CN106905095A - A kind of method that carbonyl Iron cluster cooperates with trace palladium chtalyst Sonogashira cross-coupling reactions - Google Patents

A kind of method that carbonyl Iron cluster cooperates with trace palladium chtalyst Sonogashira cross-coupling reactions Download PDF

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CN106905095A
CN106905095A CN201710104306.5A CN201710104306A CN106905095A CN 106905095 A CN106905095 A CN 106905095A CN 201710104306 A CN201710104306 A CN 201710104306A CN 106905095 A CN106905095 A CN 106905095A
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halogenated aryl
aryl hydrocarbon
phenyl
alkyl
coupling reactions
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CN106905095B (en
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刘敏
张伟强
王贤
刘小静
陈云茹
陈娜
张曦
任丹凤
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Shaanxi Normal University
First Affiliated Hospital of Medical College of Xian Jiaotong University
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First Affiliated Hospital of Medical College of Xian Jiaotong University
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Abstract

The invention discloses a kind of carbonyl Iron cluster cooperate with trace palladium chtalyst Sonogashira coupling reactions method, the method is with palladium bichloride, tri-iron dodecacarbonyl as catalyst, acetylenic ketone as part, methyl alcohol as solvent, make halogenated aryl hydrocarbon, Terminal Acetylenes, K2CO3Reaction, obtains aryl acetylene compound；The method considerably reduces the consumption of palladium metal, and operation is simple, mild condition (generally 60 DEG C or so), and functional group compatibility is good, and high income, catalyst amount is low, and yield is high.

Description

A kind of carbonyl Iron cluster collaboration trace palladium chtalyst Sonogashira cross-couplings are anti- The method answered
【Technical field】
The invention belongs to Sonogashira coupling reaction technical fields, and in particular to a kind of carbonyl Iron cluster cooperates with trace The method for measuring palladium chtalyst Sonogashira cross-coupling reactions.
【Background technology】
Sonogashira reaction be with end-group alkyne, halogenated aryl hydrocarbon or vinyl halogenated hydrocarbons be substrate synthesize aryne one Plant very effective method.Sonogashira reactions are a kind of important reactions for synthesizing C―C bond formation, are widely used in natural The synthesis of product, bioactive molecule, heterocyclic compound and molecular nanostructure etc..Classical Sonogashira coupling reactions are Carried out under the conditions of palladium copper mixed catalytic, reported to Sonogashira and Hagihara in 1975 and added in palladium catalyst Entering the cuprous iodide of 10mol% and being also catalyzed the reaction is carried out.But then it is found that in such reaction, precious metal palladium is used Amount is big, and the presence of copper causes generations of the Glaser from coupled product, and the waste and target for causing the alkynes of costliness separate tired Difficulty, and volatile acetylene copper appearance etc..
Iron with its unique advantage, such as cheap and easy to get, high-efficiency environment friendly, and gradually obtained the concern of people, either iron Be used alone or with other metal concerted catalysis, synthesis triple carbon-carbon bonds coupling reaction in all show catalytic very high Energy.1954, Kharasch and Reinmuth had found that iron can be with catalytic reaction first, subsequent 1971, and Tamura and Kochi sends out Existing molysite can be as the effective catalyst of carbon carbon coupling reaction.Bolm seminars realize halogen with ferric trichloride combination DMEDA For aromatic hydrocarbons and the arylation of alkynes, when cuprous iodide is added, the reaction can also be carried out efficiently.Taillefer et al. utilizes iron Copper catalysis system, realizes the nitrogen arylation reaction of nitrogen heterocyclic ring and halide.Vogel et al. uses ferric acetyl acetonade and iodate It is cuprous as catalyst, be catalyzed the coupling reaction of aryl iodide and terminal alkyne.These examples all illustrate palladium iron double metal, In Sonogashira cross-coupling reactions being appeared in as a kind of efficient synergistic catalyst.
Then, people need to look for a kind of material collaboration trace palladium of the alternative copper of cheap green to be catalyzed The carrying out of Sonogashira reactions.
