CN101851154A - Improved method for producing 2-alkylene alicyclic ketone - Google Patents
Improved method for producing 2-alkylene alicyclic ketone Download PDFInfo
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Abstract
The invention discloses an improved method for producing 2-alkylene alicyclic ketone. In the method, alicyclic ketone and aliphatic aldehyde are used as raw materials, and the reaction of amine type alkalescent ion exchange resin in the presence of an acid compound and metal ions is utilized to generate the 2-alkylene alicyclic ketone. After an organic phase is separated out, a catalyst system can be recycled. The 2-alkylene alicyclic ketone is an important intermediate for synthesizing a plurality of spices (such as methyl dihydrojasmonate and delta-lactone). The method gets rid of a traditional unrecoverable solution catalysis system, replaces the traditional unrecoverable solution catalysis system by a recoverable and recyclable catalysis system, reconstructs an original process by a clean production technology and also realizes the saving and the sufficient utilization of resources and environmental protection.
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-alkylene alicyclic ketone.
[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---the 2-alkylene alicyclic ketone is that raw material obtains through condensation reaction with alkanoic and alicyclic ketone:
R: alkyl
The structural representation of the structural representation 2-alkylidene group cyclopentanone of 2-alkylidene group cyclobutanone
The structural representation of 2-alkylidene group pimelinketone
The 2-alkylene alicyclic ketone is in its traditional synthesis technique, and the condensation reaction of alkanoic and alicyclic ketone 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.For this reason, we had once invented and have utilized the alternative traditional restored acid alkaline solution catalyzer that is difficult to of recyclable round-robin catalyst system to come catalysis aldehyde ketone condensation reaction (referring to CN 101654404A).
In the disclosed technology of this patent application, successfully realized having substituted the traditional technology that produces a large amount of environmental pollutions, and stopped high boiling point by-products produced generation substantially with recyclable round-robin catalyst system.But still the formation speed that exists principal product is slow, the shortcoming of the easy autohemagglutination of alkanoic, therefore is necessary this technology is further improved.
In continuing research, we find to add some metal ions in above-mentioned catalyst system, can reduce the autohemagglutination of aldehyde, accelerate the formation speed of product, further improve the selectivity and the yield of reaction.Based on this, the present patent application is proposed.
[summary of the invention]
Purpose of the present invention aims to provide the method for the production 2-alkylene alicyclic ketone of a kind of selectivity of further raising reaction and yield.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, in catalyst system, add simultaneously metal ion, can reduce the autohemagglutination of aldehyde, accelerate the formation speed of product, further improve the selectivity and the yield of reaction.
For achieving the above object, the invention discloses a kind of method of environmentally friendly production 2-alkylene alicyclic ketone, it is characterized in that may further comprise the steps:
(1) alicyclic ketone, alkanoic, weak-base ion-exchange resin, acid (property compound) and the aqueous solution of metal ion are mixed in reactor, under 25～90 ℃ of temperature, react, complete until the alkanoic primitive reaction; The mol ratio of described alicyclic ketone 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 acidic cpd and alkanoic is 0.01～10: 1, the volume ratio of described water and weak-base ion-exchange resin is 0.1～3: 1, and the mol ratio of described metal ion and alkanoic is 0.01～20: 100;
(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 lighting end that contains unreacted alicyclic ketone and some low boilers, and this lighting end can be recycled;
(4) send to according to the index of desired product to remove the product that obtains after the lighting end through step (3) that to carry out further rectification under vacuum refining, obtain qualified 2-alkylene alicyclic ketone.
The present invention is a kind of method of environmentally friendly production 2-alkylene alicyclic ketone, 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 the 2-alkylene alicyclic ketone, this method is taken into account resources conservation and environment protection simultaneously.
