CN105294418A - Method for preparing 3-methyl-2-cyclopentene-1-ketone - Google Patents
Method for preparing 3-methyl-2-cyclopentene-1-ketone Download PDFInfo
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- CN105294418A CN105294418A CN201510764423.5A CN201510764423A CN105294418A CN 105294418 A CN105294418 A CN 105294418A CN 201510764423 A CN201510764423 A CN 201510764423A CN 105294418 A CN105294418 A CN 105294418A
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- cyclopentene
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- hexanedione
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- silica alumina
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
Provided is a method for preparing 3-methyl-2-cyclopentene-1-ketone. The method includes the steps that 2.5-hexanedione is added into a weak-polarity organic solvent, a catalyst is added, a reaction is conducted for 1-12 h at 100-250 DEG C, filtration or centrifugal separation is performed after the reaction is finished, and the solid catalyst is dried and recovered; an organic phase is collected, and then 3-methyl-2-cyclopentene-1-ketone is obtained. The method has the advantages of being high in yield, simple in separation technology, efficient and economical.
Description
Technical field
The invention relates to a kind of method preparing 3-methyl-2-cyclopentene-1-one.
Technical background
3-methyl-2-cyclopentene-1-one is a kind of faint yellow to yellowish brown transparent liquid, has sweet caramel odor.Its density is 0.98g/cm
3, fusing point is 35 DEG C, and boiling point is 185-186 DEG C, and flash-point is 65 DEG C, and refractive index is 1.487-1.49, water insoluble.It can be used as spices and medicine intermediate, can synthesize multiple organic medicinal substance, comprising Trichothecenes toxin, adrenal cortex etc.It also can be used as a kind of gasoline dope and is applied in petrochemical industry, as the methylcyclopentane that can generate after its hydrogenation, have very high octane value, and energy density is up to 58%, can be used as a kind of substitute of good ethanol petrol.
3-methyl-2-cyclopentene-1-one mainly with 2,5-hexanedione for raw material, obtained by aldehyde radical cyclocondensation Dehydration.The people such as Robinson are first with 2, and 5-hexanedione is raw material, obtain 3-methyl-2-cyclopentene-1-one, but the yield of products obtained therefrom only have 40%, transformation efficiency 80% in hot sodium hydroxide solution by aldol condensation.After Matthew etc. improve experimental program, adopt the mixed solution of the very low 2.5-hexanedione of concentration and saturated sodium-chlor to join in hot alkaline solution, productive rate is 60-70%.The problems such as it is low that above-mentioned research exists product yield, and separation process is complicated, limit the application of correlation technique in industrialization.Efficiently, economic, the easy 3-methyl-2-cyclopentene-1-one that is converted into by 2,5-hexanedione has great importance for technological industrialization.
Summary of the invention
The object of the present invention is to provide a kind of productive rate high, separating technology is simple, efficient economy with 2.5-hexanedione for raw material, prepare the method for 3-methyl-2-cyclopentene-1-one.
In strong alkaline aqueous solution, 2.5-hexanedione generates except 3-methyl-2-cyclopentene-1-one except there is intramolecular dehydration, also can there is the chemical transformation of the complexity such as intermolecular dehydration polymerization, reaction product 3-methyl-2-cyclopentene-1-one is also unstable in addition, these productive rates that all have impact on reaction be separated.Patent of the present invention proposes the organic solvent introducing low-pole in reaction process, makes reactants dissolved in organic solvent, under the katalysis of acid or basic salt, is converted into 3-methyl-2-cyclopentene-1-one.
Preparation method of the present invention is as follows:
(1) 2.5-hexanedione is joined weakly polar organic solvent, add catalyzer, at 100-250 DEG C of reaction 1-12h;
(2) after reaction terminates, filter or centrifugation, solid catalyst is dried, and reclaims; Collect organic phase, obtain 3-methyl-2-cyclopentene-1-one.
As described in step (1), weakly polar organic solvent comprises: hexanaphthene, methylene dichloride, mibk or ethyl acetate etc.