【The content of the invention】
It is anti-it is an object of the invention to provide a kind of carbonyl Iron cluster collaboration trace palladium chtalyst Sonogashira cross-couplings The method answered, with solving transition metal-catalyzed Sonogashira cross-coupling reactions, the big problem of palladium metal consumption.
The present invention uses following technical scheme, a kind of carbonyl Iron cluster collaboration trace palladium chtalyst Sonogashira couplings The method of reaction, with palladium bichloride, tri-iron dodecacarbonyl as catalyst, acetylenic ketone as part, methyl alcohol as solvent, by halogenated aryl hydrocarbon, end Alkynes, K2CO3It is in molar ratio 1:(1~1.3):1, at 50~60 DEG C, 12h is reacted, obtain aryl acetylene compound；
Wherein, palladium bichloride consumption is the 0.02% of halogenated aryl hydrocarbon mole, and tri-iron dodecacarbonyl consumption rubs for halogenated aryl hydrocarbon The 0.1%~0.4% of that amount, acetylenic ketone consumption is the 1.0%~4.0% of halogenated aryl hydrocarbon mole；
The structural formula of acetylenic ketone is as follows：
Wherein, R1Represent phenyl, C1~C4Alkyl-substituted phenyl, C1~C4Appointing in alkoxy substituted phenyl, halogenophenyl Meaning is a kind of, R2Represent phenyl, C1~C4Alkyl-substituted phenyl, C1~C4Any one in alkoxy substituted phenyl, halogenophenyl.
Further, R in acetylenic ketone1The C of representative1~C4Alkyl-substituted phenyl includes 4- aminomethyl phenyls, 3- aminomethyl phenyls, 2- Any one in aminomethyl phenyl, R in acetylenic ketone1The C of representative1~C4Alkoxy substituted phenyl includes 4- methoxyphenyls；
R in acetylenic ketone2The C of representative1~C4Alkyl-substituted phenyl includes 4- aminomethyl phenyls, R in acetylenic ketone2The C of representative1~C4Alcoxyl Base substituted-phenyl includes R in 4- methoxyphenyls, acetylenic ketone2The halogenophenyl of representative includes 3- chlorphenyls.
Further, Terminal Acetylenes isR' represents phenyl, C in formula1~C4Alkyl-substituted phenyl, methoxyl group take For phenyl, halogenophenyl, C4~C8Any one in alkyl.
Further, the C that R' is represented in Terminal Acetylenes1~C4Alkyl-substituted phenyl includes 4- aminomethyl phenyls or 4- ethylphenyls, end The methoxy substitution phenyl that R' is represented in alkynes includes 4- methoxyphenyls, the C that R' is represented in Terminal Acetylenes4~C8Alkyl include 1- butyl, Any one in 1- amyl groups, 1- hexyls.
Further, halogenated aryl hydrocarbon isR in formula " represents H, C1~C4Alkyl, C1~C4Alkoxy, nitre Base, trifluoromethyl, trifluoromethoxy, CmH2m+1COOCnH2n+1、COCnH2n+1In any one, wherein, m be 1,2 or 3, n be 1st, 2 or 3.
Further, the C that R in halogenated aryl hydrocarbon " is represented1~C4Alkyl is including any in 4- methyl, 3- methyl, 4- ethyls The C that one kind, R in halogenated aryl hydrocarbon " is represented1~C4Alkoxy include 4- methoxyl groups, R in halogenated aryl hydrocarbon " represent nitro include 4- nitre Base, R in halogenated aryl hydrocarbon " represent trifluoromethyl include 4- trifluoromethyls, R in halogenated aryl hydrocarbon " represent trifluoromethoxy include The C that 4- trifluoromethoxies or 3- trifluoromethoxies, R in halogenated aryl hydrocarbon " is representedmH2m+1COOCnH2n+1Including 4-C2H5COOCH3, halogen For R in aromatic hydrocarbons " represent COCnH2n+1Including 4-COCH3, R in halogenated aryl hydrocarbon " also represent 4- bromos.
