CN102503791A - Method for producing 2-alkylene grease cyclic ketone by adopting bionic catalytic system - Google Patents
Method for producing 2-alkylene grease cyclic ketone by adopting bionic catalytic system Download PDFInfo
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Abstract
The invention discloses a method for producing 2-alkylene grease cyclic ketone by adopting a bionic catalytic system. According to the method, grease cyclic ketone and aliphatic aldehyde are used as raw materials, under the light irradiation, amido substances are used as catalysts, and reaction is carried out in the existence of protonic acid and metal ions to generate 2-alkylene grease cyclic ketone. The catalyst system after the organic phase separation can be cyclically used. The 2-alkylene grease cyclic ketone is an important midbody for synthesizing various kinds of spices (such as methyl dihydrojasmonate, delta- lactone). The traditional process has most obvious problems that a acid-base solution catalytic system is adopted, so the recovery and cyclic use difficulty of the catalyst is very high, in addition, the product yield is low, many high-boiling-point byproducts are generated, the reaction selectivity is poor, a large quantity of waste water is generated, and resource waste and environment pollution are caused. The method provided by the invention has the advantages that the traditional unrecoverable solution catalytic system is omitted and is replaced by the bionic catalytic system which can be recovered and can be cyclically used, the clean production technology is used for modifying the original process, and simultaneously, the resource saving, the sufficient utilization and the environment protection are realized.
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, the method that particularly a kind of environmentally friendly employing bionic catalysis system is produced the 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 one type of very important organic synthesis.Important intermediate-2-the alkylene alicyclic ketone of synthetic many spices (for example methyl dihydrojasmonate, delta-lactone) is that raw material obtains through condensation reaction with alkanoic and alicyclic ketone.Its structural representation is as follows:
R: alkyl
n?=?0，1，2
The 2-alkylene alicyclic ketone is in its traditional synthesis technique, and the condensation reaction of alkanoic and alicyclic ketone 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.For this reason, the applicant had once invented and has 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, CN 101851154A).
In continuing research, use for reference enzymatic mechanism, with reference to plant growth environment, reference enzyme activity influence factor; We find the bionic catalysis system of application simulation intracellular fluid; Add illumination condition simultaneously, can reduce corresponding temperature of reaction, reduce the side reactions such as autohemagglutination of aldehydes or ketones; Accelerate the formation speed of product, thereby can and further improve the selectivity and the yield of reaction.
[summary of the invention]
The object of the invention aims to provide a kind of method of production 2-alkylene alicyclic ketone of selectivity and yield of further raising reaction.The eco-friendly bionic 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 the method that a kind of bionic catalysis system is produced the 2-alkylene alicyclic ketone, it is characterized in that may further comprise the steps:
(1) aqueous solution with material, protonic acid and the metal ion of alicyclic ketone, alkanoic, amino-contained mixes in reactor drum, under illumination and 0～60 ℃ of temperature condition, reacts, and is complete until the alkanoic primitive reaction; The mol ratio of said alicyclic ketone and alkanoic is 1 ~ 15:1; The amido in the material of said amino-contained and the mol ratio of alkanoic are 0.01 ~ 10:1; The mol ratio of the amido in the material of said protonic acid and amino-contained is 0.01 ~ 10:1; The TV of said alicyclic ketone and alkanoic is 1:0.1 ~ 3 with the ratio of the volume of water, and said metals ion adds in the entry with the form of soluble salt, and wherein the mol ratio of metals ion and alkanoic is 0.01 ~ 10:1;
(2) from the reaction mixture that step (1) obtains, isolate the catalyst system and the organic phase of amino-contained material by conventional phase disengagement method;
(3) organic phase that step (2) is obtained adopts rectification under vacuum, steams the lighting end that contains the unreacted alicyclic ketone;
(4) it is refining the product that obtains through step (3) to be carried out further rectification under vacuum, obtains 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.
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 or pimelinketone 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).
[description of drawings]
Fig. 1 and Fig. 2 are respectively the 2-pentylidene ketopentamethylene that the present invention makes and the mass spectrum of 2-butylidene pimelinketone.
