Method for cross coupling reaction utilizing substituted halogenated arene and substituted aryl boric acid

A cross-coupling reaction, halogenated aromatic hydrocarbon technology, applied in the direction of organic chemistry methods, chemical instruments and methods, carboxylic acid nitrile preparation, etc. Reduce the activity and other problems, to achieve the effect of large industrial practical value, low cost and high reactivity

Inactive Publication Date: 2007-03-28
EAST CHINA UNIV OF SCI & TECH +1
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  • Abstract
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AI Technical Summary

Problems solved by technology

However, tetrakis(triphenyl)phosphine palladium is unstable and must be prepared and stored under the protection of an inert gas, so the price is also relatively expensive, and it is not suitable for large-scale preparation and use in industry
If a simple and stable catalyst is used, such as replacing tetrakis(triphenyl)phosphine palladium with palladium chloride, nickel chloride, etc., it is found that the catalytic activity will be greatly reduced under common solvents such as ethanol, toluene, tetrahydrofuran, etc.
Moreover, these simple and stable catalysts can only catalyze the reaction of brominated aromatic hydrocarbons with simpler structures and arylboronic acids; for the reaction of substrates with complex catalytic structures, the reaction yield is low and the arylboronic acid self-coupling by-products are many

Method used

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  • Method for cross coupling reaction utilizing substituted halogenated arene and substituted aryl boric acid
  • Method for cross coupling reaction utilizing substituted halogenated arene and substituted aryl boric acid
  • Method for cross coupling reaction utilizing substituted halogenated arene and substituted aryl boric acid

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Example 1 Synthesis of 4-(4-propylcyclohexyl)-4'-cyano-1,1'-biphenyl

[0027]

[0028] In the 50mL reaction flask, add 0.364g (2mmol) p-cyanobromobenzene, 0.738g (3mmol) 4-(4-propylcyclohexyl) phenylboronic acid (as number 1 in Table 1), 0.553g (4mmol) potassium carbonate, 1.7mg (0.01mmol) of palladium chloride and 4mL of pyridine; under the protection of nitrogen, the oil bath was heated to 115°C and refluxed for 5 hours. TLC showed that the bromide disappeared. After recovering the solvent under reduced pressure, the residue was separated by silica gel column chromatography (petroleum ether was the eluent) and recrystallized to obtain 0.515 g of colorless flaky crystals with a yield of 85%. Temperature (°C): Cr.133N>210.

[0029] 1 HNMR (CDCl 3 , 500MHz) δ=0.91(t, J=7.2Hz, 3H), 1.03~1.11(m, 2H), 1.21~1.25(m, 2H), 1.29~1.38(m, 3H), 1.45~1.53(m, 2H), 1.85~1.96(m, 4H), 2.48~2.57(m, 1H), 7.33(d, J=8.2Hz, 2H), 7.52(d, J=8.2Hz, 2H), 7.66~7.72(m , 4H).

Embodiment 2

[0030] Example 2 Synthesis of 4-(4-pentylcyclohexyl)-4'-cyano-1,1'-biphenyl

[0031]

[0032] In the 50mL reaction flask, add 0.364g (2mmol) p-cyanobromobenzene, 0.822g (3mmol) 4-(4-pentylcyclohexyl) phenylboronic acid (as Table 1 number 2), 0.553g (4mmol) potassium carbonate, 1.7mg (0.01mmol) of palladium chloride and 4mL of pyridine; under the protection of nitrogen, the oil bath was heated to 115°C and refluxed for 6 hours. TLC showed that the bromide disappeared. After recovering the solvent under reduced pressure, the residue was separated by silica gel column chromatography (petroleum ether was the eluent), and recrystallized to obtain 0.593 g of colorless flaky crystals with a yield of 87%. Temperature (°C): Cr.96 N>210.

[0033] 1 HNMR (CDCl 3 , 500MHz) δ=0.90(t, J=7.1Hz, 3H), 1.02~1.11(m, 2H), 1.21~1.36(m, 9H), 1.44~1.53(m, 2H), 1.85~1.97(m, 4H), 2.48~2.57(m, 1H), 7.32(d, J=8.3Hz, 2H), 7.52(d, J=8.1Hz, 2H), 7.66~7.71(m, 4H).

Embodiment 3

[0034] Example 3 Synthesis of 4-(4-propylcyclohexyl)-4'-(4-pentylcyclohexyl)-1,1'-biphenyl

[0035]

[0036] Add 0.562g (2mmol) 4-(4-propylcyclohexyl) bromobenzene to 50mL reaction flask, 0.822g (3mmol) 4-(4-pentylcyclohexyl) phenylboronic acid (as in Table 1 number 3), 0.553 g (4mmol) potassium carbonate, 1.7mg (0.01mmol) palladium chloride and 4mL pyridine; under the protection of nitrogen, the oil bath was heated to 115°C and refluxed for 5 hours, TLC showed that the bromide disappeared. After recovering the solvent under reduced pressure, the residue was separated by silica gel column chromatography (petroleum ether was the eluent) and recrystallized to obtain 0.533 g of colorless needle crystals with a yield of 62%. The purity was 99.5% as detected by HPLC, and the phase transition Temperature (°C): Cr.53S>210.

[0037] 1 HNMR (CDCl 3, 500MHz) δ=0.89~0.92(m, 6H), 1.05~1.10(m, 4H), 1.21~1.38(m, 14H), 1.44~1.52(m, 4H), 1.87~1.94(m, 8H), 2.48~2.54 (m, 2H), 7.24~7.28 (...

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Abstract

The invention relates to a method of making cross-coupling reaction using substituted and halogenated aromatic hydrocarbons and substituted aryl boracic acid, making them perform cross-coupling reaction by the action of palladium chloride catalyst in pyridine solvent at return flow temperature on alkali condition of potassium carbonate or potassium phosphate. And it is simple to operate and low-cost, the solvent is easy to get and able to recycle, the reaction activity is high, the purity of product is higher than 99.5%, the yield of product is up to 60-90%, and it has extreme industrial practical value.

Description

technical field [0001] The invention relates to a method for cross-coupling reaction, in particular to a method for carrying out cross-coupling reaction with substituted halogenated aromatic hydrocarbon and substituted arylboronic acid. Background technique [0002] In 1981, Suzuki et al. found that in Pd(PPh 3 ) 4 Under the catalysis of (tetrakis(triphenyl)phosphine palladium), bromine or iodo arene and aryl boronic acid undergo cross-coupling reaction, as shown in Reaction Formula III: [0003] [0004] Wherein, the preparation of aryl boronic acid can specifically refer to literature Jens Andersch, Carsten Tschierske, Liquid Crystals, 1996.21 (1), P51-63 and DE4410606; The preparation of bromine or iodo arene can specifically refer to literature (Wang Liangyu, Liao Songsheng, "Liquid Crystal Chemistry", Science Press, first edition in September 1988, P253); the preparation of the above raw materials can also refer to other prior art. [0005] The above-mentioned Suz...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B61/00C07C255/50C07C253/30C07C13/28C07C23/18C07C43/235
Inventor 沈冬陶晓春黄梅丰佩川
Owner EAST CHINA UNIV OF SCI & TECH
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