Further, palladium bichloride consumption is the 0.02% of halogenated aryl hydrocarbon mole, and tri-iron dodecacarbonyl consumption is halo virtue The 0.1% of hydrocarbon mole, acetylenic ketone consumption is the 4.0% of halogenated aryl hydrocarbon mole.
Further, the R in acetylenic ketone1Represent 4- methoxyphenyls, 4- aminomethyl phenyls, 3- aminomethyl phenyls, 2- aminomethyl phenyls, Any one in phenyl；R in acetylenic ketone2Represent any one in phenyl, 4- methoxyphenyls, 4- aminomethyl phenyls, 3- chlorphenyls Kind；
R' in Terminal Acetylenes represent phenyl, 4- methoxyphenyls, 4- aminomethyl phenyls, 4- ethylphenyls, 1- butyl, 1- amyl groups, Any one in 1- hexyls；
R in halogenated aryl hydrocarbon " represent H, 4- methoxyl group, 4- trifluoromethoxies, 3- trifluoromethoxies, 4- methyl, 3- methyl, 4- ethyls, 4- nitros, 4-C2H5COOCH3、4-COCH3, 4- trifluoromethyls, any one in 4- bromos.
Further, palladium bichloride consumption is the 0.02% of halogenated aryl hydrocarbon mole, and tri-iron dodecacarbonyl consumption is halo virtue The 0.1% of hydrocarbon mole, acetylenic ketone consumption is the 4.0% of halogenated aryl hydrocarbon mole.
The beneficial effects of the invention are as follows：With acetylenic ketone as part in the present invention, the collaboration Determination of Trace Palladium collaboration of carbonyl Iron cluster is urged Change the Sonogashira cross-coupling reactions of halogenated aryl hydrocarbon and Terminal Acetylenes, hence it is evident that reduce the consumption of palladium metal, operation letter It is single, mild condition (generally 60 DEG C or so), functional group compatibility is good, and high income, catalyst amount is low, and yield is high.
【Specific embodiment】
With reference to specific embodiment, the present invention is described in detail, but the scope of the present invention is not limited to these implementations Example.
Embodiment 1
By 0.11g (0.5mmol) 4- methoxyl groups iodobenzene, 0.00009g (6ppm) PdCl2、0.00025g(0.0005mmol) Fe3(CO)12, 0.0045g (0.02mmol) 1- (4- methoxyphenyls) -3- phenyl -2- acetenyl -1- ketone and 0.0689g (0.5mmol)K2CO3Add in reaction bulb, add 3ml CH3OH, adds 66 μ l (0.6mmol) phenylacetylenes, and reaction system exists 60 DEG C of reaction 12h.Through column chromatography for separation, (volume ratio with dichloromethane and petroleum ether is 0 to organic phase:1、1:100、1:50、1: 10 mixed liquor gradient elution), faint yellow solid 1- methoxyl groups -4- (phenylacetylene base) benzene is obtained, its yield is 96%.
Embodiment 2
In embodiment 1,1- used (4- methoxyphenyls) -3- phenyl -2- acetenyl -1- ketone equimolars 1,3- bis- Phenylpropyl -2- acetenyl -1- ketone is replaced, and other steps are same as Example 1, obtain 1- methoxyl groups -4- (phenylacetylene base) benzene, its Yield is 78%.
Embodiment 3
In embodiment 1,1- used (4- methoxyphenyls) -3- phenyl -2- acetenyl -1- ketone equimolar 1- (4- Methoxyphenyl) -3- (4- methoxyphenyls) -2- acetenyl -1- ketone replaces, and other steps are same as Example 1, obtain 1- first Epoxide -4- (phenylacetylene base) benzene, its yield is 72%.
Embodiment 4
In embodiment 1,1- used (4- methoxyphenyls) -3- phenyl -2- acetenyl -1- ketone equimolar 1- (4- Chlorphenyl) -3- (4- aminomethyl phenyls) -2- acetenyl -1- ketone replaces, other steps are same as Example 1, obtain 1- methoxyl groups - 4- (phenylacetylene base) benzene, its yield is 71%.