[embodiment]
The method of environmentally friendly production 2-alkylene alicyclic ketone of the present invention.Mainly may further comprise the steps:
(1) aqueous solution with material, protonic acid and the metal ion of alicyclic ketone, alkanoic, amino-contained mixes in reactor drum, under illumination and 0～60 ℃ of temperature condition, reacts, and is complete until the alkanoic primitive reaction; The mol ratio of said alicyclic ketone and alkanoic is 1 ~ 15:1; The amido in the material of said amino-contained and the mol ratio of alkanoic are 0.01 ~ 10:1; The mol ratio of the amido in the material of said protonic acid and amino-contained is 0.01 ~ 10:1; The TV of said alicyclic ketone and alkanoic is 1:0.1 ~ 3 with the ratio of the volume of water, and said metals ion adds in the entry with the form of soluble salt, and wherein the mol ratio of metals ion and alkanoic is 0.01 ~ 10:1;
(2) from the reaction mixture that step (1) obtains, isolate the catalyst system and the organic phase of amino-contained material by conventional phase disengagement method;
(3) organic phase that step (2) is obtained adopts rectification under vacuum, steams the lighting end that contains the unreacted alicyclic ketone;
(4) it is refining the product that obtains through step (3) to be carried out further rectification under vacuum, obtains qualified 2-alkylene alicyclic ketone.
Alicyclic ketone in the said step (1) is meant: cyclobutanone, the mixture of one or more in ketopentamethylene or the pimelinketone.
The material of the amino-contained in the said step (1) is meant water-fast amino-contained material and water-soluble amino-contained material, wherein:
Said water-fast amino-contained material is meant: contain the ion exchange resin of primary amine groups, contain the ion exchange resin of secondary amine or contain one or more the mixture in the ion exchange resin of tertiary amine groups;
Said water-soluble amino-contained material is meant: fatty amine, and the heterogeneous ring compound of amino-contained, or one or more mixture in the amino acid, wherein:
Said fatty amine is meant: methylamine, ethamine, propylamine, butylamine, hexylamine, n n dimetylaniline, diethylamine, dipropyl amine, Trimethylamine 99, triethylamine, tripropyl amine, quadrol, the mixture of one or more in tn or the tetramethylenediamine;
The heterogeneous ring compound of said amino-contained is meant: pyrroles, Pyrrolidine, indoles, pyridine, picoline, pyrazine, piperidines, quinoline, isoquinoline 99.9, the mixture of one or more in pyrimidine or the imidazoles;
Said amino acid is meant: L-Ala, glycocoll, proline(Pro), leucine, Isoleucine, Serine, Threonine, Methionin, methionine(Met), halfcystine, aspartic acid, Gelucystine, Xie Ansuan, the mixture of one or more in tryptophane or the Histidine.
Metals ion in the said step (1) is meant: Na
+, K
+, Ca
2+, Mg
2+, Fe
3+, Fe
2+, Mn
2+, Co
2+, Cu
2+, Ni
2+, Zn
2+, Se
4+, Sn
2+, Sn
4+, Mo
3+, Mo
5+Or Ti
4+In one or more mixture.
Protonic acid in the said step (1) is meant mineral acid or organic acid, wherein:
Said mineral acid is meant: hydrochloric acid, sulfuric acid, the mixture of one or more in phosphoric acid or the boric acid;
Said organic acid is meant: acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, Succinic Acid, Hydrocerol A, phenylformic acid, Whitfield's ointment, Xaxa, oxysuccinic acid, tartrate, gallic acid, tannic acid, valeric acid, the mixture of one or more in caproic acid or the enanthic acid.
PH3～7 of the hierarchy of control in the said step (1).
Illumination in the said step (1) is meant that wavelength region is near-ultraviolet light and the visible light of 280～760nm.
Alkanoic in the said step (1) is meant butyraldehyde, valeral, hexanal, the mixture of one or more in enanthaldehyde or the octanal.
