CN101052610A - Synthesizing of cyclopentenone - Google Patents

Synthesizing of cyclopentenone Download PDF

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CN101052610A
CN101052610A CN200580037523.2A CN200580037523A CN101052610A CN 101052610 A CN101052610 A CN 101052610A CN 200580037523 A CN200580037523 A CN 200580037523A CN 101052610 A CN101052610 A CN 101052610A
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丹尼斯·雅各比
法布里斯·凯勒
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Firmenich SA
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Abstract

The invention relates to a process for the preparation, in a single step, of substituted 2-cyclopenten-1-ones by reacting a substituted enone with an aldehyde in the presence of a catalytic system. The catalytic system consists of a metal complex, such as a Ti(Cl)3(alkoxy), and a co-ingredient, such as a carboxylic acid anhydride or an anhydrous salt.

Description

Synthesizing of cyclopentenone
Technical field
The present invention relates to the organic synthesis field, and relate to chemical formula (I) synthetic as that give a definition more accurately
Figure A20058003752300051
The one step method of Cyclopenteneone derivatives.
Background technology
Ishii etc. are at J.Org.Chem., have reported that this is synthetic by zirconium chloride derivative, for example ZrOCl by the reaction of ketone and two normal aldehyde or the synthetic Cyclopenteneone derivatives of reaction of ketenes and aldehyde in 1993,58,4497 2Or ZrCl 4Catalysis, described oxide compound is described to best catalyzer.
Yet, need for example high temperature (at 130～200 ℃, upper part of scope obtains best result, sees Table I) of strict condition by the step of Ishii report.The condition of this strictness can cause low productive rate (substituting group of for example all rings be methyl and to be reflected at when carrying out under 200 ℃ be 17%).These conditions do not have high industrial profit because they are unfavorable for the energy that environment and needs are more and produce a large amount of refuses.
Summary of the invention
In order to overcome aforesaid all or part problem, the present invention relates to carry out and the subsidiary method for preparing cyclopentenone that can cause high yield with mild conditions.
One of purpose of the present invention is the method for the compound of preparation chemical formula (I),
Figure A20058003752300061
Wherein R represents the substituted C of non-imposed selection 1-8Alkyl or alkenyl, or the substituted C of non-imposed selection 5-6Aromatic base; With
R 1, R 2, R 3And R 4Represent hydrogen atom, the substituted C of non-imposed selection at the same time or separately 1-8Alkyl or alkenyl or the substituted C of non-imposed selection 5-6Aromatic base;
Described method comprises the reaction of the aldehyde of the ketenes of chemical formula (II) and chemical formula (III), and the ketenes of chemical formula (II) is,
Figure A20058003752300062
R wherein, R 1, R 3And R 4Have with chemical formula (I) in identical implication; The aldehyde of chemical formula (III) is,
Figure A20058003752300063
R wherein 2Have with chemical formula (I) in identical implication; And
The reaction of described ketenes (II) and aldehyde (III) is to carry out under the condition that catalysis system exists, and this system comprises:
I) metal complex of at least a chemical formula (IV),
M(OR 5) 4-nX n (IV)
Wherein M is Ti (IV) or Zr (IV), R 5Represent C 1-6On behalf of halogenide and n, straight or branched alkyl, X represent 1～3 integer; With
The ii) at least a common composition that is selected from the group of forming by following material:
A) contain the alkyl of 2～10 carbon atoms or the carboxylic acid anhydride of aromatic base;
B) be selected from by Li +, Na +, K +, Cs +, Mg 2+, Ni 2+, Ca 2+, Zn 2+, Fe 3+And Al 3+Anhydrous sulfate, muriate or the bromide of the metallic cation in the group of forming;
C) a kind of insoluble inorganic substance that can generate clathrate with water; With
D) C 4-C 15Ortho ester, BF 3, N-methyl-N-trimethyl silyl-trifluoroacetamide, 1-trimethyl silyl imidazoles and ClSi (R 6) 3, R 6Represent C 1-5Alkyl.
Described radicals R, R 1, R 2, R 3And R 4The substituting group of possible non-imposed selection be the reactive group that does not influence ketenes (II) or aldehyde (III).As described R, R 1, R 2, R 3And R 4When group was represented alkyl or alkenyl, the substituent example of described non-imposed selection comprised one or two methyl, ethyl, methoxy or ethoxy.As described radicals R, R 1, R 2, R 3And R 4When representing aromatic base, the substituent example of described non-imposed selection comprises one or two methyl, ethyl, methoxyl group, oxyethyl group or nitro.