Embodiment 5
In embodiment 1,1- used (4- methoxyphenyls) -3- phenyl -2- acetenyl -1- ketone equimolar 1- (4- Chlorphenyl) -3- (4- chlorphenyls) -2- acetenyl -1- ketone replaces, and other steps are same as Example 1, obtain 1- methoxyl groups -4- (phenylacetylene base) benzene, its yield is 85%.
Embodiment 6
In embodiment 1,1- used (4- methoxyphenyls) -3- phenyl -2- acetenyl -1- ketone equimolar 1- (4- Methoxyphenyl) -3- (4- bromophenyls) -2- acetenyl -1- ketone replaces, and other steps are same as Example 1, obtain 1- methoxies Base -4- (phenylacetylene base) benzene, its yield is 98%.
Embodiment 7
In embodiment 1,1- used (4- methoxyphenyls) -3- phenyl -2- acetenyl -1- ketone equimolar 1- (4- Methoxyphenyl) -3- (4- chlorphenyls) -2- acetenyl -1- ketone replaces, and other steps are same as Example 1, obtain 1- methoxies Base -4- (phenylacetylene base) benzene, its yield is 90%.
Embodiment 8
In embodiment 1,1- used (4- methoxyphenyls) -3- phenyl -2- acetenyl -1- ketone equimolar 1- (4- Methoxyphenyl) -3- (4- fluorophenyls) -2- acetenyl -1- ketone replaces, and other steps are same as Example 1, obtain 1- methoxies Base -4- (phenylacetylene base) benzene, its yield is 87%.
Embodiment 9
In embodiment 1,1- used (4- methoxyphenyls) -3- phenyl -2- acetenyl -1- ketone equimolar 1- (4- Methoxyphenyl) -3- (3- chlorphenyls) -2- acetenyl -1- ketone replaces, and other steps are same as Example 1, obtain 1- methoxies Base -4- (phenylacetylene base) benzene, its yield is 78%.
Embodiment 10
In embodiment 1,1- used (4- methoxyphenyls) -3- phenyl -2- acetenyl -1- ketone equimolar 1- (4- Aminomethyl phenyl) -3- phenyl -2- acetenyl -1- ketone replaces, and other steps are same as Example 1, obtain 1- methoxyl groups -4- (benzene second Alkynyl) benzene, its yield is 78%.
Embodiment 11
In embodiment 1,1- used (4- methoxyphenyls) -3- phenyl -2- acetenyl -1- ketone equimolar 1- (3- Methoxyphenyl) -3- (3- chlorphenyls) -2- acetenyl -1- ketone replaces, and other steps are same as Example 1, obtain 1- methoxies Base -4- (phenylacetylene base) benzene, its yield is 76%.
Embodiment 12
In embodiment 1,1- used (4- methoxyphenyls) -3- phenyl -2- acetenyl -1- ketone equimolar 1- (2- Methoxyphenyl) -3- (3- chlorphenyls) -2- acetenyl -1- ketone replaces, and other steps are same as Example 1, obtain 1- methoxies Base -4- (phenylacetylene base) benzene, its yield is 70%.
Embodiment 13
In embodiment 1,4- methoxyl groups iodobenzene used is replaced with equimolar 4- methyl iodobenzene, other steps with implement Example 1 is identical, obtains 1- methyl -4- (phenylacetylene base) benzene, and its yield is 90%.
Embodiment 14
In embodiment 1,4- methoxyl groups iodobenzene used is replaced with equimolar 4- nitros iodobenzene, other steps with implement Example 1 is identical, obtains 1- nitros -4- (phenylacetylene base) benzene, and its yield is 83%.
Embodiment 15
In embodiment 1,4- methoxyl groups iodobenzene used is replaced with equimolar 4- ethyls iodobenzene, other steps with implement Example 1 is identical, obtains 1- ethyls -4- (phenylacetylene base) benzene, and its yield is 87%.
Embodiment 16
In embodiment 1,4- methoxyl groups iodobenzene used is replaced with equimolar 4- iodobenzenes methyl acetate, other steps with Embodiment 1 is identical, obtains 4- (phenylacetylene base) ethyl benzoate, and its yield is 83%.