Hybrid mode in the said step (1) in reactor drum can be under the room temperature:
Earlier the aqueous solution of material, protonic acid and the metal ion of alicyclic ketone, amino-contained is put into reactor drum, be warming up to temperature of reaction after, progressively add alkanoic again.Or:
The aqueous solution of material, protonic acid and metal ion that will account for alicyclic ketone, the amino-contained of total amount 10～90% is earlier put into reactor drum, be warming up to temperature of reaction after, progressively add the mixture of alkanoic or itself and remaining alicyclic ketone again.Or:
Earlier the aqueous solution of material, protonic acid and the metal ion of amino-contained is put into reactor drum, be warming up to temperature of reaction then after, add alicyclic ketone and alkanoic more simultaneously.Or:
Earlier the aqueous solution of material, protonic acid and the metal ion of amino-contained is put into reactor drum, be warming up to temperature of reaction then after, add alicyclic ketone and alkanoic more successively.Or:
Earlier the aqueous solution of material, protonic acid and the metal ion of amino-contained is put into reactor drum, be warming up to temperature of reaction then after, add the mixture of alicyclic ketone and alkanoic again.Or:
Earlier alicyclic ketone is put into reactor drum, be warming up to temperature of reaction after, add the aqueous solution of material, protonic acid and the metal ion of amino-contained more successively, add alkanoic at last in batches.Or:
The alicyclic ketone that will account for total amount 10～90% is earlier put into reactor drum, be warming up to temperature of reaction after, add the aqueous solution of material, protonic acid and the metal ion of amino-contained more successively, add the mixture of alkanoic or itself and remaining alicyclic ketone at last in batches.Or:
Earlier material, protonic acid and the metal ion aqueous solution of alicyclic ketone, the alkanoic that accounts for total amount 10～90%, amino-contained is dropped in the reactor drum and mixes, be warming up to temperature of reaction then after, progressively add remaining alicyclic ring aldehyde again.Or:
Earlier alicyclic ketone, alkanoic are dropped into reactor drum, be warming up to the mixture that adds material, protonic acid and the metal ion aqueous solution of amino-contained after the temperature of reaction.
The mol ratio of alicyclic ketone according to the invention and alkanoic is preferably 1 ~ 10:1 (mol/mol).The amido in the material of said amino-contained and the mol ratio of alkanoic are 0.01 ~ 10:1.The mol ratio of said protonic acid and amido is preferably: protonic acid: amido=0.01 ~ 5:1 (mol/mol).The TV of said alicyclic ketone and alkanoic is preferably 1:0.1 ~ 2 with the ratio of the volume of water.The mol ratio of said metals ion and alkanoic is preferably 0.01 ~ 8:1;
Reactor drum used in the present invention can be a batch reactor, also can be flow reactor.
Embodiment 1The method of a kind of employing cleaning technique Synthetic 2-alkylene alicyclic ketone (as: using cyclobutanone, a kind of in ketopentamethylene or the pimelinketone, wherein two kinds, or three kinds mixture) may further comprise the steps:
(1) mixes in the disposable input reactor drum of material, protonic acid and the metal ion aqueous solution with a certain amount of alicyclic ketone, alkanoic, amino-contained under the room temperature; Regulate pH3 ~ 4; Under illumination, be warming up to 50 ℃, under this temperature, continue reaction, complete until the alkanoic primitive reaction;
(2) from the reaction mixture that step (1) obtains, isolate the catalyst system and the organic phase of amino-contained material, catalyst system can be recycled;
(3) 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 2The method of a kind of employing cleaning technique Synthetic 2-alkylene alicyclic ketone (as: using cyclobutanone, a kind of in ketopentamethylene or the pimelinketone, wherein two kinds, or three kinds mixture) may further comprise the steps:
(1) elder generation is with the disposable reactor drum of putting into of material, protonic acid and the metal ion aqueous solution of alicyclic ketone, amino-contained; Regulate pH5 ~ 6, under illumination, be warming up to 60 ℃ after, under agitation drip alkanoic; Maintain then and continue reaction under this temperature, complete until the alkanoic primitive reaction;
(2) catalyst system and the organic phase of separation amino-contained material from the reaction mixture that step (1) obtains, catalyst system can be recycled;
