A kind of preparation method of [(1,2-disulfonyl) ethyl] arene compound

A bissulfonyl compound technology, which is applied in the field of preparation of [ethyl] aromatic hydrocarbon compounds, can solve the problems of large substitution restriction of substrate functional groups, failure to realize bissulfonylation reaction, etc., and achieves good substrate compatibility, The effect of low cost and good application prospect

Active Publication Date: 2022-05-17
TAIZHOU UNIV
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Problems solved by technology

In 2019, the Tsai group reported that α-sulfonyl-substituted ketones were used as substrates to react with dimethyl sulfoxide to achieve mesylation at the α-position of the ketone carbonyl to construct α, β-bissulfonyl products [Org. Lett.2019, 21, 1832], this method has mild conditions, but the substitution of substrate functional groups is very restrictive
However, these methods are only limited to monosulfonylation and have not achieved disulfonylation reactions

Method used

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  • A kind of preparation method of [(1,2-disulfonyl) ethyl] arene compound
  • A kind of preparation method of [(1,2-disulfonyl) ethyl] arene compound
  • A kind of preparation method of [(1,2-disulfonyl) ethyl] arene compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022]

[0023] Add K to the reaction tube sequentially 2 S 2 o 5 (3.0 equiv) and Na 2 HPO 4 (2.0 equivalents), replace the air in the test tube with high-purity nitrogen and add 2 mL of DMF as a solvent. Then p-fluorostyrene (0.2 mmol), 1-iodobutane (4.0 equivalents) and triisopropylsilane (2.0 equivalents) were sequentially added with a microsampler, and stirred at 50° C. for 24 hours. After the reaction, the reaction solution was diluted with EA, extracted with water and saturated brine respectively, then the organic layer was dried, concentrated and separated by column chromatography to obtain the corresponding 1,2-bissulfone-substituted compound 3a in 57% yield.

[0024] 1 H NMR (400MHz, CDCl 3 ) δ (ppm) 7.56 (dd, J = 8.4, 5.2Hz, 2H), 7.17 (t, J = 8.4Hz, 2H), 4.74 (dd, J = 10.7, 2.1Hz, 1H), 3.95 (dd, J =14.4, 1.9Hz, 1H), 3.69(dd, J=14.3, 10.9Hz, 1H), 2.89-2.58(m, 4H), 1.79-1.68(m, 4H), 1.43-1.27(m, 4H), 0.91-0.85 (m, 6H); 19 F NMR (376MHz, CDCl 3 ) δ-109.9--1...

Embodiment 2

[0026]

[0027] Add K to the reaction tube sequentially 2 S 2 o 5 (3.0 equiv) and Na 2 HPO 4 (2.0 equivalents), replace the air in the test tube with high-purity nitrogen and add 2 mL of DMF as a solvent. Then, 2-vinylthiophene (0.2 mmol), 1-iodobutane (4.0 equivalents) and triisopropylsilane (2.0 equivalents) were sequentially added with a micro injector, and stirred at 50° C. for 24 hours. After the reaction, the reaction solution was diluted with EA, extracted with water and saturated brine respectively, then the organic layer was dried, concentrated and separated by column chromatography to obtain the corresponding 1,2-bissulfone group-substituted compound 3b in a 70% yield.

[0028] 1 H NMR (400MHz, CDCl 3 ) δ (ppm) 7.48 (d, J = 5.0Hz, 1H), 7.32 (d, J = 3.3Hz, 1H), 7.10 (dd, J = 4.9, 3.8Hz, 1H), 5.00 (dd, J = 10.9 , 2.3Hz, 1H), 3.92(dd, J=14.6, 2.2Hz, 1H), 3.67(dd, J=14.5, 11.0Hz, 1H), 2.98-2.68(m, 2H), 2.63-2.48(m, 2H), 1.85-1.60(m, 4H), 1.44-1.20(m, 4H), 0.91...

Embodiment 3

[0030]

[0031] Add K to the reaction tube sequentially 2 S 2 o 5 (3.0 eq), Na 2 HPO 4 (2.0 equivalents) and p-phenylstyrene (0.2 mmol), after replacing the air in the test tube with high-purity nitrogen, 2 mL of DMF was added as a solvent. Then ethyl 4-iodobutyrate (4.0 eq) and triisopropylsilane (2.0 eq) were sequentially added using a micro injector, and stirred at 50° C. for 24 hours. After the reaction, the reaction solution was diluted with EA, extracted with water and saturated brine respectively, then the organic layer was dried, concentrated and separated by column chromatography to obtain the corresponding 1,2-bissulfone group-substituted compound 3c in 58% yield.

[0032] 1 HNMR (400MHz, CDCl 3 ) δ (ppm) 7.72-7.61 (m, 6H), 7.48 (t, J = 7.5Hz, 2H), 7.40 (t, J = 7.2Hz, 1H), 4.80 (d, J = 10.4Hz, 1H), 4.16-3.98(m, 5H), 3.81(dd, J=14.4, 10.9Hz, 1H), 3.08-2.73(m, 4H), 2.54-2.31(m, 4H), 2.18-1.97(m, 4H), 1.22(t, J=7.1Hz, 6H); 13 C NMR (100MHz, CDCl 3 )δ (ppm) ...

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Abstract

The invention belongs to the technical field of organic chemistry, and specifically relates to a preparation method of [(1,2-bissulfonyl)ethyl]arene compounds. In an organic solvent (such as DMF), under the action of an equivalent amount of silane and a base, alkyl halide hydrocarbons, aryl olefins and pyrosulfites react to produce [(1,2-bissulfonyl) ethyl] arenes class of compounds. The structures of these compounds have been 1 H NMR, 13 C NMR, HRMR, single crystal X-ray diffraction and other methods were characterized and confirmed. The method of the present invention realizes the difunctionalization reaction of olefins by using simple olefins as the basic carrier under mild and simple conditions, and efficiently constructs 1,2-bissulfonyl-substituted compounds in one step, greatly improving the synthesis of such compounds efficiency, and enrich the diversity of its functional groups; the reaction raw materials are easy to get, the cost is low, the operation is simple and avoids the traditional 1,2-bissulfonyl compound synthesis method with complicated steps, poor operability, and production Due to the disadvantage of low efficiency, it can be applied to large-scale preparation and has a good application prospect.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry, and in particular relates to a preparation method of [(1,2-bissulfonyl) ethyl] arene compounds. Background technique [0002] The sulfonyl segment is a very important group. Common sulfonyl-containing compounds include sulfonamide, sulfone, sulfonic acid, and sulfonate ester compounds, and this structural segment widely exists in drug molecules, pesticide molecules, and material molecules. [M. Bartholow, Top 200 Drugs of 2011. Pharmacy Times. http: / / www.pharmacytimes.com / publications / issue / 2012 / July2012 / Top-200-Drugs-of-2011, accessed on Jan 9, 2013; P.S. Santos, M.T.S. Mello, J.Mol.Struc. 1988, 178, 121; El-Hibri, M. J.; Weinberg, S.A. In Encyclopedia of Polymer Science and Technology, Ed. Mark, H.F. Wiley: New York, 2014, 179]. Among them, sulfone compounds are very important sulfonyl compounds. For example, drugs containing sulfone groups such as Eletriptan are used to treat migrain...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C317/10C07C315/00C07D333/18C07C317/44C07C317/18C07B60/00
CPCC07C317/10C07C315/00C07D333/18C07C317/44C07C317/18C07B61/02C07B2200/03
Inventor 吴劼叶盛青张俊
Owner TAIZHOU UNIV
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