;
(3) oil phase (organic phase) that step (2) is obtained adopts underpressure distillation to slough the light constituent that contains unreacted cyclopentanone and lipid acid, and this light constituent can be recycled;
(4) remove the product that obtains behind the light constituent through step (3) and send to according to the index of desired product that to carry out further underpressure distillation refining, to obtain qualified 2-alkylidene group cyclopentanone.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylidene group cyclopentanone may further comprise the steps for 5 one kinds:
(1) earlier with the disposable reactor of putting into of weak-base ion-exchange resin, lipid acid and water, be warming up to 90 ℃ then after, add cyclopentanone successively, alkanoic maintains and continues reaction under this temperature, and is complete until the alkanoic primitive reaction;
(2) isolate resin, water layer (phase) and oil phase (organic phase) from the reaction mixture that step (1) obtains, for the resin that still has reactive behavior, can be used for down, batch reaction uses deactivated resin sent for regeneration; Water then can be recycled;
(3) oil phase (organic phase) that step (2) is obtained adopts underpressure distillation to slough the light constituent that contains unreacted cyclopentanone and lipid acid, and this light constituent can be recycled;
(4) remove the product that obtains behind the light constituent through step (3) and send to according to the index of desired product that to carry out further underpressure distillation refining, to obtain qualified 2-alkylidene group cyclopentanone.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylidene group cyclopentanone may further comprise the steps for 6 one kinds:
(1) earlier cyclopentanone is put into reactor, be warming up to 25 ℃ after, add the mixture of weak-base ion-exchange resin, lipid acid and water successively, add alkanoic at last in batches.Maintain and continue reaction under this temperature, complete until the alkanoic primitive reaction;
(2) isolate resin, water layer (phase) and oil phase (organic phase) from the reaction mixture that step (1) obtains, for the resin that still has reactive behavior, can be used for down, batch reaction uses deactivated resin sent for regeneration; Water then can be recycled;
(3) oil phase (organic phase) that step (2) is obtained adopts underpressure distillation to slough the light constituent that contains unreacted cyclopentanone and lipid acid, and this light constituent can be recycled;
(4) remove the product that obtains behind the light constituent through step (3) and send to according to the index of desired product that to carry out further underpressure distillation refining, to obtain qualified 2-alkylidene group cyclopentanone.
Embodiment 7: at room temperature, 100 gram cyclopentanone, 20 gram valeraldehydes, 30mL (wet heap volume) D380 weak-base ion-exchange resin (primary amine type), 4 gram acetic acid and disposable the putting in the reactor that stirring, thermometer and reflux condensing tube are installed of 20mL water are mixed, under agitation be warming up to 50 ℃ then, under this temperature, continue reaction.Follow the tracks of the process of reaction with vapor-phase chromatography.React after 2 hours, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) is 88.2 (area) %.
Embodiment 8: earlier 100 gram cyclopentanone, 40mL (wet heap volume) D382 weak-base ion-exchange resin (secondary amine type), 8 gram valeric acids and 40mL water are put into the reactor that is equipped with thermometer, agitator, dropping funnel and reflux condensing tube, behind the heat temperature raising to 50 ℃, under agitation drip 10 gram valeraldehydes, in one hour, drip off.Maintain 90 ℃ and continue reaction down, until chromatogram content＜0.5% of valeral.Isolate resin and water layer (mutually) (following secondary response is applied mechanically), adopt underpressure distillation at first to slough the lighting end (following secondary response is applied mechanically) that contains unreacted cyclopentanone and valeric acid to oil phase, further rectification under vacuum is refining then, collect the cut of 80～85 ℃/100Pa, obtain about 17.5 gram 2-pentylidene cyclopentanone and (claim 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) content is 85.6% product, about 85% (in the aldehyde) of yield, about 1 gram of stillage residue.
Detect through GS-MS (application of gas chromatorgraphy/mass), resulting product has identical stratographic appearance time and mass spectrum, molecular weight 152 with the 2-pentylidene cyclopentanone that traditional soda solution grouting obtains.See shown in Figure 1.