Embodiment 17
In embodiment 1,4- methoxyl groups iodobenzene used is replaced with equimolar 4- trifluoromethyl iodobenzenes, other steps with Embodiment 1 is identical, obtains 1- trifluoromethyls -4- (phenylacetylene base) benzene, and its yield is 86%.
Embodiment 18
In embodiment 1,4- methoxyl groups iodobenzene used is replaced with equimolar 4- trifluoromethoxies iodobenzene, other steps It is same as Example 1,1- trifluoromethoxies -4- (phenylacetylene base) benzene is obtained, its yield is 82%.
Embodiment 19
In embodiment 1,4- methoxyl groups iodobenzene used is replaced with equimolar iodobenzene, other steps and the phase of embodiment 1 Together, 2- tolans is obtained, its yield is 89%.
Embodiment 20
In embodiment 1,4- methoxyl groups iodobenzene used is replaced with equimolar 3- methoxyl groups iodobenzene, other steps and reality Apply example 1 identical, obtain 1- methoxyl groups -3- (phenylacetylene base) benzene, its yield is 86%.
Embodiment 21
In embodiment 1,4- methoxyl groups iodobenzene used is replaced with equimolar 3- methyl iodobenzene, other steps with implement Example 1 is identical, obtains 1- methyl -3- (phenylacetylene base) benzene, and its yield is 85%.
Embodiment 22
In embodiment 1,4- methoxyl groups iodobenzene used is replaced with equimolar 3- trifluoromethyl iodobenzenes, other steps with Embodiment 1 is identical, obtains 1- trifluoromethyls -3- (phenylacetylene base) benzene, and its yield is 81%.
Embodiment 23
In embodiment 1,4- methoxyl groups iodobenzene is replaced with equimolar 3- trifluoromethoxies iodobenzene, other steps with implement Example 1 is identical, obtains 1- trifluoromethyls 3- (phenylene-ethynylene) benzene, and its yield is 81%.
Embodiment 24
In embodiment 1,4- methoxyl groups iodobenzene is replaced with equimolar 4- ethyl ketones base iodobenzene, other steps and embodiment 1 It is identical, 1- (4- (phenylene-ethynylene) phenyl) ethyl ketone is obtained, its yield is 86%.
Embodiment 25
In embodiment 1,4- methoxyl groups iodobenzene is replaced with equimolar 4- bromos iodobenzene, other steps and the phase of embodiment 1 Together, 1- bromo- 4- (phenylene-ethynylene) benzene is obtained, its yield is 88%.
Embodiment 26
In embodiment 1, phenylacetylene used is replaced with equimolar 4- Liquid Crystal Compounds Intermediate p-Ethyl-phenylacetylenes, other steps and embodiment 1 It is identical, yellow solid 1- methoxyl groups -4- (4- ethyls-phenylacetylene base) benzene is obtained, its yield is 83%.
Embodiment 27
In embodiment 1, phenylacetylene used is replaced with equimolar 3- methyl phenylacetylene, other steps and embodiment 1 It is identical, yellow solid 1- methoxyl groups -4- (3- amino-phenylacetylene base) benzene is obtained, its yield is 71%.
Embodiment 28
In embodiment 1, phenylacetylene used is replaced with equimolar 4- Methoxy-phenylacetylenes, other steps and embodiment 1 is identical, obtains 1,2- bis- (4- methoxyphenyls) acetylene, and its yield is 81%.
Embodiment 29
In embodiment 1, phenylacetylene used is replaced with equimolar 1- hexins, and other steps are same as Example 1, obtain To 1- (hex- 1- alkynyls) -4- methoxybenzenes, its yield is 73%.
Embodiment 30
In embodiment 1, phenylacetylene used equimolar 4- methyl phenylacetylene replacement, other steps and the phase of embodiment 1 Together, 1- methyl -3- ((4- methoxyphenyls) acetenyl) benzene is obtained, its yield is 81%.
Embodiment 31
In embodiment 1, phenylacetylene used equimolar 3- amino phenylacetylene replacement, other steps and the phase of embodiment 1 Together, 3- ((4- methoxyphenyls) acetenyl) aniline is obtained, its yield is 68%.
