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A kind of synthetic method of carboxylic acid ester compound

A technology of ester compounds and synthetic methods, applied in the preparation of organic compounds, carboxylic acid ester preparation, chemical instruments and methods, etc., can solve the problems of strong acid and strong alkali, unfavorable environmental protection, toxic and harmful heavy metal residues, difficult separation of products and reagents, etc. problems, to achieve good response characteristics, low equipment requirements, and good results

Active Publication Date: 2019-03-29
HANGZHOU NORMAL UNIVERSITY
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Problems solved by technology

[0002] Carboxylate is an important organic chemical intermediate and pharmaceutical intermediate. In recent research reports, most researchers use noble metals as oxidative esterification catalysts, which are expensive
The traditional synthetic methods of ester compounds focus on the preparation of carboxylic acids and alcohols under strong acid or strong base conditions, but the use of strong acids and strong bases is not conducive to environmental protection and has high requirements for production equipment, and the pressure on environmental protection is great
At the same time, this type of synthetic method is not suitable for the preparation of some special ester compounds sensitive to acid or alkali
Some researchers have used homogeneous catalysts, which have the advantages of high activity and high selectivity in the reaction, but the dosage is large, and it is not easy to separate from the products and reagents after the reaction; at the same time, there are residual problems of toxic and harmful heavy metals, which restricts its use. Practical application in industrial production

Method used

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  • A kind of synthetic method of carboxylic acid ester compound
  • A kind of synthetic method of carboxylic acid ester compound
  • A kind of synthetic method of carboxylic acid ester compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] Embodiment 1: the preparation of benzyl 4-methoxybenzoate

[0047] Take a clean 15mL high-pressure reaction bottle, add p-methoxybenzaldehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide (40.6mg, 0.11mmol), sodium azide (107.25mg, 1.65mmol), oxidant tert Butyl hydroperoxide (0.10mL, 0.825mmol) and benzyl chloride (139.24mg, 1.1mmol), solvent toluene (1.0mL), add small magnets, react at 100°C for 2h, extract with dichloromethane (3×10mL) , the organic phase was desolvated under reduced pressure, using ethyl acetate:petroleum ether=1:30 solvent as eluent, 300 mesh column chromatography silica gel as filler, and the target product (118.50mg, yield 89% obtained by column chromatography separation and purification) %).

[0048] 1 HNMR (500MHz, CDCl 3 ):δ=8.04-8.02(m,2H),7.44-7.43(m,2H),7.39-7.36(m,2H),7.34-7.31(ddd,1H),5.33(s,2H),3.83(s ,3H); 13 CNMR (125MHz, CDCl 3 ): δ=166.21, 163.47, 136.34, 131.77, 128.59, 128.16, 128.12, 122.57, 113.65, 66.41, 55.43ppm;

Embodiment 2

[0049] Embodiment 2: the preparation of methyl 4-methoxybenzoate

[0050] Take a clean 15mL high-pressure reaction bottle, add p-methoxybenzaldehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide (40.6mg, 0.11mmol), sodium azide (107.25mg, 1.65mmol), oxidant tert Butyl hydroperoxide (0.10mL, 0.825mmol), and iodomethane (156.15mg, 1.1mmol) solvent toluene (1.0mL), add a small magnet, react at 90°C for 2h, and extract with dichloromethane (3×10mL) , the organic phase was desolvated under reduced pressure, using ethyl acetate:petroleum ether=1:30 solvent as the eluent, 300 mesh column chromatography silica gel as the filler, and the target product obtained by column chromatography separation and purification (76.71mg, yield 84 %).

[0051] 1 H NMR (500MHz, CDCl 3 ):δ=8.00-7.98(d,2H),6.92-6.91(d,2H),3.88(s,3H),3.86(s,3H); 13 C NMR (125MHz, CDCl 3 ): δ=166.88, 163.33, 131.51, 122.61, 113.60, 55.41, 51.86ppm.

Embodiment 3

[0052] Embodiment 3: the preparation of ethyl 4-methoxybenzoate

[0053] Take a clean 15mL high-pressure reaction bottle, add p-methoxybenzaldehyde (74.8mg, 0.55mmol), tetrabutylammonium iodide (40.6mg, 0.11mmol), sodium azide (107.25mg, 1.65mmol), oxidant tert Butyl hydroperoxide (0.10mL, 0.825mmol), and ethyl bromide (119.86mg, 1.1mmol), solvent toluene (1.0mL), add small magnets, react at 90°C for 2h, dichloromethane (3×10mL ) extraction, the organic phase decompression precipitation, with ethyl acetate:petroleum ether=1:30 solvent is eluent, 300 mesh column chromatography silica gel is filler, the target product (83.19mg that obtains by column chromatography separation and purification, obtains rate of 84%).

[0054] 1 H NMR (500MHz, CDCl 3 ):δ=8.01-7.99(d,2H),6.92-6.90(d,2H),4.37-4.32(q,2H),3.85(s,3H),1.39-1.36(t,1H); 13 C NMR (125MHz, CDCl 3 ): δ=166.41, 163.25, 131.53, 125.92, 122.96, 114.01, 113.54, 60.63, 55.40, 14.38ppm.

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Abstract

The invention provides a synthesis method of an ester compound represented by the formula (1), the formula (2) or the formula (3), wherein the method comprises the steps: dissolving an aldehyde compound, sodium azide, tetrabutylammonium iodide and a halogenated compound in a solvent, or directly dissolving an aldehyde compound, sodium azide and tetrabutylammonium iodide in a halogenated compound, carrying out a reaction for 1-12 h at the temperature of 90-100 DEG C, and after the reaction is finished, postprocessing the reaction liquid to obtain the compound represented by the formula (1). The synthesis method has the advantages of mild reaction conditions, no participation of strong acids, strong alkalis or metals, simpliness, high efficiency, high yield, wide application range of substrates, amplified production potential, and relatively large potential economic value.

Description

(1) Technical field [0001] The invention relates to a method for synthesizing carboxylate compounds. (2) Background technology [0002] Carboxylate is an important organic chemical intermediate and pharmaceutical intermediate. In recent research reports, most researchers use noble metals as oxidative esterification catalysts, which are expensive. The traditional synthetic methods of ester compounds focus on the preparation of carboxylic acids and alcohols under strong acid or strong base conditions, but the use of strong acids and strong bases is not conducive to environmental protection and has high requirements for production equipment and great pressure on environmental protection. At the same time, this type of synthetic method is not suitable for the preparation of some special ester compounds sensitive to acid or alkali. Some researchers have used homogeneous catalysts, which have the advantages of high activity and high selectivity in the reaction, but the dosage is ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C67/00C07C67/39C07C69/92C07C69/94C07C69/76C07C69/80C07C201/12C07C205/57C07D333/38C07D307/68
CPCC07C67/00C07C67/39C07C201/12C07D307/68C07D333/38C07C69/92C07C69/94C07C69/76C07C69/80C07C205/57
Inventor 钟国富曾晓飞陈齐良沈丹丁丽媛
Owner HANGZHOU NORMAL UNIVERSITY
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