CN101851154B - Improved method for producing 2-alkylene alicyclic ketone - Google Patents
Improved method for producing 2-alkylene alicyclic ketone Download PDFInfo
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- CN101851154B CN101851154B CN2010101745653A CN201010174565A CN101851154B CN 101851154 B CN101851154 B CN 101851154B CN 2010101745653 A CN2010101745653 A CN 2010101745653A CN 201010174565 A CN201010174565 A CN 201010174565A CN 101851154 B CN101851154 B CN 101851154B
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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 Field of Fine Chemicals of chemical engineering---the preparation of spices intermediate; replace original technique with clearer production technology; realize simultaneously the saving of resource and take full advantage 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 novel compounds, is the very important organic synthesis of a class.The important intermediate of synthetic many spices (for example methyl dihydrojasmonate, delta-lactone)---2-alkylene alicyclic ketone obtains through condensation reaction take alkanoic and alicyclic ketone as raw material:
R: alkyl
The structural representation of the structural representation 2-alkylidene 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 almost high boiling point by-products produced without utility value, 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 loss and the waste of raw material and product, and the waste of the energy that indirectly causes.For this reason, we had once invented the catalyst system that utilizes recyclable circulation and substitute traditional restored acid alkaline solution catalyzer that is difficult to and come catalysis Aldol condensation reaction (referring to CN 101654404A).
In the technology of this Patent Application Publication, successfully realized having substituted the traditional technology that produces a large amount of environmental pollutions with the catalyst system of recyclable circulation, and substantially stopped high boiling point by-products produced generation.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 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 the 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 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, until the alkanoic primitive reaction is complete; 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, the concentrated water (except the water of dereaction generation) of resin-phase and process can be recycled;
(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 hardly and waste water high boiling point by-products produced without utility value, meet environmental requirement, outside a kind of characteristics of environmentally friendly production technique, after adding metal ion, reduced the by product of aldehyde autohemagglutination, thereby improved selectivity and the yield of principal product, and the formation speed of principal product also increased, and so just utilized more fully raw material resources and reduced energy dissipation.
This technique also can be applicable to the condensation reaction of cyclobutanone and alkanoic, and cyclobutanone or cyclopentanone or pimelinketone and lower aliphatic aldehyde, in the production such as the synthetic 2-ethylidene cyclopentanone of acetaldehyde, propionic aldehyde reaction (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, until the alkanoic primitive reaction is complete.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, just can think that primitive reaction is complete if it is generally acknowledged that raw material at least 99% reacts away;
(2) from the reaction mixture that step (1) obtains, isolate resin, water layer (phase) and oil phase (organic phase), the concentrated water (except the water of dereaction generation) of resin-phase and process can be recycled, be to adopt conventional phase detachment technique so-called the separation, for example filter, centrifugation goes out 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, then be warming up to temperature of reaction under the room temperature.Or:
First 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 again the mixture of alkanoic or itself and alicyclic ketone.Or:
First 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:
First weak-base ion-exchange resin, acid (property compound) and the metal ion aqueous solution are put into reactor, then be warming up to temperature of reaction after, add simultaneously the mixture of alicyclic ketone and alkanoic.Or:
First weak-base ion-exchange resin, acid (property compound) and the metal ion aqueous solution are put into reactor, then be warming up to temperature of reaction after, add successively alicyclic ketone, alkanoic.Or:
First alicyclic ketone is put into reactor, be warming up to temperature of reaction after, add successively again the mixture of weak-base ion-exchange resin, acid (property compound) and the metal ion aqueous solution, add the mixture of alkanoic or itself and alicyclic ketone at last in batches.
Alicyclic ketone in the described step (1) refers to cyclobutanone, cyclopentanone, pimelinketone, or their mixture.
Weak-base ion-exchange resin in the described step (1) refers to 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) refers to mineral acid or organic acid.Mineral acid refers to hydrochloric acid, sulfuric acid, phosphoric acid, or their two or more mixtures; Organic acid refers to 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) refers to 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 is added to the water with the form of soluble salt.
Alkanoic in the described step (1) refers to 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 batch reactor, also can be flow reactor.
