CN1986503A - Iron catalyzed styrene derivative synthesizing process with active arene and alkyne - Google Patents
Iron catalyzed styrene derivative synthesizing process with active arene and alkyne Download PDFInfo
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- CN1986503A CN1986503A CNA2006101482261A CN200610148226A CN1986503A CN 1986503 A CN1986503 A CN 1986503A CN A2006101482261 A CNA2006101482261 A CN A2006101482261A CN 200610148226 A CN200610148226 A CN 200610148226A CN 1986503 A CN1986503 A CN 1986503A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention is iron catalyzed styrene derivative synthesizing process with active arene and alkyne, and belongs to the field of chemical technology. Active arene, alkyne and iron catalyst are mixed in solvent through stirring and reacted, the reacted mixture liquid is filtered, and the filtrate is decompression distilled to eliminate solvent and column chromatographically separated to obtain styrene derivative. The styrene derivative has the structure as shown. The present invention has cheap facile iron catalyst, mild reaction condition, simple operation, environment friendship and high economic performance.
Description
Technical field
That the present invention relates to is a kind of preparation method of chemical technology field, the catalytic method by active aromatic hydrocarbons and alkynes styrene derivative synthesizing of particularly a kind of iron.
Background technology
Styrene derivatives is the important organic chemicals that is widely used in fields such as biology, medicine, organic synthesis.The preparation styrene derivatives can be realized by following three kinds of approach: (1) halogenated aryl hydrocarbon, and transition metal-catalyzed linked reaction takes place for aromatic hydrocarbons borane reagent, aromatic hydrocarbons silica reagent and alkene finishes; (2) in the presence of metal catalyst and oxygenant, finish by active aromatic hydrocarbons and alkene generation oxidative coupling; (3) finish by active aromatic hydrocarbons and alkynes generation addition reaction.Approach (1) needs the prepared beforehand arene derivatives, can form a large amount of by products after reaction finishes simultaneously, and Atom economy is bad; Approach (2) needs to use a large amount of oxygenants, can form a large amount of by products after the reaction, and Atom economy is also bad; Approach (3) aromatic hydrocarbons c h bond is directly to the phenylacetylene derivatives addition, do not form by product, Atom economy is good, the while environmental friendliness, but the catalyzer of realization approach (3) is three fluoro sulfonates of palladium (Pd), platinum (Pt), gold noble metal catalysts such as (Au) or scandium rare earth metals such as (Sc) normally, the use cost height is unfavorable for industrial application; And except using expensive catalysts, the system that has also needs to use strong acid etc. than exacting terms.
Find through literature search prior art, Fujiwara etc. are at " Science " (" science magazine ", 2000 287 volume 1992-1995 pages or leaves) delivered the paper that is entitled as " Efficient Activation of AromaticC-H Bonds for Addition to C-C Multiple Bonds " (" effectively activating the addition of aromatic hydrocarbons C-H ") to the C-C multikey, a kind of process for catalytic synthesis of styrene derivatives is proposed, but, the use of trifluoroacetic acid had both increased the cost of raw material in the method, had also increased the production cost that conversion unit increases because of acidproof requirement simultaneously; In addition, the discharging meeting of strong acid causes certain pollution to environment.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, provide a kind of iron catalytic method by active aromatic hydrocarbons and alkynes styrene derivative synthesizing, make it under room temperature or low-temperature heat condition, with iron is catalyzer, by active aromatic hydrocarbons and alkynes addition reaction taking place directly obtains styrene derivatives, and reaction conditions gentleness, easy and simple to handle, environmental friendliness, used iron catalyst is cheap, be easy to get, nontoxic.
The present invention is achieved through the following technical solutions, and the inventive method is specially: active aromatic hydrocarbons and alkynes, iron catalyst are mixed in solvent, stir, react; After reaction finishes, reaction mixture is filtered, filtrate except that after desolvating, obtains styrene derivatives through column chromatography through underpressure distillation again.
