CN105294418B - A kind of method for preparing the ketone of 3 methyl, 2 cyclopentene 1 - Google Patents
A kind of method for preparing the ketone of 3 methyl, 2 cyclopentene 1 Download PDFInfo
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- CN105294418B CN105294418B CN201510764423.5A CN201510764423A CN105294418B CN 105294418 B CN105294418 B CN 105294418B CN 201510764423 A CN201510764423 A CN 201510764423A CN 105294418 B CN105294418 B CN 105294418B
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- C07—ORGANIC CHEMISTRY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
- C07C45/66—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
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Abstract
A kind of method for preparing the ketone of 3 methyl, 2 cyclopentene 1 is that 2.5 acetyl butyryls are added into weakly polar organic solvent, adds catalyst, 1 12h is reacted at 100 250 DEG C, after reaction terminates, and filtering or centrifugation, solid catalyst drying are reclaimed；Organic phase is collected, the ketone of 3 methyl, 2 cyclopentene 1 is obtained.The present invention has yield high, and separating technology is simple, the advantage of high-efficiency and economic.
Description
Technical field
The present invention is on a kind of method for preparing 3- methyl -2- cyclopentene-1-ones.
Technical background
3- methyl -2- cyclopentene-1-ones are a kind of faint yellow to yellowish-brown transparency liquid, caramel odour with sweet tea.It
Density be 0.98g/cm3, fusing point is 35 DEG C, and boiling point is 185-186 DEG C, and flash-point is 65 DEG C, and index of refraction is 1.487-1.49, no
It is dissolved in water.It may be used as spices and medicine intermediate, a variety of organic medical substances can be synthesized, including trichothecene
Race's toxin, adrenal cortex etc..It can be also applied in petrochemical industry as a kind of gasoline additive, and such as it can be generated after hydrogenating
Methyl cyclopentane, with very high octane number, and energy density is up to 58%, can replacing as a kind of good ethanol petrol
Dai Pin.
3- methyl -2- cyclopentene-1-ones, for raw material, are dehydrated by aldehyde radical cyclizative condensation and made mainly with 2,5- acetyl butyryls
.Robinson et al., for raw material, 3- first is obtained in hot sodium hydroxide solution first with 2,5- acetyl butyryls by aldol condensation
Base -2- cyclopentene-1-ones, but the yield of products obtained therefrom only has 40%, conversion ratio 80%.Matthew etc. is improved after experimental program,
It is added to using the mixed liquor of concentration very low 2.5- acetyl butyryls and the sodium chloride of saturation in hot alkaline solution, yield is 60-70%.
It is low to there is product yield in the studies above, the problems such as separation process is complicated, limit correlation technique in terms of industrialization should
With.Efficiently, economic, the easy 3- methyl -2- cyclopentene-1-ones that are converted into 2,5- acetyl butyryls have for technological industrialization
Important meaning.
The content of the invention
It is an object of the invention to provide a kind of yield is high, separating technology is simple, high-efficiency and economic using 2.5- acetyl butyryls as
Raw material, the method for preparing 3- methyl -2- cyclopentene-1-ones.
2.5- acetyl butyryls are except that can occur intramolecular dehydration generation 3- methyl -2- cyclopentene -1- in strong alkaline aqueous solution
Outside ketone, it also occur that the complicated chemical change such as intermolecular dehydration polymerization, reaction product 3- methyl -2- cyclopentene -1- in addition
Ketone is also unstable, these yields that all have impact on reaction and separation.Patent of the present invention proposes to introduce low pole during the course of the reaction
Organic solvent so that reactant dissolve in organic solvent, acid or basic salt catalytic action under, be converted into 3- first
Base -2- cyclopentene-1-ones.
The preparation method of the present invention is as follows：
（1）2.5- acetyl butyryls are added to weakly polar organic solvent, catalyst is added, 1-12h is reacted at 100-250 DEG C；
（2）After reaction terminates, filtering or centrifugation, solid catalyst drying are reclaimed；Organic phase is collected, 3- is obtained
Methyl -2- cyclopentene-1-ones.
Such as step（1）The weakly polar organic solvent includes：Hexamethylene, dichloromethane, methylisobutylketone or ethyl acetate
Deng.
Such as step（1）The volume ratio of the 2.5- acetyl butyryls and weakly polar organic solvent is 1:5-10.
