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Preparation method of tetrahydro-1,4-methylene benzo[d][1,2]oxazepine

A technology of methylene benzene and oxazepine, which is applied in the field of preparation of tetrahydro-1,4-methylenebenzo[d][1,2]oxazepine, can solve the problem of high reaction risk , low efficiency, difficult synthesis and other problems, to achieve the effect of easy substrate synthesis and convenient source

Inactive Publication Date: 2018-04-10
HENAN NORMAL UNIV
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Problems solved by technology

In addition, the preparation of bridged ring compounds is a major difficulty in synthesis. Although people have developed some methods for compounds containing bridged ring structures, these methods often have many steps, low efficiency, high production costs, and low flexibility.
Oxazolidine compounds with bridged ring structures in the prior art generally have defects such as difficult synthesis, high reaction risk, long reaction steps, low reaction yield, and low atom economy.

Method used

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  • Preparation method of tetrahydro-1,4-methylene benzo[d][1,2]oxazepine
  • Preparation method of tetrahydro-1,4-methylene benzo[d][1,2]oxazepine

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Experimental program
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Embodiment 1

[0020] Cp*Rh(OAc) 2 (7.0mg, 0.010mmol, 0.050equiv), AgOAc (80mg, 0.500mmol, 2.50equiv) were added to a 25mL sealed tube, and magnetons and 1mL solvent CF were added under nitrogen protection 3 CH 2 OH, after stirring for 10 minutes, nitrone 2 (0.200mmol, 1.00equiv) and methylenecyclopropane 3 (0.500mmol, 2.50equiv) were added to the sealed tube, and the reaction was stirred at 40°C for 24h, diatomaceous earth Filter and wash with 15 mL of ethyl acetate. The organic layer was spin-dried and directly subjected to column chromatography to obtain product 4, with a total yield of 84%. 1 H NMR, 13 The purity by C NMR was all greater than 95%.

[0021] 1 H NMR (400MHz, CDCl 3 )δ7.80(d, J=7.8Hz, 1H), 7.44(s, 4H), 7.29(s, 1H), 7.25(t, J=7.6Hz, 1H), 7.18(t, J=7.3Hz, 1H), 7.09(d, J=7.3Hz, 1H), 5.46(d, J=5.5Hz, 1H), 4.31(d, J=4.9Hz, 1H), 2.33(s, 1H), 2.02(t, J=10.2Hz,1H),1.35(s,9H),1.18(s,9H). 13 C NMR (101MHz, CDCl 3 )δ150.1, 142.4, 136.9, 134.0, 132.8, 129.4, 127.6, 127.5, 125...

Embodiment 2

[0024] Cp*Rh(OAc) 2 (7.0mg, 0.010mmol, 0.050equiv), AgNO 2 (85mg, 0.500mmol, 2.50equiv) was added to a 25mL sealed tube, and magneton and 1mL solvent CF were added under nitrogen protection 3 CH 2 OH, after stirring for 10 minutes, nitrone 2 (0.200mmol, 1.00equiv) and methylenecyclopropane 3 (0.500mmol, 2.50equiv) were added to the sealed tube, and the reaction was stirred at 50°C for 24h, diatomaceous earth Filter and wash with 15 mL of ethyl acetate. The organic layer was spin-dried and directly carried out column chromatography to obtain product 4 with a total yield of 85%. 1 H NMR, 13 The purity by C NMR was all greater than 95%.

[0025] 1 H NMR (400MHz, CDCl 3 )δ7.80(d, J=7.8Hz, 1H), 7.44(s, 4H), 7.29(s, 1H), 7.25(t, J=7.6Hz, 1H), 7.18(t, J=7.3Hz, 1H), 7.09(d, J=7.3Hz, 1H), 5.46(d, J=5.5Hz, 1H), 4.31(d, J=4.9Hz, 1H), 2.33(s, 1H), 2.02(t, J=10.2Hz,1H),1.35(s,9H),1.18(s,9H). 13 C NMR (101MHz, CDCl 3 )δ150.1, 142.4, 136.9, 134.0, 132.8, 129.4, 127.6, 127.5, 125.9...

Embodiment 3

[0028] Cp*Rh(OAc) 2 (7.0mg, 0.010mmol, 0.050equiv), Ag 2 CO 3 (55mg, 0.200mmol, 1.00equiv) was added to a 25mL sealed tube, and magneton and 1mL solvent CF were added under nitrogen protection 3 CH 2 OH, after stirring for 10 minutes, nitrone 2 (0.200mmol, 1.00equiv) and methylenecyclopropane 3 (0.500mmol, 2.50equiv) were added to the sealed tube, and the reaction was stirred at 30°C for 24h, diatomaceous earth Filter and wash with 15 mL of ethyl acetate. The organic layer was spin-dried and directly subjected to column chromatography to obtain product 4 with a total yield of 81%. 1 H NMR, 13 The purity by C NMR was all greater than 95%.

[0029] 1 H NMR (400MHz, CDCl 3 )δ7.80(d, J=7.8Hz, 1H), 7.44(s, 4H), 7.29(s, 1H), 7.25(t, J=7.6Hz, 1H), 7.18(t, J=7.3Hz, 1H), 7.09(d, J=7.3Hz, 1H), 5.46(d, J=5.5Hz, 1H), 4.31(d, J=4.9Hz, 1H), 2.33(s, 1H), 2.02(t, J=10.2Hz,1H),1.35(s,9H),1.18(s,9H). 13 C NMR (101MHz, CDCl 3 )δ150.1, 142.4, 136.9, 134.0, 132.8, 129.4, 127.6, 127.5, ...

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Abstract

The invention discloses a preparation method of tetrahydro-1,4-methylene benzo[d][1,2]oxazepine, and belongs to the technical field of organic synthesis. The method comprises the following steps: nitrone 2 and methylene cyclopropane 3 are utilized, in the presence of a rhodium catalyst and an oxidant, an addition reaction is performed to form a bridged ring structural oxazolidine 4, then catalytichydrogenation is performed to obtain the 2-tert-butyl-5-(4-tert-butyl benzyl)-1,2,4,5-tetrahydro-1,4-methylene benzo[d][1,2]oxazepine 1. The method provided by the invention has the advantages of cheap raw materials easy to obtain, mild reaction conditions, good atomic economy, high selectivity, simple post-treatment and a high yield, and provides a rapid synthesis pathway for oxazapine compoundswith bridged ring structures.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a preparation method of tetrahydro-1,4-methylenebenzo[d][1,2]oxazepine. Background technique [0002] Bridged ring benzo [d] [1,2] oxazepine, especially a kind of preparation method of tetrahydro-1,4-methylene benzo [d] [1,2] oxazepine as very Useful synthetic intermediates widely exist in pharmaceuticals, pesticides and natural product intermediates. In addition, the preparation of bridged ring compounds is a major difficulty in synthesis. Although people have developed some methods for compounds containing bridged ring structures, these methods often have many steps, low efficiency, high production costs, and low flexibility. Oxazolidine compounds with bridged ring structures in the prior art generally have defects such as difficult synthesis, high reaction risk, long reaction steps, low reaction yield, and low atom economy. [0003] Therefore, it is of great signif...

Claims

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Application Information

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IPC IPC(8): C07D267/04C07D498/08
CPCC07D267/04C07D498/08
Inventor 白大昌于文艳李兴伟
Owner HENAN NORMAL UNIV
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