合成路线:A new synthesis of [11C]-labeled MK-801 has been reported:The reaction of 10,11-dihydro-5H-dibenzo[a,d]cycloheptene (I) with N,N-dimethyl-N'-tert-butylformamidine in refluxing toluene gives the formamidine (II),which is alkylated with butyllithium and [11C]-labeled methyl iodide in ether-cyclohexane to yield the 5-methyl derivative (III).Finally,this compound is hydrolyzed with KOH in ethylene glycol.
参考文献标题:Synthesis of C-11-labeled (+/-)-5-methyl-10,11-dihydro-5H-dibenzo[a,d]c yclohepten-5,10-imine [(+/-)-[C-11]MK801]
文献作者:Kiesewetter,D.O.; Rice,K.C.; Finn,R.D.; Monn,J.A.
参考来源:Appl Radiat Isot - Int J Radiat Appl Instrum Part A 1990,41(2),139
合成路线:The reaction of 5H-dibenzo[a,d]cyclohepten-5-one (VII) with NH3 and TiCl4 in toluene gives 5H-dibenzo[a,d]cycloheptene-5-imine (VIII),which is tosylated with p-toluenesulfonyl chloride in pyridine to yield 5-(p-toluenesulfonimino)-5H-dibenzo[a,d]cycloheptene (IX).The methylation of (IX) with methyllithium in dry THF affords 5-methyl-5-(p-toluenesulfonimido)-5H-dibenzo[a,d]cycloheptene (X),which is internally cyclized by means of KOH in diglyme at 170 C giving 5-methyl-N-(p-toluenesulfonyl)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-5,10-imine (XI).Finally,this compound is hydrolyzed with aqueous HCl in refluxing AcOH.
参考文献标题:
文献作者:Shepard,K.L.; Brenner,D.G.
参考来源:EP 0019866
合成路线: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.
参考文献标题:
文献作者:Anderson,P.S.; Christy,M.E.; Evans,B.E.
参考来源:ES 473492
合成路线: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.
参考文献标题: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
文献作者:Evans,B.E.; Engelhardt,E.L.; Remy,D.C.; Britcher,S.F.; Andderson,P.S.; Colton,C.D.; Christy,M.E.
参考来源:J Org Chem 1979,44(18),3117-27
产品链接: CAS No. 77086-21-6››