Method for preparing vinyl sulfone compound by light-promoted sulfonyl chloride and olefin coupling

Abstract

The invention discloses a method for preparing a vinyl sulfone compound by light-promoted sulfonyl chloride and olefin coupling, which comprises the following steps: by taking aryl sulfonyl chloride as shown in a formula (I) as a raw material, adding iodized salt, an olefin compound as shown in a formula (II), a solvent and alkali into a reactor, and reacting under a nitrogen atmosphere, so as to obtain the vinyl sulfone compound. In the reaction equation # imgabs0 # formula (I), an Ar group is phenyl, substituted phenyl or 3, 5-dimethylisoxazole, a substituent group on the substituted phenyl is fluorine, iodine, cyano, nitro, methyl or trifluoromethyl, in the formula (II), hydrogen on a benzene ring is substituted or not substituted by a substituent R2, and in the formula (II), hydrogen on a benzene ring is substituted or not substituted by a substituent R3. The substituent R2 is fluorine or tertiary butyl, and the substituent R1 is hydrogen or phenyl. According to the method, sulfonyl chloride which is low in cost and easy to obtain is used, aryl sulfonyl chloride and olefin compounds are efficiently promoted to prepare the vinyl sulfone compounds, illumination is adopted to replace a traditional heating reaction, a noble metal catalyst is not added, the reaction cost is low, and the safety is high.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical organic synthesis, and particularly relates to a method for preparing vinyl sulfone compounds by light-promoting coupling of sulfonyl chloride and olefin. Background Art

[0002] Vinyl sulfone is a common functional group in organic chemistry and medicinal chemistry. Because of its wide range of synthetic uses and potential biological activity, it is an important component of many natural organic compounds. It is increasingly used in the fields of chemical industry, medicine, food, etc.

[0003] The general method for synthesizing vinyl sulfone compounds reported in the literature is the Heck coupling reaction using olefins and sulfonyl chloride as raw materials. According to the needs of the reaction, researchers have developed a series of schemes for synthesizing vinyl sulfone compounds, but these methods have disadvantages such as the use of expensive transition metal catalysts, harsh reaction conditions, low atom economy, narrow substrate range, and difficulty in operation. Summary of the invention

[0004] In view of the defects existing in the prior art, the purpose of the present invention is to provide a method for preparing vinyl sulfone compounds by light-promoted coupling of sulfonyl chloride and olefin. Using cheap, easily available and highly stable aryl sulfonyl chloride as a raw material and iodine salt as a catalyst, the sulfonyl chloride and olefin compounds are catalyzed to react under the promotion of light to prepare vinyl sulfone compounds.

[0005] The technical solution adopted by the present invention is:

[0006] A method for preparing vinyl sulfone compounds by light-promoted coupling of sulfonyl chloride and olefins, the principle of which includes an electron donor (EDA) process of iodine salt under ultraviolet light irradiation, exciting olefins to form free radical intermediates, and then adding with sulfonyl radicals. Subsequently, elimination occurs under the action of a base to eliminate a portion of hydroiodic acid to obtain the desired vinyl sulfone compound. The method includes:

[0007] Using an arylsulfonyl chloride as a raw material, an iodine salt, an olefin compound as shown in formula (II), a solvent and a base are added to a reactor, and reacted under a nitrogen atmosphere and ultraviolet light to obtain a vinyl sulfone compound as shown in formula (III). The reaction equation is as follows:

[0008]

[0009] In formula (I), the Ar group is phenyl, substituted phenyl or 3,5-dimethylisoxazole, and the substituent on the substituted phenyl is fluorine, iodine, cyano, nitro, methyl or trifluoromethyl. In formula (II), the hydrogen on the benzene ring is replaced by the substituent R2 or not. When substituted, the substituent R2 is fluorine or tert-butyl, and the substituent R1 is hydrogen or phenyl.

[0010] Furthermore, the solvent is one of the following: EtOAc, THF, ACN, DCM.

[0011] Furthermore, the iodized salt is one of the following: NaI, KI.

[0012] Furthermore, the base is one of the following: K3PO4, KH2PO4, KF, Na2CO3.

[0013] Furthermore, the molar ratio of the arylsulfonyl chloride to the olefin compound is 1.0 to 1.5:1.

[0014] Furthermore, the molar ratio of the arylsulfonyl chloride to the iodine salt is 0.4-0.5:1.

[0015] Furthermore, the molar ratio of the arylsulfonyl chloride to the base is 0.5 to 1.0:1.

[0016] Furthermore, the reaction time is 12 to 16 hours.

[0017] Furthermore, the wavelength of the ultraviolet lamp is 415nm, 425nm, 455nm or 465nm.