Embodiment 9: add 100 gram cyclopentanone and 40 gram valeraldehydes in the reactor that stirring, thermometer, dropping funnel and reflux condensing tube are installed in advance, be warming up to the mixture that drops into 40mL (wet heap volume) D380 weak-base ion-exchange resin (primary amine type), 6 gram propionic acid and 4mL water after 80 ℃, continue heated and stirred after 2 hours, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) is 85.5 (area) %.
Embodiment 10: in the reactor that is equipped with thermometer, agitator, dropping funnel and reflux condensing tube, earlier with 25mL (wet heap volume) D380 weak-base ion-exchange resin (primary amine type), 0.25 gram acetic acid and the disposable reactor of putting into of 50mL water, then behind the heat temperature raising to 90 ℃, the mixture that adds 100 gram cyclopentanone and 30 gram valeraldehydes, react after 2 hours, the chromatogram content (deducting unreacted raw material) that records 2-pentylidene cyclopentanone in the reaction solution is 77.5 (area) %.
Embodiment 11: in the reactor that agitator, thermometer, dropping funnel and reflux condensing tube are housed, put into ring 100 gram cyclopentanone earlier, after being warming up to 70 ℃, add 10mL (wet heap volume) D380 weak-base ion-exchange resin (primary amine type), 2 gram acetic acid and 50mL water successively, drip 100 gram valeraldehydes at last, 1.0 hour finish, the constant temperature stirring reaction is after 2 hours, the chromatogram content (deducting unreacted raw material) that records 2-pentylidene cyclopentanone in the reaction solution is 38.5 (area) %.
Embodiment 12: add 100 gram cyclopentanone, 40mL (wet heap volume) D382 weak-base ion-exchange resin, 4 gram enanthic acid and 40mL water in the reactor that is equipped with agitator, thermometer, dropping funnel and reflux exchanger earlier, behind the heat temperature raising to 70 ℃, under agitation drip 25 gram enanthaldehydes (the dropping time is no less than 2h), dropwise the back and keep 70 ℃ of temperature, continue to stir chromatogram content＜0.5%, stop to stir until enanthaldehyde.Isolate resin and water layer (mutually) (following secondary response is applied mechanically), reaction solution is moved in the vacuum distillation apparatus distill.At first obtain containing the lighting end (following secondary response is applied mechanically) of unreacted cyclopentanone and enanthic acid, further underpressure distillation then, collect the cut of 100～110 ℃/100Pa, obtaining inferior fleuramone (claiming 2-heptene (base) cyclopentanone again) content of about 37 gram 2-is 88% product, yield 82.4% (in aldehyde), about 1.8 grams of stillage residue.
Detect through GS-MS (application of gas chromatorgraphy/mass), resulting product has identical stratographic appearance time, molecular weight 180 with the 2-heptenyl cyclopentanone that traditional soda solution grouting obtains.
Embodiment 13: put into 100 gram cyclopentanone, 40mL (wet heap volume) D382 weak-base ion-exchange resin (secondary amine type), 10 restrain oneself acid and 40mL water in the reactor that is equipped with agitator, thermometer, dropping funnel and reflux exchanger, behind the heat temperature raising to 50 ℃, under agitation drip 30 gram valeraldehydes, in one hour, drip off.Maintain 50 ℃ and continue reaction down, continue heated and stirred after 1 hour, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming 2 amylenes (base) cyclopentanone again, 2-pentylidene basic ring pentanone) is 85.5 (area) %.
Embodiment 14: add 100 gram cyclopentanone and 25 gram n-hexyl aldehydes in the reactor that stirring, thermometer, dropping funnel and reflux condensing tube are installed in advance, be warming up to and drop into the restrain oneself mixture of acid and 20mL water of 20mL (wet heap volume) D382 weak-base ion-exchange resin (secondary amine type), 15 after 80 ℃, continue heated and stirred and reflux a few hours, until chromatogram content＜0.5% of hexanal.Reaction is isolated resin and water layer (mutually) (following secondary response is applied mechanically) after finishing, and reaction solution is moved in the vacuum distillation apparatus distill.At first obtain containing the lighting end (following secondary response is applied mechanically) of unreacted cyclopentanone and caproic acid, 116～120 ℃/1995Pa cut is collected in further underpressure distillation then, obtains about 42.1 gram 2-hexylidene cyclopentanone content and be 84% product, about 85% (in the aldehyde) of yield, stillage residue 1.5 grams.
