Cyclization of methyl 6,7-epoxycitronellate to methylcyclopentane derivatives : Alkoxide induced conversion of γ-lactones to γ,δ-unsaturated acids

The reaction of sodium hydride or potassium t-butoxide with methyl epoxycitronellate (1) in dimethylformamide affords a mixture of cis,cis-puleganolide (2) and cis,trans-puleganolide (3) in high yield. When the cyclization is conducted at 110°, the isomeric 2-isopropenyl-5-methylcyclopentanecarboxylic acids (8a–d) become the major products. It is demonstrated that γ-lactones undergo alkoxide-induced elimination to afford γ,δ-unsaturated acids.     

Cyclophosphamides from aminosugars and aminonucleosides

Condensation of bis-(2-chloroethyl)phosphoramidic dichloride with 3′-amino-3′-deoxy-N,N-dimethyladenosine afforded the 2′,3′-cyclicphosphorodiamidate (III). By an improved synthesis, methyl 3-amino-3-deoxy-β-D-ribofuranoside was obtained as a model compound for conversion to the analogous 2,3-cyclicphosphorodiamidate (XII). Existence of the latter as two diastereomers due to phosphorus asymmetry was shown by nmr analysis, using comparison with the 5-(O-p-nitrobenzoate) (XIII) as a basis for assignments.     

Use of the mannich reaction in the synthesis of bispidine

A three-step synthesis of bispidine ( 1 ) is described. Mannich condensation of N-benzyl-4-piperidone, formaldehyde, and benzylamine afforded N,N′-dibenzylbispidinone ( 5 ), which was reduced under modified Wolff-Kishner conditions to yield N,N′ -dibenzylbispidine ( 6 ). Catalytic debenzylation of this compound gave 1 .     

13C-NMR. Spectroscopy of Naturally Occuring Substances. XLII. Conformational analysis of quebrachamine-like indole alkaloids and related substances

The ¹³C shifts of 16α- and 16β-substituted derivatives of quebrachamine, 14,15-dehydroquebrachamine, cleavamine, 15,20α-dihydrocleavamine and 15,20β-dihydrocleavamine are determined and correlated with possible conformations of these tetracycles. The method of analysis of the C(16) configuration of these compounds, which emanated from this study, is used for the determination of the configuration of the site of coupling of vindoline and cleavamine β-chloroindolenine.     

Dependence of the glass transition temperature of poly(methyl methacrylate) on tacticity and molecular weight

The preparation of five samples of poly(methyl methacrylate) covering a wide range of tacticity and their electron irradiation to produce series of varying molecular weight are described. The glass transition temperature T_g of each polymer was determined by DTA techniques. Plots of T_g and the reciprocal of the molecular weight are well fitted in every case by a straight line. The data are also fitted to the Gibbs-DiMarzio theory and the values of the energy and free-volume parameters obtained are discussed. A method of estimating T_g of pure syndiotactic poly(methyl methacrylate) by extrapolation is presented, the value obtained being 160°C.     

Monitoring trace anion contamination in disk drive components

Ion chromatography was used to determine trace anionic contamination on the surface of hard disk drive components. These contaminants can have a detrimental effect on device reliability and yield. Disk drive components were soaked in deionized water and these extracts were analyzed for anions. The anions fluoride, acetate, formate, acrylate, methacrylate, chloride, nitrite, bromide, nitrate, benzoate, sulfate, oxalate, phthalate and phosphate were separated on a high-performance anion-exchange column and determined at concentrations less than 1 microg/l with suppressed conductivity detection. The extract solutions were analyzed either by injecting 1 ml or by preconcentrating 5 ml. We evaluated the performance of both methods.     

Evaluation of heats of transition in scanning calorimetry

A procedure for the evaluation of heats of transition in scanning calorimetry has been developed. A formula for evaluation of the energy of fusion of a compound at its melting point is derived that takes into account the baseline shift that is attributable to the heat capacity change on melting. Several other calorimeter parameters of importance are discussed. These include heat exchange between calorimeter vessel and jacket, the time constant of the instrument, the scanning rate, and the heater placement.     

The dielectric constant and salt effects upon the acid hydrolysis of ethyl formate

The hydrolysis of ethyl formate catalysed by hydrochloric acid was studied at three temperatures in water-acetone media and in water media containing different concentrations of sodium nitrate. The effect of various ionic strengths and dielectric constants upon the rate of acid hydrolysis of ethyl formate is presented from the point of electrostatics and the results were compared to like effects upon the acid hydrolysis of ethyl acetate and methyl propionate. Neither the dielectric constant effect nor the salt effect lends itself readily to theoretical interpretation. It was assumed that a partial explanation of these anomalous results might be in the extrapolation of the acid radical to the simplest carboxylic acid. This suggestion was supported somewhat by the trends towards less adherance to the electrostatic theory at certain temperatures in the series methyl propionate, ethyl acetate and ethyl formate.     

3H-Indol-3-ols by a novel ring contraction

Treatment of α-hydroxy-α-phenyl-o-toluidide with phosphorus tribromide afforded a series of 4H-3,1-benzoxazines. These last, when reacted with potassium amide in liquid ammonia, ring contracted to 2,3-disubstituted 3H-indol-3-ols. The scope of this rearrangement was examined. The indolols on treatment with hot base were found to rearrange to indoxyls. Several of these as well as their N-alkylation products are described.