Catalyst system is renewable to be recycled except still keeping in the present invention, produce the high boiling point by-products produced and waste water of no utility value hardly, compliance with environmental protection requirements, be outside a kind of characteristics of environmentally friendly production technique, after adding metal ion, reduced the by product of aldehyde autohemagglutination, thereby improved the selectivity and the yield of principal product, and the formation speed of principal product also increased, and so just utilized raw material resources more fully and reduced energy dissipation.
This technology also can be applicable to the condensation reaction of cyclobutanone and alkanoic, and cyclobutanone or cyclopentanone or pimelinketone and lower aliphatic aldehyde, for example in the production of 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) etc.
[description of drawings]
The mass spectrum of the 2-pentylidene cyclopentanone that Fig. 1 the present invention makes;
The mass spectrum of the 2-butylidene pimelinketone that Fig. 2 the present invention makes.
[embodiment]
The method of environmentally friendly production 2-alkylene alicyclic ketone of the present invention.Mainly may further comprise the steps:
(1) a certain amount of alicyclic ketone, alkanoic, weak-base ion-exchange resin, acid (property compound) and the metal ion aqueous solution 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 lighting end that contains unreacted alicyclic ketone and some low boilers, and this lighting end can be recycled;
(4) remove the product that obtains after the lighting end 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-alkylene alicyclic ketone.
Hybrid mode in the described step (1) in reactor can be: with mixing in alicyclic ketone, alkanoic, weak-base ion-exchange resin, acid (property compound) and the metal ion aqueous solution input reactor, be warming up to temperature of reaction then under the room temperature.Or:
Earlier alicyclic ketone, weak-base ion-exchange resin, acid (property compound) and the metal ion aqueous solution are put into reactor, be warming up to temperature of reaction after, progressively add the mixture of alkanoic or itself and alicyclic ketone again.Or:
Earlier alicyclic ketone, alkanoic are dropped into reactor, be warming up to the mixture that adds weak-base ion-exchange resin, acid (property compound) and the metal ion aqueous solution after the temperature of reaction.Or:
Earlier weak-base ion-exchange resin, acid (property compound) and the metal ion aqueous solution are put into reactor, be warming up to temperature of reaction then after, add the mixture of alicyclic ketone and alkanoic simultaneously.Or:
Earlier weak-base ion-exchange resin, acid (property compound) and the metal ion aqueous solution are put into reactor, be warming up to temperature of reaction then after, add alicyclic ketone successively, alkanoic.Or:
Earlier alicyclic ketone is put into reactor, be warming up to temperature of reaction after, add the mixture of weak-base ion-exchange resin, acid (property compound) and the metal ion aqueous solution more successively, the last mixture that in batches adds alkanoic or itself and alicyclic ketone.
Alicyclic ketone in the described step (1) is meant cyclobutanone, cyclopentanone, pimelinketone, or their mixture.
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.
Acid in the described step (1) (property compound) is meant mineral acid or organic acid.Mineral acid is meant hydrochloric acid, sulfuric acid, phosphoric acid, or their two or more mixtures; Organic acid is meant acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, or their two or more mixtures.
Metal ion in the described step (1) is meant Fe
2+, Fe
3+, Ca
2+, Mg
2+, Mn
2+, Co
2+, Cu
2+, Ni
2+, Zn
2+, Se
4+, Sn
2+, Sn
4+, Mo
3+, Mo
5+, Li
+, Ti
4+, or their two or more mixtures; Described metal ion adds in the entry with the form of soluble salt.
Alkanoic in the described step (1) is meant butyraldehyde, valeral, hexanal, enanthaldehyde, octanal or their two or more mixtures.
The mol ratio of alicyclic ketone 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 1～50mL (wet heap volume) resin.Described acid (property compound) is preferably with the mol ratio of alkanoic: acid (property compound): alkanoic=0.01～8: 1 (mol/mol).The volume ratio of described water and weak-base ion-exchange resin is preferably 0.1～2: 1.The mol ratio of described metal ion and alkanoic is preferably 0.01～15: 100.