[0018] The beneficial effects of the present invention are mainly reflected in:

[0019] 1) Using cheap and readily available sulfonyl chloride, the preparation of vinyl sulfone compounds from arylsulfonyl chloride and olefin compounds is efficiently promoted.

[0020] 2) Using light to replace the traditional heating reaction, without adding precious metal catalysts, the reaction cost is low and the safety is high.

[0021] 3) The substrate has wide applicability and can obtain the corresponding vinyl sulfone compounds in good yield.

[0022] 4) The operation process is simple and efficient. DETAILED DESCRIPTION

[0023] The present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto:

[0024] Example 1: Preparation of 1-(tert-butyl)-4-(2-((4-fluorophenyl)sulfonyl)vinyl)benzene

[0025]

[0026] In a 100ml three-necked flask, add 0.388g (2.0mmol) of 4-fluorobenzenesulfonyl chloride (Formula I, R = 4-F), 0.320g (2.0mmol) of 4-tert-butylstyrene, 0.664g (4.0mmol) of potassium iodide, 0.849g (4.0mmol) of tripotassium phosphate and 40ml of ethyl acetate in sequence, stir for 12h under nitrogen atmosphere and 425nm ultraviolet lamp. After the reaction is completed, add 50mL of ethyl acetate to dilute, then add 50ml of water to wash three times, wash with saturated brine, dry with anhydrous sodium sulfate, filter and concentrate to obtain 0.509g of 1-(tert-butyl)-4-(2-((4-fluorophenyl)sulfonyl)vinyl)benzene, with a purity of 98% and a yield of 80% (based on olefins). H NMR spectrum: 1 H NMR (400MHz, CDCl3) δ8.00-7.95(m,2H),7.69(d,J=15.4Hz,1H),7.45(s,4H),7.26-7.21(m,2H),6.82(d,J=15.4Hz,1H),1.33(s,9H).

[0027] Example 2: Preparation of 1-(tert-butyl)-4-(2-((4-iodophenyl)sulfonyl)vinyl)benzene

[0028]

[0029] In a 100 ml single-necked flask, 0.664 g (2.2 mmol) of 4-iodobenzenesulfonyl chloride (Formula I, R=4-I), 0.320 g (2.0 mmol) of 4-tert-butylstyrene, 0.659 g (4.4 mmol) of sodium iodide, 0.499 g (3.7 mmol) of potassium dihydrogen phosphate and 40 ml of acetonitrile were added in sequence, and stirred for 13 h under nitrogen atmosphere and 415 nm ultraviolet lamp. After the reaction, 50 mL of ethyl acetate was added to dilute, and then 50 ml of water was added to wash three times, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated to obtain 0.741 g of 1-(tert-butyl)-4-(2-((4-iodophenyl)sulfonyl)vinyl)benzene with a purity of 99% and a yield of 87% (based on olefin).

[0030] H NMR spectrum: 1 H NMR (400MHz, CDCl3) δ7.93-7.90(m,2H),7.71-7.65(m,3H),7.44(s,4H),6.80(d,J=15.4Hz,1H),1.33(s,9H).

[0031] Example 3: Preparation of 1-(tert-butyl)-4-(2-((4-(trifluoromethyl)phenyl)sulfonyl)vinyl)benzene

[0032]

[0033] In a 100 ml single-necked flask, 0.510 g (2.4 mmol) of 4-trifluoromethylbenzenesulfonyl chloride (Formula I, R = 4-CF3), 0.320 g (2.0 mmol) of 4-tert-butylstyrene, 0.996 g (6.0 mmol) of potassium iodide, 0.199 g (3.4 mmol) of potassium fluoride and 40 ml of tetrahydrofuran were added in sequence, and stirred for 14 h under nitrogen atmosphere and irradiation with a 455 nm ultraviolet lamp. After the reaction was completed, 50 mL of ethyl acetate was added to dilute, and then 50 ml of water was added to wash three times, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated to obtain 0.663 g of 1-(tert-butyl)-4-(2-((4-(trifluoromethyl)phenyl)sulfonyl)vinyl)benzene with a purity of 99% and a yield of 90% (calculated as olefin).

[0034] H NMR spectrum: 1 H NMR (400MHz, CDCl3) δ8.10(d,J=8.3Hz,2H),7.83(d,J=8.5Hz,2H),7.75(d,J=15.4Hz,1H),7.46(s,4H),6.82(d,J=15.4Hz,1H),1.34(s,9H).

