摘要:

Infrared, ultraviolet, and nuclear magnetic resonance spectra of the following compounds are reported: 2-indanone (I),trans- andcis-hexahydro-2-indanone (V and XI), 1-chloro-2-indanone-1,3,3-d3(III), 1-bromo-2-indanone-1,3,3-d3(IV), 1-chloro-trans-hexahydro-2-indanone (VII), 1-bromo-trans-hexahydro-2-indanone (VIII), some deuterated forms of these compounds, 2-chlorocyclohexanone-2,6,6-d3, and 2-bromocyclohexanone-2,6,6-d3.2-Indanone andtrans-hexahydro-2-indanone each display two peaks in the carbonyl infrared region with intensity ratios of approximately 40:1. The origin of these doublets is discussed.Nuclear magnetic resonance spectra were determined to indicate the presence or absence of ring mobility, and spin–spin coupling data were used to support some of the conclusions deduced from the infrared data for some of the compounds.

ISSN:0008-4042    

DOI:10.1139/v66-109

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

Hydrogen exchange ins-trinitrobenzene has been observed in the medium 90% dimethylformamide – 10% deuterium oxide containing sodium deuteriooxide (0.01 M). The proton transfer process betweens-trinitrobenzene and base is therefore established. The factors which may contribute to the importance of the proton transfer process relative to the formation of Meisenheimer-type complexes are considered.

ISSN:0008-4042    

DOI:10.1139/v66-110

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

First-order analysis of the 60 Mc.p.s. proton magnetic resonance spectra of 1α-methoxy-2β-acetoxy-3α-bromocyclohexane, 1α-methoxy-2α-acetoxy-3β-bromocyclohexane, 1α-methoxy-2β-bromo-3α-acetoxycyclohexane, 1α-methoxy-2α-bromo-3β-acetoxycyclohexane, and the corresponding diol diacetates confirmed the stereochemical interrelationships of substituents which were assigned previously on chemical grounds, and demonstrated that the compounds exist in chair conformations. The chemical shifts of the methoxy methyl and acetoxy methyl protons did not provide reliable criteria for the assignment of conformations to these substituents in this series. The coupling constants of the methine protons followed, in general, the pattern predicted by the Karplus equation, and the smallerJ2,3values observed in thecis,transcompounds relative to those in thetrans,transcompounds are interpreted mainly on the basis of conformational equilibration, upon which is superimposed a small dihedral angular distortion or a remote substituent orientational effect.

ISSN:0008-4042    

DOI:10.1139/v66-111

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

The mass spectra of the monohydroxyquinolines, the monomethoxyquinolines, N-methyl-2-quinolone, and N-methyl-4-quinolone have been recorded. The isomeric hydroxy compounds vary somewhat in the stability of the molecular ion, but all show the same fragmentation mechanism. Two general fragmentation patterns are discernible in the spectrum of each of the monomethoxyquinolines, but there is considerable variation among the isomers in the extent to which the two patterns occur. In addition, 8-methoxyquinoline undergoes a peculiar fragmentation wherein all three methyl hydrogens are lost. The 3-methoxy compound is unusual in that loss of 43 mass units from the molecular ion occurs in one step. Deuterium- and13C-labelling experiments have proved to be useful in interpreting the fragmentation pathways. The spectra of the two N-methylquinolones prove that O to N methyl rearrangement does not occur to any significant extent upon electron impact.

ISSN:0008-4042    

DOI:10.1139/v66-112

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

An examination of the mass spectra of the products isolated from a Favorsky rearrangement of 17α-bromopregnenolone acetate (Marker's conditions) in deuterated solvents offers a clue to the reaction mechanism. The stereochemical implications and the mass fragmentation pattern of the products examined are discussed.

ISSN:0008-4042    

DOI:10.1139/v66-113

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

The preparation of a number of polypeptides whose sequences are found in the actinomycin D molecule is described. The 4-methyl-3-hydroxyanthranoyl derivatives cf these peptides were also prepared as possible substrates for an enzyme that forms the phenoxazinone system of the antibiotic.

ISSN:0008-4042    

DOI:10.1139/v66-114

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

Several new 3-hydroxy-4-oxa type steroidal hemiacetals (V and VII) have been prepared by diborane reduction of the corresponding δ-lactones. A detailed proton magnetic resonance study of the hemiacetal (IXa) derived from 3-oxo-4-oxa-5α-cholestane (VIII) indicated that diborane reduction led in each case to an epimeric mixture. Treating hemiacetal IXawith methanol – hydrochloric acid gave a mixture of acetals IXband IXc. Pure specimens of the epimeric acetals were obtained by preparative thin-layer chromatography, and configurational assignments based on proton magnetic resonance studies were provided for each isomer. Allowing lactone VIII (in tetrahydrofuran solution) to react with 1 equivalent of diborane during 4 min resulted in approximately 80% conversion into hemiacetal IXa, and provided an illustration of the potential utility of the reduction reaction.

ISSN:0008-4042    

DOI:10.1139/v66-115

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

A convenient synthesis (I → IVa) starting with N-bis(2-chloroethyl)amine has been devised for obtaining N-(2-bromoethyl)-N-(2-chloroethyl)amine. Several N-alkyl (IVband VIII) and N-benzyl (VII) derivatives of the unsymmetrically halogenated amine (IVa) were prepared for cancer chemotherapeutic evaluation.

ISSN:0008-4042    

DOI:10.1139/v66-116

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

In methylene chloride or ether solution, phenylmethanesulfonyl chloride reacts with triethylamine to give a mixture consisting primarily oftrans-stilbene andcisdiphenylethylene sulfone. In cyclohexane the same reagents yield principally a material which is shown to be a roughly 2:1 mixture ofcis- andtrans-oxythiobenzoyl chlorides (I and II, respectively). The latter compounds represent the first examples of geometrical isomerism about a double bond in which one of the atoms of the double bond is outside the first short period of the Periodic Table.

ISSN:0008-4042    

DOI:10.1139/v66-117

出版商:NRC Research Press    

年代:1966

数据来源: NRC

摘要:

The reaction between some compounds containing thioamide groups and cyanuric chloride was investigated. Evidence is presented that the reaction proceeds on the thioamide sulfur and not on the nitrogen as postulated earlier. The reaction with thiourea was used for the preparation of trithiocyanuric acid, as well as for the preparation of 3-chloro-6(1H)-pyridazinethione or 3-mercapto-6(1H)-pyridazinethione, and presents a new and convenient method for the synthesis of these compounds.

ISSN:0008-4042    

DOI:10.1139/v66-118

出版商:NRC Research Press    

年代:1966

数据来源: NRC