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-alkylene alicyclic ketone may further comprise the steps for 1 one kinds:
(1) will mix in a certain amount of alicyclic ketone, alkanoic, weak-base ion-exchange resin, acid (property compound) and the disposable input reactor of the metal ion aqueous solution under the room temperature, 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 lighting end that contains unreacted alicyclic ketone and some low boilers, and this lighting end can be recycled;
(4) remove the product that obtains after the lighting end 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-alkylene alicyclic ketone.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylene alicyclic ketone may further comprise the steps for 2 one kinds:
(1) earlier with alicyclic ketone, weak-base ion-exchange resin, acid (property compound) and the disposable reactor of putting into of the metal ion aqueous solution, after being warming up to 50 ℃, 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 lighting end that contains unreacted alicyclic ketone and low boilers, and this lighting end can be recycled;
(4) remove the product that obtains after the lighting end 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-alkylene alicyclic ketone.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylene alicyclic ketone may further comprise the steps for 3 one kinds:
(1) earlier a certain amount of alicyclic ketone, alkanoic are dropped into reactor, be warming up to the mixture that drops into weak-base ion-exchange resin, acid (property compound) and the metal ion aqueous solution 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 lighting end that contains unreacted alicyclic ketone and low boilers, and this lighting end can be recycled;
(4) remove the product that obtains after the lighting end 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-alkylene alicyclic ketone.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylene alicyclic ketone may further comprise the steps for 4 one kinds:
(1) earlier with weak-base ion-exchange resin, acid (property compound) and the disposable reactor of putting into of the metal ion aqueous solution, after being warming up to 80 ℃ then, the mixture that adds alicyclic ketone and 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 lighting end that contains unreacted alicyclic ketone and low boilers, and this lighting end can be recycled;
(4) remove the product that obtains after the lighting end 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-alkylene alicyclic ketone.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylene alicyclic ketone may further comprise the steps for 5 one kinds:
(1) earlier with weak-base ion-exchange resin, acid (property compound) and the disposable reactor of putting into of the metal ion aqueous solution, after being warming up to 90 ℃ then, add alicyclic ketone successively, 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 lighting end that contains unreacted alicyclic ketone and low boilers, and this lighting end can be recycled;
(4) remove the product that obtains after the lighting end 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-alkylene alicyclic ketone.
Embodiment adopts the method for cleaning technique Synthetic 2-alkylene alicyclic ketone may further comprise the steps for 6 one kinds:
(1) earlier alicyclic ketone is put into reactor, be warming up to 25 ℃ after, add the mixture of weak-base ion-exchange resin, acid (property compound) and the metal ion aqueous solution 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 lighting end that contains unreacted alicyclic ketone and low boilers, and this lighting end can be recycled;
(4) remove the product that obtains after the lighting end 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-alkylene alicyclic ketone.
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, 0.01 gram neutralized verdigris and 20mL water put in the reactor that stirring, thermometer and reflux condensing tube are installed mix, 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 5 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 91.7 (area) %.
Simultaneously, except not adding the neutralized verdigris and be the contrast experiment under all identical situation of other reaction conditions, 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, 2 gram manganous nitrates 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 three hours, 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), oil phase is adopted underpressure distillation.At first slough the lighting end (following secondary response is applied mechanically) that contains unreacted cyclopentanone and valeric acid, further rectification under vacuum is refining then, collect the cut of 80～85 ℃/100Pa, obtain about 17.8 gram 2-pentylidene cyclopentanone and (claim 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) content is 87.2% product, about 88% (in the aldehyde) of yield.
Simultaneously, except not adding the manganous nitrate and be the contrast experiment, about 85% (in the aldehyde) of yield of product 2-pentylidene cyclopentanone (claiming 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) under all identical situation of other reaction conditions.
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, 12 gram zinc chloride and 40mL water after 80 ℃, continue heated and stirred after 6 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 90.5 (area) %.
