Synthesis of (−)- and (+)-2-hydroxy-6-keto-N-methylmorphinans, their O-methyl ethers, and 2-deoxy congeners

Abstract

HELMUT SCHMIDHAMMER and ARNOLD BROSSI. Can. J. Chem. 60, 3055 (1982).Bischler-Napieralski cyclization of the known phenylacetamide 1, followed by selective ether cleavage of the 3,4-dihydroisoquinoline 2 and sodium borohydride reduction, afforded the tetrahydroisoquinoline 4. Optical resolution of 4 with tartaricacid gave the optical isomers 4a, b , which were converted into the 6-ketomorphinans 9 0 , b and their 0-methyl ethers 100, b by the following reaction sequence: Birch reduction, N-formylation of the dihydro bases, Grewe cyclization, removal of the N-formyl protecting groups, reductive N-methylation, and 0-methylation. The 2-deoxy congeners 1241, b were obtained from 9 a , b by phenyltetrazolylation, and catalytic removal of the heterocyclic ether function. The (-)-enantiomer 1% obtained by this synthesis was identical with material prepared from natural morphine, and exhibited the high antinociceptive potency already reported.HELMUT SCHMIDHAMMER et ARNOLD BROSSI. Can. J. Chem. 60,3055 (1982). La reaction de cyclisation de Bischler-Napieralski de la phenylacetamide 1 suivie du clivage selectif de 1'Cther de la dihydro-3,4 isoquinolCine 2 et de la reduction par le borohydrure de sodium, conduit la tCtrahydroisoquinoleine 4. La rCsolution optique du compose 4 avec I'acide tartrique permet d'obtenir les isomeres optiques 4a ,b que I'on transforme en cCto-6 morphinans 9a,b et en leurs ethers 0-methyliques 10a,b selon les reactions suivantes: la rCduction de Birch, la N-formylation des bases dihydro, la cyclisation de Grewe, le clivage des groupes protecteurs N-formyle, la N-mithylation reductive et 1'0-methylation. On obtient les

Synthesis and Solution Properties of Deferoxamine Amides

“…19 The off-white precipitate of DFO formamide was isolated by vacuum evaporation and filtration followed by re-crystallization from n-propanol (90% yield). The DFO dissolved during refluxing and the resulting formylated DFO derivative precipitated after subsequent cooling.…”

Palladium Grafted Functionalized Nanomaterial: An Efficient Catalyst for the CO2 Fixation of Amines and Production of Organic Carbamates

“…Heating with phenyl or ethyl formate is comparatively a better method, but the procedure requires very high‐temperature and it is more time ‐ consuming . An attractive path for formamide synthesis is the N‐formylation reaction between CO 2 and amines with suitable reducing agent.…”

A General and Efficient Method for the Formylation of Amines Catalyzed by Bromodimethylsulfonium Bromide

“…此后, 文献报道的甲酰化试剂主要有三 氯乙醛 [9] 、二环己基碳二亚胺 [3] 或 1-乙基-(3-二甲基氨基 丙基)碳二亚胺盐酸盐 [10] 活化的甲酸, 活化的甲酸酯 [11] , 甲酸乙酯 [12] , 甲酸铵 [13] , 乙酸甲酸酐 [14] , 甲酸与活性 锌 [15] 或 ZnO [16] , 1,1,3,3-四甲基胍离子液体 [17] , 固相支载 的甲酸和甲酸盐 [18] . 最近, 有文献报道用甲酸作为甲酰 化试剂, 用甲苯共沸除水 [19] 的方法.…”