1 one kinds of methods that adopt cleaning technique to synthesize the 2-alkylene alicyclic ketone of embodiment may further comprise the steps:
(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, then be warming up to 30 ℃, under this temperature, continue reaction, until the alkanoic primitive reaction is complete;
(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 lower batch reaction and use 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.
2 one kinds of methods that adopt cleaning technique to synthesize the 2-alkylene alicyclic ketone of embodiment may further comprise the steps:
(1) first 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, then maintain and continue reaction under this temperature, until the alkanoic primitive reaction is complete;
(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 lower batch reaction and use 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.
3 one kinds of methods that adopt cleaning technique to synthesize the 2-alkylene alicyclic ketone of embodiment may further comprise the steps:
(1) first 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 ℃, then maintain and continue reaction under this temperature, until the alkanoic primitive reaction is complete;
(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 lower batch reaction and use 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.
4 one kinds of methods that adopt cleaning technique to synthesize the 2-alkylene alicyclic ketone of embodiment may further comprise the steps:
(1) first with weak-base ion-exchange resin, acid (property compound) and the disposable reactor of putting into of the metal ion aqueous solution, then after being warming up to 80 ℃, the mixture that adds alicyclic ketone and alkanoic maintains and continues reaction under this temperature, until the alkanoic primitive reaction is complete;
(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 lower batch reaction and use 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.
5 one kinds of methods that adopt cleaning technique to synthesize the 2-alkylene alicyclic ketone of embodiment may further comprise the steps:
(1) first with weak-base ion-exchange resin, acid (property compound) and the disposable reactor of putting into of the metal ion aqueous solution, then after being warming up to 90 ℃, add successively alicyclic ketone, alkanoic, maintain and continue reaction under this temperature, until the alkanoic primitive reaction is complete;
(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 lower batch reaction and use 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.
6 one kinds of methods that adopt cleaning technique to synthesize the 2-alkylene alicyclic ketone of embodiment may further comprise the steps:
(1) first alicyclic ketone is put into reactor, be warming up to 25 ℃ after, add successively the mixture of weak-base ion-exchange resin, acid (property compound) and the metal ion aqueous solution, add at last alkanoic in batches.Maintain and continue reaction under this temperature, until the alkanoic primitive reaction is complete;
(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 lower batch reaction and use 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, then under agitation be warming up to 50 ℃, 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 again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 91.7 (area) %.
Simultaneously, except not adding the neutralized verdigris and other reaction conditions all is the contrast experiment in the identical situation, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 88.2 (area) %.
Embodiment 8: first 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, after being heated to 50 ℃, under agitation drip 10 gram valeraldehydes, in three hours, drip off.Maintain 90 ℃ of lower continuation and react, until the chromatogram content of valeral＜0.5%.Isolate resin and water layer (mutually) (lower secondary response is applied mechanically), oil phase is adopted underpressure distillation.At first slough the lighting end (lower secondary response is applied mechanically) that contains unreacted cyclopentanone and valeric acid, then further rectification under vacuum is refining, collect the cut of 80～85 ℃/100Pa, obtain about 17.8 gram 2-pentylidene cyclopentanone and (claim again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) content is 87.2% product, about 88% (in the aldehyde) of yield.
Simultaneously, except not adding the manganous nitrate and other reaction conditions all is the contrast experiment, about 85% (in the aldehyde) of yield of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) in the identical situation.
Detect appearance time and mass spectrum that resulting product and the 2-pentylidene cyclopentanone that traditional soda solution grouting obtains have identical chromatogram, molecular weight 152 through GS-MS (application of gas chromatorgraphy/mass).As shown in Figure 1.
Embodiment 9: add in advance 100 gram cyclopentanone and 40 gram valeraldehydes in the reactor that stirring, thermometer, dropping funnel and reflux condensing tube are installed, 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 again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 90.5 (area) %.
Simultaneously, except not adding the zinc chloride and other reaction conditions all is the contrast experiment in the identical situation, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 85.5 (area) %.
Embodiment 10: in the reactor that is equipped with thermometer, agitator, dropping funnel and reflux condensing tube, first 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 after being heated 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 other reaction conditions all is the contrast experiment in the identical situation, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 71.5 (area) %.