Simultaneously, except not adding the zinc chloride and be the contrast experiment under all identical situation of other reaction conditions, 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 phosphoric acid, 5 gram nickelous nitrate and the disposable reactors 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 78.1 (area) %.
Simultaneously, except not adding the nickelous nitrate and be the contrast experiment under all identical situation of other reaction conditions, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) is 71.5 (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 sulfuric acid, 10 gram ferrous sulfate and 50mL water successively, drip 100 gram valeraldehydes at last, finished in 1 hour, behind the constant temperature stirring reaction 2 hours, the chromatogram content (deducting unreacted raw material) that records 2-pentylidene cyclopentanone in the reaction solution is 50.3 (area) %.
Simultaneously, except not adding the ferrous sulfate and be the contrast experiment under all identical situation of other reaction conditions, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) is 38.5 (area) %.
Embodiment 12: add 100 gram cyclopentanone, 40mL (wet heap volume) D382 weak-base ion-exchange resin, 4 gram enanthic acid, 5 gram iron trichloride and 40mL water in the reactor that is equipped with agitator, thermometer, dropping funnel and reflux exchanger earlier, behind the heat temperature raising to 60 ℃, under agitation drip 25 gram enanthaldehydes, the dropping time is no less than 0.5h, dropwise the back and keep 60 ℃ 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 37.5 gram 2-is 88% product, yield 83.7% (in aldehyde).
Simultaneously, except not adding iron trichloride, and temperature of reaction be 70 ℃ outer and be the contrast experiment under the situation that other reaction conditions is all identical, the yield of the inferior fleuramone of product 2-(claiming 2-heptene (base) cyclopentanone again) is 82.4% (in aldehyde) %.
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, 0.1 gram cobaltous acetate 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 6 hours, 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-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) is 92.1 (area) %.
Simultaneously, except not adding the cobaltous acetate and be the contrast experiment under all identical situation of other reaction conditions, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) is 86.5 (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, 0.2 gram titanium tetrachloride 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, further underpressure distillation then, collect 116～120 ℃/1995Pa cut, obtain about 42.5 gram 2-hexylidene cyclopentanone content and be 85% product, about 87.1% (in the aldehyde) of yield.
Simultaneously, except not adding the titanium tetrachloride and be the contrast experiment under all identical situation of other reaction conditions, the yield of product 2-hexylidene cyclopentanone is about 85% (in aldehyde) %.
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 85 gram cyclopentanone, 40mL (wet heap volume) D382 weak-base ion-exchange resin (secondary amine type), 2 gram butyric acid, 1 gram tin protochloride 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 the mixed solution of 15 gram butyraldehyde-ns and 15 gram cyclopentanone, in 6 hours, 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 29.1 gram 2-butylidene cyclopentanone (claiming 2-butylene (base) cyclopentanone again) content is the product of 84 (area) %.About 85% (in the aldehyde) of productive rate.
Simultaneously, except not adding the tin protochloride and be the contrast experiment under all identical situation of other reaction conditions, the yield of product 2-butylidene cyclopentanone (claiming 2-butylene (base) cyclopentanone again) is about 82% (in aldehyde) %.
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 80 gram cyclopentanone, 40mL (wet heap volume) D382 weak-base ion-exchange resin (secondary amine type), 4 gram acetic acid, 1 gram lithium acetate 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 the mixing solutions of 20 gram n-octaldehydes and 20 gram cyclopentanone, in 2 hours, 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 88.7 (area) %.
Simultaneously, except not adding the lithium acetate and be the contrast experiment under all identical situation of other reaction conditions, 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, 1 gram hydrochloric acid, 0.5 gram tin tetrachloride 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 70 ℃ 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 89.6 (area) %.
Simultaneously, except not adding the tin tetrachloride and be the contrast experiment under all identical situation of other reaction conditions, 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, 6.5 gram magnesium chlorides and 20mL 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 72.3 (area) %.
Simultaneously, except not adding the magnesium chloride and be the contrast experiment under all identical situation of other reaction conditions, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) is 63.1 (area) %.