According to specific implementations of the present invention, R represents C 1-8Alkyl or alkenyl or the substituted C of non-imposed selection 5-6Aromatic base, perhaps R 1, R 2, R 3And R 4Represent hydrogen atom, C at the same time or separately 1-8Alkyl or alkenyl or the substituted C of non-imposed selection 5-6Aromatic base.
According to described embodiment, R represents C especially 1-8Alkyl or alkenyl, R 1, R 2, R 3And R 4Represent hydrogen atom, C at the same time or separately 1-8Alkyl or alkenyl.
In another embodiment of the present invention, the ketenes of chemical formula (I), wherein R represent methylidene, ethyl or amyl group or the substituted phenyl of non-imposed selection have been obtained by corresponding compounds (II) and compound (III).Perhaps or simultaneously, R 1, R 2, R 3And R 4Represent hydrogen atom, methyl, ethyl or amyl group or the substituted phenyl of non-imposed selection at the same time or separately.
Especially according to described embodiment, R represent methylidene, ethyl or amyl group, and R 1, R 2, R 3And R 4Represent hydrogen atom, methyl, ethyl or amyl group at the same time or separately.
According to any one above-mentioned embodiment, R 4Represent hydrogen atom.Especially, described R, R 1, R 2Or R 3Represent methylidene, ethyl or the substituted phenyl of non-imposed selection at the same time or separately, or only be methyl or ethyl, and R 4Represent hydrogen atom.
According to another embodiment of the present invention, according to diagram 1, in the presence of the identical catalysis system of the inventive method, ketone (II) can obtain by ketone (V) and ketone (VI) or aldehyde (VI) one original position that reacts.
Diagram 1
Figure A20058003752300081
Wherein R, R 1, R 3And R 4Have the implication identical with the above.
Therefore the invention still further relates to the method that further contains above-mentioned steps.
Suitable ketone (II), (V) or concrete example (VI) are diethyl ketone, benzophenone, methyl benzophenone, ethyl benzophenone or n-hexyl ketone.
Suitable aldehyde (III) or concrete example (VI) are acetaldehyde, formaldehyde, propionic aldehyde or phenyl aldehyde.
According to another embodiment of the present invention, this method comprises that the first step that diethyl ketone and acetaldehyde one are reacted to obtain the ketone of chemical formula (II), next reacts with acetaldehyde.
According to the embodiment of the present invention, the mol ratio of ketenes (II) and aldehyde (III) is between 1.1/1～1/6, more preferably between 1/1～1/5, even more preferably between 1/1.1～1/5.In addition, the mol ratio of ketone (V) and compound (VI) is between 1/1～1/8, more preferably between 1/2.5～1/6 and even more preferably between 1/3～1/5.
As mentioned above, method of the present invention is carried out under the condition that catalysis system exists, this catalysis system by metal complex with become to be grouped into altogether.Metal complex is used with substoichiometric or the catalytic amount with respect to initial aldehydes or ketones.
Metal complex has general formula:
M(OR 5) 4-nX n (IV)
M wherein, n, R 5Has the above implication that provides with X.According to specific implementations of the present invention, M represents Ti (IV), R 5Represent straight or branched C 3-4On behalf of Cl atom and index n, alkyl, X represent 2 or 3.
Particularly when not carrying out purifying, the application of the mixture of the metal complex of chemical formula (IV) also is easily when catalyzer original position before it uses is synthetic in described method.
According to specific implementations of the present invention, the common composition of catalysis system is selected from by the alkyl carboxylic acid acid anhydride that contains 4～8 carbon atoms or aromatic base carboxylic acid anhydride, BF 3, ClSi (R 6) 3(R 6Represent C 1-5Alkyl) and be selected from by Na +, K +, Mg 2+, Ca 2+, Zn 2+, Fe 3+The group that the anhydrous vitriol of the metallic cation in the group of forming, muriate or bromide are formed.
Preferably, this common composition is selected from by diacetyl oxide, propionic anhydride or butyryl oxide, BF 3, ClSi (R 6) 3(R 6Represent methylidene or ethyl), anhydrous Na 2SO 4Or K 2SO 4And Mg 2+, Fe 3+Or Zn 2+Anhydrous chloride or the group formed of bromide.
