CN110734354A - method for preparing biaryl compound from alcohol compound - Google Patents

method for preparing biaryl compound from alcohol compound Download PDF

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CN110734354A
CN110734354A CN201910977586.XA CN201910977586A CN110734354A CN 110734354 A CN110734354 A CN 110734354A CN 201910977586 A CN201910977586 A CN 201910977586A CN 110734354 A CN110734354 A CN 110734354A
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reaction
alcohol
compound
compounds
preparing biaryl
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CN110734354B (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

Abstract

The invention provides methods for preparing biaryl compounds from alcohol compounds, which comprises the following steps of sequentially adding the alcohol compounds, sodium borohydride and iodine (the molar ratio is 1:2-3: 0.5-1) into a reaction tube containing an acetonitrile solvent, sealing the tube, heating to 100 ℃ for reaction for 10-20 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.

Description

method for preparing biaryl compound from alcohol compound
Technical Field
The invention relates to dehydroxylation coupling reaction of organic alcohol compounds, in particular to a method for preparing biaryl compounds by constructing C-C bonds through dehydroxylation coupling of alcohol compounds, which belongs to types of compounds.
Background
Biaryl compounds occur in organic compounds as important skeletal structural unit At present, the catalyst is mainly obtained by the reductive coupling reaction of metal catalysis organic halide, while the alkyl halide is synthesized by the corresponding alcohol compound, and the alcohol is easily purchased from commercial sources, therefore, the development of a method for deoxidizing and coupling the alcohol compound in organic syntheses to directly construct a C-C bond has important significance2I(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 methods for preparing biaryl compounds by constructing C-C bonds through dehydroxylation and coupling of alcohol compounds, which have high yield, low cost and environmental friendliness.
The reaction equation of methods for preparing biaryl compounds from alcohol compounds provided by the invention is as follows, 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)δ7.29(t,J＝7.6Hz,4H),7.20(t,J＝7.8Hz,6H),2.93(s,4H).13C NMR(151MHz,CDCl3)δ141.93(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)δ7.11(s,8H),2.87(s,4H),2.34(s,6H).13CNMR(151MHz,CDCl3)δ139.00(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, 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)δ7.36(d,J＝4.9Hz,2H),7.16(d,J＝6.6Hz,6H),3.04(s,4H).13C NMR(151MHz,CDCl3)δ139.08(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)δ7.25-7.12(m,6H),7.02(d,J＝7.0Hz,2H),2.88(s,4H).13C NMR(151MHz,CDCl3)δ143.31(s),134.27(s),129.78(s),128.70(s),126.80(s),126.45(s),37.39(s).
Figure BDA0002234148890000032
Example 5
In a dry 25mL reaction tube, add p-4-Chlorobenzyl alcohol (0.5mmol), NaBH4(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)δ7.22(d,J＝7.2Hz,4H),7.04(d,J＝7.3Hz,4H),2.85(s,4H).13C NMR(151MHz,DMSO)δ141.25(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)δ7.26(d,J＝8.0Hz,4H),7.08(t,J＝8.0Hz,2H),3.24(s,4H).13C NMR(151MHz,CDCl3)δ136.78(s),136.03(s),128.29(s),128.02(s),29.82(s).
Figure BDA0002234148890000041

Claims (3)

1, methods for preparing biaryl compounds from alcohol compounds, characterized in that the reaction equation is as follows, wherein R is aryl.
2. The method of preparing biaryl compounds according to claim 1, comprising the steps of: 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.
3. 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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114621044A (en) * 2020-12-12 2022-06-14 中国科学院大连化学物理研究所 Method for preparing bibenzyl compound

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

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)

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Title
MARIAPPAN PERIASAMY等: "Methods of enhancement of reactivity and selectivity of sodium borohydride for applications in organic synthesis", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 *
TOSHIKI NISHINO等: "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(", 《THE CHEMICAL SOCIETY OF JAPAN》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114621044A (en) * 2020-12-12 2022-06-14 中国科学院大连化学物理研究所 Method for preparing bibenzyl compound

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