Embodiment 11: in the reactor that agitator, thermometer, dropping funnel and reflux condensing tube are housed, put into first ring 100 gram cyclopentanone, after being warming up to 70 ℃, add successively 10mL (wet heap volume) D380 weak-base ion-exchange resin (primary amine type), 2 gram sulfuric acid, 10 gram ferrous sulfate and 50mL water, drip at last 100 gram valeraldehydes, 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 other reaction conditions all is the contrast experiment in the identical situation, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 38.5 (area) %.
Embodiment 12: add first 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, after being heated to 60 ℃, under agitation drip 25 gram enanthaldehydes, time for adding is no less than 0.5h, dropwise rear maintenance temperature 60 C, continue to stir until the chromatogram content of enanthaldehyde＜0.5% stops to stir.Isolate resin and water layer (mutually) (lower secondary response is applied mechanically), reaction solution is moved in the vacuum distillation apparatus distill.At first obtain containing the lighting end (lower secondary response is applied mechanically) of unreacted cyclopentanone and enanthic acid, then further underpressure distillation, collect the cut of 100～110 ℃/100Pa, obtaining inferior fleuramone (claiming again 2-heptene (base) cyclopentanone) 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 is that 70 ℃ of outer and other reaction conditionss all are the contrast experiment in the identical situation, and the yield of the inferior fleuramone of product 2-(claiming again 2-heptene (base) cyclopentanone) is 82.4% (in aldehyde) %.
Detect the appearance time that resulting product and the 2-heptenyl cyclopentanone that traditional soda solution grouting obtains have identical chromatogram, molecular weight 180 through GS-MS (application of gas chromatorgraphy/mass).
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, after being heated to 50 ℃, under agitation drip 30 gram valeraldehydes, in 6 hours, drip off.Maintaining 50 ℃ of lower continuation reacts, continue heated and stirred after 1 hour, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 92.1 (area) %.
Simultaneously, except not adding the cobaltous acetate and other reaction conditions all is the contrast experiment in the identical situation, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 86.5 (area) %.
Embodiment 14: add in advance 100 gram cyclopentanone and 25 gram n-hexyl aldehydes in the reactor that stirring, thermometer, dropping funnel and reflux condensing tube are installed, 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 the chromatogram content of hexanal＜0.5%.Reaction is isolated resin and water layer (mutually) (lower 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 (lower secondary response is applied mechanically) of unreacted cyclopentanone and caproic acid, then further underpressure distillation, 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 other reaction conditions all is the contrast experiment in the identical situation, the yield of product 2-hexylidene cyclopentanone is about 85% (in aldehyde) %.
Detect the appearance time that resulting product and the 2-hexylidene cyclopentanone that traditional soda solution grouting obtains have identical chromatogram, molecular weight 166 through GS-MS (application of gas chromatorgraphy/mass).
Embodiment 15: first 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, after being heated to 50 ℃, under agitation drip the mixed solution of 15 gram butyraldehyde-ns and 15 gram cyclopentanone, in 6 hours, drip off.Maintain 50 ℃ of lower continuation and react, until the chromatogram content of butyraldehyde＜0.5%.Isolate resin and water layer (mutually) (lower secondary response is applied mechanically), adopt underpressure distillation at first to slough the lighting end (lower secondary response is applied mechanically) that contains unreacted cyclopentanone and butyric acid to oil phase, then further rectification under vacuum, collect the cut of 82～86 ℃/8mmHg, obtaining 29.1 gram 2-butylidene cyclopentanone (claiming again 2-butylene (base) cyclopentanone) content is the product of 84 (area) %.About 85% (in the aldehyde) of productive rate.
Simultaneously, except not adding the tin protochloride and other reaction conditions all is the contrast experiment in the identical situation, the yield of product 2-butylidene cyclopentanone (claiming again 2-butylene (base) cyclopentanone) is about 82% (in aldehyde) %.
Detect the appearance time that resulting product and the crotyl cyclopentanone that traditional soda solution grouting obtains have identical chromatogram, molecular weight 138 through GS-MS (application of gas chromatorgraphy/mass).
Embodiment 16: add first 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, after being heated to 70 ℃, under agitation drip the mixing solutions of 20 gram n-octaldehydes and 20 gram cyclopentanone, in 2 hours, drip off.Maintain 50 ℃ of lower continuation and react after 2 hours, the chromatogram content (deducting unreacted raw material) of the octylene cyclopentanone of product 2-(claiming again 2-octene (base) cyclopentanone) is 88.7 (area) %.
