CN1699312A - Process for preparing biphenyl - Google Patents
Process for preparing biphenyl Download PDFInfo
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- CN1699312A CN1699312A CN 200510026391 CN200510026391A CN1699312A CN 1699312 A CN1699312 A CN 1699312A CN 200510026391 CN200510026391 CN 200510026391 CN 200510026391 A CN200510026391 A CN 200510026391A CN 1699312 A CN1699312 A CN 1699312A
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Abstract
Disclosed is a process for preparing biphenyl, which comprises using substituted benzene as raw material, producing phenyl benzene through the self coupling at the presence of palladium catalyst, oxidizer, organic acid, and organic solvent actions. The advantages of the invention include simple reaction steps, mild reaction condition, easy operation, and less environmental contamination.
Description
Technical field
The present invention relates to a kind of preparation method's of organic compound, particularly a kind of biphenyl preparation method.
Background technology
Biphenyl compound is at biology, and fields such as medicine and material demonstrate its critical role day by day, needs to use in large quantities the aromatic hydrocarbons linked reaction in its building-up process.
In the research of aromatic hydrocarbons linked reaction, for the known reaction of people is Ullmann reaction (J.Chem.Ber.1901,34,2174.), promptly halogenated aryl hydrocarbon does to generate under the condition of reductive agent the reaction of biphenyl compound at copper.
The aromatic hydrocarbons linked reaction that is widely used in synthetic field is Suzuki reaction (Synth.Commun., 1981,11,513.) at present, and promptly aromatic halides and fragrant boric acid or fragrant boric acid ester under palladium catalysis linked reaction take place.
But, in these aromatic hydrocarbons linked reactions, usually need change the aromatic carbon hydrogen bond into other forms of key earlier, as carbon-halogen bond etc., and then generate required new key.And the by product that produces of this class reaction is metal-salts such as the borate of metering or copper.Like this, not only in organic synthesis, increased reactions steps, improved cost, nor be an eco-friendly method.
Based on above reason, the reaction that utilizes transition metal direct activation aromatic carbon hydrogen bond is focus of research always.
Sasson, Y. etc. be at Adv.Synth.Cata1.2001, discloses the method that the hydrocarbon key direct activation of a kind of phenyl ring prepares biphenyl in 5,343.This method comprises the hydrocarbon key of phenyl ring, at palladium catalyst, and under the acting in conjunction of a promotor such as divalent cobalt, manganous salt, divalence zirconates and a diacetylmethane, direct activation and coupling generates biphenyl.This preferred oxygen of reaction system institute or air pressure are 0.4～1.2MPa, and preferred temperature of reaction is 85～115 ℃.The zeroth order palladium of generation during wherein oxygen or air react as the oxygenant oxidation, thus reach the purpose that palladium can recycle.This method not only needs stress reaction equipment, and is the round-robin of finishing reaction and palladium catalyst under the intensification condition.
And Fujiwara, Y. etc. are at Org.Lett., disclose with oxygenant in 1999,1 (13), 2097., J.Organomet.Chem.1999,580,290. the zeroth order palladium is oxidizing to the divalence palladium, reach the method for catalyzed reaction.Oxygenants such as this method use palladium and benzoquinones, tert-butyl peroxide hydrogen, Potassium Persulphate, under the temperature of reaction and condition of normal pressure of gentleness, just can realize through hydrocarbon key direct activation synthesizing styrene compounds and phenylformic acid, and the zeroth order palladium can be oxidizing to the divalence palladium, reach the purpose of catalyzed reaction.
Summary of the invention
The purpose of this invention is to provide a kind of under the condition of gentleness, on the phenyl ring hydrocarbon key under the acting in conjunction of palladium catalyst, organic acid and oxygenant, thereby the coupling of both direct activation aromatic carbon hydrogen bond generates biphenyl, realizes the round-robin method of palladium catalyst again.
