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Method for preparing alpha-alkynyl gamma-cyano functionalized ketones from allyl alcohol

A technology of cyano function and allyl alcohol, which is applied in the field of difunctionalization reaction of free radical process, can solve the problems of expensive transition metals and ligands, metal residues in products, etc., and achieves a wide range of substrates and mild reaction conditions , the effect of high yield

Active Publication Date: 2020-04-03
CHANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the past, the synthesis of γ-cyanoketones usually involved catalytic equivalents of transition metals, various complex ligands and excess oxidants (Org.Lett . 2012,14,9,2414; ACS Catal.2018,8,11324; Angew.Chem.Int.Ed.2016,55,2866.), transition metals and ligands are expensive in the above method, and the metal residues in the product and other unavoidable disadvantages

Method used

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  • Method for preparing alpha-alkynyl gamma-cyano functionalized ketones from allyl alcohol
  • Method for preparing alpha-alkynyl gamma-cyano functionalized ketones from allyl alcohol
  • Method for preparing alpha-alkynyl gamma-cyano functionalized ketones from allyl alcohol

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Experimental program
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Effect test

Embodiment 1

[0030] Embodiment 1: Preparation of 4-benzoyl-4-methyl-6-phenyl-5-hexynenitrile

[0031] [4-benzoyl-4-methyl-6-phenylhex-5-ynenitrile]

[0032]

[0033] In the dried Schlenk tube, add in sequence: 2-methyl-3,5-diphenyl-1-en-4-yn-3-ol (0.2mmol, 49.6mg), di-tert-butyl Peroxide (0.6mmol, 87.6mg), acetonitrile 3mL, and the above-mentioned Schlenk tube was stirred at a temperature of 120°C for 12h. The reaction was terminated, and the solvent was removed on a rotary evaporator. Finally, it was separated by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1:10) to obtain 4-benzoyl-4-methyl-6-phenyl-5-hexynenitrile (38.5mg , Isolation yield: 67%), the compound is a yellow oil.

[0034] NMR data: 1 H NMR (CDCl 3 ,400MHz):δ8.34-8.32(m,2H),7.59-7.56(m,1H),7.49-7.45(m,2H),7.40-7.29(m,5H),2.67-2.58(m,3H) ,2.10-2.03(m,1H),1.72(s,3H); 13 C NMR (100MHz, CDCl 3 )δ197.5, 134.5, 133.1, 131.3, 129.7, 128.6, 128.3, 128.1, 122.1, 119.7, 89.4, 87.8, 45.8, 35.2, ...

Embodiment 2

[0035] Embodiment 2: Preparation of 4-benzoyl-4-methyl-6-(4-propylphenyl)-5-hexynenitrile

[0036] [4-benzoyl-4-methyl-6-(4-propylphenyl)hex-5-ynenitrile]

[0037]

[0038]In the dried Schlenk tube, add successively: 2-methyl-3-phenyl-5-(4-propylphenyl)pent-1-en-4-yn-3-ol (0.2mmol , 58mg), di-tert-butyl peroxide (0.6mmol, 87.6mg), acetonitrile 3mL, and the above-mentioned Schlenk tube was stirred at a temperature of 120°C for 12h. The reaction was terminated, and the solvent was removed on a rotary evaporator. Finally, it was separated by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1:10) to obtain 4-benzoyl-4-methyl-6-(4-propylphenyl)-5- Hexynenitrile (36.8 mg, isolated yield: 56%), the compound was a yellow oil.

[0039] NMR data: 1 H NMR (CDCl 3 ,400MHz):δ8.34-8.32(m,2H),7.59-7.55(m,1H),7.48-7.44(m,2H),7.31-7.29(m,2H),7.14-7.12(m,2H) ,2.67-2.56(m,5H),2.08-2.01(m,1H),1.71(s,3H),1.67-1.58(m,2H),0.95-0.91(m,3H); 13 C NMR (100MHz, CDCl 3...

Embodiment 3

[0040] Example 3: Preparation of 4-benzoyl-4-methyl-6-(4-p-tolyl)-5-hexynenitrile

[0041] [4-benzoyl-4-methyl-6-(4-propylphenyl)hex-5-ynenitrile]

[0042]

[0043] In the dried Schlenk tube, add successively: 2-methyl-3-phenyl-5-(p-tolyl)-1-en-4-yn-3-ol (0.2mmol, 52.4mg) , di-tert-butyl peroxide (0.6mmol, 87.6mg), acetonitrile 3mL, and the above-mentioned Schlenk tube was stirred at a temperature of 120°C for 12h. The reaction was terminated, and the solvent was removed on a rotary evaporator. Finally, it was separated by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1:10) to obtain 4-benzoyl-4-methyl-6-(4-p-tolyl)-5-hexane Alkynenitrile (36.8 mg, isolated yield: 56%), the compound was a yellow oil.

[0044] NMR data: 1 H NMR (CDCl 3 ,400MHz):δ8.34-8.32(m,2H),7.59-7.55(m,1H),7.48-7.44(m,2H),7.29-7.27(m,2H),7.13-7.11(m,2H) ,2.69-2.57(m,3H),2.35(s,3H),2.09-2.02(m,1H),1.71(s,3H); 13 C NMR (100MHz, CDCl 3 )δ197.6, 138.8, 134.5, 133.0, 131.2...

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Abstract

The invention belongs to the technical field of bifunctionalization reaction in a free radical process, and particularly relates to a method for preparing alpha-alkynyl gamma-cyano functionalized ketones from allyl alcohol; the bifunctionalization reaction of alpha-aryl alpha-alkynyl allyl alcohol and alkyl nitriles is researched, and a series of alpha-alkynyl gamma-cyano functionalized ketones are prepared. The method comprises the specific process steps: adding raw material allyl alcohol, an initiator and a nitrile solvent into a dehydrated and deoxidized Schlenk tube in proportion, puttingthe Schlenk tube into an oil bath pan at the temperature of 120 DEG C, and stirring for 12 hours; and finally, carrying out silica gel column chromatography to obtain the alpha-alkynyl gamma-cyano functionalized ketone products. The invention relates to the formation of alkyl nitrile free radicals, followed by intermolecular addition of the alkyl nitrile free radicals and olefins and migration of1,2-alkynyl, and a series of alpha-alkynyl gamma-cyano functionalized ketones are obtained.

Description

technical field [0001] The invention belongs to the technical field of difunctionalization reaction of free radical course, and specifically relates to the difunctionalization reaction of α-aryl α-alkynyl allyl alcohol, especially relates to the use of organic peroxides to promote nitriles and α-aryl Difunctionalization of α-alkynyl allyl alcohols to give α-alkynyl-γ-cyano-functional ketones in moderate yields. Background technique [0002] Free radical-mediated difunctionalization of alkenes is a hot topic in organic chemistry. Among them, the difunctionalization of unactivated alkenes through intramolecular functional group migration has attracted the attention of many researchers. Among them, Academician Tu Yongqiang published a review titled "Radical aryl migration reactions and synthetic applications" on Chemical Society Reviews, and discussed in detail the radical aryl migration reaction of α,α-diaryl allyl alcohol and its synthetic application , the whole process pr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C253/30C07C255/40C07D307/54C07D333/24C07B41/06
CPCC07C253/30C07D307/54C07D333/24C07C255/40C07B41/06Y02P20/584
Inventor 孙松金盛楠成江周聪
Owner CHANGZHOU UNIV
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