CN110734354B - Method for preparing biaryl compound from alcohol compound - Google Patents

Method for preparing biaryl compound from alcohol compound Download PDF

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CN110734354B
CN110734354B CN201910977586.XA CN201910977586A CN110734354B CN 110734354 B CN110734354 B CN 110734354B CN 201910977586 A CN201910977586 A CN 201910977586A CN 110734354 B CN110734354 B CN 110734354B
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CN110734354A (en
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郭志强
庞腾飞
魏学红
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Shanxi University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons

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Abstract

The invention provides a method for preparing biaryl compounds from alcohol compounds, which comprises the following steps: sequentially adding an alcohol compound, sodium borohydride and iodine (the molar ratio is 1:2-3: 0.5-1) into a reaction tube filled with an acetonitrile solvent, sealing the reaction tube, heating to 100 ℃ for reaction for 10-20 hours, quenching the reaction with water after the reaction is completed, drying an organic phase by anhydrous magnesium sulfate, and rotationally evaporating the solvent to obtain a target product. The method has the advantages of convenient operation, easy separation of products, high yield, small environmental pollution and the like, is an ideal method for producing the hydrocarbon with high energy density by using the oxygen-enriched biomass raw material, and has important practical value.

Description

Method for preparing biaryl compound from alcohol compound
Technical Field
The invention relates to a dehydroxylation coupling reaction of an organic alcohol compound, in particular to a method for preparing a biaryl compound by constructing a C-C bond through dehydroxylation coupling of an alcohol compound.
Background
Biaryl compounds are widely present in organic compounds as important skeleton structural units, and can also be used as starting materials for synthesis of natural products, high-molecular polymers and chemical drugs, and play an important role in organic synthetic chemistry. Currently, the industry is primarily achieved by metal catalyzed reductive coupling of organic halides, whereas alkyl halides are generally synthesized from the corresponding alcohol compounds, and alcohols are readily available from commercial sources. Therefore, the development of a method for directly constructing the C-C bond by the deoxidation coupling of the alcohol compound in organic synthesis has important significance. So far, few reports have been made on the method for synthesizing biaryl compounds by the dehydroxylation coupling reaction of alcohol compounds, mainlyThe catalyst is metal titanium compound, organic metal vanadium compound, ReO2I(PPh3)2And copper promoted La/Me3SiCl reaction system. Because the vanadium, lanthanum, rhenium and other catalysts are expensive, and the range of the alcohol substrate of the catalytic reductive conjugate is limited, the novel conversion is realized by finding out a more economical and more active catalyst, and the method is an ideal method for producing high-energy-density hydrocarbons by using oxygen-enriched biomass raw materials and has important practical value.
Disclosure of Invention
The invention aims to provide a method for preparing a biaryl compound by constructing a C-C bond through dehydroxylation coupling of an alcohol compound, which has high yield, low cost and environmental friendliness.
The invention provides a method for preparing biaryl compounds from alcohol compounds, which has the following reaction equation, wherein R is aryl;
Figure BDA0002234148890000011
the method for preparing the biaryl compound comprises the following steps: adding an alcohol compound, sodium borohydride and iodine into a reaction tube containing an acetonitrile solvent in sequence, sealing the reaction tube, heating to 100 ℃ for reaction for 10-24 hours, quenching with water after the reaction is completed, drying an organic phase by anhydrous magnesium sulfate, and rotationally evaporating the solvent to obtain a target product.
In the step, the molar ratio of the alcohol compound to the sodium borohydride to the iodine is 1:2-3: 0.5-1; preferably 1:2: 1.
Compared with the prior art, the method has the advantages of no need of noble metal catalyst, simple and convenient operation, high yield, easy separation and purification of products, low cost, small environmental pollution and the like.
Drawings
FIG. 1 preparation of 1, 2-diphenylethane from example 11H NMR chart
FIG. 2 Process for the preparation of 1, 2-diphenylethane prepared in example 113C NMR chart
Detailed Description
The following specific examples are given only for the purpose of illustrating the present invention in detail and are not intended to limit the scope of the present invention.
Example 1
To a dry 25mL reaction tube, benzyl alcohol (0.5mmol), NaBH was added in that order4(1.0mmol)，I2(0.5mmol), anhydrous acetonitrile (2mL), sealed tube, reaction at 100 ℃ for 24 hours, cooling to room temperature, adding 10mL water to quench the reaction, extracting three times with ethyl acetate, combining the organic phases, drying over anhydrous magnesium sulfate, and purifying the crude product by column chromatography. The target product is obtained, yield: 96 percent.1H NMR(600MHz,CDCl3)7.29(t,J＝7.6Hz,4H),7.20(t,J＝7.8Hz,6H),2.93(s,4H).13C NMR(151MHz,CDCl3)141.93(s),128.53(d,J＝17.4Hz),126.05(s),38.10(s).
Figure BDA0002234148890000021
Example 2
To a dry 25mL reaction tube was added p-methylbenzyl alcohol (0.5mmol), NaBH in that order4(1.0mmol)，I2(0.5mmol), anhydrous acetonitrile (2mL), tube sealing, reacting the reaction at 100 ℃ for 24 hours, cooling to room temperature, adding 10mL of water to quench the reaction, extracting with ethyl acetate three times, combining the organic phases, drying over anhydrous magnesium sulfate, and separating and purifying the crude product by column chromatography. The target product is obtained, yield: 95 percent.1H NMR(600MHz,CDCl3)7.11(s,8H),2.87(s,4H),2.34(s,6H).13C NMR(151MHz,CDCl3)139.00(s),135.43(s),129.14(s),128.43(s),37.79(s),21.17(s).
Figure BDA0002234148890000022
Example 3
To a dry 25mL reaction tube was added p-2-chlorobenzyl alcohol (0.5mmol), NaBH in that order4(1.0mmol)，I2(0.5mmol), anhydrous acetonitrile (2mL), tube sealing, and reactionThe reaction mass was reacted at 100 ℃ for 24 hours, cooled to room temperature, quenched with 10mL of water, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate and the crude product was purified by column chromatography. The target product is obtained, yield: 89 percent.1H NMR(600MHz,CDCl3)7.36(d,J＝4.9Hz,2H),7.16(d,J＝6.6Hz,6H),3.04(s,4H).13C NMR(151MHz,CDCl3)139.08(s),134.14(s),130.75(s),129.61(s),127.70(s),126.91(s),33.96(s).
Figure BDA0002234148890000031
Example 4
To a dry 25mL reaction tube was added p-3-chlorobenzyl alcohol (0.5mmol), NaBH in that order4(1.0mmol)，I2(0.5mmol), anhydrous acetonitrile (2mL), tube sealing, reacting the reaction at 100 ℃ for 24 hours, cooling to room temperature, adding 10mL of water to quench the reaction, extracting with ethyl acetate three times, combining the organic phases, drying over anhydrous magnesium sulfate, and separating and purifying the crude product by column chromatography. The target product is obtained, yield: 89 percent.1H NMR(600MHz,CDCl3)7.25-7.12(m,6H),7.02(d,J＝7.0Hz,2H),2.88(s,4H).13C NMR(151MHz,CDCl3)143.31(s),134.27(s),129.78(s),128.70(s),126.80(s),126.45(s),37.39(s).
Figure BDA0002234148890000032
Example 5
To a dry 25mL reaction tube, p-4-chlorobenzyl alcohol (0.5mmol), NaBH were added in sequence4(1.0mmol)，I2(0.5mmol), anhydrous acetonitrile (2mL), tube sealing, reacting the reaction at 100 ℃ for 24 hours, cooling to room temperature, adding 10mL of water to quench the reaction, extracting with ethyl acetate three times, combining the organic phases, drying over anhydrous magnesium sulfate, and separating and purifying the crude product by column chromatography. The target product is obtained, yield: 89 percent.1H NMR(600MHz,CDCl3)7.22(d,J＝7.2Hz,4H),7.04(d,J＝7.3Hz,4H),2.85(s,4H).13C NMR(151MHz,DMSO)141.25(s),129.10(s),128.59(s),126.20(s),77.37(s),77.16(s),76.95(s),42.07(s).
Figure BDA0002234148890000033
Example 6
2, 6-dichlorobenzyl alcohol (0.5mmol), NaBH were added to a dry 25mL reaction tube in that order4(1.0mmol)，I2(0.5mmol), anhydrous acetonitrile (2mL), tube sealing, reacting the reaction at 100 ℃ for 24 hours, cooling to room temperature, adding 10mL of water to quench the reaction, extracting with ethyl acetate three times, combining the organic phases, drying over anhydrous magnesium sulfate, and separating and purifying the crude product by column chromatography. The target product is obtained, yield: 81 percent.1H NMR(600MHz,CDCl3)7.26(d,J＝8.0Hz,4H),7.08(t,J＝8.0Hz,2H),3.24(s,4H).13C NMR(151MHz,CDCl3)136.78(s),136.03(s),128.29(s),128.02(s),29.82(s).
Figure BDA0002234148890000041

