CN101456790A - Method for preparing diaryl alcohol by catalyzing addition reaction of aryl boric acid and aldehyde by nickel - Google Patents
Method for preparing diaryl alcohol by catalyzing addition reaction of aryl boric acid and aldehyde by nickel Download PDFInfo
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- CN101456790A CN101456790A CNA2008102286135A CN200810228613A CN101456790A CN 101456790 A CN101456790 A CN 101456790A CN A2008102286135 A CNA2008102286135 A CN A2008102286135A CN 200810228613 A CN200810228613 A CN 200810228613A CN 101456790 A CN101456790 A CN 101456790A
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Abstract
The invention relates to a method for preparing diaryl alcohol by catalyzing addition reaction of catalytic aryl boronic acid to aldehyde through nickel, which belongs to the technical field of fine chemistry industry. The method is characterized in that a nickel salt taken as a catalyst catalyzes the nucleophilic addition reaction of the aryl boronic acid and the aldehyde in a low-carbon alcohol solvent or a mixed solvent of toluene and low-carbon alcohol in the presence of alkaline and at a reaction temperature of between 60 and 90 DEG C, wherein the reaction formula is shown in (1). The invention has the advantage of providing an economic, simple and convenient method for preparing a diaryl alcohol compound. The method takes the easily obtained low-carbon alcohol with low toxicity and low price or the mixed solution of the toluene and the low-carbon alcohol as a solvent and the nickel salt with cheap price as the catalyst to catalyze the nucleophilic addition reaction of the aryl boronic acid to the aldehyde. The nickel salt catalyst has high catalytic activity and good selectivity, is sable in the air, and can be commercially purchased. The nucleophilic addition reaction of the nickel catalytic aryl boronic acid to the aldehyde is characterized in that heating reaction is performed in the low-carbon alcohol or the mixed solvent of the toluene and the low-carbon alcohol in the presence of the alkaline, and reaction products are easy to separate and have high yield.
Description
Technical field
The invention belongs to the fine chemical technology field, relate to economy, the simple and convenient process for preparing of 2-diaryl alcohol compounds, particularly prepare the 2-diaryl alcohol that is connected with other reactive groups on the phenyl ring.
Background technology
The 2-diaryl alcohol compounds is widely used in the synthetic of medicine, agricultural chemicals and natural product, is the very important fine chemical product of a class.Usually adopt the nucleophilic addition(Adn) of organomagnesium reagent or organolithium reagent and aromatic aldehyde to prepare the 2-diaryl alcohol compounds, though the reactive behavior height of these two kinds of organometallic reagents, but its functional group's compatibility is bad, can not only react with aldehyde radical, also can with functional group reactionses such as ester group, nitro, cyano group, limited its range of application.In recent years, bibliographical information is in the presence of rhodium catalyst, and organotin reagent and aryl boric acid can carry out nucleophilic addition(Adn) to aldehyde, and (organotin is relevant: Qi, S. to generate 2-diaryl alcohol; Moro M.; Inoue Y.Chem.Commun., 1997,1621-1622; Qi, S.; Moro, M.; Fukuhara, H.; Kawanishi T.; Inoue Y.Tetrahedron, 2003,59, the 4351-4361. phenylo boric acid is relevant: Sakai, M.; Ueda, M.; Miyaura, N.Angew Chem.Int.Ed., 1998,37,3279-3281; Ueda, M.; Miyaura, N.J.Org.Chem., 2000,65,4450-4452; F ü rstner, A.; Krause, H.Adv.Synth.Catal., 2001,343,343-350; Son, S.U.; Kim, S.B.; Reingold, J.A.; Carpenter, G.B.; Sweigart, D.A.J.Am.Chem.Soc., 2005,127,12238-12239; Huang, R.; Shaughnessy, k.H.Chem.Commun., 2005,4484-4486.).Though this has improved functional group's compatibility,, expensive rhodium catalyst has limited it in industrial large-scale application.2005, reported first such as Ohta pass through Pd
2(dba)
3CHCl
3Catalytic aryl boric acid prepares method (Yamamoto, the T. of 2-diaryl alcohol to the nucleophilic addition of aldehyde; Ohta, T.; Ito, Y.Org.Lett., 2005,7,4153-4155.).In recent years, handle catalyzer and electronic material, its price is risen steadily because palladium is widely used in vehicle exhaust.Therefore, seek cheap catalyst, be used for the catalysis aryl boric acid nucleophilic addition of aldehyde is prepared the 2-diaryl alcohol compounds, have important practical significance.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method that the addition reaction of aldehyde is prepared 2-diaryl alcohol by nickel catalysis aryl boric acid.
