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Method for synthesizing 1,2-benzothiazine compound by rhodium (III) catalyzed C-H activation reaction

A technology of benzothiazine and compounds, applied in the field of benzothiazine compounds, can solve the problems of explosive carcinogenicity and poor stability

Pending Publication Date: 2021-09-24
SICHUAN UNIV
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  • Abstract
  • Description
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  • Application Information

AI Technical Summary

Problems solved by technology

However, a series of properties such as poor stability, explosiveness and potential carcinogenicity limit the practical research of diazo compounds. [1]

Method used

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  • Method for synthesizing 1,2-benzothiazine compound by rhodium (III) catalyzed C-H activation reaction
  • Method for synthesizing 1,2-benzothiazine compound by rhodium (III) catalyzed C-H activation reaction
  • Method for synthesizing 1,2-benzothiazine compound by rhodium (III) catalyzed C-H activation reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Implementation Example 1: Synthesis of Compound 3a

[0020]

[0021] In a clean pressure-resistant bottle equipped with a magnetic stir bar, add S -Phenyl- S -Methylsulfoiminosulfone (15.5 mg, 0.10 mmol), 2-(phenyl-λ 3 -iodoalkylene)cyclohexane-1,3-dione (37.7 mg, 0.12 mmol), bis(hexafluoroantimonate)triacetonitrile(pentamethylcyclopentadienyl)rhodium(III) (4.2 mg , 0.005 mmol) and trifluoroethanol (2.0 mL), stirred in an oil bath at 50 ℃ for 8 h under air atmosphere;

[0022] After the reaction was completed, it was directly separated and purified by silica gel column chromatography to obtain 22.5 mg of the product, a white solid, with a yield of 91%; 1 H NMR (400 MHz, Chloroform- d )δ 9.10 (d, J = 8.6 Hz, 1H), 7.78 (d, J =8.0 Hz, 1H), 7.68 (t, J = 8.0 Hz, 1H), 7.46 (t, J = 7.6 Hz, 1H), 3.40 (s,3H), 2.86 – 2.72 (m, 2H), 2.59 (t, J = 6.6 Hz, 2H), 2.07 – 1.96 (m, 2H). 13 CNMR (100 MHz, Chloroform- d )δ 196.2, 166.2, 134.3, 133.9, 127.4, 126.8, 123.2, 1...

Embodiment 2

[0023] Implementation Example 2: Synthesis of Compound 3b

[0024]

[0025] In a clean pressure-resistant bottle equipped with a magnetic stir bar, add S -(4-methoxyphenyl)- S -Methylsulfoximine (18.5 mg, 0.10 mmol), 5,5-Dimethyl-2-(phenyl-λ 3 -iodoalkylene)cyclohexane-1,3-dione (41.0 mg, 0.12 mmol), bis(hexafluoroantimonate)triacetonitrile(pentamethylcyclopentadienyl)rhodium(III) (4.2 mg , 0.005 mmol) and trifluoroethanol (2.0 mL), stirred in an oil bath at 50 ℃ for 8 h under air atmosphere;

[0026] After the reaction was completed, the product was directly separated and purified by silica gel column chromatography to obtain 23 mg of the product, a white solid, with a yield of 83%; 1 H NMR (400 MHz, Chloroform- d )δ 8.90 (d, J = 2.5 Hz, 1H), 7.69 (d, J = 8.8Hz, 1H), 7.00 (dd, J = 8.8, 2.5 Hz, 1H), 3.93 (s, 3H), 3.36 (s, 3H), 2.74 –2.61 (m, 2H), 2.51 – 2.40 (m, 2H), 1.09 (s, 6H). 13 C NMR (100 MHz, Chloroform- d )δ 196.7, 165.7, 164.0, 136.8, 125.5, 116.2, 110....

Embodiment 3

[0027] Implementation Example 3: Synthesis of Compound 3c

[0028]

[0029] In a clean pressure-resistant bottle equipped with a magnetic stir bar, add S,S -Diphenyliminosulfone (21.7 mg, 0.10 mmol), 2-(phenyl-λ 3 -iodoalkylene)cyclohexane-1,3-dione (37.7 mg, 0.12 mmol), bis(hexafluoroantimonate)triacetonitrile(pentamethylcyclopentadienyl)rhodium(III) (4.2 mg , 0.005 mmol) and trifluoroethanol (2.0 mL), stirred in an oil bath at 50 ℃ for 8 h under air atmosphere;

[0030] After the reaction was completed, it was directly separated and purified by silica gel column chromatography to obtain 25 mg of the product, a white solid, with a yield of 81%; 1 H NMR (400 MHz, Chloroform- d )δ 9.19 (d, J = 8.6 Hz, 1H), 7.92 – 7.84 (m,2H), 7.68 (t, J = 7.5 Hz, 1H), 7.64 – 7.56 (m, 3H), 7.33 – 7.28 (m, 2H), 2.94 – 2.88 (m, 2H), 2.72 – 2.57 (m, 2H), 2.13 – 2.04 (m, 2H ). 13 C NMR (100 MHz, Chloroform- d )δ 196.6, 166.2, 138.8, 134.2, 134.1, 133.3, 129.3, 128.7, 127.0, 126.6, 124.8, ...

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Abstract

The invention relates to a method for synthesizing a 1,2-benzothiazine compound by rhodium (III) catalyzed C-H activation reaction. According to the invention, S-aryl imino sulfone is used as a raw material, and a 1,2-benzothiazine skeleton is efficiently constructed through a C-H activation / cyclization reaction catalyzed by transition metal rhodium with a carbene precursor iodine ylide. Compared with a traditional synthesis method, the method does not need additional additives, and post-treatment is simple and convenient; high temperature and high pressure are not needed, reaction time is short, and conditions are relatively mild; the method has the advantages of wide substrate application range, simple operation steps and high product yield.

Description

technical field [0001] The invention relates to a method for synthesizing 1,2-benzothiazine compounds through the C-H activation reaction of rhodium (III)-catalyzed iodine ylide as a carbene precursor and iminosulfone. Specifically based on S -Aryl iminosulfones and iodine ylides are used as raw materials to construct 1,2-benzothiazine skeletons through C-H activation / cyclization reactions catalyzed by rhodium (III), which belongs to the field of chemical synthesis. Background technique [0002] Diazo compounds are an important class of carbene precursors and have very important applications in organic synthesis. However, a series of properties such as poor stability, explosiveness and potential carcinogenicity limit the practical research of diazo compounds. [1] . Iodine ylides can generate carbene under conditions such as transition metal catalyst catalysis, thermal decomposition or photochemistry, and its synthesis is simple, its properties are relatively stable, espec...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D279/02
CPCC07D279/02
Inventor 海俐吴勇陈健吴周平刘雪忻李祉飏
Owner SICHUAN UNIV
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