CN101654404B - Method for producing 2-alkylidene cyclopentanone - Google Patents
Method for producing 2-alkylidene cyclopentanone Download PDFInfo
- Publication number
- CN101654404B CN101654404B CN2009100706907A CN200910070690A CN101654404B CN 101654404 B CN101654404 B CN 101654404B CN 2009100706907 A CN2009100706907 A CN 2009100706907A CN 200910070690 A CN200910070690 A CN 200910070690A CN 101654404 B CN101654404 B CN 101654404B
- Authority
- CN
- China
- Prior art keywords
- ketopentamethylene
- exchange resin
- alkanoic
- weak
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 which can 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 achieves the 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 midbody; 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 ketopentamethylene.
[background technology]
The condensation reaction of aldehydes and ketone is the reaction commonly used that increases carbochain, can form many new compounds, is one type of very important organic synthesis.Synthetic many spices (for example methyl dihydrojasmonate, delta-lactone) important intermediate---2-alkylidene group ketopentamethylene is that raw material obtains through condensation reaction with alkanoic and ketopentamethylene:
2-alkylidene group ketopentamethylene is in its traditional synthesis technique, and the condensation reaction of alkanoic and ketopentamethylene is in the presence of liquid acid or alkaline catalysts, to carry out.This catalystsystem 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, and causes 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 and to utilize 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]
The object of the invention is intended to overcome the problem that traditional technology exists, and a kind of method of environmentally friendly production 2-alkylidene group ketopentamethylene 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 realizing above-mentioned purpose, the invention discloses a kind of method of environmentally friendly production 2-alkylidene group ketopentamethylene, it is characterized in that may further comprise the steps:
(1) ketopentamethylene, alkanoic, weak-base ion-exchange resin, lipid acid and water are mixed in reactor drum, under 25～90 ℃ of temperature, react, complete until the alkanoic primitive reaction; The mol ratio of said ketopentamethylene and alkanoic is 1～15: 1; The proportioning of said 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 said lipid acid and alkanoic is 0.01～2: 1, and the volume ratio of said 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, 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 ketopentamethylene 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 ketopentamethylene.
The present invention is a kind of method of environmentally friendly production 2-alkylidene group ketopentamethylene, 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 ketopentamethylene, this method is taken into account resources conservation and environment protection simultaneously.
The present invention and catalyzer be difficult to recycling use, produce more almost do not have utility value high boiling point by-products produced with great amount of wastewater, 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 ketopentamethylene and acetaldehyde, propionic aldehyde reaction Synthetic 2-ethylidene ketopentamethylene (claim not only 2-ethene (base) ketopentamethylene), 2-propylidene ketopentamethylene (but also claiming 2-propylene (base) ketopentamethylene).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 ketopentamethylene that Fig. 1 makes for the present invention.
[embodiment]
The method of environmentally friendly production 2-alkylidene group ketopentamethylene of the present invention.Mainly may further comprise the steps:
(1) a certain amount of ketopentamethylene, alkanoic, weak-base ion-exchange resin, lipid acid and water are mixed in reactor drum, 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, spinning goes out the resin phase, water and organic phase because of natural layering for about two separate mutually;
(3) oil phase (organic phase) that step (2) is obtained adopts underpressure distillation to slough the light constituent that contains unreacted ketopentamethylene 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 ketopentamethylene.
Hybrid mode in the said step (1) in reactor drum can be: under the room temperature ketopentamethylene, alkanoic, weak-base ion-exchange resin, lipid acid and water dropped in the reactor drum and mixes, be warming up to temperature of reaction then after, progressively add alkanoic again.Or:
Earlier ketopentamethylene, weak-base ion-exchange resin, lipid acid and water are put into reactor drum, be warming up to temperature of reaction after, drip alkanoic.Or:
Earlier ketopentamethylene, alkanoic are dropped into reactor drum, 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 drum, be warming up to temperature of reaction then after, add the mixture of ketopentamethylene and alkanoic simultaneously.Or:
Earlier weak-base ion-exchange resin, lipid acid and water are put into reactor drum, be warming up to temperature of reaction then after, add ketopentamethylene successively, alkanoic.Or:
Earlier ketopentamethylene is put into reactor drum, 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 said 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 said 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 said step (1) is meant butyraldehyde, valeral, hexanal, enanthaldehyde, octanal or their two or more mixtures.
The mol ratio of ketopentamethylene according to the 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 said lipid acid and alkanoic is preferably: lipid acid: alkanoic=0.05～1: 1 (mol/mol).The volume ratio of said water and weak-base ion-exchange resin is preferably 0.1～2: 1.