Technical scheme of the present invention is as follows:
1. catalyzer is a nickel salt, is meant Ni (ClO
4)
26H
2O, Ni (OAc)
24H
2O, Ni (NO
3)
26H
2O or NiCl
26H
2O;
2. nickel catalysis aryl boric acid is to the nucleophilic addition of aldehyde:
This is reflected in the mixed solvent of low-carbon alcohol solvent or toluene and low-carbon alcohol solvent, the existence of alkali, temperature of reaction are carried out under 60-90 ℃, sees reaction formula (1).
Described aldehyde, be meant phenyl ring the neighbour, or the aromatic aldehyde that replaced by R base of contraposition, R is meant straight chained alkyl, cyclohexane radical derivative, phenyl derivatives, alkoxyl group, carbonyl or the halogen of hydrogen, 1-12 carbon, and aromatic boric acid is meant the neighbour of phenylo boric acid or the derivative that contraposition is replaced by R ' base; R ' is meant straight chained alkyl, cyclohexane radical derivative, phenyl derivatives, alkoxyl group, carbonyl or the halogen of hydrogen, 1-12 carbon;
Described low-carbon alcohol solvent is meant methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol;
Described alkali is meant potassiumphosphate, a hypophosphite monohydrate potassium or three hypophosphite monohydrate potassium;
Described adduct 2-diaryl alcohol compounds is the alcohol compound that is generated by above-mentioned nucleophilic addition;
Effect of the present invention and benefit are:
The catalyzer low price, active high, selectivity is good, stable in the air.
Raw material aryl boric acid economy be easy to get, nontoxic, to air-stable, and functional group's compatibility is good, allows to be connected with other functional groups (as ester group, ketone, chlorine, fluorine etc.) on the phenyl ring of aromatic aldehyde.Under heating, alkaline condition, aryl boric acid is good to the nucleophilic addition selectivity of aldehyde, productive rate is high.
3. solvent for use low toxicity, cheap and easy to get.
4. reaction product is easy to separate, through column chromatography get final product pure product.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme.
Embodiment 1:
Step 1 will be equipped with the 20mL reaction flask and the superpure nitrogen gas phase that stir magneton and connect, and find time, fills the nitrogen triplicate, then, carry out subsequent operations by the method for handling sensitive materials in the air.
Step 2 adds the Virahol of 3mL deoxidation, dehydration in reaction flask, then, and with aldehyde (1.0mmol), aryl boric acid (1.5mmol or 2.0mmol), potassiumphosphate (2.0mmol) and catalyst n i (ClO
4)
26H
2O (0.03mmol) adds in the bottle successively, and at 60 ℃ of following stirring reaction certain hours, reaction process utilizes thin layer plate or gas-chromatography monitoring.
After step 3 reaction finished, concentration of reaction solution was removed catalyzer through short silicagel column, uses the column chromatography purified product again, is developping agent with normal hexane and ethyl acetate mixed solution.
Embodiment 2:
Step 1 will be equipped with the 20mL reaction flask and the superpure nitrogen gas phase that stir magneton and connect, and find time, fills the nitrogen triplicate, then, carry out subsequent operations by the method for handling sensitive materials in the air.
Step 2 adds the Virahol of 3mL deoxidation, dehydration in reaction flask, then, and with aldehyde (1.0mmol), aryl boric acid (1.5mmol or 2.0mmol), potassiumphosphate (2.0mmol) and catalyst n i (ClO
4)
26H
2O (0.03mmol) adds in the bottle successively, and at 80 ℃ of following stirring reaction certain hours, reaction process utilizes thin layer plate or gas-chromatography monitoring.
After step 3 reaction finished, concentration of reaction solution was removed catalyzer through short silicagel column, uses the column chromatography purified product again, is developping agent with normal hexane and ethyl acetate mixed solution.
Embodiment 3:
Step 1 will be equipped with the 20mL reaction flask and the superpure nitrogen gas phase that stir magneton and connect, and find time, fills the nitrogen triplicate, then, carry out subsequent operations by the method for handling sensitive materials in the air.
Step 2 adds the Virahol of 3mL deoxidation, dehydration in reaction flask, then, and with aldehyde (1.0mmol), aryl boric acid (1.5mmol or 2.0mmol), potassiumphosphate (2.0mmol) and catalyst n i (ClO
4)
26H
2O (0.03mmol) adds in the bottle successively, and at 90 ℃ of following stirring reaction certain hours, reaction process utilizes thin layer plate or gas-chromatography monitoring.