Reaction equation of the present invention is as follows:
Wherein, R is one or more power supplying groups, R
1, R
2Be substituting groups such as hydrogen, alkyl, aryl, carbonyl or carboxyl.
Described active aromatic hydrocarbons, its chemical structure are shown in (I), and R is one or more power supplying groups.As trimethylbenzene.
Described alkynes, its chemical structure shown in (II), R
1, R
2Be substituting groups such as hydrogen, alkyl, aryl, carbonyl or carboxyl.
Described active aromatic hydrocarbons and alkynes also can be present in the same compound simultaneously, and this compound chemical structure formula is as follows:
Wherein, R is one or more power supplying groups, R
1Be substituting groups such as hydrogen, alkyl, aryl, carbonyl or carboxyl.The styrene derivatives that the intramolecularly addition reaction obtains into ring can take place in this compounds.As coumarin kind compound, its chemical structural formula is as follows:
Wherein, R is one or more power supplying groups, R
1Be substituting groups such as hydrogen, alkylaryl, carbonyl or carboxyl.
Described iron catalyst is a trivalent iron salt, as Anhydrous Ferric Chloride, six crystal water iron(ic) chloride, Iron triperchlorate, three fluosulfonic acid iron.
Described solvent is an organic nitro-compound, as Nitromethane 99Min., nitroethane, oil of mirbane.
Described reaction, the reaction times is 1.0-48 hour, temperature of reaction is 20～100 ℃.
Described iron catalyst, its molal quantity are the 5.0%-50% of the amount of substance of alkynes.
Described active aromatic hydrocarbons, its molal quantity be alkynes amount of substance 1.0-10 doubly.
The present invention because uses cheap, low toxicity, the iron that conveniently is easy to get is catalyzer, utilizes active aromatic hydrocarbons and alkynes direct addition to obtain styrene derivatives, avoided because of the use halogenated aryl hydrocarbon aryl borane reagent, aryl silica reagent and the by product that produces.The use of iron catalyst greatly reduces the use cost of catalyzer, helps industrial application.In addition, this reaction can be carried out at ambient temperature, and reaction reagent need not to carry out processed, and reaction system also need not water conservation in the reaction process, and is easy and simple to handle.
The present invention at room temperature, the active aromatic hydrocarbons of raw material, alkynes and iron catalyst stirring reaction in solvent obtain styrene derivatives.Its beneficial effect is: (1) catalyst system therefor ferron is cheap nontoxic reagent, and the industrial goods supply and marketing is arranged, and need not preparation in advance, and handles conveniently; (2) use of iron catalyst greatly reduces the cost of reaction, helps industrial application; (3) organic nitro-compound of Shi Yonging avoids using strong acid as solvent, and the industrial goods supply and marketing is arranged, and need not preparation in advance, has reduced production and equipment cost; (4) reaction can be carried out in room temperature, and room temperature range is wide, is not subjected to weather effect, and is easy and simple to handle, save energy.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
At room temperature (20 ℃), in the 10mL round-bottomed flask, add trimethylbenzene (360.5mg, 3.0mmol), phenylacetylene (102.2mg, 1.0mmol) and FeCl
3(16.2mg 0.10mmol), stirs in the 0.5mL Nitromethane 99Min., and after 5 hours, stopped reaction filters, and underpressure distillation removes and desolvates, and column chromatography for separation obtains product 1-(2 ', 4 ', 6 '-trimethylphenyl)-1-vinylbenzene 142.3mg, and yield is 64%.
Embodiment 2
At room temperature (20 ℃), in the 10mL round-bottomed flask, add trimethylbenzene (120.5mg, 1.0mmol), phenylacetylene (102.2mg, 1.0mmol) and FeCl
3(16.2mg 0.10mmol), stirs in the 0.5mL Nitromethane 99Min..After 5 hours, stopped reaction.Gas-chromatography records product 1-(2 ', 4 ', 6 '-trimethylphenyl)-1-vinylbenzene 142.3mg, and yield is 64%.