Such as step（1）Described catalyst includes acidic catalyst and base catalyst.
Acidic catalyst is as described above：ZSM-5 zeolite molecular sieve（Silica alumina ratio is 5-50, optimal than being 15-20）、Hβ
Type molecular sieve（Silica alumina ratio is 5-70, optimal than being 20-25）, SAPO-11 molecular sieves（Silica alumina ratio is 0.1-40, and optimal ratio is
0.1-1）, USY molecular sieve（Silica alumina ratio is 1-50, optimal than being 1-15）.
Such as（1）Described base catalyst includes：Sodium metasilicate, sodium carbonate, sodium sulfite, sodium hydrogensulfite, potassium carbonate or
Calcium acetate etc..
Such as（1）The quality of the catalyst is 1g with the volume ratio of 2.5- acetyl butyryls:0.5-2mL.
The present invention has following advantage：
（1）The present invention realizes that the dehydration of 2.5- acetyl butyryls prepares 3- from solid acid alkali catalytic agent in weakly polar organic solvent
Methyl -2- cyclopentene-1-ones, reaction yield height (reaching as high as 98%), product is easily isolated with catalyst after reaction, operate compared with
To be simple.The results show, which introduces weak polar solvent, can significantly improve the selectivity and yield of reaction, further, since reaction
Thing and product are all dissolved in weakly polar organic solvent, and catalyst, reaction product and molten can be just realized using simple method
The separation of agent.
（2）Whole course of reaction, it is safe and reliable, again pollution will not be produced to environment.
Brief description of the drawings
Fig. 1 is the product of the present invention13C nuclear magnetic spectrums.
Embodiment
Embodiment 1：
Into container, sequentially add：1ml2.5- acetyl butyryls, 6ml hexamethylenes, 0.6g sodium carbonate, and uniformly mix.It will hold
Device is placed in isothermal reactor, under conditions of stirring, is reacted 5 hours at 160 DEG C.Reaction is dropped rapidly to system after terminating
Normal temperature.By reaction solution, the organic phase separation of solid phase carries out qualitative and quantitative analysis to organic phase, as a result shows 2,5- acetyl butyryls
Conversion ratio be that the yields of 91%, 3- methyl -2- cyclopentene-1-ones is 88%.Fig. 1 is the nuclear-magnetism C spectrograms of products therefrom.
Embodiment 2：
1ml2.5- acetyl butyryls are added in container, 10ml hexamethylenes and 1.7g sodium metasilicate is subsequently added into, are well mixed.
Container is placed in 180 DEG C of isothermal reactors, is stirred continuously, is reacted 5 hours.After reaction terminates, container is put into ice bath, is made anti-
It should quench, system temperature is dropped rapidly to room temperature.Reaction product is taken out, organic phase and solid catalyst is centrifuged, collection has
Machine phase.Qualitative and quantitative analysis is carried out to obtained component, the conversion ratio for as a result showing 2,5- acetyl butyryls is 90%, 3- methyl -2- rings
The yield of amylene -1- ketone is 89%.
Embodiment 3：
First 1ml raw material 2.5- acetyl butyryls are added in container, 10ml methylisobutylketones, 1.5g SAPO-11 is subsequently added into
Molecular sieve（Silica alumina ratio is 1）.It is put into reactor, stirs after well mixed, 220 DEG C of isothermal reactions 8 hours.Reaction is completed, will
Reaction product is placed in low temperature and quenched, and temperature is rapidly decreased to normal temperature.Centrifuge afterwards, collect organic phase, it is determined
Property and quantitative analysis, the conversion ratio for as a result showing 2,5- acetyl butyryls is that the yield of 82%, 3- methyl -2- cyclopentene-1-ones is 80%.
Embodiment 4：
1ml2.5- acetyl butyryls are added in container, 10ml hexamethylenes and 0.6g sodium metasilicate is subsequently added into, are well mixed.
Container is placed in 180 DEG C of isothermal reactors, is stirred continuously, is reacted 5 hours.After reaction terminates, container is put into ice bath, is made anti-
It should quench, system temperature is dropped rapidly to room temperature.Reaction product is taken out, organic phase and solid catalyst is centrifuged, collection has
Machine phase.Qualitative and quantitative analysis is carried out to obtained component, the conversion ratio for as a result showing 2,5- acetyl butyryls is 99%, 3- methyl -2- rings
The yield of amylene -1- ketone is 98%.