The concrete preparation method of a kind of biphenyl of the present invention is as follows:
In reaction vessel, add substituted benzene, palladium catalyst, oxygenant, organic acid and organic solvent, wherein the mole number of substituted benzene is 1～100 times of palladium catalyst, the oxygenant mole number is 2～100 times of palladium catalyst, the organic acid mole number is 5～100 times of palladium catalyst, the organic solvent mole number is 100～200 times of palladium catalyst, 0 ℃～80 ℃ following stirring reactions 5～48 hours, after reaction finishes, in reaction mixture, add the methylene dichloride dilution, be washed to the pH value then to neutral, water again with dichloromethane extraction once merges organic phase, use anhydrous magnesium sulfate drying, filter, the pressure reducing and steaming methylene dichloride gets biphenyl through column chromatography for separation again.
The substituted benzene that the present invention uses has electron donating group or hydrogen, and benzene, toluene or methyl-phenoxide are wherein arranged.
The palladium catalyst that the present invention uses has palladium or trifluoracetic acid palladium.
The oxygenant that the present invention uses has Potassium Persulphate or neutralized verdigris, and the oxygenant mole number is 2～100 times of palladium catalyst, and the concentration of oxygenant is crossed to hang down and can be caused the efficient of oxidation zeroth order palladium not high.
The present invention uses the organic acid acid group to have strong sucting electronic effect, and trifluoroacetic acid, trichoroacetic acid(TCA), dichloro acetic acid, Monochloro Acetic Acid or acetate are wherein arranged.
The present invention with an organic solvent has methylene dichloride, dioxane, normal hexane, trifluoroacetic acid, trichoroacetic acid(TCA), dichloro acetic acid, Monochloro Acetic Acid, acetate, benzene or methyl-phenoxide etc.
It is as follows that the present invention prepares the chemical equation of biphenyl:
Biphenyl preparation method's of the present invention characteristics are to utilize the hydrocarbon key direct activation of phenyl ring generation coupling, must not change the aromatic carbon hydrogen bond into other forms of key earlier, as carbon-halogen bond or carbon boron key, and then generate required new key, so reactions steps of the present invention is simple.Simultaneously, because reaction does not generate by products such as metal halide or borate, do not need to handle these by products, environmental pollution is little.Simultaneously, the reaction among the present invention can be carried out at ambient temperature, and oxygenant is also cheap and easy to get, does not need heat energy and heating installation, thus easy and simple to handle, the reaction conditions gentleness.
Embodiment
Below by embodiment in detail the present invention is described in detail, but the scope of the invention is not limited to following embodiment.
Embodiment 1
At 20 ℃, in the 10ml round-bottomed flask, add benzene (200mg, 2.5mmol), palladium (11.7mg, 0.05mmol), Potassium Persulphate (672.5mg, 2.5mmol) and the 1ml trifluoroacetic acid, 21 hours stopped reaction of magnetic agitation.Add methylene dichloride 10ml in reaction mixture, washing then (10ml * 3 time) to pH value is neutrality.Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter the pressure reducing and steaming methylene dichloride.Column chromatography for separation gets biphenyl 47.2mg, is white solid, and the TON value is 6.0.(TON value, i.e. product mole number/catalyzer mole number, the cycle index of expression catalyzer in catalyzed reaction)
Embodiment 2
At 20 ℃, (200mg, 2.5mmol), (11.6mg, 0.05mmol), (502.4mg 2.5mmol) He in the 0.6ml trifluoroacetic acid stirs neutralized verdigris palladium to add benzene in the 10ml round-bottomed flask.24 hours stopped reaction of magnetic agitation.Add methylene dichloride 10ml in reaction mixture, washing then (10ml * 3 time) to pH value is neutrality.Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter the pressure reducing and steaming methylene dichloride.Column chromatography for separation gets biphenyl 12.6mg, and the TON value is 1.6.
Embodiment 3
At 75～80 ℃, (400mg, 5.1mmol), (27.1mg, 0.12mmol), (662.8mg is 3.3mmol) with the 0.5ml trifluoroacetic acid for neutralized verdigris for palladium to add benzene in the 10ml round-bottomed flask.24 hours stopped reaction of magnetic agitation.Add methylene dichloride 10ml in reaction mixture, washing then (10ml * 3 time) to pH value is neutrality.Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter the pressure reducing and steaming methylene dichloride.Column chromatography for separation gets biphenyl 58.1mg, and the TON value is 3.1.