Embodiment 3
At room temperature (20 ℃), in the 10mL round-bottomed flask, add trimethylbenzene (1200.5mg, 10.0mmol), phenylacetylene (102.2mg, 1.0mmol) and FeCl
3(16.2mg 0.10mmol), stirs in the 0.5mL Nitromethane 99Min..After 2 hours, stopped reaction.Gas-chromatography records product 1-(2 ', 4 ', 6 '-trimethylphenyl)-1-vinylbenzene 190.0mg, and yield is 85%.
Embodiment 4
At room temperature (20 ℃), in the 10mL round-bottomed flask, add trimethylbenzene (360.5mg, 3.0mmol), phenylacetylene (102.2mg, 1.0mmol) and FeCl
3(81.0mg 0.5mmol), stirs in the 1.5mL Nitromethane 99Min..After 1 hour, stopped reaction.Gas-chromatography records product 1-(2 ', 4 ', 6 '-trimethylphenyl)-1-vinylbenzene 189.0mg, and yield is 85%.
Embodiment 5
At room temperature (20 ℃), in the 10mL round-bottomed flask, add trimethylbenzene (721.5mg, 6.0mmol), phenylacetylene (102.2mg, 1.0mmol) and FeCl
3(16.2mg 0.10mmol), stirs in the 0.5mL Nitromethane 99Min..After 5 hours, stopped reaction.Gas-chromatography records product 1-(2 ', 4 ', 6 '-trimethylphenyl)-1-vinylbenzene 189.0mg, and yield is 85%.
Embodiment 6
Heat 60 ℃, in the 10mL round-bottomed flask, add trimethylbenzene (360.5mg, 3.0mmol), phenylacetylene (102.2mg, 1.0mmol) and FeCl
3(8.1mg 0.05mmol), stirs in 0.5 mL Nitromethane 99Min..After 5 hours, stopped reaction.Gas-chromatography records product 1-(2 ', 4 ', 6 '-trimethylphenyl)-1-vinylbenzene 164.5mg, and yield is 74%.
Embodiment 7
At room temperature (20 ℃), in the 10mL round-bottomed flask, add trimethylbenzene (360.5mg, 3.0mmol), 4-anisole acetylene (132.2mg, 1.0mmol) and FeCl
3(16.2mg 0.10mmol), stirs in the 0.5mL Nitromethane 99Min..After 5 hours, stopped reaction.Filter, underpressure distillation removes and desolvates.Column chromatography for separation obtains product 1-2 ', and 4 ', 6 '-trimethylphenyl-1-4 '-methoxy styrene 201.6mg, yield are 80%.
Embodiment 8
At room temperature (20 ℃), in the 10mL round-bottomed flask, add trimethylbenzene (360.5mg, 3.0mmol), 4-chlorobenzene acetylene (136.6mg, 1.0mmol) and FeCl
3(16.2mg 0.10mmol), stirs in the 0.5mL Nitromethane 99Min..After 6 hours, stopped reaction.Filter, underpressure distillation removes and desolvates.Column chromatography for separation obtains product 1-2 ', and 4 ', 6 '-trimethylphenyl-1-4 '-chloro-styrene 177.2mg, yield are 69%.
Embodiment 9
Heat 55 ℃, in the 10mL round-bottomed flask, add trimethylbenzene (360.5mg, 3.0mmol), the 1-phenyl-allylene (116.2mg, 1.0mmol) and FeCl
3(16.2mg 0.10mmol), stirs in the 0.5mL Nitromethane 99Min..After 12 hours, stopped reaction.Filter, underpressure distillation removes and desolvates.Column chromatography for separation obtains product (Z/E)-1-2 ', 4 ', 6 '-trimethylphenyl-1-phenylallene 151.2mg, and yield is 68%.
