Preparing method of aromatic nitrile or alkenyl nitrile compound

A compound, aromatic nitrile technology, applied in the field of preparation of aromatic nitrile or alkenyl nitrile compounds, can solve the problems of poor substrate universality, expensive catalysts and ligands, poor functional group compatibility, etc.

Pending Publication Date: 2019-08-13
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] The technical problem to be solved by the present invention is to overcome the shortcomings such as expensive catalysts and ligands used in the preparation methods of existing aromatic nitriles or alkenyl nitriles, poor functional group compatibility, poor substrate universality, etc., thus providing A kind of preparation method of aromatic nitrile or alkenyl nitrile compound

Method used

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  • Preparing method of aromatic nitrile or alkenyl nitrile compound
  • Preparing method of aromatic nitrile or alkenyl nitrile compound
  • Preparing method of aromatic nitrile or alkenyl nitrile compound

Examples

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preparation example 1

[0099]

[0100] General preparation process: add p-iodophenol (1equiv), boric acid (1.2equiv), 5% Pd / CaCO to the round bottom bottle 3 (1.5mol%), K 2 CO 3 (2equiv), EtOH and water are dissolved, heated to 80°C under reflux, and TLC detects the reaction. After returning to room temperature, celite was filtered to remove the precipitate, the reaction was quenched with saturated brine, extracted with ethyl acetate, the organic phase was washed with water, washed with saturated brine, dried with anhydrous magnesium sulfate, filtered and concentrated, and then separated and purified.

[0101]

[0102] Silica gel column chromatography, eluent: petroleum ether / ethyl acetate / dichloromethane=8:1:1 to pure dichloromethane, the product is a white solid 1.81g, the yield is 91%. m.p=81.0-82.9℃. 1 H NMR(400MHz, CDCl 3 ): δ3.85(s,3H), 5.47(brs,1H), 6.84-6.89(m,3H), 7.07(s,1H), 7.12(d,J=7.6Hz,1H), 7.32(dd, J = 8.0 Hz, 1H), 7.45 (d, J = 7.6 Hz, 2H). 13 C NMR(100MHz, CDCl 3 ): δ55.30,112.07,112.48...

preparation example 2

[0106]

[0107] Phenol (1equiv) in a round bottom bottle is dissolved in ethyl acetate, and Et is added under ice water bath 3 After adding N(2equiv), MsCl(1.3equiv), remove the ice-water bath and react at room temperature. TLC detects that the reaction is complete. The reaction was quenched by adding water, extracted with ethyl acetate, the organic phase was washed with water, dried over anhydrous magnesium sulfate, filtered through silica gel, and the filtrate was concentrated and separated and purified.

[0108]

[0109] Silica gel column chromatography, eluent: petroleum ether / ethyl acetate=4:1, the product is light yellow liquid, the yield is 98%. 1 HNMR(400MHz, CDCl 3 ): δ0.93(t,J=7.2Hz,3H),1.32-1.38(m,2H),1.55-1.63(m,2H),2.61(t,J=7.6Hz,2H),3.11(s, 3H), 7.17-7.26 (m, 4H). 13 C NMR(100MHz, CDCl 3 ): δ13.83,22.21,33.44,34.94,37.09,121.63,129.79,142.28,147.18.IR(neat):3029,2957,2932,2860,1503,1365,1330,1197,1173,1147,1113,1018 ,968,865,841,814,776,740,681.HRMS(ESI)calcd for C ...

preparation example 3

[0121]

[0122] P-Aldehyde phenol (1.22g, 10mmol) in a round bottom bottle was dissolved in 30mL ethyl acetate, and Et was added at 0℃ 3 N (2.8 mL, 20 mmol), MsCl (1.0 mL, 13 mmol), the ice-water bath was removed after the addition, and the reaction was carried out at room temperature. TLC detected that the reaction was complete. Add water to quench the reaction, extract with ethyl acetate, wash the organic phase with water, wash with saturated brine, dry with anhydrous magnesium sulfate, filter with silica gel, concentrate the filtrate and proceed to the next reaction.

[0123] Dissolve the product from the previous step in 20mL MeOH and 20mL DCM, add NaBH in batches 4 (491.8mg, 13mmol). After the addition, the reaction was carried out at room temperature. TLC detected that the reaction was complete. Add saturated ammonium chloride to quench the reaction, extract with DCM, wash the organic phase with water, wash with saturated brine, dry with anhydrous sodium sulfate, filter and ...

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Abstract

The invention discloses a preparing method of an aromatic nitrile or alkenyl nitrile compound. The preparing method comprises the following step that under protection of inert gas, an aryl or heteroaryl sulphonate compound shown in a formula II or an alkenyl sulphonate compound shown in a formula IV and a cyanation reagent are subjected to a cross-coupling reaction as is shown below in a solvent under the condition of the presence of a nickel complex, metal zinc and an additive to obtain the aromatic nitrile or alkenyl nitrile compound, wherein 4-dimethylamiopryidine (DMAP) is adopted as the additive, and zinc cyanide is adopted as the cyanation reagent. By means of the preparing method, cyanation of aryl sulphonate, heteroaryl sulphonate or alkenyl sulphonate can be simply and efficientlyachieved with a cheap catalysis system; moreover, the functional group compatibility and substrate universality are good, and a better application prospect and higher using value are provided for achieving industrial synthesis of the aromatic nitrile or alkenyl nitrile compound.

Description

Technical field [0001] The invention relates to the field of organic chemistry, in particular to a method for preparing aromatic nitrile or alkenyl nitrile compounds. Background technique [0002] As excellent reaction intermediates in organic chemistry, aromatic nitrile compounds have been widely used in the fields of biology, medicine, pesticides, and functional materials. For example, 2,4-dinitro-6-cyanoaniline is an important intermediate for the production of excellent bright blue diazo dyes; 4-bromo-2,6-difluorobenzonitrile is a synthetic method with moderate An important synthetic intermediate for excellent liquid crystal materials with dielectric anisotropy; at the same time, many natural products and clinical drugs contain cyano groups, such as the antitumor drug Letrozole, β inhibitor Bucindolol, kinase inhibitor Neratinib, cardiovascular drug cromakalim, Anti-HIV drug Etravirine, anti-gout drug Febuxostat, antidepressant Citalopram, diabetes drug alogliptin, etc. The...

Claims

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Application Information

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IPC IPC(8): C07C253/16C07C255/56C07C255/54C07C255/50C07C255/53C07C255/57C07C255/51C07C255/52C07D317/68C07D213/85C07D215/48C07J41/00C07D333/24C07C255/31C07C255/34C07C255/58
CPCC07C253/16C07D317/68C07D213/85C07D215/48C07J41/0094C07D333/24C07C255/31C07C255/34C07C255/54C07C255/56C07C255/50C07C255/53C07C255/57C07C255/51C07C255/52C07C255/58
Inventor 刘元红甘易
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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