Embodiment 19: earlier 100 gram cyclopentanone, 100mL (wet heap volume) D301T weak-base ion-exchange resin (tertiary amine-type), 5 gram acetic acid, 0.1 gram molybdic chloride and 20mL 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 15 gram valeraldehydes in batches.Maintain 90 ℃ 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 80.2 (area) %.
Simultaneously, except not adding the molybdic chloride and be the contrast experiment under all identical situation of other reaction conditions, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) is 75.2 (area) %.
Embodiment 20: earlier 100 gram cyclopentanone, 40mL (wet heap volume) D382 weak-base ion-exchange resin (secondary amine type), 10 gram acetic acid, 0.01 gram molybdenum pentachloride and 20mL water are put into the reactor that thermometer, agitator, dropping funnel and reflux condensing tube are housed, behind the heat temperature raising to 60 ℃, under agitation add 30 gram valeraldehydes in batches.Maintain 60 ℃ and continue reaction down after 6 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 82.5 (area) %.
Simultaneously, except not adding the molybdenum pentachloride and be the contrast experiment under all identical situation of other reaction conditions, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) is 65.7 (area) %.
Embodiment 21: earlier 100 gram cyclopentanone, 40mL (wet heap volume) D380 weak-base ion-exchange resin (primary amine type), 1 gram acetic acid, 5 gram selenic chlorides and 20mL water are put into the reactor that thermometer, agitator, dropping funnel and reflux condensing tube are housed, behind the heat temperature raising to 40 ℃, under agitation add 30 gram valeraldehydes in batches.Maintain 60 ℃ and continue reaction down after 10 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 86.8 (area) %.
Simultaneously, except not adding the selenic chloride and be the contrast experiment under all identical situation of other reaction conditions, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming 2-amylene (base) cyclopentanone again, 2-pentylidene basic ring pentanone) is 79.1 (area) %.
Embodiment 22: earlier 40mL (wet heap volume) D380 weak-base ion-exchange resin (primary amine type), 1 gram valeric acid, 5 gram titanium tetrachlorides and 20mL water are put into the reactor that thermometer, agitator, dropping funnel and reflux condensing tube are housed, behind the heat temperature raising to 50 ℃, under agitation add 10 gram butyraldehyde-ns and 30 gram pimelinketone mixing solutionss in batches.Maintain 50 ℃ and continue reaction down after 10 hours, the chromatogram content (deducting unreacted raw material) of product 2-butylidene pimelinketone (claiming 2-butylene (base) pimelinketone again, 2-fourth fork basic ring hexanone) is 84.7 (area) %.Detect through GS-MS (application of gas chromatorgraphy/mass), the molecular weight of products obtained therefrom is 152, and its mass spectrum is seen Fig. 2.
Embodiment 23: earlier 30 gram cyclobutanones and 10 gram valeraldehydes are put into the reactor that thermometer, agitator, dropping funnel and reflux condensing tube are housed, drop into 20mL (wet heap volume) D382 weak-base ion-exchange resin (secondary amine type), 1 gram butyric acid, 5.5 gram nitrocalcite and 20mL water behind the heat temperature raising to 90 ℃.Maintain 90 ℃ and continue reaction down after 3 hours, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclobutanone (claiming 2-amylene (base) cyclobutanone again, 2-pentylidene basic ring butanone) is 83.6 (area) %.Detect through GS-MS (application of gas chromatorgraphy/mass), the molecular weight of products obtained therefrom is 138.