Embodiment 32
In embodiment 1, phenylacetylene used is replaced with equimolar 1- heptyne, and other steps are same as Example 1, obtain 1- methoxyl groups -4- (hept- 1- alkynyls)-benzene, its yield is 71%.
Embodiment 33
In embodiment 1, phenylacetylene used is replaced with equimolar 1- octynes, and other steps are same as Example 1, obtain 1- methoxyl groups -4- (octyl- 1- alkynyls) benzene, its yield is 69%.

Claims (9)

1. a kind of method that carbonyl Iron cluster cooperates with trace palladium chtalyst Sonogashira coupling reactions, it is characterised in that with chlorine Change palladium, tri-iron dodecacarbonyl are catalyst, acetylenic ketone is part, methyl alcohol is solvent, by halogenated aryl hydrocarbon, Terminal Acetylenes, K2CO3In molar ratio It is 1:(1~1.3):1, at 50~60 DEG C, 12h is reacted, obtain aryl acetylene compound；
Wherein, palladium bichloride consumption is the 0.02% of halogenated aryl hydrocarbon mole, and tri-iron dodecacarbonyl consumption is halogenated aryl hydrocarbon mole 0.1%~0.4%, acetylenic ketone consumption for halogenated aryl hydrocarbon mole 1.0%~4.0%；
The structural formula of the acetylenic ketone is as follows：
Wherein, R1Represent phenyl, C1~C4Alkyl-substituted phenyl, C1~C4It is any one in alkoxy substituted phenyl, halogenophenyl Kind, R2Represent phenyl, C1~C4Alkyl-substituted phenyl, C1~C4Any one in alkoxy substituted phenyl, halogenophenyl.
2. the method that carbonyl Iron cluster as claimed in claim 1 cooperates with trace palladium chtalyst Sonogashira coupling reactions, its It is characterised by, R in acetylenic ketone1The C for representing1~C4Alkyl-substituted phenyl includes 4- aminomethyl phenyls, 3- aminomethyl phenyls, 2- methyl Any one in phenyl, R in acetylenic ketone1The C for representing1~C4Alkoxy substituted phenyl includes 4- methoxyphenyls；
R in acetylenic ketone2The C for representing1~C4Alkyl-substituted phenyl includes 4- aminomethyl phenyls, R in acetylenic ketone2The C for representing1~C4 Alkoxy substituted phenyl includes R in 4- methoxyphenyls, acetylenic ketone2The halogenophenyl for representing includes 3- chlorphenyls.
3. the method that carbonyl Iron cluster as claimed in claim 1 cooperates with trace palladium chtalyst Sonogashira coupling reactions, its It is characterised by, described Terminal Acetylenes isR' represents phenyl, C in formula1~C4Alkyl-substituted phenyl, methoxy substitution Phenyl, halogenophenyl, C4~C8Any one in alkyl.
4. the method that carbonyl Iron cluster as claimed in claim 3 cooperates with trace palladium chtalyst Sonogashira coupling reactions, its It is characterised by,
The C that R' is represented in Terminal Acetylenes1~C4Alkyl-substituted phenyl includes 4- aminomethyl phenyls or 4- ethylphenyls, R' generations in Terminal Acetylenes The methoxy substitution phenyl of table includes 4- methoxyphenyls, the C that R' is represented in Terminal Acetylenes4~C8Alkyl include 1- butyl, Any one in 1- amyl groups, 1- hexyls.
5. the method that carbonyl Iron cluster as claimed in claim 3 cooperates with trace palladium chtalyst Sonogashira coupling reactions, its It is characterised by, described halogenated aryl hydrocarbon isR in formula " represents H, C1~C4Alkyl, C1~C4Alkoxy, nitre Base, trifluoromethyl, trifluoromethoxy, CmH2m+1COOCnH2n+1、COCnH2n+1In any one, wherein, m be 1,2 or 3, n be 1st, 2 or 3.