After step 3 reaction finished, concentration of reaction solution was removed catalyzer through short silicagel column, uses the column chromatography purified product again, is developping agent with normal hexane and ethyl acetate mixed solution.
Reaction result sees Table 1:
Annotate: be isolated yield in the table.
Claims (2)
1. one kind prepares the method for 2-diaryl alcohol by nickel catalysis aryl boric acid to the addition reaction of aldehyde, it is characterized in that:
(1) catalyzer is a nickel salt, is meant Ni (ClO
4)
26H
2O, Ni (OAc)
24H
2O, Ni (NO
3)
26H
2O or NiCl
26H
2O;
(2) this is reflected in the mixed solvent of low-carbon alcohol solvent or toluene and low-carbon alcohol solvent, the existence of alkali, temperature of reaction carry out under 60-90 ℃, sees reaction formula (1);
Described aldehyde, be meant phenyl ring the neighbour, or the aromatic aldehyde that replaced by R base of contraposition, R is meant straight chained alkyl, cyclohexane radical derivative, phenyl derivatives, alkoxyl group, carbonyl or the halogen of hydrogen, 1-12 carbon, and aromatic boric acid is meant the neighbour of phenylo boric acid or the derivative that contraposition is replaced by R ' base; R ' is meant straight chained alkyl, cyclohexane radical derivative, phenyl derivatives, alkoxyl group, carbonyl or the halogen of hydrogen, 1-12 carbon;
Described low-carbon alcohol solvent is meant methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol;
Described alkali is meant potassiumphosphate, a hypophosphite monohydrate potassium or three hypophosphite monohydrate potassium;
Described adduct 2-diaryl alcohol compounds is the alcohol compound that is generated by above-mentioned nucleophilic addition.
2. according to claim 1ly a kind ofly by nickel catalysis aryl boric acid the addition reaction of aldehyde is prepared the method for 2-diaryl alcohol, it is characterized in that: temperature of reaction is carried out under 80 ℃.
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|---|---|---|---|
| CN2008102286135A CN101456790B (en) | 2008-11-04 | 2008-11-04 | Method for preparing diaryl alcohol by catalyzing addition reaction of aryl boric acid and aldehyde by nickel |
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|---|---|
| CN101456790A true CN101456790A (en) | 2009-06-17 |
| CN101456790B CN101456790B (en) | 2012-02-22 |
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Cited By (5)
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|---|---|---|---|---|
| CN102584511A (en) * | 2011-01-05 | 2012-07-18 | 郑建鸿 | Preparation method for secondary alcohol |
| TWI396678B (en) * | 2010-12-07 | 2013-05-21 | Nat Univ Tsing Hua | Method for secondary alcohols synthesis |
| CN106748771A (en) * | 2016-12-28 | 2017-05-31 | 浙江师范大学 | A kind of preparation method of 6 fluoroalkyl ketone |
| CN109265319A (en) * | 2017-07-17 | 2019-01-25 | 中国科学院化学研究所 | The preparation method of two (miscellaneous) aryl first alcohol compounds |
| CN110724033A (en) * | 2019-10-19 | 2020-01-24 | 滁州学院 | Method for preparing alcohol by Suzuki reaction without exogenous base |
-
2008
- 2008-11-04 CN CN2008102286135A patent/CN101456790B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI396678B (en) * | 2010-12-07 | 2013-05-21 | Nat Univ Tsing Hua | Method for secondary alcohols synthesis |
| CN102584511A (en) * | 2011-01-05 | 2012-07-18 | 郑建鸿 | Preparation method for secondary alcohol |
| CN106748771A (en) * | 2016-12-28 | 2017-05-31 | 浙江师范大学 | A kind of preparation method of 6 fluoroalkyl ketone |
| CN106748771B (en) * | 2016-12-28 | 2019-08-06 | 浙江师范大学 | A kind of preparation method of 6- fluoroalkyl ketone |
| CN109265319A (en) * | 2017-07-17 | 2019-01-25 | 中国科学院化学研究所 | The preparation method of two (miscellaneous) aryl first alcohol compounds |
| CN109265319B (en) * | 2017-07-17 | 2021-02-05 | 中国科学院化学研究所 | Preparation method of di (hetero) arylcarbinol compound |
| CN110724033A (en) * | 2019-10-19 | 2020-01-24 | 滁州学院 | Method for preparing alcohol by Suzuki reaction without exogenous base |
| CN110724033B (en) * | 2019-10-19 | 2023-06-09 | 滁州学院 | Method for preparing alcohol by using Suzuki reaction without exogenous alkali |
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| CN101456790B (en) | 2012-02-22 |
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