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Method for preparing nitrile from primary alcohol

A primary alcohol and catalyst technology, which is applied in the field of catalyzing primary alcohols to prepare nitriles, can solve the problems of harsh reaction conditions, high cost, and high reaction temperature, and achieve the effects of strong substrate applicability, convenient operation, and easy availability of raw materials

Inactive Publication Date: 2017-06-20
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, there are many defects in these methods: stoichiometric toxic metal cyanide is used as a cyanide source; by-products such as inorganic salts are produced, which easily cause secondary pollution of the product; the reaction atom economy and selectivity are poor; the reaction conditions are harsh (high temperature and high pressure); Complicated processing, high cost, etc.
The catalyzer of this reaction is high iodine compound cost is bigger, and pollution is bigger
[Vatele Jean-Michel, synlett, 2014,25(9), 1275.] In summary, there are many shortcomings and deficiencies in the method for synthesizing nitrile in the prior art, as: the cost is higher, not green enough, and the reaction Higher temperature, longer reaction cycle, etc.

Method used

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  • Method for preparing nitrile from primary alcohol
  • Method for preparing nitrile from primary alcohol
  • Method for preparing nitrile from primary alcohol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030]

[0031] In a 150mL thick-walled pressure-resistant tube equipped with magnetic stirring, under an air atmosphere, add benzyl alcohol (that is, the R in the structural formula (I) 1 H) 1.0mmol (108.1mg), ammonia water (1.6mol / L) 5.0mL, cuprous iodide 5mol% (9.5mg), TEMPO 5mol% (7.8mg), react at 100°C for 15h, after the reaction is completed, The reaction solution was cooled to room temperature and extracted with ethyl acetate (3×5.0 mL). The organic layers were combined and concentrated in vacuo to remove ethyl acetate to obtain a crude product. The crude product was purified by column chromatography (petroleum ether: ethyl acetate = 10:1) to obtain the pure target product. 94.9mg was obtained, the yield was 92%.

[0032] Proton nuclear magnetic resonance spectrum: 1H NMR (500MHz, CDCl3): δ7.61–7.53 (m, 3H), 7.43 (t, J=7.8Hz, 2H).

[0033] Carbon NMR spectrum: 13C NMR (125MHz, CDCl3): δ132.5, 131.8, 128.9, 118.5, 112.1.

Embodiment 2

[0035]

[0036] The reactant used is p-methyl benzyl alcohol (i.e. R in the structural formula (I) 1 For para-position COOH) 1.0mmol (152.1mg), experimental method and step are with embodiment 1, ammoniacal liquor (1.8mol / L) 3.0mL, the consumption of catalyzer cuprous bromide is 8mol% (11.5mg), the consumption of TEMPO is 5mol% (7.8mg), the reaction temperature was 120°C, and the reaction time was 24h. The crude product was purified by column chromatography (petroleum ether: ethyl acetate = 5:1) to obtain the pure target product, 129.4mg, yield 88% .

[0037] Proton nuclear magnetic resonance spectrum: 1H NMR (500MHz, CDCl3): δ8.23 (d, J=8.4Hz, 1H), 7.81 (d, J=8.4Hz, 1H).

[0038] Carbon NMR spectrum: 13C NMR (125MHz, CDCl3): δ169.1, 133.1, 132.4, 130.6, 117.7, 117.2.

Embodiment 3

[0040]

[0041] The reactant used is o-methoxybenzyl alcohol (that is, R in the structural formula (I) is ortho-position OCH 3 ) 1.0mmol (138.2mg), experimental method and step are with embodiment 1, ammoniacal liquor (1.7mol / L) 5.0mL, the consumption of catalyzer cuprous chloride is 8mol% (7.9mg), and the consumption of TEMPO is 8mol% (12.5 mg), the reaction temperature was 120°C, and the reaction time was 24 h. The crude product was purified by column chromatography (petroleum ether: ethyl acetate = 10:1) to obtain the pure target product, 123.9 mg, yield 93%.

[0042] Proton NMR spectrum: 1H NMR (500MHz, CDCl3): δ7.57–7.51(m,2H), 7.04–6.95(m,2H), 3.93(s,3H).

[0043] Carbon NMR spectrum: 13C NMR (125MHz, CDCl3): δ161.2, 134.3, 133.7, 120.7, 116.4, 111.3, 101.8.

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Abstract

The invention discloses a method for preparing nitrile from primary alcohol through catalytic oxidation. The method comprises the following steps: taking primary alcohol shown in Formula (I) or Formula (III) as a raw material, copper salt as a catalyst, air as an oxidizer, TEMPO (2,2,6,6-tetramethyl piperidine oxynitride) as an oxidizing aid and ammonia water as a cocatalyst and solvent, reacting at 80-120 DEG C for 15-30 hours, and performing posttreatment on the reaction solution after the reaction is completed to obtain the nitrile shown in Formula (II) or Formula (IV).The method disclosed by the invention is high in reaction conversion rate and yield, convenient to operate, low in cost and safe in reaction; and the whole process is environment-friendly and causes no pollution. The formulas are shown in the specification.

Description

[0001] (1) Technical field [0002] The invention relates to a method for preparing nitriles by catalyzing primary alcohols. [0003] (2) Background technology [0004] Nitrile compounds are one of the most important organic synthetic intermediates in organic synthetic chemistry, and are widely used in fine chemicals such as pesticides, medicines, and dyes. Traditionally, most nitrile compounds are mainly prepared by Sandmeyer reaction, nucleophilic substitution reaction of halogen-containing compounds with metal cyanides or cyanation reaction of aryl C–H bonds. However, there are many defects in these methods: stoichiometric toxic metal cyanide is used as a cyanide source; by-products such as inorganic salts are produced, which easily cause secondary pollution of the product; the reaction atom economy and selectivity are poor; the reaction conditions are harsh (high temperature and high pressure); The processing is cumbersome and the cost is higher. In the past few decades, ...

Claims

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Application Information

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IPC IPC(8): C07B43/08C07C253/00C07C255/50C07C255/57C07C255/54C07C319/20C07C323/62C07C255/52C07C255/34C07D213/84C07D307/68C07D333/38
CPCC07B43/08C07C253/00C07C319/20C07D213/84C07D307/68C07D333/38C07C255/50C07C255/57C07C255/54C07C323/62C07C255/52C07C255/34
Inventor 张国富赵以勇张贵华丁成荣俞艺栋吕井辉
Owner ZHEJIANG UNIV OF TECH
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