Detect through GS-MS (application of gas chromatorgraphy/mass), resulting product has identical stratographic appearance time, molecular weight 166 with the 2-hexylidene cyclopentanone that traditional soda solution grouting obtains.
Embodiment 15: earlier 100 gram cyclopentanone, 40mL (wet heap volume) D382 weak-base ion-exchange resin (secondary amine type), 2 gram butyric acid and 40mL water are put into the reactor that is equipped with thermometer, agitator, dropping funnel and reflux condensing tube, behind the heat temperature raising to 50 ℃, under agitation drip 15 gram butyraldehyde-ns, in one hour, drip off.Maintain 50 ℃ and continue reaction down, until chromatogram content＜0.5% of butyraldehyde.Isolate resin and water layer (mutually) (following secondary response is applied mechanically), adopt underpressure distillation at first to slough to oil phase and contain unreacted cyclopentanone and butyro-lighting end (following secondary response is applied mechanically), further rectification under vacuum then, collect the cut of 82～86 ℃/8mmHg, obtaining 27.4 gram 2-butylidene cyclopentanone (claiming 2-butylene (base) cyclopentanone again) content is the product of 84 (area) %.About 80% (in the aldehyde) of productive rate, about 1 gram of stillage residue.
Detect through GS-MS (application of gas chromatorgraphy/mass), resulting product has identical stratographic appearance time, molecular weight 138 with the crotyl cyclopentanone that traditional soda solution grouting obtains.
Embodiment 16: add 100 gram cyclopentanone, 40mL (wet heap volume) D382 weak-base ion-exchange resin (secondary amine type), 4 gram acetic acid and 40mL water in the reactor that is equipped with agitator, thermometer, dropping funnel and reflux exchanger earlier, behind the heat temperature raising to 70 ℃, under agitation drip 20 gram n-octaldehydes, in 0.5 hour, drip off.Maintain 50 ℃ and continue reaction down after 2 hours, the chromatogram content (deducting unreacted raw material) of the octylene cyclopentanone of product 2-(claiming 2-octene (base) cyclopentanone again) is 85.5 (area) %.
Embodiment 17: add 100 gram cyclopentanone, 40mL (wet heap volume) D380 weak-base ion-exchange resin (primary amine type), 4 gram acetic acid and 5mL water in the reactor that agitator, thermometer, dropping funnel and reflux exchanger are installed earlier, behind the heat temperature raising to 70 ℃, under agitation drip 30 gram valeraldehydes, in 2 hours, drip off.Maintain 40 ℃ and continue reaction down after 1 hour, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) is 86.9 (area) %.
Embodiment 18: earlier 100 gram cyclopentanone, 40mL (wet heap volume) D301T weak-base ion-exchange resin (tertiary amine-type), 0.5 gram acetic acid and 1mL water are put into the reactor that thermometer, agitator, dropping funnel and reflux condensing tube are housed, behind the heat temperature raising to 90 ℃, under agitation add 30 gram valeraldehydes in batches.Maintain 50 ℃ and continue reaction down after 4 hours, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) is 60.1 (area) %.
Claims (10)
1, a kind of method of producing 2-alkylidene group cyclopentanone is characterized in that may further comprise the steps:
(1) cyclopentanone, alkanoic, weak-base ion-exchange resin, lipid acid and water are mixed in reactor, under 25～90 ℃ of temperature, react, complete until the alkanoic primitive reaction; The mol ratio of described cyclopentanone and alkanoic is 1～15: 1, the proportioning of described weak-base ion-exchange resin and alkanoic is: the wet heap of 0.1～50mL volume weak-base ion-exchange resin/every gram alkanoic, the mol ratio of described lipid acid and alkanoic is 0.01～2: 1, and the volume ratio of described water and weak-base ion-exchange resin is 0.1～3: 1;
(2) from the reaction mixture that step (1) obtains, isolate resin phase, water and organic phase;
(3) organic phase that step (2) is obtained adopts rectification under vacuum to slough the light constituent that contains unreacted cyclopentanone and fatty acid catalyst;
(4) to carry out further rectification under vacuum refining to remove the product that obtains behind the light constituent through step (3), obtains qualified 2-alkylidene group cyclopentanone.