Embodiment 4
At 75～80 ℃, (800mg, 10.2mmol), (9.1mg, 0.04mmol), (727.5mg is 2.7mmol) with 1.5 gram trichoroacetic acid(TCA)s (molten state), 24 hours stopped reaction of magnetic agitation for Potassium Persulphate for palladium to add benzene in the 10ml round-bottomed flask.Add methylene dichloride 10ml in reaction mixture, washing then (10ml * 3 time) to pH value is neutrality.Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter.Record biphenyl 11.8mg (in be designated as naphthalene) with GC, the TON value is 1.9.
Embodiment 5
At 60 ℃, in the 10ml round-bottomed flask, add benzene (400mg, 5.1mmol), palladium (14.8mg, 0.07mmol), Potassium Persulphate (6897mg, 2.6mmol) and the 1ml dichloro acetic acid, 24 hours stopped reaction of magnetic agitation.Add methylene dichloride 10ml in reaction mixture, washing then (10ml * 3 time) to pH value is neutrality.Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter.Record biphenyl 15.9mg (in be designated as naphthalene) with GC, the TON value is 1.6.
Embodiment 6
At 20 ℃, in the 10ml round-bottomed flask, add methyl-phenoxide (216mg, 2mmol), palladium (6.7mg, 0.03mmol), Potassium Persulphate (646.6mg, 2.39mmol), 0.1ml trifluoroacetic acid and 1ml methylene dichloride, 40 hours stopped reaction of magnetic agitation.In reaction mixture, add saturated potassium hydrogen carbonate solution adjust pH to neutral, filter the back with methylene dichloride (10ml * 3 time) extracted organic phase.Anhydrous magnesium sulfate drying filters the pressure reducing and steaming methylene dichloride.Column chromatography for separation gets biphenyl methyl ether 8.1mg (comprise 4-4 ' dimethoxy-biphenyl, 4-3 ' dimethoxy-biphenyl and 3-3 ' dimethoxy-biphenyl, wherein 4-4 ' dimethoxy-biphenyl accounts for 73%, determines content by the NMR spectrogram), and the TON value is 1.26.
Embodiment 7
At 20 ℃, in the 10ml round-bottomed flask, add methyl-phenoxide (108mg, 1mmol), palladium (12.1mg, 0.05mmol), Potassium Persulphate (682.7mg, 2.5mmol) and the 1ml trifluoroacetic acid, 17 hours stopped reaction of magnetic agitation.In reaction mixture, add saturated potassium hydrogen carbonate solution adjust pH to neutral, filter the back with methylene dichloride (10ml * 3 time) extracted organic phase.Anhydrous magnesium sulfate drying filters the pressure reducing and steaming methylene dichloride.Column chromatography for separation gets biphenyl methyl ether 11.7mg, and the TON value is 1.02.
Embodiment 8
At 20 ℃, in the 10ml round-bottomed flask, add methyl-phenoxide (108mg, 1mmol), palladium (10.9mg, 0.05mmol), Potassium Persulphate (702.4mg, 2.6mmol), trichoroacetic acid(TCA) (255.4mg, 1.6mmol) with the 1ml methylene dichloride, 24 hours stopped reaction of magnetic agitation.Add methylene dichloride 10ml in reaction mixture, washing then (10ml * 3 time) to pH value is neutrality.Water again with methylene dichloride 10ml extraction once.Merge organic phase, use anhydrous magnesium sulfate drying, filter the pressure reducing and steaming methylene dichloride.Column chromatography for separation gets biphenyl methyl ether 13.2mg, and the TON value is 1.2.
Claims (6)
1. the preparation method of a biphenyl is characterized in that the preparation method is as follows:
In reaction vessel, add substituted benzene, palladium catalyst, oxygenant, organic acid and organic solvent, wherein the mole number of substituted benzene is 1～100 times of palladium catalyst, the oxygenant mole number is 2～100 times of palladium catalyst, the organic acid mole number is 5～100 times of palladium catalyst, the organic solvent mole number is 100～200 times of palladium catalyst, 0 ℃～80 ℃ following stirring reactions 5～48 hours, after reaction finishes, in reaction mixture, add the methylene dichloride dilution, be washed to the pH value then to neutral, water again with dichloromethane extraction once merges organic phase, use anhydrous magnesium sulfate drying, filter, the pressure reducing and steaming methylene dichloride gets biphenyl through column chromatography for separation again.
