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【结 构 式】

【分子编号】20574

【品名】2-[(Z)-1-acetyl-2-(2-nitrophenyl)ethenyl]-1,3,2lambda(5)-dioxaphosphinan-2-one

【CA登记号】

【 分 子 式 】C13H14NO6P

【 分 子 量 】311.231062

【元素组成】C 50.17% H 4.53% N 4.5% O 30.84% P 9.95%

与该中间体有关的原料药合成路线共 2 条

合成路线1

该中间体在本合成路线中的序号:(IX)

The reaction of trimethylene glycol (I) with PCl3 gives 2-chloro-1,3,2-dioxaphosphorinane (II), which is condensed with propargyl alcohol (III) by means of triethylamine in acetonitrile to give a mixture of 2-allenyl- and 2-propargyl-2-oxo-1,3,2-dioxaphosphorinane (IV and V). The reaction of this mixture with isobutylamine in acetonitrile affords 2-(2-isobutylamino-1-propenyl)-2-oxo-1,3,2-dioxaphosphorinane (VI). The hydrolysis of the enamine (VI) with malonic acid gives 2-acetonyl-2-oxo-1,3,2-dioxaphosphorinane (VII), which is condensed with isobutyl-(2-nitrobenzylidene)amine (VIII) to yield 2-[1-(2-nitrobenzylidene)-2-oxopropyl]-2-oxo-1,3,2-dioxaphosphorinane (IX). Finally, this compound is cyclized with methyl 3-aminocrotonate (X) in refluxing acetonitrile.

1 Morita, I.; Tsuda, M.; Kise, M.; Sugiyama, M.; Improved synthesis of methyl 2, 6-dimethyl-4-(2-nitrophenyl)-5-(2-oxo-1,3, 2-dioxaphosphorinan-2-yl)-1, 4-dihydropyridine-3-carboxylate (DHP-218). Chem Pharm Bull 1988, 36, 3, 1139-42.
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) 14685 1,3-propanediol; Trimethylene Glycol 504-63-2 C3H8O2 详情 详情
(II) 20567 2-chloro-1,3,2-dioxaphosphinane C3H6ClO2P 详情 详情
(III) 16664 Propargyl Alcohol; 2-propyn-1-ol 107-19-7 C3H4O 详情 详情
(IV) 20569 2-(1,2-propadienyl)-1,3,2lambda(5)-dioxaphosphinan-2-one C6H9O3P 详情 详情
(V) 20570 2-(1-propynyl)-1,3,2lambda(5)-dioxaphosphinan-2-one C6H9O3P 详情 详情
(VI) 20571 2-[(E)-2-(isobutylamino)-1-propenyl]-1,3,2lambda(5)-dioxaphosphinan-2-one C10H20NO3P 详情 详情
(VII) 20572 2-(2-oxopropyl)-1,3,2lambda(5)-dioxaphosphinan-2-one C6H11O4P 详情 详情
(VIII) 20573 2-methyl-N-[(Z)-(2-nitrophenyl)methylidene]-1-propanamine; N-isobutyl-N-[(Z)-(2-nitrophenyl)methylidene]amine C11H14N2O2 详情 详情
(IX) 20574 2-[(Z)-1-acetyl-2-(2-nitrophenyl)ethenyl]-1,3,2lambda(5)-dioxaphosphinan-2-one C13H14NO6P 详情 详情
(X) 11372 Methyl (E)-3-amino-2-butenoate; Methyl 3-aminocrotonate C5H9NO2 详情 详情
(XI) 12963 Malonic acid 141-82-2 C3H4O4 详情 详情

合成路线2

该中间体在本合成路线中的序号:(III)

The condensation of Cyclic acetonylphosphonate (II), obtained from bromoacetone and cyclic phosphite (I) by an Arbuzov reaction, with o-nitrobenzaldehyde in the presence of piperidine - AcOH salt in boiling benzene gives benzylidene phosphonale (III), which is cyclized with methyl 3-aminocrotonate (IV) in reflux in 2-propanol affording methyl 2,6-dimethyl-4-(2-nitrophenyl)-5-(2 oxo-1,3,2-dioxaphosphorinan-2-yl)-1,4 dihydro-pyridine-3 carboxylate.

1 Kimura, K.; Morita, I. (Nippon Shinyaku Co., Ltd.); 1,4-Dihydropyridine-3-carboxylate derivs.. AU 8541405; BE 0902210; EP 0159040; ES 8606276; FR 2563222; GB 2157695; JP 1985248693; US 5036059 .
2 Kimura, K.; DHP-218. Drugs Fut 1987, 12, 3, 212.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
11370 2-Nitrobenzaldehyde 552-89-6 C7H5NO3 详情 详情
20549 1-bromoacetone 598-31-2 C3H5BrO 详情 详情
(I) 22929 2-methoxy-1,3,2-dioxaphosphinane C4H9O3P 详情 详情
(II) 20572 2-(2-oxopropyl)-1,3,2lambda(5)-dioxaphosphinan-2-one C6H11O4P 详情 详情
(III) 20574 2-[(Z)-1-acetyl-2-(2-nitrophenyl)ethenyl]-1,3,2lambda(5)-dioxaphosphinan-2-one C13H14NO6P 详情 详情
Extended Information