(3) 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 3The method of a kind of employing cleaning technique Synthetic 2-alkylene alicyclic ketone (as: using cyclobutanone, a kind of in ketopentamethylene or the pimelinketone, wherein two kinds, or three kinds mixture) may further comprise the steps:
(1) earlier a certain amount of alicyclic ketone, alkanoic are dropped into reactor drum; Regulate pH6 ~ 7; At illumination and 30 ℃ of mixtures that drop into material, protonic acid and the metal ion aqueous solution of amino-contained down, maintain then and continue reaction under this temperature, complete until the alkanoic primitive reaction;
(2) catalyst system and the organic phase of separation amino-contained material from the reaction mixture that step (1) obtains, catalyst system can be recycled;
(3) 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 4The method of a kind of employing cleaning technique Synthetic 2-alkylene alicyclic ketone (as: using cyclobutanone, a kind of in ketopentamethylene or the pimelinketone, wherein two kinds, or three kinds mixture) may further comprise the steps:
(1) elder generation is with the disposable reactor drum of putting into of material, protonic acid and the metal ion aqueous solution of amino-contained; Regulate pH ~ 4.5, under illumination and 20 ℃, add the mixture of alicyclic ketone and alkanoic; Maintain and continue reaction under this temperature, complete until the alkanoic primitive reaction;
(2) from the reaction mixture that step (1) obtains, isolate the catalyst system and the organic phase of amino-contained material, catalyst system can be recycled;
(3) 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 5The method of a kind of employing cleaning technique Synthetic 2-alkylene alicyclic ketone (as: using cyclobutanone, a kind of in ketopentamethylene or the pimelinketone, wherein two kinds, or three kinds mixture) may further comprise the steps:
(1) earlier with the disposable reactor drum of putting into of material, protonic acid and the metal ion aqueous solution of amino-contained, in pH ~ 5, under illumination and 5 ℃, add alicyclic ketone 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 the catalyst system and the organic phase of the material of amino-contained, catalyst system can be recycled;
(3) 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 6The method of a kind of employing cleaning technique Synthetic 2-alkylene alicyclic ketone (as: using cyclobutanone, a kind of in ketopentamethylene or the pimelinketone, wherein two kinds, or three kinds mixture) may further comprise the steps:
(1) earlier alicyclic ketone is put into reactor drum, regulate pH ~ 3.5, under illumination and 45 ℃, add the mixture of material, protonic acid and the metal ion aqueous solution of amino-contained 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 the catalyst system and the organic phase of amino-contained material, catalyst system can be recycled;
(3) 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 ketopentamethylene, 20 gram valeraldehydes, 30mL (wet heap volume) D380 weak-base ion-exchange resin (primary amine type), 4 gram oxalic acid, 0.01 gram neutralized verdigris and 20 mL water are put in the reactor drum that stirring, TM and reflux condensing tube are installed mixed.Regulate pH ~ 3.5, under the irradiation of sunlight, stir and be warming up to 40 ℃ 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 ketopentamethylene (claiming 2-amylene (base) ketopentamethylene again, 2-pentylidene basic ring pentanone) is 92.0 (area) %.
Embodiment 8:Earlier 100 gram ketopentamethylene, 40 mL (wet heap volume) D382 weak-base ion-exchange resin (secondary amine type), 8 gram Hydrocerol As, 2 gram manganous nitrates and 40mL water are put into the reactor drum that is equipped with TM, whisking appliance, tap funnel and reflux condensing tube.Regulate pH4 ~ 5, under the light source irradiation of wavelength 400～600nm, behind the heat temperature raising to 35 ℃, under agitation drip 10 gram valeraldehydes, in three hours, drip off.Maintain 50 ℃ 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 ketopentamethylene and valeric acid; Further rectification under vacuum is refining then; Collect the cut of 80 ~ 85 ℃/100Pa; Obtaining about 17.8 gram 2-pentylidene ketopentamethylene (claiming 2-amylene (base) ketopentamethylene again, 2-pentylidene basic ring pentanone) content is 87.5% product, about 88.5% (in the aldehyde) of yield.
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 20 gram ethamine, 6 gram Succinic Acid, 12 gram zinc chloride and 40mL water after 50 ℃.Regulate pH4 ~ 5, under the irradiation of the incandescent light of 100w, continue heated and stirred after 6 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 90.7 (area) %.