As described in step (1), the volume ratio of 2.5-hexanedione and weakly polar organic solvent is 1:5-10.
Catalyzer as described in step (1) comprises an acidic catalyst and basic catalyst.
An acidic catalyst as above is: (silica alumina ratio is 5-50 to ZSM-5 zeolite molecular sieve, best than being 15-20), (silica alumina ratio is 5-70 to H beta molecular sieve, best than being 20-25), (silica alumina ratio is 0.1-40 to SAPO-11 molecular sieve, best than being 0.1-1), USY molecular sieve (silica alumina ratio is 1-50, best than being 1-15).
Basic catalyst as described in (1) comprises: water glass, sodium carbonate, S-WAT, sodium bisulfite, salt of wormwood or calcium acetate etc.
As described in (1), the quality of catalyzer and the volume ratio of 2.5-hexanedione are 1g:0.5-2mL.
The present invention has following advantage:
(1) the present invention selects solid acid alkali catalytic agent in weakly polar organic solvent, to realize 2.5-hexanedione Dehydration for 3-methyl-2-cyclopentene-1-one, reaction yield high (reaching as high as 98%), reaction after product is easy to be separated with catalyzer, operates comparatively simple.The results show introduces selectivity and the productive rate that weak polar solvent can significantly improve reaction, in addition, because reactant and product are all dissolved in weakly polar organic solvent, adopts simple method just can realize catalyzer, reaction product is separated with solvent.
(2) whole reaction process, safe and reliable, can not produce again pollute environment.
Accompanying drawing explanation
Fig. 1 is product of the present invention
13c nuclear magnetic spectrum.
Embodiment
Embodiment 1:
To in container, add successively: 1ml2.5-hexanedione, 6ml hexanaphthene, 0.6g sodium carbonate, and Homogeneous phase mixing.Container is placed in isothermal reactor, under the condition stirred, 160 DEG C of reactions 5 hours.System is made to be dropped rapidly to normal temperature after reaction terminates.By reaction soln, solid phase organic phase is separated, and carries out qualitative and quantitative analysis to organic phase, and the transformation efficiency of result display 2,5-hexanedione is the yield of 91%, 3-methyl-2-cyclopentene-1-one is 88%.Fig. 1 is the nuclear-magnetism C spectrogram of products therefrom.
Embodiment 2:
1ml2.5-hexanedione is joined in container, then adds 10ml hexanaphthene and 1.7g water glass, mix.Container is placed in 180 DEG C of isothermal reactors, constantly stirs, react 5 hours.After reaction terminates, ice bath put into by container, and reaction is quenched, and system temperature is dropped rapidly to room temperature.Take out reaction product, centrifugation organic phase and solid catalyst, collect organic phase.Carry out qualitative and quantitative analysis to obtained component, the transformation efficiency of result display 2,5-hexanedione is the yield of 90%, 3-methyl-2-cyclopentene-1-one is 89%.
Embodiment 3:
First 1ml raw material 2.5-hexanedione is joined in container, then add 10ml mibk, 1.5gSAPO-11 molecular sieve (silica alumina ratio is 1).Put into reactor after mixing, stir, 220 DEG C of isothermal reactions 8 hours.Reaction completes, and reaction product is placed in low temperature and quenches, and makes temperature be down to normal temperature rapidly.Centrifugation afterwards, collects organic phase, carries out qualitative and quantitative analysis to it, and the transformation efficiency of result display 2,5-hexanedione is the yield of 82%, 3-methyl-2-cyclopentene-1-one is 80%.
Embodiment 4:
1ml2.5-hexanedione is joined in container, then adds 10ml hexanaphthene and 0.6g water glass, mix.Container is placed in 180 DEG C of isothermal reactors, constantly stirs, react 5 hours.After reaction terminates, ice bath put into by container, and reaction is quenched, and system temperature is dropped rapidly to room temperature.Take out reaction product, centrifugation organic phase and solid catalyst, collect organic phase.Carry out qualitative and quantitative analysis to obtained component, the transformation efficiency of result display 2,5-hexanedione is the yield of 99%, 3-methyl-2-cyclopentene-1-one is 98%.
