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Preparation method of 4-bromoethyl-2-trimethylsilyl ethynylbenzene-1-sulfuryl fluoride

A technology of trimethylsilyl and ethynylbenzene, applied in the field of preparation of 4-bromomethyl-2-trimethylsilylethynylbenzene-1-sulfonyl fluoride, which can solve the unfavorable environmental safety and sustainable development of waste liquid , high preparation cost, many steps, etc.

Pending Publication Date: 2018-11-06
CHENGDU CHEMPARTNER
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is that the preparation method of the existing sulfonyl fluoride compound A has expensive raw materials, high preparation cost, many steps, low-temperature anhydrous preparation conditions, and cumbersome post-treatment. The yield is low, and a large amount of waste liquid is produced, which is not conducive to the safe and sustainable development of the environment, and is not conducive to the promotion of industrial applications

Method used

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  • Preparation method of 4-bromoethyl-2-trimethylsilyl ethynylbenzene-1-sulfuryl fluoride
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  • Preparation method of 4-bromoethyl-2-trimethylsilyl ethynylbenzene-1-sulfuryl fluoride

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0093] Embodiment 1, the preparation of compound II-1

[0094]

[0095] Add glacial acetic acid (300mL) and cuprous chloride (13.9g) successively in the reaction vessel, feed sulfur dioxide gas at room temperature for 1 hour, cool to 0°C to obtain reaction solution A; add compound I- 1 (13.0g), glacial acetic acid (100mL) and concentrated hydrochloric acid (12mL), stirred and cooled to 0°C, added sodium nitrite (5.3g), stirred for 1 hour to obtain reaction solution B; Added into the reaction solution A, the obtained mixed reaction solution was stirred for 2 hours, extracted with ethyl acetate, washed with water after the combined organic phase, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography to obtain compound II-1 (yellow solid, 13.3 g, yield 70%).

[0096] In other implementations, the starting material 2-bromo-4-methylaniline (compound I-1) can be replaced by 2-chloro-4-methylaniline or 2-iodo-4-methylaniline.

Embodiment 2

[0097] Embodiment 2, the preparation of compound III-1

[0098]

[0099] Compound II-1 (6.0 g), acetonitrile (40 mL) and potassium fluoride (13.0 g) were sequentially added into the reaction vessel, and the reaction solution was stirred at 25°C for 12 hours. The reaction solution was filtered, and the filtrate was concentrated. The concentrated residue was purified by column chromatography to obtain compound III-1 (light yellow solid, 4.8 g, yield 85%).

[0100] In other implementations, potassium fluoride may be replaced by sodium fluoride, cesium fluoride, or tetrabutylammonium fluoride.

[0101] Acetonitrile can be replaced by N,N-dimethylformamide and N,N-dimethylacetamide.

Embodiment 3

[0102] Embodiment 3, the preparation of compound IV

[0103]

[0104] Compound III-1 (4.5 g) and tetrahydrofuran (40 mL) were added into the reactor, followed by trimethylsilyne (6.1 g), cuprous iodide (340 mg) and triethylamine (9.0 g) in sequence. The reaction solution was stirred under nitrogen atmosphere at 25°C for 20 minutes, and then the catalyst bistriphenylphosphine palladium dichloride (2.5 g) was added, and stirred at 70°C for 12 hours. The reaction solution was concentrated, and the concentrated residue was purified by column chromatography to obtain compound IV (yellow solid, 4.0 g, yield 83%).

[0105] In other implementation cases, the above tetrahydrofuran can be replaced by toluene, ethylene glycol dimethyl ether, 1,4-dioxane, acetonitrile, ethyl acetate, N,N-dimethylformamide;

[0106] Triethylamine can be replaced by diisopropylethylamine;

[0107] Bistriphenylphosphinepalladium dichloride can be replaced by tetrakistriphenylphosphinepalladium.

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Abstract

The invention discloses a preparation method of 4-bromoethyl-2-trimethylsilyl ethynylbenzene-1-sulfuryl fluoride. The preparation method comprises the steps of taking 2-halogen-4-methylaniline as a raw material for diazotization, sulfonylation, fluoridation, alkynyl coupling reaction, and benzyl bromide substitution reaction to form 4-bromoethyl-2-trimethylsilyl ethynylbenzene-1-sulfuryl fluoride.According to the preparation method of 4-bromoethyl-2-trimethylsilyl ethynylbenzene-1-sulfuryl fluoride, 4-bromoethyl-2-trimethylsilyl ethynylbenzene-1-sulfuryl fluoride is prepared by a brand-new route; the preparation cost is greatly lowered; compared with the existing preparation method, ultralow temperature and anhydrous operation are not required; the operation is more convenient, simpler, and easier to control; potential safety hazards on an operator are reduced; an operation safety grade of production is lowered; no strong acid is generated during post-treatment; and the method is green and environmentally-friendly and facilitates environmental protection and industrial popularization and application.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a preparation method of 4-bromomethyl-2-trimethylsilylethynylbenzene-1-sulfonyl fluoride. Background technique [0002] In recent years, the determination of the intracellular target of biologically active compounds is one of the key issues in chemical biology and drug development. As an important technology in functional proteomics, small molecule probes play an increasingly important role in the study of determining the intracellular targets of biologically active compounds. Sulfonyl fluoride (SF)-based reactive probes have become important tools in chemical biology and molecular pharmacology. Sulfonyl fluoride can modify most amino acid side chains, but generally only interacts with proteins in specific environments. Under the same physiological conditions, arylsulfonyl fluorides are hydrolyzed more slowly than aliphatic sulfonyl fluorides, so they are more commonl...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/08
CPCC07F7/083
Inventor 廖健宇李坤周稹胡权芳
Owner CHENGDU CHEMPARTNER
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