Embodiment 10
Heat 60 ℃, in the 10mL round-bottomed flask, add p-Xylol (318.5mg, 3.0mmol), phenylacetylene (102.2mg, 1.0mmol) and FeCl
3(16.2mg 0.10mmol), stirs in the 0.5mL Nitromethane 99Min..After 6 hours, gas-chromatography records product 1-1 ', 4 '-3,5-dimethylphenyl-1-vinylbenzene 175.0mg, and yield is 84%.
Embodiment 11
Heat 80 ℃, in the 10mL round-bottomed flask, add trimethylbenzene (360.5mg, 3.0mmol), ethyl phenylpropiolate (174.2mg, 1.0mmol) and FeCl
3(16.2mg 0.10mmol), stirs in the 0.5mL Nitromethane 99Min..After 38 hours, stopped reaction.Filter, underpressure distillation removes and desolvates.Column chromatography for separation obtains product (Z/E)-1-2 ', 4 ', 6 '-trimethylphenyl-1-cinnamic acid ethyl ester 123.6mg, and yield is 42%.
Embodiment 12
Heat 60 ℃, in the 10mL round-bottomed flask, add naphthalene (384.6mg, 3.0mmol), phenylacetylene (102.2mg, 1.0mmol) and FeCl
3(16.2mg 0.10mmol), stirs in the 0.5mL Nitromethane 99Min..After 5 hours, gas-chromatography records product 1-naphthyl-1-vinylbenzene 118.7mg, and yield is 52%.
Embodiment 13
Heat 90-100 ℃, in the 10mL round-bottomed flask, add phenylpropiolic acid-β-naphthalene ester (58.0mg, 0.2mmol) and FeCl
3(6.7mg 0.04mmol), stirs in 1.0mL oil of mirbane.After 38 hours, stopped reaction.Filter, underpressure distillation removes and desolvates.Column chromatography for separation obtains product 4-benzene generation-benzo [6,7]-tonka bean camphor and 4-benzene generation-benzo [5,6]-tonka bean camphor mixture (ratio 42/58) 34.0mg, and yield is 58%.
Embodiment 14
At room temperature (20 ℃), in the 10mL round-bottomed flask, add trimethylbenzene (360.5mg, 3.0mmol), phenylacetylene (102.2mg, 1.0mmol) and FeCl
36H
2(27.5mg 0.10mmol), stirs in the 0.5mL Nitromethane 99Min. O.After 24 hours, stopped reaction.Gas-chromatography records product 1-(2 ', 4 ', 6 '-trimethylphenyl)-1-vinylbenzene 13.7mg, and yield is 9%.
Embodiment 14
At room temperature (20 ℃), in the 10mL round-bottomed flask, add trimethylbenzene (360.5mg, 3.0mmol), phenylacetylene (102.2mg, 1.0mmol) and FeCl
36H
2(27.5mg 0.10mmol), stirs in the 0.5mL Nitromethane 99Min. O.After 24 hours, stopped reaction.Gas-chromatography records product 1-(2 ', 4 ', 6 '-trimethylphenyl)-1-vinylbenzene 13.7mg, and yield is 9%.
Embodiment 15
At room temperature (20 ℃), in the 10mL round-bottomed flask, add trimethylbenzene (360.5mg, 3.0mmol), phenylacetylene (102.2mg, 1.0mmol), FeCl
3(16.1mg 0.10mmol), stirs in 0.5mL oil of mirbane.After 5 hours, stopped reaction.Gas-chromatography records product 1-(2 ', 4 ', 6 ' trimethylphenyl)-1-vinylbenzene 121.0mg, and yield is 55%.
Embodiment 16
At room temperature (20 ℃), in the 10mL round-bottomed flask, add trimethylbenzene (360.5mg, 3.0mmol), phenylacetylene (102.2mg, 1.0mmol), FeCl
3(16.1mg 0.10mmol), stirs in the 0.5mL nitroethane.After 5 hours, stopped reaction.Gas-chromatography records product 1-(2 ', 4 ', 6 '-trimethylphenyl)-1-vinylbenzene 185.0mg, and yield is 82%.
