【结 构 式】 |
【分子编号】33070 【品名】7-amino-4-methyl-2H-1,4-benzoxazin-3(4H)-one 【CA登记号】 |
【 分 子 式 】C9H10N2O2 【 分 子 量 】178.19068 【元素组成】C 60.66% H 5.66% N 15.72% O 17.96% |
合成路线1
该中间体在本合成路线中的序号:(VI)Benzoxazinone (IV) was prepared by condensation of 2-amino-5-nitrophenol (I) with either chloroacetyl chloride (II) in the presence of NaHCO3 or ethyl bromoacetate (III) in the presence of KF. Subsequent N-alkylation of (IV) with iodomethane provided (V). After reduction of the nitro group of (V) to amine (VI) by hydrogenation over Pd/C, condensation with benzyl chloroformate afforded carbamate (VII). The chiral oxazolidinone (IX) was obtained by reaction of (VII) with (-)-(R)-glycidyl butyrate (VIII) in the presence of butyllithium in THF at low temperature. Conversion of (IX) to mesylate, followed by displacement with NaN3 gave azide (X). Amine (XI) was then obtained by either hydrogenation of (X) over Pd/C or by reduction with trimethyl phosphite. Finally, reaction of (XI) with acetyl chloride and triethylamine provided the title acetamide.
【1】 Haebich, D.; Haerter, M.; Bartel, S.; Riedl, B.; Stolle, A.; Raddatz, S.; Kroll, H.P.; Guarnieri, W.; Endermann, R.; Wild, H.; Rosentreter, U.; Ruppelt, M.; Synthesis and antibacterial activity of novel heteroaryl oxazolidinones: II. Benzoxazinone- and benzthiazinone-oxazolidinones. 39th Intersci Conf Antimicrob Agents Chemother (Sept 26 1999, San Francisco) 1999, Abst F566. |
【2】 Shridhar, D.R.; et al.; A facile synthesis of 2-alkyl(aryl)-6- and -7-nitro-3-oxo-3,4-dihydro-2H-1,4-benzoxazines. Synthesis 1982, 986. |
【3】 Endermann, R.; Habich, D.; Ruppelt, M.; Raddatz, S.; Rosentreter, U.; Riedl, B.; Bartel, S.; Wild, H.; Stolle, A.; Guarnieri, W.; Kroll, H.-P. (Bayer AG); Novel bicyclene-substd. oxazolidinones. DE 19802239; WO 9937641 . |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
(I) | 33067 | 2-amino-5-nitrophenol | 121-88-0 | C6H6N2O3 | 详情 | 详情 |
(II) | 11296 | 2-Chloroacetyl chloride; Chloroacetic chloride | 79-04-9 | C2H2Cl2O | 详情 | 详情 |
(III) | 16640 | Ethyl 2-bromoacetate; Ethyl bromoacetate | 105-36-2 | C4H7BrO2 | 详情 | 详情 |
(IV) | 33068 | 7-nitro-2H-1,4-benzoxazin-3(4H)-one | C8H6N2O4 | 详情 | 详情 | |
(V) | 33069 | 4-methyl-7-nitro-2H-1,4-benzoxazin-3(4H)-one | C9H8N2O4 | 详情 | 详情 | |
(VI) | 33070 | 7-amino-4-methyl-2H-1,4-benzoxazin-3(4H)-one | C9H10N2O2 | 详情 | 详情 | |
(VII) | 33071 | benzyl 4-methyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-7-ylcarbamate | C17H16N2O4 | 详情 | 详情 | |
(VIII) | 18385 | (2R)oxiranylmethyl butyrate;(R)-glycidyl butyrate | 60456-26-0 | C7H12O3 | 详情 | 详情 |
(IX) | 33072 | 7-[(5R)-5-(hydroxymethyl)-2-oxo-1,3-oxazolidin-3-yl]-4-methyl-2H-1,4-benzoxazin-3(4H)-one | C13H14N2O5 | 详情 | 详情 | |
(X) | 33073 | 7-[(5R)-5-(azidomethyl)-2-oxo-1,3-oxazolidin-3-yl]-4-methyl-2H-1,4-benzoxazin-3(4H)-one | C13H13N5O4 | 详情 | 详情 | |
(XI) | 33074 | 7-[(5S)-5-(aminomethyl)-2-oxo-1,3-oxazolidin-3-yl]-4-methyl-2H-1,4-benzoxazin-3(4H)-one | C13H15N3O4 | 详情 | 详情 |