Reactor drum 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 ketopentamethylene may further comprise the steps for 1 one kinds:
(1) under the room temperature with mixing in the disposable input reactor drum of a certain amount of ketopentamethylene, 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) from the reaction mixture that step (1) obtains, isolate resin, water layer (phase) and oil phase (organic phase), 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 ketopentamethylene 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 ketopentamethylene.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylidene group ketopentamethylene may further comprise the steps for 2 one kinds:
(1) earlier with the disposable reactor drum of putting into of ketopentamethylene, 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) from the reaction mixture that step (1) obtains, isolate resin, water layer (phase) and oil phase (organic phase), 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 ketopentamethylene 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 ketopentamethylene.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylidene group ketopentamethylene may further comprise the steps for 3 one kinds:
(1) earlier a certain amount of ketopentamethylene, alkanoic are dropped into reactor drum, 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) from the reaction mixture that step (1) obtains, isolate resin, water layer (phase) and oil phase (organic phase), 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 ketopentamethylene 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 ketopentamethylene.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylidene group ketopentamethylene may further comprise the steps for 4 one kinds:
(1) earlier with the disposable reactor drum of putting into of weak-base ion-exchange resin, lipid acid and water, be warming up to 80 ℃ then after, add the mixture of ketopentamethylene and alkanoic, maintain and continue under this temperature to react, complete until the alkanoic primitive reaction;
(2) from the reaction mixture that step (1) obtains, isolate resin, water layer (phase) and oil phase (organic phase), 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 ketopentamethylene 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 ketopentamethylene.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylidene group ketopentamethylene may further comprise the steps for 5 one kinds:
(1) earlier with the disposable reactor drum of putting into of weak-base ion-exchange resin, lipid acid and water, be warming up to 90 ℃ then after, add ketopentamethylene successively, alkanoic maintains and continues reaction under this temperature, and is complete until the alkanoic primitive reaction;
(2) from the reaction mixture that step (1) obtains, isolate resin, water layer (phase) and oil phase (organic phase), 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 ketopentamethylene 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 ketopentamethylene.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylidene group ketopentamethylene may further comprise the steps for 6 one kinds:
(1) earlier ketopentamethylene is put into reactor drum, 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) from the reaction mixture that step (1) obtains, isolate resin, water layer (phase) and oil phase (organic phase), 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 ketopentamethylene 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 ketopentamethylene.
Embodiment 7: at room temperature; 100 gram ketopentamethylene, 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 drum that stirring, TM 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 ketopentamethylene (claiming 2-amylene (base) ketopentamethylene again, 2-pentylidene basic ring pentanone) is 88.2 (area) %.
Embodiment 8: earlier 100 gram ketopentamethylene, 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 drum that is equipped with TM, whisking appliance, tap 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 ketopentamethylene and valeric acid to oil phase, further rectification under vacuum is refining then, collects the cut of 80～85 ℃/100Pa; Obtain about 17.5 gram 2-pentylidene ketopentamethylene and (claim 2-amylene (base) ketopentamethylene 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 ketopentamethylene that traditional soda solution grouting obtains.See shown in Figure 1.
Embodiment 9: in the reactor drum that stirring, TM, tap funnel and reflux condensing tube are installed, add 100 gram ketopentamethylene and 40 gram valeraldehydes 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 ketopentamethylene (claiming 2-amylene (base) ketopentamethylene again, 2-pentylidene basic ring pentanone) is 85.5 (area) %.
Embodiment 10: in the reactor drum that is equipped with TM, whisking appliance, tap 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 drum of putting into of 50mL water; Then behind the heat temperature raising to 90 ℃; Add the mixture of 100 gram ketopentamethylene and 30 gram valeraldehydes, react after 2 hours, the chromatogram content (deducting unreacted raw material) that records 2-pentylidene ketopentamethylene in the reaction solution is 77.5 (area) %.
Embodiment 11: in the reactor drum that whisking appliance, TM, tap funnel and reflux condensing tube are housed; Put into ring 100 gram ketopentamethylene earlier, be warming up to 70 ℃ after, 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 ketopentamethylene in the reaction solution is 38.5 (area) %.
Embodiment 12: in the reactor drum that is equipped with whisking appliance, TM, tap funnel and reflux exchanger, add 100 gram ketopentamethylene, 40mL (wet heap volume) D382 weak-base ion-exchange resin, 4 gram enanthic acid and 40mL water 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 ketopentamethylene and enanthic acid; Further underpressure distillation then; Collect the cut of 100～110 ℃/100Pa; Obtaining inferior fleuramone (claiming 2-heptene (base) ketopentamethylene 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 ketopentamethylene that traditional soda solution grouting obtains.
Embodiment 13: in the reactor drum that is equipped with whisking appliance, TM, tap funnel and reflux exchanger, put into 100 gram ketopentamethylene, 40mL (wet heap volume) D382 weak-base ion-exchange resin (secondary amine type), 10 restrain oneself acid and 40mL water; 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 ketopentamethylene (claiming 2 amylenes (base) ketopentamethylene again, 2-pentylidene basic ring pentanone) is 85.5 (area) %.