2. the preparation method of a kind of biphenyl according to claim 1 is characterized in that substituted benzene is selected from benzene, toluene or methyl-phenoxide.
3. the preparation method of a kind of biphenyl according to claim 1 is characterized in that palladium catalyst is selected from palladium or trifluoracetic acid palladium.
4. the preparation method of a kind of biphenyl according to claim 1 is characterized in that oxygenant is selected from Potassium Persulphate or neutralized verdigris.
5. the preparation method of a kind of biphenyl according to claim 1 is characterized in that organic acid is selected from trifluoroacetic acid, trichoroacetic acid(TCA), dichloro acetic acid, Monochloro Acetic Acid or acetate.
6. the preparation method of a kind of biphenyl according to claim 1 is characterized in that organic solvent is selected from methylene dichloride, dioxane, normal hexane, trifluoroacetic acid, trichoroacetic acid(TCA), dichloro acetic acid, Monochloro Acetic Acid, acetate, benzene or methyl-phenoxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100263915A CN1326818C (en) | 2005-06-02 | 2005-06-02 | Process for preparing biphenyl |
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| CNB2005100263915A CN1326818C (en) | 2005-06-02 | 2005-06-02 | Process for preparing biphenyl |
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| CN1699312A true CN1699312A (en) | 2005-11-23 |
| CN1326818C CN1326818C (en) | 2007-07-18 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100519490C (en) * | 2007-05-23 | 2009-07-29 | 浙江工业大学 | Synthesis method for biphenyl compound |
| CN101302227B (en) * | 2008-07-09 | 2010-12-22 | 中国科学院上海有机化学研究所 | Method for synthesizing 3,3'-purrocoline compounds |
| CN101265147B (en) * | 2008-05-08 | 2011-05-11 | 上海交通大学 | Method for preparing biaryl |
| CN103086837A (en) * | 2013-02-07 | 2013-05-08 | 中国科学院长春应用化学研究所 | Preparation method of tetramethyl biphenyl |
| CN103880573A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Preparation method for biphenyl-type compound |
| CN102816040B (en) * | 2008-11-28 | 2015-07-08 | 南开大学 | Oxidative coupling preparation method of phenanthrene, binaphthol and biphenyl derivatives under participation of manganese dioxide or m-chloroperoxybenzoic acid |
| CN107353227A (en) * | 2016-05-09 | 2017-11-17 | 浙江工业大学 | A kind of method that mechanical force promotes lower synthesis biphenyl O- methyl oximido ether compound and biphenylyl carbonyl class compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55141417A (en) * | 1979-04-24 | 1980-11-05 | Ube Ind Ltd | Production of biphenyls |
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2005
- 2005-06-02 CN CNB2005100263915A patent/CN1326818C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100519490C (en) * | 2007-05-23 | 2009-07-29 | 浙江工业大学 | Synthesis method for biphenyl compound |
| CN101265147B (en) * | 2008-05-08 | 2011-05-11 | 上海交通大学 | Method for preparing biaryl |
| CN101302227B (en) * | 2008-07-09 | 2010-12-22 | 中国科学院上海有机化学研究所 | Method for synthesizing 3,3'-purrocoline compounds |
| CN102816040B (en) * | 2008-11-28 | 2015-07-08 | 南开大学 | Oxidative coupling preparation method of phenanthrene, binaphthol and biphenyl derivatives under participation of manganese dioxide or m-chloroperoxybenzoic acid |
| CN103880573A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Preparation method for biphenyl-type compound |
| CN103086837A (en) * | 2013-02-07 | 2013-05-08 | 中国科学院长春应用化学研究所 | Preparation method of tetramethyl biphenyl |
| CN103086837B (en) * | 2013-02-07 | 2016-03-23 | 中国科学院长春应用化学研究所 | A kind of preparation method of tetramethyl biphenyl |
| CN107353227A (en) * | 2016-05-09 | 2017-11-17 | 浙江工业大学 | A kind of method that mechanical force promotes lower synthesis biphenyl O- methyl oximido ether compound and biphenylyl carbonyl class compound |
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| CN1326818C (en) | 2007-07-18 |
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Granted publication date: 20070718 Termination date: 20100602 |