Embodiment 5：
1ml2.5- acetyl butyryls are added in container, 8ml ethyl acetate and 0.8g sodium metasilicate is subsequently added into, are well mixed.
Container is placed in 140 DEG C of isothermal reactors, is stirred continuously, is reacted 7 hours.After reaction terminates, container is put into ice bath, is made anti-
It should quench, system temperature is dropped rapidly to room temperature.Reaction product is taken out, organic phase and solid catalyst is centrifuged, collection has
Machine phase.Qualitative and quantitative analysis is carried out to obtained component, the conversion ratio for as a result showing 2,5- acetyl butyryls is 85%, 3- methyl -2- rings
The yield of amylene -1- ketone is 81%.
Embodiment 6：
Into container, sequentially add：1ml2.5- acetyl butyryls, 5mL dichloromethane, 0.5g H beta molecular sieves（Silica alumina ratio is
25）, and uniformly mix.Container is placed in isothermal reactor, under conditions of stirring, with 200 DEG C of steady temperatures, reaction 12 is small
When.Container is placed in low temperature environment by reaction after terminating, and system is dropped rapidly to normal temperature.By reaction solution, solid phase organic phase
Separation, retains organic phase, and qualitative and quantitative analysis is carried out to organic phase, and the conversion ratio for as a result showing 2,5- acetyl butyryls is 84%,
The yield of 3- methyl -2- cyclopentene-1-ones is 80%.
Embodiment 7：
First 1ml raw material 2.5- acetyl butyryls are added in container, 7ml methylisobutylketones, 0.7g Carbon Dioxides is subsequently added into
Potassium.It is put into reactor, stirs after well mixed, 250 DEG C of isothermal reactions 5 hours.Reaction is completed, and reaction product is placed on into low temperature
Middle quenching, makes temperature be rapidly decreased to normal temperature.Centrifuge afterwards, collect organic phase, qualitative and quantitative analysis is carried out to it, as a result
The conversion ratio of display 2,5- acetyl butyryls is that the yield of 86%, 3- methyl -2- cyclopentene-1-ones is 81%.
Embodiment 8：
1ml2.5- acetyl butyryls are added in container, 9ml hexamethylenes and 0.9g sodium metasilicate is subsequently added into, are well mixed.Will
Container is placed in 250 DEG C of isothermal reactors, is stirred continuously, and is reacted 1 hour.After reaction terminates, container is put into ice bath, makes reaction
Quenching, system temperature is dropped rapidly to room temperature.Reaction product is taken out, organic phase and solid catalyst is centrifuged, collected organic
Phase.Qualitative and quantitative analysis is carried out to obtained component, the conversion ratio for as a result showing 2,5- acetyl butyryls is 84%, 3- methyl -2- rings penta
The yield of alkene -1- ketone is 80%.
Embodiment 9：
Into container, sequentially add：1ml2.5- acetyl butyryls, 8ml ethyl acetate, 1.6g calcium acetates, and uniformly mix.Will
Container is placed in isothermal reactor, under conditions of stirring, with 120 DEG C of steady temperatures, is reacted 5 hours.Reaction will be held after terminating
Device is placed in low temperature environment, system is dropped rapidly to normal temperature.By reaction solution, the organic phase separation of solid phase retains organic phase, right
Organic phase carries out qualitative and quantitative analysis, and the conversion ratio for as a result showing 2,5- acetyl butyryls is 87%, 3- methyl -2- cyclopentene-1-ones
Yield be 83%.
Embodiment 10：
First 1ml raw material 2.5- acetyl butyryls are added in container, 6ml methylisobutylketones, 0.6g sodium metasilicate is subsequently added into.
It is put into reactor, stirs after well mixed, 200 DEG C of isothermal reactions 1 hour.Reaction is completed, and reaction product is placed in low temperature
Quenching, makes temperature be rapidly decreased to normal temperature.Centrifuge afterwards, collect organic phase, qualitative and quantitative analysis is carried out to it, as a result shown
The conversion ratio for showing 2,5- acetyl butyryls is that the yield of 90%, 3- methyl -2- cyclopentene-1-ones is 84%.