Embodiment 14: in the reactor drum that stirring, TM, tap funnel and reflux condensing tube are installed, add 100 gram ketopentamethylene and 25 gram n-hexyl aldehydes 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 refluxed several 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 ketopentamethylene and caproic acid; 116～120 ℃/1995Pa cut is collected in further underpressure distillation then, obtains about 42.1 gram 2-hexylidene ketopentamethylene 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 ketopentamethylene that traditional soda solution grouting obtains.
Embodiment 15: earlier 100 gram ketopentamethylene, 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 drum that is equipped with TM, whisking appliance, tap 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 ketopentamethylene 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 ketopentamethylene (claiming 2-butylene (base) ketopentamethylene 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 ketopentamethylene that traditional soda solution grouting obtains.
Embodiment 16: in the reactor drum that is equipped with whisking appliance, TM, tap funnel and reflux exchanger, add 100 gram ketopentamethylene, 40mL (wet heap volume) D382 weak-base ion-exchange resin (secondary amine type), 4 gram acetic acid and 40mL water 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 ketopentamethylene of product 2-(claiming 2-octene (base) ketopentamethylene again) is 85.5 (area) %.
Embodiment 17: in the reactor drum that whisking appliance, TM, tap funnel and reflux exchanger are installed, add 100 gram ketopentamethylene, 40mL (wet heap volume) D380 weak-base ion-exchange resin (primary amine type), 4 gram acetic acid and 5mL water 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 ketopentamethylene (claiming 2-amylene (base) ketopentamethylene again, 2-pentylidene basic ring pentanone) is 86.9 (area) %.
Embodiment 18: earlier 100 gram ketopentamethylene, 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 drum that TM, whisking appliance, tap 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 ketopentamethylene (claiming 2-amylene (base) ketopentamethylene again, 2-pentylidene basic ring pentanone) is 60.1 (area) %.
Claims (7)
1. method of producing 2-alkylidene group ketopentamethylene is characterized in that may further comprise the steps:
(1) ketopentamethylene, alkanoic, weak-base ion-exchange resin, lipid acid and water are mixed in reactor drum, under 25～90 ℃ of temperature, react, complete until the alkanoic primitive reaction; The mol ratio of said ketopentamethylene and alkanoic is 1～15: 1; The proportioning of said 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 said lipid acid and alkanoic is 0.01～2: 1, and the volume ratio of said 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 ketopentamethylene 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 ketopentamethylene;
In the step (1), said weak-base ion-exchange resin is a primary amine type ion exchange resin, secondary amine type ion exchange resin or tertiary amine-type ion exchange resin; Said lipid acid is acetic acid, propionic acid, butyric acid, valeric acid, caproic acid or enanthic acid; Said alkanoic is a butyraldehyde, valeral, hexanal, enanthaldehyde or octanal.
2. according to the described method of claim 1; It is characterized in that the hybrid mode in reactor drum is in the said step (1): earlier ketopentamethylene, weak-base ion-exchange resin, lipid acid and water are put into reactor drum; After being warming up to temperature of reaction, progressively add alkanoic again.
3. according to the described method of claim 1; It is characterized in that the hybrid mode in reactor drum is in the said step (1): earlier weak-base ion-exchange resin, lipid acid and water are put into reactor drum; After being warming up to temperature of reaction then, more simultaneously or add ketopentamethylene and alkanoic successively.
4. according to the described method of claim 1; It is characterized in that the hybrid mode in reactor drum is in the said step (1): earlier ketopentamethylene is put into reactor drum; 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.
5. according to the described method of claim 1, it is characterized in that the proportioning of said weak-base ion-exchange resin and alkanoic is: the wet heap of 1～20mL volume weak-base ion-exchange resin/every gram alkanoic.
6. according to the described method of claim 1, the mol ratio that it is characterized in that said lipid acid and alkanoic is 0.05～1: 1.
