5-methylene-5,11-dihydro-10H-dibenzo[a,d]cyclohepten-10-one -Drug Synthesis Database

【结构式】

【分子编号】35926

【品名】5-methylene-5,11-dihydro-10H-dibenzo[a,d]cyclohepten-10-one

【CA登记号】

【分子式】C₁₆H₁₂O

【分子量】220.27068

【元素组成】C 87.25% H 5.49% O 7.26%

与该中间体有关的原料药合成路线共 2 条

合成路线1 合成路线2

合成路线1

该中间体在本合成路线中的序号：(III)

The reaction of 10-bromo-5H-dibenzo[a,d]cyclohepten-5-one (I) with N-methylpiperazine (A) by means of potassium tert-butoxide in refluxing tert-butanol gives 10-(N-methylpiperazin-1-yl)-5H-dibenzo[a,d]cyclohepten-5-one (II), which by treatment first with methyllithium in ether and then with refluxing ethanolic HCl is converted into 5-methylene-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-10-one (III). The reaction of (III) with hydroxylamine in refluxing methanol yields 5-methylene-10-hydroxyimino-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (IV), which is reduced with sodium cyanoborohydride in methanol to afford 5-methylene-10-hydroxamino-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (V). The internal reaction of (V) in refluxing xylene gives 5-(hydroxymethyl)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5,10-imine (V), which is reduced with Zn in hot acetic acid.

参考文献中间体

合成目标

【1】 Evans, B.E.; Engelhardt, E.L.; Remy, D.C.; Britcher, S.F.; Andderson, P.S.; Colton, C.D.; Christy, M.E.; Transannular reaction of dibenzo[a,d]cycloalkenes. 1. Synthesis of dibenzo[a,d]cycloocten-6,12-imines and dibenzo[a,d]cyclohepten-5,10-imines. J Org Chem 1979, 44, 18, 3117-27.
【2】 Thorpe, P.J.; Castaner, J.; Serradell, M.N.; Blancafort, P.; MK-801. Drugs Fut 1983, 8, 2, 120.

中间体序号	中间体编号	品名	CAS号	分子式	供应商	用于合成
(A)	10061	1-Methylpiperazine; 1-Methyl piperazine; N-Methylpiperazine	109-01-3	C₅H₁₂N₂	详情	详情
(I)	35924	10-bromo-5H-dibenzo[a,d]cyclohepten-5-one		C₁₅H₉BrO	详情	详情
(II)	35925	10-(4-methyl-1-piperazinyl)-5H-dibenzo[a,d]cyclohepten-5-one		C₂₀H₂₀N₂O	详情	详情
(III)	35926	5-methylene-5,11-dihydro-10H-dibenzo[a,d]cyclohepten-10-one		C₁₆H₁₂O	详情	详情
(IV)	35927	5-methylene-5,11-dihydro-10H-dibenzo[a,d]cyclohepten-10-one oxime		C₁₆H₁₃NO	详情	详情
(V)	35928	10-(hydroxyamino)-5-methylene-5H-dibenzo[a,d]cycloheptene; N-(5-methylene-5H-dibenzo[a,d]cyclohepten-10-yl)hydroxylamine		C₁₆H₁₃NO	详情	详情
(VI)	35929	16-azatetracyclo[7.6.1.0(2,7).0(10,15)]hexadeca-2,4,6,10,12,14-hexaen-1-ylmethanol		C₁₆H₁₅NO	详情	详情

合成路线2

该中间体在本合成路线中的序号：(III)

Intermediate (III) can be obtained as follows: The reaction of (I) with piperidine (B) by means of potassium tertbutoxide in refluxing tert-butanol gives 10-(1-piperidyl)-5H-dibenzo[a,d]cyclohepten-5-one (XII), which by reaction with methyllithium in ether is converted into 5-hydroxy-5-methyl-10-(1-piperidyl)-5H-dibenzo[a,d]cycloheptene (XIII). Finally, the dehydration of (XIII) in refluxing ethanolic HCl yields (III), already obtained.

参考文献中间体

合成目标

【1】 Anderson, P.S.; Christy, M.E.; Evans, B.E.; ES 473492 .
【2】 Thorpe, P.J.; Castaner, J.; Serradell, M.N.; Blancafort, P.; MK-801. Drugs Fut 1983, 8, 2, 120.

中间体序号	中间体编号	品名	CAS号	分子式	供应商	用于合成
(B)	10158	Piperidine	110-89-4	C₅H₁₁N	详情	详情
(I)	35924	10-bromo-5H-dibenzo[a,d]cyclohepten-5-one		C₁₅H₉BrO	详情	详情
(III)	35926	5-methylene-5,11-dihydro-10H-dibenzo[a,d]cyclohepten-10-one		C₁₆H₁₂O	详情	详情
(XII)	35930	10-(1-piperidinyl)-5H-dibenzo[a,d]cyclohepten-5-one		C₂₀H₁₉NO	详情	详情
(XIII)	35931	5-methyl-10-(1-piperidinyl)-5H-dibenzo[a,d]cyclohepten-5-ol		C₂₁H₂₃NO	详情	详情

Extended Information