Simultaneously, except not adding the lithium acetate and other reaction conditions all is the contrast experiment in the identical situation, the chromatogram content (deducting unreacted raw material) of the octylene cyclopentanone of product 2-(claiming again 2-octene (base) cyclopentanone) is 85.5 (area) %.
Embodiment 17: add first 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, after being heated to 70 ℃, under agitation drip 30 gram valeraldehydes, in 2 hours, drip off.Maintain 70 ℃ of lower continuation and react after 1 hour, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 89.6 (area) %.
Simultaneously, except not adding the tin tetrachloride and other reaction conditions all is the contrast experiment in the identical situation, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 86.9 (area) %.
Embodiment 18: first 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, after being heated to 90 ℃, under agitation add 30 gram valeraldehydes in batches.Maintain 50 ℃ of lower continuation and react after 4 hours, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 72.3 (area) %.
Simultaneously, except not adding the magnesium chloride and other reaction conditions all is the contrast experiment in the identical situation, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 63.1 (area) %.
Embodiment 19: first 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, after being heated to 90 ℃, under agitation add 15 gram valeraldehydes in batches.Maintain 90 ℃ of lower continuation and react after 4 hours, the chromatogram content (deducting unreacted raw material) of product 2 pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 80.2 (area) %.
Simultaneously, except not adding the molybdic chloride and other reaction conditions all is the contrast experiment in the identical situation, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 75.2 (area) %.
Embodiment 20: first 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, after being heated to 60 ℃, under agitation add 30 gram valeraldehydes in batches.Maintain 60 ℃ of lower continuation and react after 6 hours, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 82.5 (area) %.
Simultaneously, except not adding the molybdenum pentachloride and other reaction conditions all is the contrast experiment in the identical situation, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 65.7 (area) %.
Embodiment 21: first 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, after being heated to 40 ℃, under agitation add 30 gram valeraldehydes in batches.Maintain 60 ℃ of lower continuation and react after 10 hours, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 86.8 (area) %.
Simultaneously, except not adding the selenic chloride and other reaction conditions all is the contrast experiment in the identical situation, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclopentanone (claiming again 2-amylene (base) cyclopentanone, the 2-pentylidene cyclopentanone) is 79.1 (area) %.
Embodiment 22: first 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, after being heated to 50 ℃, under agitation add 10 gram butyraldehyde-ns and 30 gram pimelinketone mixing solutionss in batches.Maintain 50 ℃ of lower continuation reactions after 10 hours, the chromatogram content (deducting unreacted raw material) of product 2-butylidene pimelinketone (claiming again 2-butylene (base) pimelinketone, 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: first 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 after being heated to 90 ℃.Maintain 90 ℃ of lower continuation and react after 3 hours, the chromatogram content (deducting unreacted raw material) of product 2-pentylidene cyclobutanone (claiming again 2-amylene (base) cyclobutanone, 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 (7)
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, until the alkanoic primitive reaction is complete; 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;
Described alicyclic ketone refers to cyclobutanone, cyclopentanone, pimelinketone, or their mixture;
Described weak-base ion-exchange resin refers to primary amine type ion exchange resin, secondary amine type ion exchange resin, tertiary amine-type ion exchange resin, or their two or more mixtures;
Described metal ion refers to 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 acidic cpd refers to mineral acid or organic acid, and mineral acid refers to hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, or their two or more mixtures; Organic acid refers to acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, or their two or more mixtures;
(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): first 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 again the mixture of alkanoic or itself and alicyclic ketone.
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): first the aqueous solution of weak-base ion-exchange resin, acidic cpd and metal ion is put into reactor, then after being warming up to temperature of reaction, more simultaneously or add successively alicyclic ketone and alkanoic.
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): first alicyclic ketone is put into reactor, after being warming up to temperature of reaction, the aqueous solution that adds successively again weak-base ion-exchange resin, acidic cpd and metal ion adds at last the mixture of alkanoic or itself and alicyclic ketone in batches.
5. according to claim 1 or the described either 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 either 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 either method of 2-4, it is characterized in that described metal ion is added to the water with the form of soluble salt.
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| 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 |
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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 |
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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 |
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