Two or three application that is total to mixture of ingredients also is possible.
Metal complex can be added in the reaction medium in very big concentration range.As the indefiniteness example, can quote the catalyst concn in 0.01～0.20 molar equivalent scope with respect to starting ketone (II) or molar weight (V).Preferably, the concentration of metal complex will be at 0.01～0.10 molar equivalent.Needless to say the suitable concentration of catalyzer will be decided by the character of metal complex and the reaction times of expectation.
Composition can be added in the reaction medium in very big concentration range altogether.As the indefiniteness example, can quote relatively and the salt concn of concentration in 0.05～1.2 molar equivalent scope of starting ketone (II) or mole number (V).Preferably, the concentration of salt will be at 0.10～0.60 molar equivalent.Yet in another preferred embodiment, the concentration of salt is 0.20～0.50 molar equivalent.Needless to say the suitable concentration of additive will depend on the character of salt.
The inventive method can be carried out under the condition of existence or disappearance solvent, and it is favourable still implementing under anhydrous condition in any case, wherein refers to here that by " anhydrous " water content is lower than 1wt%, preferably is lower than 0.1wt%.When the needs solvent, it is possible using the mixture of pure solvent or solvent.Described solvent must be compatible with the reaction conditions chemistry, promptly do not hinder reaction and do not make catalyzer deactivation, for example Weak solvent or non-ligand solvent.The preferred solvent that is used for the inventive method has and is higher than 60 ℃ boiling point and is selected from the group of being made up of ether, ester, aromatic solvent and straight or branched or cyclic hydrocarbon.More preferably, solvent is a for example butylacetate of ester.
And solvent can be starting ketone (II) or (V) or initial aldehyde (III) or (VI).
The temperature of implementing the inventive method is between 60 ℃～140 ℃, preferably between 70 ℃～100 ℃ or 70 ℃～110 ℃.Certainly those skilled in the art also can come the selective reaction temperature according to the fusing point of starting product and the finished product and boiling point and/or possible solvent.
The present invention will describe in further detail by the mode of following examples, temperature with degree centigrade represent (℃); The NMR spectroscopic data is at CDCl 3In write down with the instrument of 360MHz, chemical shift δ is to be standard with TMS, represents that with ppm coupling constant J represents with Hz, and all abbreviations have the common implication of this area.
Embodiment
Embodiment 1
2,3,4,5-tetramethyl--2-cyclopentenes-1-ketone synthetic
A) preparation of metal catalyst solution
Contain TiCl 3(O iPr) catalytic solution of complex compound can according to E.V.Vedejs etc. at J.Org.Chem., (1988), 53, the step of describing in 1593 but use TiCl 4And Ti (O iPr) 4Complex compound obtains as initial substance.In order to obtain to have the catalytic solution that concentration is 1.3mmole metal in every gram catalytic solution, changed the amount of using.
All solution that obtain are not further operated and are used.
B) preparation 2,3,4,5-tetramethyl--2-cyclopentenes-1-ketone
The acetate butyric acid of 2000g (23.2mol) in the round-bottomed flask that mechanical stirrer, dropping funnel and reflux exchanger are housed, pack into as the starting ketone of solvent, the Magnesium Chloride Anhydrous of 0.35 molar equivalent and contain the aforesaid titanium catalytic solution of three chloro titanium propanolate complex compounds of 0.06 molar equivalent with 75%w/w.The suspension liquid that obtains is stirred and is heated to 90 ℃ tempestuously.Dropwise add through 3 hours at 90 ℃ of acetaldehyde then 2 molar equivalents.Reaction continued other one hour and was cooled to 40 ℃.Reaction mixture neutralizes with 10% acetic acid aqueous solution hydrolysis and with 20% wet chemical.Breadboard Suhl pool filled column (Sulzer packed column) is gone in the organic phase straight-forward fractional distillation that obtains thus obtain trans: the title compound of the isomer mixture of cis=85: 15, productive rate is 27% (B.p.=70 during P=8mbar～80 ℃) and ketenes (II) (4-methyl-4-hexene-3-one), productive rate are 31% (B.p.=45 during P=8mbar～65 ℃).
1H-NMR (trans-isomer(ide)): 1.15 (d 3H); (1.19 d 3H); (1.68 s 3H); (1.88 m 1H); (1.98 s 3H); (2.25 m 1H).