Embodiment 11：
Into container, sequentially add：1.5ml2.5- acetyl butyryls, 5mL dichloromethane, 0.7g type ZSM 5 molecular sieves（Sial
Than for 20）, and uniformly mix.Container is placed in isothermal reactor, under conditions of stirring, with 200 DEG C of steady temperatures, reaction
12 hours.Container is placed in low temperature environment by reaction after terminating, and system is dropped rapidly to normal temperature.By reaction solution, solid phase has
Machine is separated, and retains organic phase, and qualitative and quantitative analysis is carried out to organic phase, and the conversion ratio for as a result showing 2,5- acetyl butyryls is
The yield of 85%, 3- methyl -2- cyclopentene-1-ones is 80%.
Embodiment 12：
First 1ml raw material 2.5- acetyl butyryls are added in container, 8ml methylisobutylketones, 2.0g USY molecules is subsequently added into
Sieve（Silica alumina ratio is 5）.It is put into reactor, stirs after well mixed, 180 DEG C of isothermal reactions 5 hours.Reaction is completed, and will be reacted
Product is placed in low temperature and quenched, and temperature is rapidly decreased to normal temperature.Centrifuge afterwards, collect organic phase, it is carried out it is qualitative and
Quantitative analysis, the conversion ratio for as a result showing 2,5- acetyl butyryls is that the yield of 89%, 3- methyl -2- cyclopentene-1-ones is 83%.
Claims (3)
1. a kind of method for preparing 3- methyl -2- cyclopentene-1-ones, it is characterised in that comprise the following steps：
（1）2.5- acetyl butyryls are added to weakly polar organic solvent, catalyst is added, 1-12h is reacted at 100-250 DEG C；
（2）After reaction terminates, filtering or centrifugation, solid catalyst drying are reclaimed；Collect organic phase, obtain 3- methyl-
2- cyclopentene-1-ones；
The weakly polar organic solvent is hexamethylene, dichloromethane, methylisobutylketone or ethyl acetate；
Described catalyst is acidic catalyst and base catalyst；
Described acidic catalyst is：ZSM-5 zeolite molecular sieve that silica alumina ratio is 15-20, silica alumina ratio are that 20-25 is H β type molecules
The USY molecular sieve that the SAPO-11 molecular sieves or silica alumina ratio that sieve, silica alumina ratio are 0.1-1 are 1-15；
Described base catalyst is sodium metasilicate, sodium carbonate, potassium carbonate or calcium acetate.
2. a kind of method for preparing 3- methyl -2- cyclopentene-1-ones as claimed in claim 1, it is characterised in that step（1）Institute
The volume ratio for stating 2.5- acetyl butyryls and weakly polar organic solvent is 1:5-10.
3. a kind of method for preparing 3- methyl -2- cyclopentene-1-ones as claimed in claim 1, it is characterised in that
Step（1）The quality of the catalyst is 1g with the volume ratio of 2.5- acetyl butyryls:0.5-2mL.
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| CN106349037A (en) * | 2016-08-26 | 2017-01-25 | 安徽金邦医药化工有限公司 | 3-methyl-2-cyclopentene-1-ketone catalytic preparation method |
| CN107226778A (en) * | 2017-06-02 | 2017-10-03 | 天津市安凯特科技发展有限公司 | A kind of synthetic method of dihydro jasmone |
| CN110550993B (en) * | 2019-08-30 | 2021-10-29 | 天津大学 | Preparation method of alkyl-substituted tetrahydrodicyclopentadiene dimer and application of alkyl-substituted tetrahydrodicyclopentadiene dimer as jet fuel |
| CN114409519A (en) * | 2021-12-16 | 2022-04-29 | 江苏宏邦化工科技有限公司 | Method for synthesizing cis-jasmone |
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| US5763664A (en) * | 1995-12-01 | 1998-06-09 | Albemarle Corporation | Process for preparing cyclopentenones |
| JPH10130192A (en) * | 1996-10-31 | 1998-05-19 | Mitsui Chem Inc | Production of 2-cycloalken-1-one compounds |
| CN103030543B (en) * | 2011-09-29 | 2014-10-15 | 中国石油化工股份有限公司 | Method for preparing 4-hexene-3-ketone by carrying out dehydration on 4-hydroxy-3-hexanone |
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