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Method for preparing aromatic alkynes through cross-coupling of nitroaromatic hydrocarbons and aryl-terminated alkynes under catalysis of transition metal

A transition metal catalyzed, nitroaromatic hydrocarbon technology, applied in the direction of condensation between hydrocarbons and non-hydrocarbons to produce hydrocarbons, halogenated hydrocarbon preparation, organic chemical methods, etc. Achieving a wide range of effects

Active Publication Date: 2018-10-02
HUNAN UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Transition metal palladium copper (Pd / Cu) catalyzed Sonogashira coupling reaction of terminal alkynes and halogenated arenes is one of the most effective methods for preparing aromatic alkynes, which has the advantages of high yield and mild reaction conditions, but has the following disadvantages: (1 ) Halogenated hydrocarbons often need to be prepared through multi-step reactions under harsh conditions, the price is more expensive and the halogens pollute the environment; (2) when there are multiple coupling sites, the coupling product and the halogenated hydrocarbon raw material and by-products Have similar polarity and be difficult to separate by column chromatography; Stable reagents and high pressure reaction conditions, the overall yield is low and the product is difficult to separate

Method used

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  • Method for preparing aromatic alkynes through cross-coupling of nitroaromatic hydrocarbons and aryl-terminated alkynes under catalysis of transition metal
  • Method for preparing aromatic alkynes through cross-coupling of nitroaromatic hydrocarbons and aryl-terminated alkynes under catalysis of transition metal
  • Method for preparing aromatic alkynes through cross-coupling of nitroaromatic hydrocarbons and aryl-terminated alkynes under catalysis of transition metal

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] At room temperature, add 0.5mmol nitrobenzene, 0.6mmol phenylacetylene, 0.05mmol Pd(acac) into a 50mL two-necked flask 2 , 0.05mmol CuI, 0.1mmol BrettPhos, 2.0mmol i-Pr 2 NH and 10 mL of toluene, and then the flask was placed in an oil bath reactor with magnetic stirring, and the reaction was carried out at 100 ° C for 18 h. After the reaction was completed, 10 mL of n-hexane was added for extraction and separation, and the product diphenylacetylene was obtained by column chromatography with a yield of 93%.

[0028] Diphenylacetylene is white powder

[0029] 1 H NMR (500MHz, CDCl 3 ):δ7.32-7.37(m,6H),7.52-7.56(m,4H).

Embodiment 2

[0031] The structural formula of the target product is as follows:

[0032]

[0033]The steps are the same as in Example 1, using nitrobenzene and 4-methylphenylacetylene as raw materials.

[0034] The target product is a white solid with a yield of 92%.

[0035] 1 H NMR (500MHz, CDCl 3 ):δ2.36(s,3H),7.16(d,J=7.9Hz,2H),7.30-7.35(m,3H),7.43(d,J=7.9Hz,2H),7.52-7.54(m, 2H); 13 C NMR (125MHz, CDCl 3 ): δ21.49, 88.67, 89.52, 120.10, 123.39, 128.05, 128.29, 129.08, 131.45, 131.50, 138.35.

Embodiment 3

[0037] The structural formula of the target product is as follows:

[0038]

[0039] The steps are the same as in Example 1, using p-nitroanisole and phenylacetylene as raw materials.

[0040] The target product is a white solid with a yield of 88%.

[0041] 1 H NMR (500MHz, CDCl 3 ): δ3.83(s,3H),6.87(d,J=8.8Hz,2H),7.29-7.36(m,3H),7.46-7.48(m,2H),7.50-7.52(m,2H); 13 C NMR (125MHz, CDCl 3 ): δ55.26, 88.04, 89.35, 113.96, 115.34, 123.56, 127.92, 128.25, 131.42, 133.03, 159.58.

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Abstract

The invention discloses a method for preparing aromatic alkynes through cross-coupling of nitroaromatic hydrocarbons and aryl-terminated alkynes under the catalysis of transition metal. The method comprises a step of subjecting nitroaromatic hydrocarbons and aryl-terminated alkynes to a cross-coupling reaction in a solution system of a palladium-containing catalyst, a copper-containing catalyst, aphosphine ligand and an amine ligand in a protective atmosphere so as to obtain aromatic alkynes. According to the method, the cheap, easily available and polar nitroaromatic hydrocarbons are used asan electrophilic reagent for synthesis of the aromatic alkynes, so a series of advantages in traditional Sonogashira coupling can be compensated. The method of the invention has the following advantages: (1) usage of expensive halogenated hydrocarbons hard to prepare can be avoided; (2) in the process of multiple coupling reactions, the polarity of nitro groups allows coupling products to have polarity different from the polarity of raw materials and by-products, so the coupling products can be easily separated through column chromatography; and (3) the transition metal is employed for homogeneous catalysis, so cross-coupling is expected to be smoothly carried out under mild conditions, and the tolerance range of function groups is wide.

Description

technical field [0001] The present invention relates to a method for synthesizing aromatic alkynes, in particular to a method for synthesizing aromatic alkynes by cross-coupling terminal aryl alkynes with nitroaromatics as electrophile synthons under transition metal catalysis, It belongs to the field of organic synthesis. Background technique [0002] The two carbon atoms of the alkyne bond adopt sp hybridization to form two π bonds that are perpendicular to each other and the molecular axis, and the molecular structure is linear. made of. Alkynes are a class of compounds containing alkyne bonds. They have a unique linear rigid structure and conjugated system. They are widely used in the fields of medicine and optoelectronic materials. For example, the rigid linear lipophilic alkyne derivatives have certain biological activities and can be used Antibacterial and anticancer, etc.; π-conjugated aromatic alkynes have a rigid skeleton and abundant π electrons, which are often...

Claims

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Application Information

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IPC IPC(8): C07B37/00C07C2/86C07C15/54C07C41/30C07C43/215C07C43/225C07C17/263C07C25/24C07C253/30C07C255/50C07D333/08
CPCC07B37/00C07C2/86C07C17/263C07C41/30C07C253/30C07C2531/30C07D333/08C07C15/54C07C43/215C07C25/24C07C255/50C07C43/225
Inventor 彭丽芬廖凌燕赵文静唐子龙
Owner HUNAN UNIV OF SCI & TECH
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