7. according to the described method of claim 1, the volume ratio that it is characterized in that said water and weak-base ion-exchange resin is 0.1～2: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100706907A CN101654404B (en) | 2009-09-29 | 2009-09-29 | Method for producing 2-alkylidene cyclopentanone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100706907A CN101654404B (en) | 2009-09-29 | 2009-09-29 | Method for producing 2-alkylidene cyclopentanone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101654404A CN101654404A (en) | 2010-02-24 |
| CN101654404B true CN101654404B (en) | 2012-10-31 |
Family
ID=41708891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100706907A Active CN101654404B (en) | 2009-09-29 | 2009-09-29 | Method for producing 2-alkylidene cyclopentanone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101654404B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851154B (en) * | 2010-05-18 | 2013-01-16 | 天津理工大学 | Improved method for producing 2-alkylene alicyclic ketone |
| CN102503791B (en) * | 2011-11-25 | 2014-01-15 | 天津理工大学 | Method for producing 2-alkylene grease cyclic ketone by adopting bionic catalytic system |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3158644A (en) * | 1960-02-25 | 1964-11-24 | Firmenich & Cie | Alicyclic ketoesters and process for their manufacture |
| CN1421429A (en) * | 2001-11-30 | 2003-06-04 | 高砂香料工业株式会社 | Process for producing 2-alkyl-2-cyclopentenone |
| CN1511818A (en) * | 2002-12-26 | 2004-07-14 | ������������ʽ���� | Process for preparing 2-(alkyl) cyclic ketone |
-
2009
- 2009-09-29 CN CN2009100706907A patent/CN101654404B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3158644A (en) * | 1960-02-25 | 1964-11-24 | Firmenich & Cie | Alicyclic ketoesters and process for their manufacture |
| CN1421429A (en) * | 2001-11-30 | 2003-06-04 | 高砂香料工业株式会社 | Process for producing 2-alkyl-2-cyclopentenone |
| CN1511818A (en) * | 2002-12-26 | 2004-07-14 | ������������ʽ���� | Process for preparing 2-(alkyl) cyclic ketone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101654404A (en) | 2010-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8721842B2 (en) | Catalytic reaction-rectification integrated process and specialized device thereof | |
| CN1077093C (en) | Preparation of polyalcohols | |
| CN101654404B (en) | Method for producing 2-alkylidene cyclopentanone | |
| CN104876795A (en) | Synthesis of guerbet alcohols | |
| CN101337884A (en) | Method for preparing 2-Butoxyethyl acetate by continuous esterification reaction | |
| CN104045554A (en) | Method for preparing ethylene glycol diacetate | |
| CN105061167A (en) | Method for preparing hydroxy neovaleraldehyde by condensing formaldehyde and isobutyraldehyde | |
| JP5800554B2 (en) | Method for producing C1-C4 alkyl nitrite | |
| CN101085711B (en) | Method for synthesizing ethyl benzene and diethyl benzene | |
| CN101851154B (en) | Improved method for producing 2-alkylene alicyclic ketone | |
| CN1140530C (en) | Method for removing dissolved silicate from solvent directly synthesized from alcohol-silicon | |
| CN101157603A (en) | Environment-friendly method for synthesizing acetylacetone | |
| CN101423528B (en) | Method for preparing mercaptoalkyl alkoxy silane | |
| CN102408430A (en) | Synthetic process and special equipment for substituted bis [tetraphenylporphinatoiron] | |
| CN103539214B (en) | Method for treating organic wastewater generated in preparing ethylene through ethanol dehydration | |
| CN102093180A (en) | Method for continuously producing unsaturated aldehyde compound | |
| CN101985419A (en) | Method for preparing ethylene glycol ethyl ether acetate | |
| CN105032473B (en) | A kind of method using the sulfuric acid modified catalyst preparation dialkoxy methanes for the treatment of nanoscale HZSM 5 | |
| CN101434539B (en) | Preparation of benzyl acetate | |
| CN102285883B (en) | Method for synthesizing tributyl citrate (TBC) by adopting composite ionic liquid catalyst | |
| CN101186566B (en) | Method for preparing acetylacetone by using D301 type alkalescent anion exchange resin as catalyst | |
| CN204342703U (en) | The reaction and rectification device of low pressure oxo process butyraldehyde | |
| CN103420752A (en) | Separation refinement method for ethylene preparation through biomass ethanol dehydration | |
| CN102604099A (en) | Method for effectively processing industrial waste n-propyl trifunctional silane | |
| CN102503791B (en) | Method for producing 2-alkylene grease cyclic ketone by adopting bionic catalytic system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160202 Address after: 300382 Tianjin city Xiqing District Jingwu Town Industrial Zone Patentee after: Tianjin Ankaite Catalyst Co.,Ltd. Address before: Jin Lai highway Nanhe Industrial Park 300382 Tianjin District of Xiqing City Patentee before: Tianjin Kai Ao Biological Products Co., Ltd. |
|
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 300382 Tianjin city Xiqing District Jingwu Town Industrial Zone Patentee after: Tianjin ankaite Technology Development Co. Ltd. Address before: 300382 Tianjin city Xiqing District Jingwu Town Industrial Zone Patentee before: Tianjin Ankaite Catalyst Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220608 Address after: 475500 north side of middle section of Haoyue Avenue, Zhuangtou, Weishi County, Kaifeng City, Henan Province Patentee after: HENAN WEI YUAN BIOTECHNOLOGY CO.,LTD. Address before: 300382 Industrial Zone, Jingwu Town, Xiqing District, Tianjin Patentee before: TIANJIN ANKAITE TECHNOLOGY DEVELOPMENT Co.,Ltd. |