Claims (10)
1. the method for an improved production 2-alkylene alicyclic ketone is characterized in that may further comprise the steps:
(1) aqueous solution with alicyclic ketone, alkanoic, weak-base ion-exchange resin, acidic cpd and metal ion mixes in reactor, reacts under 25～90 ℃ of temperature, and is complete until the alkanoic primitive reaction; The mol ratio of described alicyclic ketone 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 acidic cpd and alkanoic is 0.01～10: 1, the volume ratio of described water and weak-base ion-exchange resin is 0.1～3: 1, and the mol ratio of described metal ion and alkanoic is 0.01～20: 100;
(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 lighting end that contains unreacted alicyclic ketone and some low boilers;
(4) to carry out further rectification under vacuum refining to remove the product that obtains after the lighting end through step (3), obtains qualified 2-alkylene alicyclic ketone.
2. in accordance with the method for claim 1, it is characterized in that the hybrid mode in reactor is in the described step (1): earlier the aqueous solution of alicyclic ketone, weak-base ion-exchange resin, acidic cpd and metal ion is put into reactor, after being warming up to temperature of reaction, progressively add the mixture of alkanoic or itself and alicyclic ketone again.
3. in accordance with the method for claim 1, it is characterized in that the hybrid mode in reactor is in the described step (1): earlier the aqueous solution of weak-base ion-exchange resin, acidic cpd and metal ion is put into reactor, after being warming up to temperature of reaction then, more simultaneously or add alicyclic ketone and alkanoic successively.
4. in accordance with the method for claim 1, it is characterized in that the hybrid mode in reactor is in the described step (1): earlier alicyclic ketone is put into reactor, after being warming up to temperature of reaction, the aqueous solution that adds weak-base ion-exchange resin, acidic cpd and metal ion more successively adds at last the mixture of alkanoic or itself and alicyclic ketone in batches.
5. according to claim 1 or the described arbitrary method of 2-4, the mol ratio that it is characterized in that described acidic cpd and alkanoic is 0.01～8: 1.
6. according to claim 1 or the described arbitrary 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.
7. according to claim 1 or the described arbitrary method of 2-4, it is characterized in that alicyclic ketone is meant cyclobutanone, cyclopentanone, pimelinketone, or their mixture in the described step (1).
8. according to claim 1 or the described arbitrary method of 2-4, 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.
9. according to claim 1 or the described arbitrary method of 2-4, it is characterized in that the metal ion in the described step (1) is meant Fe
2+, Fe
3+, Ca
2+, Mg
2+, Mn
2+, Co
2+, Cu
2+, Ni
2+, Zn
2+, Se
4+, Sn
2+, Sn
4+, Mo
3+, Mo
5+, Li
+, Ti
4+, or their two or more mixtures; Described metal ion adds in the entry with the form of soluble salt.
10. according to claim 1 or the described arbitrary method of 2-4, it is characterized in that the acidic cpd in the described step (1) is meant mineral acid or organic acid, mineral acid is meant hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, or their two or more mixtures; Organic acid is meant acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, or their two or more mixtures.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN104892386A (en) * | 2015-05-25 | 2015-09-09 | 张家港市振方化工有限公司 | Synthesis method of 2-heptamethylene cyclopentanone |
| 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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| CN1082026A (en) * | 1993-03-30 | 1994-02-16 | 沈阳药学院 | The 2-[N-substituted amine alkyl]-5-(E)-alkane methylene radical or Ben Yajiaji cyclopentanone derivatives and relevant using method |
| 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 |
| CN101654404A (en) * | 2009-09-29 | 2010-02-24 | 天津市凯奥生物制品有限公司 | Method for producing 2-alkylidene cyclopentanone |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1082026A (en) * | 1993-03-30 | 1994-02-16 | 沈阳药学院 | The 2-[N-substituted amine alkyl]-5-(E)-alkane methylene radical or Ben Yajiaji cyclopentanone derivatives and relevant using method |
| 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 |
| CN101654404A (en) * | 2009-09-29 | 2010-02-24 | 天津市凯奥生物制品有限公司 | Method for producing 2-alkylidene cyclopentanone |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN104892386A (en) * | 2015-05-25 | 2015-09-09 | 张家港市振方化工有限公司 | Synthesis method of 2-heptamethylene cyclopentanone |
| 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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