Embodiment 10:In the reactor drum that is equipped with TM, whisking appliance, tap funnel and reflux condensing tube, earlier with 10 gram glycocoll, 0.25 gram phosphoric acid, 1 gram tartrate, 5 gram nickelous nitrate and the disposable reactor drums of putting into of 50 mL water; Regulate pH6～7; Behind the heat temperature raising to 60 ℃, add the mixture that 100 gram ketopentamethylene and 30 restrain valeraldehydes in xenon lamp irradiation down; React after 2 hours, the chromatogram content (deducting unreacted raw material) that records 2-pentylidene ketopentamethylene in the reaction solution is 80.1 (area) %.
Embodiment 11:In the reactor drum that whisking appliance, TM, tap funnel and reflux condensing tube are housed, put into ring 50 gram ketopentamethylene earlier, be warming up to 50 ℃ after, add 20 grams, 40% monomethylamine aqueous solution, 20 gram propionic acid, 10 gram ferrous sulfate and 50 mL water successively.Regulate pH～5, under solar radiation, drip 10 gram valeraldehydes, finished in 4 hours.Behind the constant temperature stirring reaction 2 hours, stop to stir.Obtain about 53 gram oil phases, the chromatogram content that records 2-pentylidene ketopentamethylene wherein is about 26.7 (area) %, calculated yield about 80%.
Embodiment 12:In the reactor drum that is equipped with whisking appliance, TM, tap funnel and reflux exchanger, add 100 gram ketopentamethylene, 2 gram proline(Pro), 4 gram Whitfield's ointments, 5 gram iron trichloride and 40mL water earlier.Regulate pH～3, adopt the xenon lamp irradiation, behind the heat temperature raising to 40 ℃, under agitation drip 25 gram enanthaldehydes (the dropping time is no less than 2h) simultaneously, dropwise the back and keep 40 ℃ 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 37.7 gram 2-is 88% product, yield 84.2% (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 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 dimethylamine agueous solution, 10 gram oxysuccinic acid, the 0.1 gram sodium acetate and the 40mL water of 50 gram ketopentamethylene, 5.0 grams 40%.Regulate pH～3, under solar radiation, behind the heat temperature raising to 45 ℃, under agitation drip 30 gram valeraldehydes, in 2 hours, drip off.Maintain 45 ℃ and continue reaction down, continue heated and stirred after 3 hours, the chromatogram content of product 2-pentylidene ketopentamethylene (claiming 2-amylene (base) ketopentamethylene again, 2-pentylidene basic ring pentanone) is 37.5 (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 the mixture that drops into 1 gram aspartic acid, 15 gram gallic acids, 0.2 gram titanium tetrachloride and 20mL water after 50 ℃.Regulate pH～3, under the xenon lamp irradiation, 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; Further underpressure distillation then; Collect 116～120 ℃/1995 Pa cuts, obtain about 42.5 gram 2-hexylidene ketopentamethylene content and be 85% product, about 87.1% (in the aldehyde) of yield.
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, 0.5 gram Methionin, 2 gram Xaxa, 1 gram tin protochloride and 40mL water are put into the reactor drum that is equipped with TM, whisking appliance, tap funnel and reflux condensing tube.Regulate pH～3, in the xenon lamp irradiation down, behind the heat temperature raising to 40 ℃, under agitation drip 15 and restrain butyraldehyde-ns, in 6 hours, drip off.Maintain 40 ℃ 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 29.1 gram 2-butylidene ketopentamethylene (claiming 2-butylene (base) ketopentamethylene again) content is the product of 84 (area) %.About 85% (in the aldehyde) of productive rate.
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, 5.0 gram halfcystines, 4 gram propanedioic acid, 1 gram vitriolate of tartar and 40mL water earlier.Regulate pH～3, in the sodium vapor lamp irradiation down, behind the heat temperature raising to 50 ℃, under agitation drip 20 and restrain n-octaldehydes, in 2 hours, 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 89.7 (area) %.