13C-NMR (trans-isomer(ide)): 8.5; 14.6; 15.1; 17.7; 46.2; 48.4; 134.5; 171.6; 211.0.
Embodiment 2
3,4-diethyl-2,5-dimethyl-2-cyclopentenes-1-ketone synthetic
The butylacetate of 265g (3.08mol) in the round-bottomed flask that mechanical stirrer, dropping funnel and reflux exchanger are housed, pack into as the diethyl ketone of solvent, the Magnesium Chloride Anhydrous of 0.36 molar equivalent and contain the aforesaid titanium catalytic solution of three chloro titanium propanolate complex compounds of 0.053 molar equivalent with 252g.The suspension liquid that obtains is stirred and is heated to 85 ℃ tempestuously.Dropwise add through 2 hours at 85 ℃ of propionic aldehyde then 2.1 molar equivalents.Reaction continued other one hour and was cooled to 40 ℃.Reaction mixture is with 10% acetic acid aqueous solution (500g) hydrolysis, decants and with 10% acetic acid aqueous solution (200g) and the sodium-chlor washing of 50g.Then with organic phase with 20% solution of potassium carbonate washed twice.
At Na 2SO 4After the last drying, with solvent evaporation.(419.6g) distills by Vigreux column with thick product, make it pass through the fractionation of Fischer fractional column then, obtain productive rate and be 17% title compound (during P=3mbar B.p.=58 ℃) and productive rate and be 32% ketenes (II) (4-methyl-4-teracrylic acid-ketone) (during P=43mbar B.p.=84 ℃).
MS：166(76)；151(37)；138(100)；137(94)；109(72)；67(54)；41(30)。
1H-NMR：2.52(1H；m)；2.29(2H；m)；2.01(1H；dq；2.5Hz；8Hz)；1.90-1.80(1H；m)；1.69(3H；br?s)；1.34-1.22(1H；m)；1.17(3H；d；J＝6Hz)；1.10(3H；d；J＝7Hz)；0.94(3H；d；J＝8Hz)。
13C-NMR：211.8(s)；175.9(s)；134.4(s)；50.5(d)；45.2(d)；25.2(t)；21.8(t)；16.9(q)，11.8(q)；11.4(q)；8.0(q)。
Embodiment 3
Synthesizing of various chemical formulas (I) compound
The general step of cyclopentenone method
The butylacetate pure or that have 75%w/w of 1 molar equivalent in the round-bottomed flask that mechanical stirrer, dropping funnel and reflux exchanger are housed, pack into as starting ketone (seeing for details following), the Magnesium Chloride Anhydrous of 0.35 molar equivalent and the aforesaid titanium catalytic solution that contains three chloro titanium propanolate complex compounds of 0.05 molar equivalent of solvent.The suspension liquid that obtains is stirred and is heated to 90～100 ℃ tempestuously.Under 90～100 ℃, the aldehyde of chemical formula (III) was dropwise added through 3 hours then.Being reflected at 90～100 ℃ continued other one hour and is cooled to 40 ℃.Reaction mixture is with 10% hydrochloric acid soln hydrolysis, and with 20% wet chemical neutralization.