6. the method that carbonyl Iron cluster as claimed in claim 5 cooperates with trace palladium chtalyst Sonogashira coupling reactions, its It is characterised by,
The C that R in halogenated aryl hydrocarbon " is represented1~C4Alkyl includes any one in 4- methyl, 3- methyl, 4- ethyls, halo The C that R in aromatic hydrocarbons " is represented1~C4Alkoxy include 4- methoxyl groups, R in halogenated aryl hydrocarbon " represent nitro include 4- nitros, halogen For R in aromatic hydrocarbons " represent trifluoromethyl include 4- trifluoromethyls, R in halogenated aryl hydrocarbon " represent trifluoromethoxy include 4- trifluoros The C that methoxyl group or 3- trifluoromethoxies, R in halogenated aryl hydrocarbon " is representedmH2m+1COOCnH2n+1Including 4-C2H5COOCH3, halogenated aryl hydrocarbon The COC that middle R " is representednH2n+1Including 4-COCH3, R in halogenated aryl hydrocarbon " also represent 4- bromos.
7. carbonyl Iron cluster as claimed in claim 1 or 2 cooperates with the side of trace palladium chtalyst Sonogashira coupling reactions Method, it is characterised in that the palladium bichloride consumption is the 0.02% of halogenated aryl hydrocarbon mole, tri-iron dodecacarbonyl consumption is halo virtue The 0.1% of hydrocarbon mole, acetylenic ketone consumption is the 4.0% of halogenated aryl hydrocarbon mole.
8. the method that carbonyl Iron cluster as claimed in claim 5 cooperates with trace palladium chtalyst Sonogashira coupling reactions, its It is characterised by,
R in the acetylenic ketone1Represent appointing in 4- methoxyphenyls, 4- aminomethyl phenyls, 3- aminomethyl phenyls, 2- aminomethyl phenyls, phenyl Meaning is a kind of；R in the acetylenic ketone2Represent any one in phenyl, 4- methoxyphenyls, 4- aminomethyl phenyls, 3- chlorphenyls；
R' in the Terminal Acetylenes represent phenyl, 4- methoxyphenyls, 4- aminomethyl phenyls, 4- ethylphenyls, 1- butyl, 1- amyl groups, Any one in 1- hexyls；
R in the halogenated aryl hydrocarbon " represent H, 4- methoxyl group, 4- trifluoromethoxies, 3- trifluoromethoxies, 4- methyl, 3- methyl, 4- ethyls, 4- nitros, 4-C2H5COOCH3、4-COCH3, 4- trifluoromethyls, any one in 4- bromos.
9. the method that trace palladium chtalyst Sonogashira coupling reactions are cooperateed with such as carbonyl Iron cluster as claimed in claim 8, Characterized in that, the palladium bichloride consumption is the 0.02% of halogenated aryl hydrocarbon mole, tri-iron dodecacarbonyl consumption is halogenated aryl hydrocarbon The 0.1% of mole, acetylenic ketone consumption is the 4.0% of halogenated aryl hydrocarbon mole.
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CN107365256A (en) * 2017-08-09 2017-11-21 龙岩学院 The three core vanadium clusters and its synthetic method of a kind of propeller configurations
CN110124742A (en) * 2019-05-28 2019-08-16 万华化学集团股份有限公司 A method of by alkynol partial hydrogenation prepare enol catalyst and preparation method and utilize the catalyst preparation enol

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CN105859495A (en) * 2016-05-05 2016-08-17 陕西师范大学 Acetyenic-ketone-promoted CuI-catalyzed method for conducting Sonogashira coupled reaction

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107365256A (en) * 2017-08-09 2017-11-21 龙岩学院 The three core vanadium clusters and its synthetic method of a kind of propeller configurations
CN110124742A (en) * 2019-05-28 2019-08-16 万华化学集团股份有限公司 A method of by alkynol partial hydrogenation prepare enol catalyst and preparation method and utilize the catalyst preparation enol
CN110124742B (en) * 2019-05-28 2023-05-26 万华化学集团股份有限公司 Catalyst for preparing enol by partial hydrogenation of alkynol, preparation method thereof and method for preparing enol by using catalyst

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