Claims (10)
1, the catalytic method by active aromatic hydrocarbons and alkynes styrene derivative synthesizing of a kind of iron is characterized in that described method is: active aromatic hydrocarbons and alkynes, iron catalyst are mixed, stir, react in solvent; After reaction finishes, reaction mixture is filtered, filtrate except that after desolvating, obtains styrene derivatives through column chromatography through underpressure distillation again; The chemical structural formula of described styrene derivatives is:
Wherein, R is one or more power supplying groups, R
1, R
2Be hydrogen, alkyl, aryl, carbonyl or carboxyl.
2, the catalytic method by active aromatic hydrocarbons and alkynes styrene derivative synthesizing of iron according to claim 1 is characterized in that, described active aromatic hydrocarbons, and its chemical structural formula is as follows:
Wherein, R is one or more electron-donating groups.
3, the catalytic method by active aromatic hydrocarbons and alkynes styrene derivative synthesizing of iron according to claim 1 is characterized in that, described alkynes, and its chemical structural formula is as follows:
Wherein, R
1, R
2Be hydrogen, alkyl, aryl, carbonyl or carboxyl.
4, the catalytic method by active aromatic hydrocarbons and alkynes styrene derivative synthesizing of iron according to claim 1 is characterized in that, described active aromatic hydrocarbons and alkynes are present in the compound simultaneously, and this compound chemical structure formula is as follows:
Wherein, R is one or more electron-donating groups, R
1Be hydrogen, alkyl, aryl, carbonyl or carboxyl.
5, the catalytic method by active aromatic hydrocarbons and alkynes styrene derivative synthesizing of iron according to claim 1 is characterized in that described iron catalyst is a trivalent iron salt.
6, the catalytic method by active aromatic hydrocarbons and alkynes styrene derivative synthesizing of iron according to claim 5 is characterized in that, described trivalent iron salt is Anhydrous Ferric Chloride, six crystal water iron(ic) chloride, Iron triperchlorate or three fluosulfonic acid iron.
7, the catalytic method by active aromatic hydrocarbons and alkynes styrene derivative synthesizing of iron according to claim 1 is characterized in that described solvent is an organic nitro-compound.
8, the catalytic method by active aromatic hydrocarbons and alkynes styrene derivative synthesizing of iron according to claim 7 is characterized in that described organic nitro-compound is Nitromethane 99Min., nitroethane or oil of mirbane.
9, the catalytic method by active aromatic hydrocarbons and alkynes styrene derivative synthesizing of iron according to claim 1 is characterized in that, described reaction, and the reaction times is 1.0-48 hour, temperature of reaction is 20～100 ℃.
10, the catalytic method by active aromatic hydrocarbons and alkynes styrene derivative synthesizing of iron according to claim 1 is characterized in that, described iron catalyst, its molal quantity be alkynes amount of substance 5.0% to 50%; Described active aromatic hydrocarbons, its molal quantity are 1.0 to 10.0 times of amount of substance of alkynes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101482261A CN100494128C (en) | 2006-12-28 | 2006-12-28 | Method for synthesizing styrene derivative from active arene and alkyne catalyzed by iron |
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| CNB2006101482261A CN100494128C (en) | 2006-12-28 | 2006-12-28 | Method for synthesizing styrene derivative from active arene and alkyne catalyzed by iron |
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| CN1986503A true CN1986503A (en) | 2007-06-27 |
| CN100494128C CN100494128C (en) | 2009-06-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085458A (en) * | 2015-08-20 | 2015-11-25 | 潘星星 | Synthesis method of coumarin derivatives |
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2006
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085458A (en) * | 2015-08-20 | 2015-11-25 | 潘星星 | Synthesis method of coumarin derivatives |
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Granted publication date: 20090603 Termination date: 20111228 |