Claims (2)

1. A method for preparing biaryl compounds from alcohol compounds is characterized by comprising the following steps:
the reaction equation is as follows, wherein R is aryl;
Figure DEST_PATH_IMAGE001
；
the preparation method comprises the following steps: adding an alcohol compound, sodium borohydride and iodine into a reaction tube containing an acetonitrile solvent in sequence, sealing the reaction tube, heating to 100 ℃ for reaction for 10-24 hours, quenching with water after the reaction is completed, drying an organic phase by anhydrous magnesium sulfate, and rotationally evaporating the solvent to obtain a target product.
2. The method of claim 1, wherein the reaction step comprises the following steps in terms of molar ratio of alcohol compound: sodium borohydride: iodine = 1:2-3: 0.5-1.
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Citations (2)

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CN101643378A (en) * 2009-09-02 2010-02-10 中国农业大学 Method for synthesizing aryl-linking compound
CN102816051A (en) * 2011-06-10 2012-12-12 苏州卫生职业技术学院 Process for synthesizing 4-chlorophenyl ethanol

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101643378A (en) * 2009-09-02 2010-02-10 中国农业大学 Method for synthesizing aryl-linking compound
CN102816051A (en) * 2011-06-10 2012-12-12 苏州卫生职业技术学院 Process for synthesizing 4-chlorophenyl ethanol

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Deoxygenative Dimerization of Benzylic and Allylic Alcohols, and Their Ethers and Esters Using Lanthanum Metal and Chlorotrimethylsilane in the Presence of a Catalytic Amount of Iodine and Copper(;Toshiki Nishino等;《The Chemical Society of Japan》;20030331;第76卷(第3期);第635–641页 *
Methods of enhancement of reactivity and selectivity of sodium borohydride for applications in organic synthesis;Mariappan Periasamy等;《Journal of Organometallic Chemistry》;20000908;第609卷(第1-2期);第137–151页 *

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