The organic phase straight-forward fractional distillation that obtains enters breadboard Suhl pool filled column.The result is comprehensively as follows:
Experiment A)
Starting ketone: 4-methyl-4-hexene-3-one
Initial aldehyde: phenyl aldehyde (1.2 molar equivalent)
Product: 4-phenyl-2,3,5-trimethylammonium-2-cyclopentenes-1-ketone+3-phenyl-2,4,5-trimethylammonium-2-cyclopentenes-1-ketone (20/80)
Productive rate: 25% (based on employed starting ketone)
Productive rate: 45% (based on the starting ketone that transforms)
Analysis (3-phenyl-2,4,5-trimethylammonium-2-cyclopentenes-1-ketone) for principal product:
1H-NMR：1.08(d，3H)；1.25(d，3H)；1.88(s，3H)；2.05(m，1H)；2.85(m，1H)；7.3-7.5(m，5H)。
13C-NMR：9.5；15.5；19；45；48.5；127-129(6C)；135；170.5；211。
Experiment B)
Starting ketone: 4-methyl-4-hexene-3-one
Initial aldehyde: 10-undecenal (0.9 molar equivalent)
Product: 4-(9-decene base)-2,3,5-trimethylammonium-2-cyclopentenes-1-ketone+3-(9-decene base)-2,4,5-trimethylammonium-2-cyclopentenes-1-ketone (33/66)
Productive rate: 36% (based on employed starting ketone)
Productive rate: 72% (based on the starting ketone that transforms)
The analysis of the mixture that obtains:
1H-NMR：1.15(d)；1.17(d)；1.25-1.40(m)；1.70(s)；1.90(m)；2.0(s)；2.05(m)；2.35(m)；2.50(m)；4.95(m，2H)；5.80(m，1H)。
13C-NMR：8；15；17；18；27；28-30；33；34；44；47；49；52；114；135；135.5；139；171；175.5；211。
Experiment C)
Starting ketone: 5-ethyl-4-methyl-4-teracrylic acid-ketone
Initial aldehyde: acetaldehyde (1.2 molar equivalent)
Product:
4,4-diethyl-2,3,5-trimethylammonium-2-cyclopentenes-1-ketone
Productive rate: 40% (based on starting ketone)
Productive rate: 58% (based on the starting ketone that transforms)
The analysis of product:
1H-NMR：0.45(t，3H)；0.78(t，3H)；1.08(d，3H)；1.35-1.70(m，4H)；1.70(s，3H)；1.85(s，3H)；2.20(q，1H)。
13C-NMR：7.95；8.75；9.60；10.10；12.30；27.55；29.95；46.40；51.85；136.3；171.1；210.3。
Experiment D)
Starting ketone: diethyl ketone
Initial aldehyde: phenyl aldehyde (3.0 molar equivalent)
Product:
3,4-phenylbenzene-2,5-dimethyl-2-cyclopentenes-1-ketone cis/trans: 15/85
Productive rate: 32% (based on the starting ketone that uses)
The productive rate of ketone (II): 24% (based on the starting ketone that uses)
The analysis of product:
Trans-isomer(ide)
1H-NMR：1.34(d，J＝7.17，3H)；2.02(s，3H)；2.40(dq，J 1＝7.17，J 2＝2.56，1H)；3.97(sb，1H)；7.0-7.3(m?10H)
13C-NMR：10.1；15.3；51.25；56.33；126-129(10CH)；135.2；136.7；142；167；210.9
Cis-isomeride
1H-NMR：0.75(d，J＝7.68，3H)；2.08(s，3H)；2.92(m，1H)；4.6(d，J＝6.14，1H)；7.0-7.3(m，10H)
13C-NMR：9.8；12.3；45.5；52.5；126-129(10CH)；135.7；136.9；139.2；166.3；211.4
Experiment E)
Starting ketone: 1-3 diphenyl acetone
Initial aldehyde: acetaldehyde (3.0 molar equivalent)
Product:
3,4-dimethyl-2,5-phenylbenzene-2-cyclopentenes-1-ketone cis/trans: 15/85
Productive rate: 48% (based on the initial aldehyde that uses)
The productive rate of ketone (II): 36% (based on the starting ketone that uses)
The analysis of product:
Trans-isomer(ide)
1H-NMR：1.35(d，J＝6.65，3H)；2.17(s，3H)；2.87(dq，J 1＝6.65，J 2＝3.07，1H)；3.23(d，J＝3.07，1H)；7.1-7.4(m，10H)
13C-NMR：15.9；18.1；47.7；60.7；126-129(10CH)；131.8；138.9；139.5；174；205。
Cis-isomeride
1H-NMR：0.8(d，J＝7.17，3H)；2.15(s，3H)；3.15(m，1H)；3.95(d，J＝7.17，1H)；7.1-7.4(m，10H)。
13C-NMR：16.1；16.3；42.8；56.7；126-129(11CH)；137.7；139.7；174.7；206.5

Claims (8)

1. the method for preparing the compound of chemical formula (I),
Figure A2005800375230002C1
Wherein R represents the substituted C of non-imposed selection 1～8Alkyl or alkenyl or the substituted C of non-imposed selection 5～6Aromatic base; With
R 1, R 2, R 3And R 4Represent hydrogen atom, the substituted C of non-imposed selection at the same time or separately 1～8Alkyl or alkenyl or the substituted C of non-imposed selection 5～6Aromatic base;
Described method comprises the reaction of the aldehyde of the ketenes of chemical formula (II) and chemical formula (III), and the ketenes of chemical formula (II) is,