[0035] Example 4: Preparation of 4-((4-(tert-butyl)phenylvinyl)sulfonyl)benzonitrile

[0036]

[0037] In a 100 ml single-necked flask, 0.522 g (2.6 mmol) of 4-cyanobenzenesulfonyl chloride (Formula I, R = 4-CN), 0.320 g (2.0 mmol) of 4-tert-butylstyrene, 0.896 g (5.9 mmol) of sodium iodide, 0.496 g (4.7 mmol) of sodium carbonate and 40 ml of dichloromethane were added in sequence, and stirred for 16 h under nitrogen atmosphere and irradiation with a 465 nm ultraviolet lamp. After the reaction was completed, 50 mL of ethyl acetate was added to dilute, and then 50 ml of water was added to wash three times, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated to obtain 0.624 g of 4-((4-(tert-butyl)styryl)sulfonyl)benzonitrile with a purity of 98% and a yield of 96% (based on olefin).

[0038] H NMR spectrum: 1H NMR (400MHz, CDCl3) δ7.98(d,J=8.2Hz,2H),7.76(d,J=8.1Hz,2H),7.65(d,J=15.3Hz,1H),7.36(s,4H),6.72(d,J=15.4Hz,1H),1.24(s,9H).

[0039] Example 5: Preparation of 1-(tert-butyl)-4-(2-p-toluenesulfonylvinyl)benzene

[0040]

[0041] In a 100ml single-necked flask, 0.532g (2.8mmol) of p-toluenesulfonyl chloride (Formula I, R=CH3), 0.320g (2.0mmol) of 4-tert-butylstyrene, 0.664g (4.0mmol) of potassium iodide, 0.849g (4.0mmol) of tripotassium phosphate and 40ml of ethyl acetate were added in sequence, and stirred for 15h under nitrogen atmosphere and 425nm ultraviolet lamp. After the reaction, 50mL of ethyl acetate was added to dilute, and then 50ml of water was added to wash three times, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated to obtain 0.578g of 1-(tert-butyl)-4-(2-toluenesulfonylvinyl)benzene with a purity of 98% and a yield of 92% (calculated as olefin).

[0042] H NMR spectrum: 1 H NMR (400MHz, CDCl3) δ7.86–7.82(m,2H),7.67(d,J=15.4Hz,1H),7.43(d,J=0.6H z,4H),7.35(d,J=7.9Hz,2H),6.82(d,J=15.4Hz,1H),2.45(s,3H),1.33(s,9H).

[0043] Example 6: Preparation of 1-(tert-butyl)-4-(2-((4-nitrophenyl)sulfonyl)vinyl)benzene

[0044]

[0045] In a 100ml single-necked flask, 4-nitrobenzenesulfonyl chloride, (Formula I, R = NO2) 0.566g (3.0mmol), 0.320g (2.0mmol) 4-tert-butylstyrene, 0.896g (5.8mmol) sodium iodide, 0.199g (3.4mmol) potassium fluoride and 40ml tetrahydrofuran were added in sequence, and stirred for 14h under nitrogen atmosphere and 415nm ultraviolet lamp. After the reaction, 50mL ethyl acetate was added to dilute, and then 50ml water was added to wash three times, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated to obtain 0.414g of 1-(tert-butyl)-4-(2-((4-nitrophenyl)sulfonyl)vinyl)benzene, with a purity of 98% and a yield of 60% (based on olefins). H NMR spectrum: 1 H NMR (400MHz, CDCl3) δ8.33-8.28(m,2H),8.09-8.03(m,2H),7.68(d,J=15.4Hz,1H),7.37(d,J=1.1Hz,4H),6.74(d,J=15.4Hz,1H),1.24(s,9H).

[0046] Example 7: Preparation of 1-(tert-butyl)-4-(2-(phenylsulfonyl)vinyl)benzene

[0047]

[0048] In a 100ml single-necked flask, benzenesulfonyl chloride, (Formula I, R=H) 0.422g (2.4mmol), 0.320g (2.0mmol) 4-tert-butylstyrene, 0.896g (5.9mmol) sodium iodide, 0.499g (3.7mmol) potassium dihydrogen phosphate and 40ml ethyl acetate were added in sequence, and stirred for 13h under nitrogen atmosphere and 455nm ultraviolet lamp. After the reaction, 50mL ethyl acetate was added to dilute, and then 50ml water was added to wash three times, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated to obtain 0.546g of 1-(tert-butyl)-4-(2-(phenylsulfonyl)vinyl)benzene with a purity of 99% and a yield of 91% (calculated as olefin).

[0049] H NMR spectrum: 1 H NMR (400MHz, CDCl3) δ7.99–7.95(m,2H),7.70(d,J=15.4Hz,1H),7.65–7.60(m,1H ),7.58–7.54(m,2H),7.44(d,J=2.0Hz,4H),6.84(d,J=15.4Hz,1H),1.33(s,9H).

