Preparation method of sulfur/oxygen ester-containing aromatic hydrocarbon compound

A technology of oxyester-based aromatic hydrocarbons and compounds, which is applied in the field of preparation of sulfur-containing/oxyester-based aromatic compounds, can solve problems such as difficulty in obtaining and synthesis of sulfur-containing/oxyester-based aromatic compounds, and achieve various forms, low cost, The effect of simple preparation process

Pending Publication Date: 2022-03-11
WUHAN INSTITUTE OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The purpose of the present invention is to overcome above-mentioned technical deficiency, propose a kind of preparation method of sulfur / oxygen ester group arene compound, solve the technical problem that the synthetic difficulty of sulfur / oxygen ester group aromatic compound in the prior art, is not easy to obtain

Method used

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  • Preparation method of sulfur/oxygen ester-containing aromatic hydrocarbon compound
  • Preparation method of sulfur/oxygen ester-containing aromatic hydrocarbon compound
  • Preparation method of sulfur/oxygen ester-containing aromatic hydrocarbon compound

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preparation example Construction

[0025] The invention provides a method for preparing a sulfur / oxygen ester-based arene compound. The structural formula of the sulfur / oxygen-containing arene compound is:

[0026]

[0027] Among them, X is S or O; Y is S or O; Z is F, Cl, Br, I, CN, NO 2 、CF 3 , COOEt, hydrocarbon group or alkoxy group, Z can be monosubstituted or polysubstituted, and the substitution position on the aromatic ring is not limited.

[0028] The preparation method of the sulfur-containing / oxygen ester-based arene compound comprises:

[0029] A, react substituted benzoyl chloride and tert-butylmercaptan under the effect of organic base and first organic solvent to obtain substituted benzoic acid tert-butyl thioester; Reaction formula is:

[0030]

[0031] Among them, Z is F, Cl, Br, I, CN, NO 2 、CF 3 , COOEt, hydrocarbon group or alkoxy group, Z can be monosubstituted or polysubstituted, and the substitution position on the aromatic ring is not limited;

[0032] B. Carry out bromine-mag...

Embodiment 1

[0045] The synthesis of embodiment 1 tert-butylthio 3-chlorobenzoate

[0046]

[0047] Add 3-chlorobenzoyl chloride (20mmol), tert-butylmercaptan (24mmol), and triethylamine (30mmol) into the reaction tube, slowly add 10mL of tetrahydrofuran, stir at room temperature for 1 hour, and monitor the reaction with TLC. After the reaction was completed, it was quenched with sodium hypochlorite, and the aqueous phase was extracted with ethyl acetate, and the organic phases were combined and dried with anhydrous sodium sulfate, and the organic phase was concentrated, and the crude product was separated by column chromatography to obtain 4.509 g of product 3-chlorobenzoic acid tert-butylthioester (shallow Yellow oily liquid), yield 98.8%, purity ≥ 95%. figure 1 It is the synthetic 3-chlorobenzoic acid tert-butylthio ester of the embodiment of the present invention 1 1 H NMR characterization spectrum.

[0048] 1 H NMR (400MHz, CDCl 3 ):δ(ppm)7.29-7.25(m,1H),7.71(d,J=8Hz,1H),7.41(d...

Embodiment 2

[0050] Synthesis of embodiment 2 tert-butyl 3-chlorobenzoate

[0051]

[0052] Under anhydrous and oxygen-free conditions, 48 ​​mmol of isopropylmagnesium chloride Grignard reagent was added to a THF solution of m-chlorobromobenzene (40 mmol), and reacted at room temperature for 1 hour. After the bromine-magnesium exchange reaction was completed, the mixed system was cooled to 0-5° C., and 48 mmol of di-tert-butyl dicarbonate was added thereto, and the reaction was monitored by TLC. After the reaction was completed, it was quenched with aqueous citric acid solution. The aqueous phase was extracted with ethyl acetate, the organic phases were combined and dried with anhydrous sodium sulfate, the organic phase was concentrated, and the crude product was separated by column chromatography to obtain 10.354 g of the product tert-butyl 3-chlorobenzoate (white solid), the yield was 61%, and the purity was ≥ 95%. figure 2 It is the synthetic 3-chlorobenzoic acid tert-butyl ester ...

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Abstract

The invention discloses a preparation method of a sulfur / oxygen ester-containing aromatic hydrocarbon compound. The preparation method comprises the following steps: A, carrying out reaction on substituted benzoyl chloride and tert-butyl mercaptan to obtain substituted tert-butyl thiobenzoate; b, reacting substituted bromobenzene with an isopropylmagnesium chloride Grignard reagent, then cooling, adding di-tert-butyl dicarbonate, and reacting to obtain substituted tert-butyl benzoate; c, carrying out reflux reaction on the substituted benzoic acid tert-butyl thioester and a Lawson reagent to obtain substituted benzyl dithio-tert-butyl ester; and D, reacting the substituted tert-butyl benzoate or the substituted tert-butyl benzoate with TMPMgCl.LiCl, and then carrying out a demetallization reaction by adopting an iodine elementary substance to obtain substituted 2-iodobenzoic acid tert-butyl thioester or substituted 2-iodobenzoic acid tert-butyl ester. The sulfur / oxygen ester-containing aromatic hydrocarbon compound obtained by the method has various forms, the preparation process is simple, green, efficient, low in cost, high in speed and easy to operate, an important material source is provided for modification of the sulfur / oxygen ester-containing aromatic hydrocarbon compound, and the method has important application value.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a method for preparing aromatic compounds containing sulfur / oxygen ester groups. Background technique [0002] Sulfur / oxyester-containing aromatic compounds are widely found in natural products, and their unique biological activities make them widely used in various pesticides, such as the insecticide isofenphos-methyl, the acaricide pyraclofen, and the fungicide Reagent aracid benzene-S-methyl and so on. In order to realize the diverse synthesis or subsequent functionalization of aromatic compounds containing sulfur / oxygen ester groups, organic chemists have made beneficial attempts in this field. However, because sulfur-containing organic compounds generally have characteristics such as foul odor, easy oxidation, and possible poisoning of metal catalysts, the synthesis of sulfur-containing / oxygen ester-based aromatic compounds is relatively difficult, and there are f...

Claims

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Application Information

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IPC IPC(8): C07C327/26C07C327/36C07C67/307C07C69/78
CPCC07C327/26C07C327/36C07C67/307C07C69/78
Inventor 董志兵周宇
Owner WUHAN INSTITUTE OF TECHNOLOGY
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