Embodiment 5:
1ml2.5-hexanedione is joined in container, then adds 8ml ethyl acetate and 0.8g water glass, mix.Container is placed in 140 DEG C of isothermal reactors, constantly stirs, react 7 hours.After reaction terminates, ice bath put into by container, and reaction is quenched, and system temperature is dropped rapidly to room temperature.Take out reaction product, centrifugation organic phase and solid catalyst, collect organic phase.Carry out qualitative and quantitative analysis to obtained component, the transformation efficiency of result display 2,5-hexanedione is the yield of 85%, 3-methyl-2-cyclopentene-1-one is 81%.
Embodiment 6:
To in container, add successively: 1ml2.5-hexanedione, 5mL methylene dichloride, 0.5gH beta molecular sieve (silica alumina ratio is 25), and Homogeneous phase mixing.Container is placed in isothermal reactor, under the condition stirred, with 200 DEG C of steady temperatures, reacts 12 hours.After reaction terminates, container is placed in low temperature environment, makes system be dropped rapidly to normal temperature.By reaction soln, solid phase organic phase is separated, and retains organic phase, carries out qualitative and quantitative analysis to organic phase, and the transformation efficiency of result display 2,5-hexanedione is the yield of 84%, 3-methyl-2-cyclopentene-1-one is 80%.
Embodiment 7:
First 1ml raw material 2.5-hexanedione is joined in container, then add 7ml mibk, 0.7g Anhydrous potassium carbonate.Put into reactor after mixing, stir, 250 DEG C of isothermal reactions 5 hours.Reaction completes, and reaction product is placed in low temperature and quenches, and makes temperature be down to normal temperature rapidly.Centrifugation afterwards, collects organic phase, carries out qualitative and quantitative analysis to it, and the transformation efficiency of result display 2,5-hexanedione is the yield of 86%, 3-methyl-2-cyclopentene-1-one is 81%.
Embodiment 8:
1ml2.5-hexanedione is joined in container, then adds 9ml hexanaphthene and 0.9g water glass, mix.Container is placed in 250 DEG C of isothermal reactors, constantly stirs, react 1 hour.After reaction terminates, ice bath put into by container, and reaction is quenched, and system temperature is dropped rapidly to room temperature.Take out reaction product, centrifugation organic phase and solid catalyst, collect organic phase.Carry out qualitative and quantitative analysis to obtained component, the transformation efficiency of result display 2,5-hexanedione is the yield of 84%, 3-methyl-2-cyclopentene-1-one is 80%.
Embodiment 9:
To in container, add successively: 1ml2.5-hexanedione, 8ml ethyl acetate, 1.6g calcium acetate, and Homogeneous phase mixing.Container is placed in isothermal reactor, under the condition stirred, with 120 DEG C of steady temperatures, reacts 5 hours.After reaction terminates, container is placed in low temperature environment, makes system be dropped rapidly to normal temperature.By reaction soln, solid phase organic phase is separated, and retains organic phase, carries out qualitative and quantitative analysis to organic phase, and the transformation efficiency of result display 2,5-hexanedione is the yield of 87%, 3-methyl-2-cyclopentene-1-one is 83%.
Embodiment 10:
First 1ml raw material 2.5-hexanedione is joined in container, then add 6ml mibk, 0.6g water glass.Put into reactor after mixing, stir, 200 DEG C of isothermal reactions 1 hour.Reaction completes, and reaction product is placed in low temperature and quenches, and makes temperature be down to normal temperature rapidly.Centrifugation afterwards, collects organic phase, carries out qualitative and quantitative analysis to it, and the transformation efficiency of result display 2,5-hexanedione is the yield of 90%, 3-methyl-2-cyclopentene-1-one is 84%.
