Method for synthesizing cyclic sulphoxide imine, sulfenamide and sulfamide by stereospecificty

A technology for sulfoximine and sulfenamide, which is applied in the field of efficient preparation of cyclic sulfoximine, can solve the problems of limited, unreported, and high cost of preparing cyclic sulfoximine, and achieves high stereospecificity, The effect of low cost and high yield

Inactive Publication Date: 2010-03-10
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
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Problems solved by technology

[0008] 2006, 45, 633. There are relevant reports on the synthesis of this type of compound, but due to the defects in the free radical reaction, the preparation of cyclic sulfinamides from this method is greatly restricted, and for cyclic fluorine-containing sulfinamides Sulfonamide has not been reported in the literature
According to the method of document J.Org.Chem.1997,62,7047. report, take saccharin (saccharin) as starting material, can synthesize cyclic sulfonamide through steps such as nucleophilic addition, asymmetric hydrogenation, but this method cost higher, lower yield

Method used

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  • Method for synthesizing cyclic sulphoxide imine, sulfenamide and sulfamide by stereospecificty
  • Method for synthesizing cyclic sulphoxide imine, sulfenamide and sulfamide by stereospecificty
  • Method for synthesizing cyclic sulphoxide imine, sulfenamide and sulfamide by stereospecificty

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Table 1

[0027]

[0028] Table 2

[0029]

[0030] Typical preparation method of cyclic sulfoximine 1:

[0031] At room temperature, to 4a (0.3mmol, 0.120g), 5a (0.9mmol, 0.268g), CH 3 CsF (1.5mmol, 0.228g) was added to the mixture of CN (5.0mL) and reacted at room temperature for 12h, followed by TLC to complete the reaction. Quenched with water, Et 2 O extraction (30mL×3), anhydrous MgSO 4 dry. The solvent was removed, and column chromatography (ethyl acetate:petroleum ether=1:3) gave 0.124g of product 1a with a yield of 87%.

[0032]

[0033] Mp: 138-140°C.[α] D 22 -45.1 (c 0.8, CHCl 3 ). 1 H NMR: δ8.03-7.87(m, 5H), 7.69-7.55(m, 3H), 7.47(t, J=7.4Hz, 3H), 7.26(d, J=7.4Hz, 3H), 1.47(s , 9H). 19 FNMR: δ-97.7 (d, J=233.9Hz, 1F), -100.0 (d, J=233.8Hz, 1F). 13 C NMR: δ 148.0 (d, J = 1.5Hz), 139.1, 136.2, 135.1, 134.8, 133.2, 131.3, 130.1, 128.9, 128.4, 128.2, 127.7 (d, J = 4.4Hz), 126.2 (d, J = 2.8 Hz), 123.8, 122.9 (t, J = 298.0 Hz), 63.8, 24.9 (d,...

Embodiment 2

[0087] table 3

[0088]

[0089] Typical preparation method of cyclic sulfoximine 1t:

[0090] At 0°C, Mg (4.0 mmol, 0.096g), the system naturally rose to room temperature, reacted for 8h, and TLC tracked the completion of the reaction. Add water, Et 2 O extraction (30mL×3), anhydrous MgSO 4 dry. The solvent was removed, and column chromatography (ethyl acetate:petroleum ether=1:3) yielded 0.063g of product 1t with a yield of 94%.

[0091]

[0092] [α] D 21 +20.2 (c 1.1, CHCl 3 ). 1 H NMR: δ7.83(d, J=7.8Hz, 1H), 7.80-7.70(q, J=7.4Hz, 3H), 7.63(t, J=7.4Hz, 1H), 7.55(t, J=7.5 Hz, 1H), 7.35-7.21(m, 3H), 6.15(t, J=55.9Hz, 1H), 1.61(s, 9H). 19 F NMR: δ-122.3 (dd, J=271.7, 56.9Hz, 1F), -123.4 (dd, J=271.7, 56.9Hz, 1F). 13 C NMR: δ147.7, 141.0, 136.9, 133.6, 130.6, 129.3, 128.7, 127.9(t, J=1.9Hz), 127.6(t, J=1.9Hz), 124.6, 118.2(t, J=250.7Hz) , 80.1 (t, J=21.8Hz), 63.9, 25.7. MS (ESI, m / z): 336.1 (M+H + ).HRMS(ESI): calcd.for C 18 h 19 f 2 NOS: (M+H + ): 336.12...

Embodiment 3

[0110] Table 4

[0111]

[0112] Typical preparation method of cyclic sulfinamide 2:

[0113] At -78°C, to 1a (0.2mmol, 0.084g), CH 2 Cl 2 (8mL) was slowly added to the mixture of pre-made HCl (Dioxane) (1.6mL, 2.5M) 【The HCl gas into the Dioxane, Dioxane as a carrier to absorb the HCl gas as a reactant, take Dioxane 1.6 containing 2.5M HCl gas mL], reacted at this temperature for 1h, and followed the completion of the reaction by TLC. Then add saturated NaHCO 3 Neutralize hydrochloric acid. CH 2 Cl 2 Extraction (30mL×3), anhydrous MgSO 4 dry. The solvent was removed, and column chromatography (ethyl acetate:petroleum ether=1:3) yielded 0.082g of product 2a with a yield of 98%.

[0114]

[0115] 1 H NMR: δ7.90(d, J=6.6Hz, 2H), 7.86-7.75(m, 3H), 7.69(t, J=7.3Hz, 2H), 7.60-7.46(m, 4H), 7.33(d , J=6.0Hz, 3H), 6.47(s, 1H). 19 F NMR: δ-99.3 (d, J=238.2Hz, 1F), -100.9 (d, J=238.1Hz, 1F). 13 C NMR: δ145.5, 137.9, 135.8, 135.4, 133.6, 131.9, 130.6, 130.4, 129.2, 129...

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Abstract

The invention relates to a method for synthesizing cyclic sulphoxide imine, sulfenamide and sulfamide by stereospecificty; the method comprises the following steps of: under the condition of room temperature, sulphinyl imine 4 and benzyne precursor 5 have reaction for 1-15h under the initiation of organic solvent and CsF, the cyclic sulphoxide imine 1 is generated; when the cyclic sulphoxide imine1 contains sulfonyl, the sulfonyl inside a molecule can be successfully removed under the condition of Mg/HOAc/AcONaDMF/H2O, and the cyclic sulphoxide imine 1 is obtained; under the condition of HCl(dioxane), the cyclic sulphoxide imine 1 is successfully transformed into the cyclic sulfenamide 2; and after the cyclic sulfenamide 2 is oxidized by m CPBA, the cyclic sulfamide 3 is obtained. The method has the characteristics of low cost, high yield, mild reaction condition, environmental protection, good repeatability and the like.

Description

technical field [0001] The invention relates to an efficient method for preparing cyclic sulfoximine, cyclic sulfinamide and cyclic sulfonamide. The cyclic compound obtained by the method has very wide applications in the fields of asymmetric synthesis, fluorine-containing drugs and fluorine-containing materials. Background technique [0002] Fluorochemicals have important applications in drug design and materials chemistry. Selectively introducing fluorine atoms or fluorine-containing groups into organic molecules can greatly improve the original physiological activity of the parent molecule. Therefore, research on selective fluorination and fluoroalkylation reactions has also received more and more attention in the fields of pesticides, medicine, and material science. Although the research on fluorination and trifluoromethylation reactions is quite mature, the research on difluoromethylation reactions is still relatively less. Since difluoromethyl (-CF 2 H) and hydroxy...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D275/06
Inventor 胡金波张来俊
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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