[0050] Example 8: Preparation of 4-((4-fluorophenylvinyl)sulfonyl)-3,5-dimethylisoxazole

[0051]

[0052] In a 100 ml single-necked flask, 0.429 g (2.2 mmol) of 3,5-dimethylisoxazole-4-sulfonyl chloride, 0.244 g (2.0 mmol) of 4-fluorostyrene, 0.664 g (4.0 mmol) of potassium iodide, 0.849 g (4.0 mmol) of tripotassium phosphate and 40 ml of acetonitrile were added in sequence, and stirred for 14 h under nitrogen atmosphere and 425 nm ultraviolet lamp. After the reaction was completed, 50 mL of ethyl acetate was added to dilute, and then 50 ml of water was added to wash three times, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated to obtain 0.489 g of 4-((4-fluorostyryl)sulfonyl)-3,5-dimethylisoxazole with a purity of 98% and a yield of 87% (based on olefin).

[0053] H NMR spectrum: 1 H NMR (400MHz, CDCl3)7.63(d,J=15.4Hz,1H),7.51(td,J=5.8,2.8Hz,2H),7.15–7.10(m,2H),6.77(d,J=15.4Hz,1H),2.69(s,3H),2.40(s,3H).

[0054] Example 9: Preparation of 4-((2,2-diphenylethylene))sulfonyl)-3,5-dimethylisoxazole

[0055]

[0056] In a 100ml single-necked flask, add 0.507g (2.6mmol) of 3,5-dimethylisoxazole-4-sulfonyl chloride, 0.396g (2.2mmol) of 1,1-stilbene, 0.896g (5.8mmol) of sodium iodide, 0.496g (4.7mmol) of sodium carbonate and 40ml of tetrahydrofuran in sequence, stir for 12h under nitrogen atmosphere and 465nm ultraviolet lamp. After the reaction is completed, add 50mL of ethyl acetate to dilute, then add 50ml of water to wash three times, wash with saturated brine, dry with anhydrous sodium sulfate, filter and concentrate to obtain 0.536g of 4-((2,2-stilbene))sulfonyl)-3,5-dimethylisoxazole, with a purity of 98% and a yield of 79% (based on olefins). H NMR spectrum: 1H NMR(400MHz,CDCl3)δ7.36–7.26(m,7H),7.21–7.11(m,3H),7.06–7.02(m,2H),6.97(s,1H),2.24(s,3H),2.12(s,3H)。

Claims

1. A method for preparing vinyl sulfone compounds by light-promoted coupling of sulfonyl chloride and olefin, characterized in that: The method comprises: Using an arylsulfonyl chloride as a raw material, an iodine salt, an olefin compound as shown in formula (II), a solvent and a base are added to a reactor, and reacted under a nitrogen atmosphere and ultraviolet light to obtain a vinyl sulfone compound as shown in formula (III). The reaction equation is as follows: In formula (I), the Ar group is phenyl, substituted phenyl or 3,5-dimethylisoxazole, and the substituent on the substituted phenyl is fluorine, iodine, cyano, nitro, methyl or trifluoromethyl. In formula (II), the hydrogen on the benzene ring is replaced by the substituent R2 or not. When substituted, the substituent R2 is fluorine or tert-butyl, and the substituent R1 is hydrogen or phenyl.

2. The method for preparing vinyl sulfone compounds by light-promoted coupling of sulfonyl chloride and olefin as claimed in claim 1, characterized in that: The solvent is one of the following: EtOAc, THF, ACN, DCM.

3. The method for preparing vinyl sulfone compounds by light-promoted coupling of sulfonyl chloride and olefin as claimed in claim 1, characterized in that: The iodized salt is one of the following: NaI, KI.

4. The method for preparing vinyl sulfone compounds by light-promoted coupling of sulfonyl chloride and olefin as claimed in claim 1, characterized in that: The base is one of the following: K3PO4, KH2PO4, KF, Na2CO3.

5. The method for preparing vinyl sulfone compounds by light-promoted coupling of sulfonyl chloride and olefin as claimed in claim 1, characterized in that: The molar ratio of the arylsulfonyl chloride to the olefin compound is 1.0-1.5:

1.

6. The method for preparing vinyl sulfone compounds by light-promoted coupling of sulfonyl chloride and olefin as claimed in claim 1, characterized in that: The molar ratio of the arylsulfonyl chloride to the iodine salt is 0.4-0.7:

1.

7. The method for preparing vinyl sulfone compounds by light-promoted coupling of sulfonyl chloride and olefin as claimed in claim 1, characterized in that: The molar ratio of the arylsulfonyl chloride to the base is 0.5-1.0:

1.

8. The method for preparing vinyl sulfone compounds by light-promoted coupling of sulfonyl chloride and olefin as claimed in claim 1, characterized in that: The reaction time is 12 to 16 hours.

9. The method for preparing vinyl sulfone compounds by light-promoted coupling of sulfonyl chloride and olefin as claimed in claim 1, characterized in that: The wavelength of the ultraviolet lamp is 415nm, 425nm, 455nm or 465nm.

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