R wherein, R 1, R 3And R 4Have with chemical formula (I) in identical implication; The aldehyde of chemical formula (III) is,
Figure A2005800375230002C3
R wherein 2Have with chemical formula (I) in identical implication; And
The reaction of described ketenes (II) and aldehyde (III) is to carry out under the condition that catalysis system exists, and this system comprises:
I) metal complex of at least a chemical formula (IV),
M(OR 5) 4-nX n (IV)
Wherein M is Ti (IV) or Zr (IV), R 5Represent C 1-6On behalf of halogenide and n, straight or branched alkyl, X represent 1～3 integer; With
The ii) at least a common composition that is selected from the group of forming by following material:
A) contain the alkyl carboxylic acid acid anhydride or the aromatic base carboxylic acid anhydride of 2～10 carbon atoms;
B) be selected from by Li +, Na +, K +, Cs +, Mg 2+, Ni 2+, Ca 2+, Zn 2+, Fe 3+And Al 3+Anhydrous sulfate, muriate or the bromide of the metallic cation in the group of forming;
C) a kind of insoluble inorganic substance that can generate clathrate with water; With
D) C 4-C 15Ortho ester, BF 3, N-methyl-N-trimethyl silyl-trifluoroacetamide, 1-trimethyl silyl imidazoles and ClSi (R 6) 3, R 6Represent C 1-5Alkyl.
2. method according to claim 1 is characterized in that R represents C 1～8Alkyl or alkenyl; With
R 1, R 2, R 3And R 4Represent hydrogen atom, C at the same time or separately 1-8Alkyl or alkenyl.
3. method according to claim 1 is characterized in that R represent methylidene, ethyl or amyl group or the substituted phenyl of non-imposed selection.
4. method according to claim 1 is characterized in that R 1, R 2, R 3And R 4Represent hydrogen atom, methyl, ethyl or amyl group or the substituted phenyl of non-imposed selection at the same time or separately.
5. method according to claim 1 is characterized in that R, R 1, R 2Or R 3Represent methylidene, ethyl or the substituted phenyl of non-imposed selection at the same time or separately, and R 4Represent hydrogen atom.
6. according to the described method of claim 1, it is characterized in that under the defined catalysis system existence condition as claim 1, obtain ketenes (II) by the original position that reacts of the aldehydes or ketones one with the ketone of chemical formula V and chemical formula (VI), the ketone of chemical formula V is,
Figure A2005800375230003C1
The aldehydes or ketones of chemical formula (VI) is,
Figure A2005800375230004C1
R wherein, R 1, R 3And R 4Have with claim 1 in identical implication.
7. method according to claim 1 is characterized in that M represents Ti (IV), R 5Represent straight or branched C 3-4Alkyl, X are represented the Cl atom, and index n represents 2 or 3.
8. method according to claim 5, the common composition that it is characterized in that catalyst system are selected from by the alkyl carboxylic acid acid anhydride that contains 4～8 carbon atoms or aromatic base carboxylic acid anhydride, BF 3, ClSi (R 6) 3, and be selected from by Na +, K +, Mg 2+, Ca 2+, Zn 2+, Fe 3+The group that the anhydrous sulfate of the metallic cation in the group of forming, muriate or bromide are formed, wherein R 6Represent C 1-5Alkyl.
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Cited By (2)

* Cited by examiner, † Cited by third party
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CN102040586A (en) * 2010-11-10 2011-05-04 兰州安杰利生物化学科技有限公司 Method for synthesizing 4,5-dichloro-1,2-dithiocyclopentenone
CN104910000A (en) * 2015-05-25 2015-09-16 张家港市振方化工有限公司 Preparation method of 2-heptylidene-cyclopentanon

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102040586A (en) * 2010-11-10 2011-05-04 兰州安杰利生物化学科技有限公司 Method for synthesizing 4,5-dichloro-1,2-dithiocyclopentenone
CN102040586B (en) * 2010-11-10 2012-12-12 兰州安杰利生物化学科技有限公司 Method for synthesizing 4,5-dichloro-1,2-dithiocyclopentenone
CN104910000A (en) * 2015-05-25 2015-09-16 张家港市振方化工有限公司 Preparation method of 2-heptylidene-cyclopentanon

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