Embodiment 11:
To in container, add successively: 1.5ml2.5-hexanedione, 5mL methylene dichloride, 0.7gZSM-5 type molecular sieve (silica alumina ratio is 20), and Homogeneous phase mixing.Container is placed in isothermal reactor, under the condition stirred, with 200 DEG C of steady temperatures, reacts 12 hours.After reaction terminates, container is placed in low temperature environment, makes system be dropped rapidly to normal temperature.By reaction soln, solid phase organic phase is separated, and retains organic phase, carries out qualitative and quantitative analysis to organic phase, and the transformation efficiency of result display 2,5-hexanedione is the yield of 85%, 3-methyl-2-cyclopentene-1-one is 80%.
Embodiment 12:
First 1ml raw material 2.5-hexanedione is joined in container, then add 8ml mibk, 2.0gUSY molecular sieve (silica alumina ratio is 5).Put into reactor after mixing, stir, 180 DEG C of isothermal reactions 5 hours.Reaction completes, and reaction product is placed in low temperature and quenches, and makes temperature be down to normal temperature rapidly.Centrifugation afterwards, collects organic phase, carries out qualitative and quantitative analysis to it, and the transformation efficiency of result display 2,5-hexanedione is the yield of 89%, 3-methyl-2-cyclopentene-1-one is 83%.
Claims (8)
1. prepare a method for 3-methyl-2-cyclopentene-1-one, it is characterized in that comprising the steps:
(1) 2.5-hexanedione is joined weakly polar organic solvent, add catalyzer, at 100-250 DEG C of reaction 1-12h;
(2) after reaction terminates, filter or centrifugation, solid catalyst is dried, and reclaims; Collect organic phase, obtain 3-methyl-2-cyclopentene-1-one.
2. a kind of method preparing 3-methyl-2-cyclopentene-1-one as claimed in claim 1, is characterized in that step (1) described weakly polar organic solvent comprises hexanaphthene, methylene dichloride, mibk or ethyl acetate.
3. a kind of method preparing 3-methyl-2-cyclopentene-1-one as claimed in claim 1, is characterized in that the volume ratio of the described 2.5-hexanedione of step (1) and weakly polar organic solvent is 1:5-10.
4. a kind of method preparing 3-methyl-2-cyclopentene-1-one as claimed in claim 1, is characterized in that the catalyzer described in step (1) comprises an acidic catalyst and basic catalyst.
5. a kind of method preparing 3-methyl-2-cyclopentene-1-one as claimed in claim 4, is characterized in that described an acidic catalyst is: the SAPO-11 molecular sieve that silica alumina ratio is the ZSM-5 zeolite molecular sieve of 5-50, silica alumina ratio be 5-70 is H beta molecular sieve, silica alumina ratio is 0.1-40 or silica alumina ratio are the USY molecular sieve of 1-50.
6. a kind of method preparing 3-methyl-2-cyclopentene-1-one as claimed in claim 5, is characterized in that the silica alumina ratio of described ZSM-5 zeolite molecular sieve to be the silica alumina ratio of 15-20, H beta molecular sieve is that the silica alumina ratio of 20-25, SAPO-11 molecular sieve be the silica alumina ratio of 0.1-1 or USY molecular sieve is 1-15.
7. a kind of method preparing 3-methyl-2-cyclopentene-1-one as claimed in claim 1, is characterized in that
Basic catalyst described in step (1) comprises: water glass, sodium carbonate, S-WAT, sodium bisulfite, salt of wormwood or calcium acetate.
8. a kind of method preparing 3-methyl-2-cyclopentene-1-one as claimed in claim 1, is characterized in that the quality of step (1) described catalyzer and the volume ratio of 2.5-hexanedione are 1g:0.5-2mL.
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| CN201510764423.5A CN105294418B (en) | 2015-11-11 | 2015-11-11 | A kind of method for preparing the ketone of 3 methyl, 2 cyclopentene 1 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN110550993A (en) * | 2019-08-30 | 2019-12-10 | 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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2015
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| US5276199A (en) * | 1993-02-11 | 1994-01-04 | Ethyl Corporation | Process for preparing cyclopentenones |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110550993A (en) * | 2019-08-30 | 2019-12-10 | 天津大学 | Preparation method of alkyl-substituted tetrahydrodicyclopentadiene dimer and application of alkyl-substituted tetrahydrodicyclopentadiene dimer as jet fuel |
| 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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