2, in accordance with the method for claim 1, it is characterized in that the weak-base ion-exchange resin in the described step (1) is meant primary amine type ion exchange resin, secondary amine type ion exchange resin, tertiary amine-type ion exchange resin or their two or more mixtures.
3, in accordance with the method for claim 1, it is characterized in that the lipid acid in the described step (1) is meant acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid or their two or more mixtures.
4, in accordance with the method for claim 1, it is characterized in that the alkanoic in the described step (1) is meant butyraldehyde, valeral, hexanal, enanthaldehyde, octanal or their two or more mixtures.
5, according to claim 1 or the described method of 2-4, it is characterized in that the hybrid mode in reactor is in the described step (1): earlier cyclopentanone, weak-base ion-exchange resin, lipid acid and water are put into reactor, after being warming up to temperature of reaction, progressively add alkanoic again.
6, according to claim 1 or the described method of 2-4, it is characterized in that the hybrid mode in reactor is in the described step (1): earlier weak-base ion-exchange resin, lipid acid and water are put into reactor, after being warming up to temperature of reaction then, more simultaneously or add cyclopentanone and alkanoic successively.
7, according to claim 1 or the described method of 2-4, it is characterized in that the hybrid mode in reactor is in the described step (1): earlier cyclopentanone is put into reactor, after being warming up to temperature of reaction, add weak-base ion-exchange resin, lipid acid and water more successively, add alkanoic at last in batches.
8, according to claim 1 or the described method of 2-4, it is characterized in that the proportioning of described weak-base ion-exchange resin and alkanoic is: the wet heap of 1～20mL volume weak-base ion-exchange resin/every gram alkanoic.
9, according to claim 1 or the described method of 2-4, the mol ratio that it is characterized in that described lipid acid and alkanoic is 0.05～1: 1.
10, according to claim 1 or the described method of 2-4, the volume ratio that it is characterized in that described water and weak-base ion-exchange resin is 0.1～2: 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851154A (en) * | 2010-05-18 | 2010-10-06 | 天津理工大学 | Improved method for producing 2-alkylene alicyclic ketone |
| CN102503791A (en) * | 2011-11-25 | 2012-06-20 | 天津理工大学 | Method for producing 2-alkylene grease cyclic ketone by adopting bionic catalytic system |
| CN103044374A (en) * | 2012-12-26 | 2013-04-17 | 淮安万邦香料工业有限公司 | Synthesis method of delta-dodecalactone |
| CN104910000A (en) * | 2015-05-25 | 2015-09-16 | 张家港市振方化工有限公司 | Preparation method of 2-heptylidene-cyclopentanon |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH382731A (en) * | 1960-02-25 | 1964-10-15 | Firmenich & Cie | Process for the preparation of alicyclic keto esters |
| JP2003171336A (en) * | 2001-11-30 | 2003-06-20 | Takasago Internatl Corp | Method for producing 2-alkyl-2-cyclopentenone |
| US7057077B2 (en) * | 2002-12-26 | 2006-06-06 | Kao Corporation | Method for producing 2- (alkyl) cycloalkenone |
-
2009
- 2009-09-29 CN CN2009100706907A patent/CN101654404B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851154A (en) * | 2010-05-18 | 2010-10-06 | 天津理工大学 | Improved method for producing 2-alkylene alicyclic ketone |
| CN101851154B (en) * | 2010-05-18 | 2013-01-16 | 天津理工大学 | Improved method for producing 2-alkylene alicyclic ketone |
| CN102503791A (en) * | 2011-11-25 | 2012-06-20 | 天津理工大学 | Method for producing 2-alkylene grease cyclic ketone by adopting bionic catalytic system |
| CN103044374A (en) * | 2012-12-26 | 2013-04-17 | 淮安万邦香料工业有限公司 | Synthesis method of delta-dodecalactone |
| CN103044374B (en) * | 2012-12-26 | 2014-10-29 | 淮安万邦香料工业有限公司 | Synthesis method of delta-dodecalactone |
| CN104910000A (en) * | 2015-05-25 | 2015-09-16 | 张家港市振方化工有限公司 | Preparation method of 2-heptylidene-cyclopentanon |
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| CN101654404B (en) | 2012-10-31 |
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