A method for preparing 3,4-dihydrobenzo[b][1,4]oxazine derivatives
A technology of dihydrobenzene and oxazine, applied in the field of preparing 3,4-dihydrobenzo[b][1,4]oxazine derivatives, which can solve the problems of high metal catalyst price and difficult removal of metal residues, etc. Achieve the effect of large industrialization potential, high reactivity, and wide range of substrates
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Embodiment 1
[0081] The synthesis of embodiment 1,3-(2-thiophene)-3,4-dihydrobenzo[b][1,4]oxazine (see structural formula I-a)
[0082] according to figure 1 Shown synthetic route prepares the compound shown in formula I-a, concrete operation is as follows:
[0083]In the glove box, 3-(2-thiophene)benzo[b][1,4]oxazine (shown in formula II-a) (0.086g, 0.4mmol), tris(pentafluoro phenyl)borane (0.0051 g, 0.01 mmol), and 0.2 mL of toluene. Put the reaction sleeve into the autoclave and tighten the autoclave, fill it with hydrogen gas at 20bar, and react at 50°C for 6h; after the reaction is completed, remove the solvent, and the conversion rate is >99% as measured by NMR. The specific conditions are as follows: The specification of the analysis column is 20cm in diameter × 200cm in height, the filler is 200-300 mesh silica gel, and the column is packed with petroleum ether. The eluent is a mixture of ethyl acetate and petroleum ether with a volume ratio of 1:10. The flow rate is 10mL / min, e...
Embodiment 2
[0086] The synthesis of embodiment 2,3-(1-naphthyl)-3,4-dihydrobenzo[b][1,4]oxazine (see structural formula I-b)
[0087] according to figure 2 The shown synthetic route prepares the compound shown in formula I-b, concrete operations are as follows:
[0088] In the glove box, successively add 3-(1-naphthyl)benzo[b][1,4]oxazine (shown in formula II-b) (0.104g, 0.4mmol), three (five Fluorophenyl)borane (0.0051 g, 0.01 mmol), and 0.2 mL of toluene. Put the reaction sleeve into the autoclave and tighten the autoclave, fill it with hydrogen gas at 20bar, and react at 50°C for 6h; The specification of the analysis column is 20cm in diameter × 200cm in height, the filler is 200-300 mesh silica gel, and the column is packed with petroleum ether. The eluent is a mixture of ethyl acetate and petroleum ether with a volume ratio of 1:10. The flow rate is 10mL / min, eluting with 10 times column volume of eluent, collecting the eluate of the 9th column volume, removing the solvent to obt...
Embodiment 3
[0091] Embodiment 3, the synthesis of 3-(3,4-dichlorophenyl)-3,4-dihydrobenzo[b][1,4]oxazine (see structural formula I-c)
[0092] according to image 3 The shown synthetic route prepares the compound shown in formula I-c, concrete operations are as follows:
[0093] In the glove box, sequentially add 3-(3,4-dichlorophenyl)benzo[b][1,4]oxazine (shown in formula II-c) (0.111g, 0.4mmol) to the sleeve , tris(pentafluorophenyl)borane (0.0051 g, 0.01 mmol), and 0.2 mL of toluene. Put the reaction sleeve into the autoclave and tighten the autoclave, fill it with hydrogen gas at 20bar, and react at 50°C for 6h; after the reaction is completed, remove the solvent, and the conversion rate is >99% as measured by NMR. The specific conditions are as follows: The specification of the analysis column is 20cm in diameter × 200cm in height, the filler is 200-300 mesh silica gel, and the column is packed with petroleum ether. The eluent is a mixture of ethyl acetate and petroleum ether with ...
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