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A kind of (z)-4-trifluoromethyl-5-sulfanyl-4-pentenone derivative and its preparation method

A technology of trifluoromethyl and thienium trifluoromethanesulfonate, applied in the field of -4-trifluoromethyl-5-sulfanyl-4-pentenone derivatives and their preparation, can solve the problem of There are no problems such as olefin addition products, and the effect of wide application range of substrates, good functional group compatibility and simple operation is achieved.

Active Publication Date: 2022-03-29
ZHEJIANG NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the long-range C-H functionalization initiated by the free radical addition of alkynes has been realized. However, this reaction often undergoes migration of the free radical addition atom and then is cyclized to form a ring instead of an alkene addition product.

Method used

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  • A kind of (z)-4-trifluoromethyl-5-sulfanyl-4-pentenone derivative and its preparation method
  • A kind of (z)-4-trifluoromethyl-5-sulfanyl-4-pentenone derivative and its preparation method
  • A kind of (z)-4-trifluoromethyl-5-sulfanyl-4-pentenone derivative and its preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Take a dry reaction tube, add tris(2,2-bipyridyl)ruthenium dichloride (3.0mg, 0.004mmol), sodium bicarbonate (33.6mg, 0.4mmol), S shown in structural formula 2 under nitrogen atmosphere -(Trifluoromethyl)dibenzothiophenium trifluoromethanesulfonate (160.0mg, 0.40mmol), alkyne thioether (38mg, 0.2mmol) represented by structural formula 1a was then added to 2 mL of dry dimethylmethylene Sulfone forming reaction system. Under the irradiation of 20W blue light, the system was stirred at room temperature 25°C for 8h, quenched by adding 15mL of water, extracted three times with ethyl acetate (10mL), combined, the organic phase was washed with saturated edible water, and dried over anhydrous sodium sulfate. After the organic phase was concentrated, it was separated by silica gel (300-400 mesh) column chromatography to obtain 41 mg of a light yellow liquid represented by structural formula 3a, with a yield of 75%.

[0031] Product Spectrum Analysis 1 H NMR (600MHz, CDCl 3 )δ...

Embodiment 2

[0035] Except that the alkyne thioether derivative shown in structural formula 1b was used instead of the alkyne thioether derivative shown in structural formula 1a in Example 1, the rest of the operation steps were the same as in Example 1, yield: 73%, light yellow liquid shown in structural formula 3b.

[0036] Product Spectrum Analysis 1 H NMR (600MHz, CDCl 3)δ7.95–7.94(m,2H),7.59–7.56(m,1H),7.48–7.46(m,2H),6.53(s,1H),3.16(t,J=7.4Hz,2H),2.73 (q, J=7.4Hz, 2H), 2.71–2.67(m, 2H), 1.31(t, J=7.4Hz, 3H); 13 C NMR (151MHz, CDCl 3 )δ198.5, 136.7, 135.5(q, J=3.2Hz), 133.2, 128.6, 127.9, 124.6(q, J=275.1Hz), 122.8(q, J=29.9Hz), 37.7, 29.3(q, J=1.9 Hz), 27.1 (q, J=1.7Hz), 15.3; 19 F NMR (565MHz, CDCl 3 )δ-61.5; HRMS (ESI) calcd for C 14 h 15 f 3 OSNa(M+Na) + 311.0688, found 311.0690.

[0037] The reaction formula is as follows:

[0038]

Embodiment 3

[0040] Except that the alkyne thioether derivative represented by structural formula 1c was used to replace the alkyne thioether represented by structural formula 1a in Example 1, the remaining operating steps were the same as in Example 1, yield: 76%, light yellow liquid represented by structural formula 3c.

[0041] Product Spectrum Analysis 1 H NMR (600MHz, CDCl 3 )δ7.85(d, J=8.1Hz, 2H), 7.26(d, J=8.0Hz, 2H), 6.46(s, 1H), 3.13(t, J=7.5Hz, 2H), 2.66(t, J=7.5Hz, 2H), 2.41(s, 3H), 2.34(s, 3H); 13 C NMR (151MHz, CDCl 3 )δ198.1, 144.1, 137.2(q, J=3.2Hz), 134.2, 129.3, 128.1, 124.6(q, J=275.1Hz), 122.7(q, J=29.8Hz), 37.5, 27.0(q, J=1.8 Hz), 21.6, 18.4 (q, J=2.1Hz); 19 F NMR (565MHz, CDCl 3 )δ-61.5; HRMS (ESI) calcd for C 14 h 15 f 3 OSNa(M+Na) + 311.0688,found 311.0689.

[0042] The reaction formula is as follows:

[0043]

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Abstract

The invention discloses a derivative of (Z)-4-trifluoromethyl-5-sulfanyl-4-pentenone and a preparation method thereof. (Trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate, three (2,2 bipyridyl) ruthenium dichloride, alkali and solvent are added and mixed, and a reaction system is formed under blue light irradiation. After the reaction is completed, the Post-treatment to obtain a (Z)-4-trifluoromethyl-5-sulfanyl-4-pentenone derivative of the structure of formula I. The invention realizes the stereoselective synthesis of a (Z)-4-trifluoromethyl-5-sulfanyl-4-pentenone derivative in one step. The reaction condition is mild, the substrate has a wide application range, the reaction yield is good, and the operation is simple, which provides a new way for the synthesis of compounds containing trifluoromethyl pentenoids.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and specifically relates to a (Z)-4-trifluoromethyl-5-sulfanyl-4-pentenone derivative and a preparation method thereof. Background technique [0002] The C-H bond is the simplest and most common functional group in organic compounds. The selective oxidation of hydrocarbons to synthesize oxygen-containing organic chemical products occupies an extremely important position in industrial synthesis, especially in petrochemicals. However, the selective oxidation of hydrocarbons faces many problems. First of all, due to the high activation energy of the C-H bond of saturated hydrocarbons, it is difficult to oxidize, and usually requires the addition of high temperature and high pressure or an equivalent strong oxidant. Secondly, target products such as alcohols, ketones, aldehydes, and acids are mostly thermodynamically unstable intermediate compounds, which are easily further deeply oxidized. These ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B61/00C07C319/20C07C323/22C07F7/18
CPCC07B61/02C07C319/20C07F7/1892C07F7/1804C07B2200/09C07C323/22
Inventor 罗芳朱钢国商甜波张岩舒陈云
Owner ZHEJIANG NORMAL UNIVERSITY
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