Embodiment 17:In the reactor drum that whisking appliance, TM, tap funnel and reflux exchanger are installed, add 100 gram ketopentamethylene, 0.3 gram piperidines, 4 gram propionic acid, 1 gram boric acid, 0.5 gram calcium chloride and 5mL water earlier.Regulate pH4～5, under solar radiation, behind the heat temperature raising to 50 ℃, under agitation drip 30 gram valeraldehydes, in 2 hours, drip off.Maintain 50 ℃ 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 90.1 (area) %.
Embodiment 18:With 100 gram ketopentamethylene, 40mL (wet heap volume) D301T weak-base ion-exchange resin (tertiary amine-type), 0.5 gram phosphoric acid, 3 gram phenylformic acid, 5 gram magnesium chlorides and 20mL water are put into the reactor drum that TM, whisking appliance, tap funnel and reflux condensing tube are housed earlier.Regulate pH4～5, under solar radiation, behind the heat temperature raising to 50 ℃, 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 80.5 (area) %.
Embodiment 19:Earlier 100 gram ketopentamethylene, 0.1 gram pyridine, 5 gram butyric acid, 5 gram molybdic chlorides and 20mL water are put into the reactor drum that TM, whisking appliance, tap funnel and reflux condensing tube are housed.Regulate pH4～5, under solar radiation, behind the heat temperature raising to 50 ℃, 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 86.2 (area) %.
Embodiment 20:Earlier 100 gram ketopentamethylene, 0.8 gram pyrroles, 10 gram acetic acid, 5 gram molybdenum pentachlorides and 20mL 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 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 ketopentamethylene (claiming 2-amylene (base) ketopentamethylene again, 2-pentylidene basic ring pentanone) is 82.5 (area) %.
Embodiment 21:Earlier 100 gram ketopentamethylene, 1.0 gram pyrimidines, 2 gram acetic acid, 1 gram tannic acid, 5 gram selenic chlorides and 20mL 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 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 ketopentamethylene (claiming 2-amylene (base) ketopentamethylene again, 2-pentylidene basic ring pentanone) is 86.8 (area) %.
Embodiment 22:Earlier 50 gram pimelinketone, 0.1 gram indoles, 1 gram acetate, 5 gram titanium tetrachlorides and 20mL 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 50 ℃, under agitation add 10 gram butyraldehyde-ns 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) %.Its mass spectrum is seen Fig. 2.
Claims (10)
1. method that adopts the bionic catalysis system to produce the 2-alkylene alicyclic ketone is characterized in that may further comprise the steps:
(1) aqueous solution with material, protonic acid and the metal ion of alicyclic ketone, alkanoic, amino-contained mixes in reactor drum, under illumination and 0～60 ℃ of temperature condition, reacts, and is complete until the alkanoic primitive reaction; The mol ratio of said alicyclic ketone and alkanoic is 1 ~ 15:1; The amido in the material of said amino-contained and the mol ratio of alkanoic are 0.01 ~ 10:1; The mol ratio of the amido in the material of said protonic acid and amino-contained is 0.01 ~ 10:1; The TV of said alicyclic ketone and alkanoic is 1:0.1 ~ 3 with the ratio of the volume of water, and said metals ion adds in the entry with the form of soluble salt, and wherein the mol ratio of metals ion and alkanoic is 0.01 ~ 10:1;
(2) from the reaction mixture that step (1) obtains, isolate the catalyst system and the organic phase of amino-contained material by conventional phase disengagement method;
(3) organic phase that step (2) is obtained adopts rectification under vacuum, steams the lighting end that contains the unreacted alicyclic ketone;
(4) it is refining the product that obtains through step (3) to be carried out further rectification under vacuum, obtains qualified 2-alkylene alicyclic ketone.
2. according to the described method of claim 1, it is characterized in that the alicyclic ketone in the said step (1) is meant: cyclobutanone, the mixture of one or more in ketopentamethylene or the pimelinketone.
