. Can. J. Chem. 55,895 (1977). Alkyl 4-chloromethyl-1,2,3,4-tetrahydro-6-methyl-2-oxopyrimidine-5-carboxylates are obtained from the reaction of 1,2-dichloroethyl ethyl ether with alkyl3-ureidocrotonates, Reaction of the chloromethyl compounds with basic nudeophilic reagents causes ring expansion and leads, in high yield, to 7-substituted 2,3,6,7-tetrahydro-2-oxo-lH-1,3-diazepine derivatives. In the case of sulfhydryl ion, intramolecular Michael addition follows ring expansion and gives derivatives of 3-oxo-8-thia-2,4-diazabicyclo[3.2.l]octane, whose structures are established by spectroscopic examination and chemical degradation. The alkyl 7-alkoxy-2,3,6,7-tetrahydro-2-oxo-lH-1,3-diazepine-5-carboxylates react rapidly with acid to give alkyl l-carbamoyl-2-methylpyrrole-3-carboxylates. Mechanisms are suggested for these rearrangement reactions.
The condensation of 2,3,4,6-tetra-0-acetyl-a-D-glucopyranosyl bromide with a variety of nitro alcohols led to nitroalkyl P-D-glucopyranoside tetraacetates. The following nitro alcohols were employed: 3-nitro-I-propanol, 2-nitro-1-propanol, 1-nitro-2-propanol, 2-nitro-1-butanol, 2-nitro-3-pentanol, and 2-methyl-2-nitro-1-propanol. The free 3-nitropropyl and 2-methyl-2-nitropropyl glycosides were obtained from their tetraacetates by deacetylation with sodium methoxide, whereas methanolysis catalyzed by methyl p-toluenesulfonate was employed for deacetylation of the other tetraacetates. Evidence for the presence of epimers in glycosides having a chiral center in the aglycon was obtained. Physical dataof synthetic3-nitropropyl PD-glucopyranoside agreed with those of miserotoxin, the poisonous principle recently isolated from Astrngnius miser varieties.La condensation du bromure de tCtra-0-acktyl-2,3,4,6 a-D-glucopyranosyl avec plusieurs nitro alcools a conduit aux tttraacktates de nitroalcoyl du PD-glucopyranosides. On a employe les nitro alcools qui suivent: nitro-3 propanol-1, nitro-2 propanol-1 , nitro-1 propanol-2, nitro-2 butanol-1, nitro-2 pentanol-3, et m6thyl-2 nitro-2 propanol-1. Les nitropropyl-3 et mCthyl-2 nitropropyl-2 glycosides libres ont CtC obtenus a partir de leur t6traacCtates par deacttylation par le methylate de sodium, alors que la mkthanolyse catalysee par lep-tolubnesulfonate de mCthyle a CtC utiliste pour la dCacCtylation des autres tetraacktates. On a mis en Cvidence la prCsence d'Cpimtres dans les glycosides possCdant u n centre chiral dans I'aglycon. Des donnCes physiques pour le nitropropyl-3 PD-glucopyranoside sont en accord avec celles de la mistrotoxine, I'entit6 toxique rkcemment isolCe des variCtCs d'Astrngnlrrs miser.[Traduit par le journal]Can. J. Chem., 51, 2828 (1973)
Several transformations starting from trrrns,trnt1s-2-nitrocyclohexane-1,3-diol (1) and its diacetate (2) were carried out as model reactions for synthetic work on nitro sugars. They included methylation with diazomethane, dehydration, dehydroacetylation, nucleophilic elimination-additions with alcohols, and bromination. The monomethyl ether of 1 (3), the monomethyl ether acetate (51, the dimethyl and dibenzyl ethers (4 and 9), bromonitro compounds derived from 1 and 4 (13 and 14), and four 3-substituted 2-nitrocyclohexenes with methoxyl, ethoxyl, acetoxyl, and hydroxyl groups as substituents (6, 8, 7, and 11, respectively) were obtained in these studies. The nitronate formation of 1 and 4 and attendant production of nitroolefins was investigated by U.V. spectroscopy.Plusieurs transformations portant sur le trnns,tr(rns nitro-2 cyclohexane diol-1,3 (1) et son diacetate (2) ont CtC effectuCes pour servir de modtles d e reaction a un travail de synthese sur les nitrosucres. Elles comprennent des rnCthylations par le diazomkthane, des dCshydratations, des dCshydroacCtylations, des Climination-additions nucleophiles avec les alcools e t des bromations. Au cours d e cette Ctude,
Die Umsetzung des Chlormethyl‐1,2,3,4‐tetrahydro‐pyrimidin‐2‐ons (I) mit Natriummethylat in Methanol oder Natriumcyanid in Dimethyl‐sulfoxid ergibt unter Ringerweiterung die Methoxy‐ und Cyan‐diazepinone (II) bzw. (III), die 1Ff durch Behandlung mit Methanol/Chlorwasserstoff bzw. Salzsäure in das Pyrrol (IV) übergeführt werden.
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