(Z)-4-trifluoromethyl-5-thio-alkyl-4-pentenone derivative and preparation method therefor

Abstract

The invention discloses a (Z)-4-trifluoromethyl-5-thio-alkyl-4-pentenone derivative and a preparation method therefor. The method comprises the steps of adding and mixing alkyne thioether with a structure represented by a formula II, S-(trifluoromethyl)dibenzothiophene onium trifluoromethyl sulfonate with a structure represented by a formula III, ruthenium tri(2,2-bipyridyl)dichloride, alkali anda solvent, forming a reaction system under blue-light irradiation, and carrying out aftertreatment after a reaction is completed, thereby obtaining the (Z)-4-trifluoromethyl-5-thio-alkyl-4-pentenone derivative with a structure represented by a formula I. According to the method, the stereoselective synthesis of the (Z)-4-trifluoromethyl-5-thio-alkyl-4-pentenone derivative is achieved in one step.The reaction conditions are mild, the substrate applicable range is broad, the reaction yield is good, the operation is simple, and a new way is provided for synthesis of trifluoromethyl containing pentenone compounds.

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 ...

Examples

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]

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 ...

Examples

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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