3. according to the described method of claim 1, it is characterized in that the material of the amino-contained in the said step (1) is meant water-fast amino-contained material and water-soluble amino-contained material, wherein:
Said water-fast amino-contained material is meant: contain the ion exchange resin of primary amine groups, contain the ion exchange resin of secondary amine or contain one or more the mixture in the ion exchange resin of tertiary amine groups;
Said water-soluble amino-contained material is meant: fatty amine, and the heterogeneous ring compound of amino-contained, or one or more mixture in the amino acid, wherein:
Said fatty amine is meant: methylamine, ethamine, propylamine, butylamine, hexylamine, n n dimetylaniline, diethylamine, dipropyl amine, Trimethylamine 99, triethylamine, tripropyl amine, quadrol, the mixture of one or more in tn or the tetramethylenediamine;
The heterogeneous ring compound of said amino-contained is meant: pyrroles, Pyrrolidine, indoles, pyridine, picoline, pyrazine, piperidines, quinoline, isoquinoline 99.9, the mixture of one or more in pyrimidine or the imidazoles;
Said amino acid is meant: L-Ala, glycocoll, proline(Pro), leucine, Isoleucine, Serine, Threonine, Methionin, methionine(Met), halfcystine, aspartic acid, Gelucystine, Xie Ansuan, the mixture of one or more in tryptophane or the Histidine.
4. according to the described method of claim 1, it is characterized in that the metals ion in the said step (1) is meant: Na
+, K
+, Ca
2+, Mg
2+, Fe
3+, Fe
2+, Mn
2+, Co
2+, Cu
2+, Ni
2+, Zn
2+, Se
4+, Sn
2+, Sn
4+, Mo
3+, Mo
5+Or Ti
4+In one or more mixture.
5. according to the described method of claim 1, it is characterized in that the protonic acid in the said step (1) is meant mineral acid or organic acid, wherein:
Said mineral acid is meant: hydrochloric acid, sulfuric acid, the mixture of one or more in phosphoric acid or the boric acid;
Said organic acid is meant: acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, Succinic Acid, Hydrocerol A, phenylformic acid, Whitfield's ointment, Xaxa, oxysuccinic acid, tartrate, gallic acid, tannic acid, valeric acid, the mixture of one or more in caproic acid or the enanthic acid.
6. according to the described method of claim 1, it is characterized in that pH3～7 of the hierarchy of control in the said step (1).
7. according to the described method of claim 1, it is characterized in that the illumination in the said step (1) is meant that wavelength region is near-ultraviolet light and the visible light of 280～760nm.
8. according to claim 1 or the described arbitrary method of 2-6; It is characterized in that the hybrid mode in reactor drum is in the said step (1): the aqueous solution of material, protonic acid and metal ion that will account for alicyclic ketone, the amino-contained of total amount 10～90% is earlier put into reactor drum; After being warming up to temperature of reaction, progressively add the mixture of alkanoic or itself and remaining alicyclic ketone again.
9. according to claim 1 or the described arbitrary method of 2-6; It is characterized in that the hybrid mode in reactor drum is in the said step (1): elder generation puts into reactor drum with the aqueous solution of material, protonic acid and the metal ion of amino-contained; After being warming up to temperature of reaction then; Again simultaneously or add alicyclic ketone and alkanoic successively, or add their mixture.
10. according to claim 1 or the described arbitrary method of 2-6; It is characterized in that the hybrid mode in reactor drum is in the said step (1): the alicyclic ketone that will account for total amount 10～90% is earlier put into reactor drum; After being warming up to temperature of reaction; The aqueous solution that adds material, protonic acid and the metal ion of amino-contained more successively adds at last the mixture of alkanoic or itself and remaining alicyclic ketone in batches.
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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 |
Citations (4)
| 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 |
| JPS5748934A (en) * | 1980-09-10 | 1982-03-20 | Nippon Zeon Co Ltd | Preparation of 2-substituted cycloalkanone |
| 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 |
| CN101851154A (en) * | 2010-05-18 | 2010-10-06 | 天津理工大学 | Improved method for producing 2-alkylene alicyclic ketone |
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Patent Citations (4)
| 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 |
| JPS5748934A (en) * | 1980-09-10 | 1982-03-20 | Nippon Zeon Co Ltd | Preparation of 2-substituted cycloalkanone |
| 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 |
| CN101851154A (en) * | 2010-05-18 | 2010-10-06 | 天津理工大学 | Improved method for producing 2-alkylene alicyclic ketone |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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