摘要:

The microbiological oxidation of 2-acetamido-2-deoxy-D-glucitol byAcetobacter suboxydensyielded a crystalline ketose which is shown to be 5-acetamido-5-deoxy-L-xylohexulose.

ISSN:0008-4042    

DOI:10.1139/v61-121

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

Reactions of N- and S-substituted thiosemicarbazones with Cu(I) have been examined. No complexes are formed when the S atom is substituted and(or) when the N2hydrogen atom is replaced by Me. 4,4-Dimethyl derivatives not only give the usual 1:1 complexes, but also 2:1 complexes (2 thiosemicarbazones to 1 copper) in which copper has been oxidized to Cu(II). Reactions of thiosemicarbazones with Cu(II) give 1:1, 2:1, and probably a mixture which corresponds to 2:3 complexes. A discussion on the possible structures for the 1:1 complexes is given and they are best represented as polymers, the metal being bonded to the sulphur and to a nitrogen atom of the thioseraicarbazide portion of the molecule. Infrared spectra of these compounds have been examined, particularly in the 1100 cm−1region where a strong to medium band disappears in going from thiosemicarbazones to copper complexes. It is suggested that this band is due to the C=S vibration.

ISSN:0008-4042    

DOI:10.1139/v61-122

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

Boron trifluoride and anhydrous hydrazine react rapidly at 25°invacuoyielding a 1:1 complex compound, BF3•N2H4(m.p. 87°), while at higher temperatures, or with diethyl ether as solvent, they form complex mixtures containing 52.2 to 63.5 mole percent BF3; but in tetrahydrofuran solution the 2:1 adduct, 2BF3•N2H4(m.p. 260°) is formed. The X-ray powder diffraction pattern of BF3•N2H4consists of 28 lines from which a unit cell with triclinic symmetry was calculated. The thermal decomposition of BF3•N2H4is complex, yielding in part N2, NH3, NH4BF4, and BN. Hydrolysis of BF3•N2H4yields a mixture of hydroxyfluoroborate ions. At −80°, BF3•N2H4absorbs NH3to form a diammoniate which liberates NH3slowly at higher temperatures. Partial displacement of BF3from BF3•N2H4by HCl and partial absorption of HCl by BF3•N2H4occur simultaneously at 110°.Infrared spectra of BF3•N2H4and 2BF3•N2H4have been measured in the range of 4000 to 650 cm−1and frequency assignments have been made.

ISSN:0008-4042    

DOI:10.1139/v61-123

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

Chlorinated derivatives of metameconine were formed for the first time. Partial demethylation of the derivatives with sulphuric acid occurred in highly selective fashion at the methoxyl ortho to the halogen, without regard to the relative position of the carbonyl group which is known to be highly directive for demethylations in the absence of halogen. The phenolic products of the demethylations are needed for the synthesis of sterically hindered diphenyl ethers. They showed a type of intermolecular hydrogen bonding in the crystal which was markedly subject to steric interference by the halogen atoms.

ISSN:0008-4042    

DOI:10.1139/v61-124

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

The syntheses ofN-L-seryl-D-glucosamine,N-glycyl-D-glucosamine,N-L-glutamyl-D-glucosamine, and 1-O-β-L-seryl-N-acetyl-D-glucosaminide are described. TheseD-glucosamine derivatives may result from the fragmentation of some glycoproteins. The chemical properties of these compounds indicate thatN-peptides are relatively stable in acid solution but unstable in neutral and alkaline solution. The seryl glucosaminide is relatively stable in alkaline solution but is hydrolyzed by acid.

ISSN:0008-4042    

DOI:10.1139/v61-125

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

The acetylation of some mono-, N,N-, and N,N′-dialkylguanidines was studied using ethyl acetate and acetic anhydride. Except for the N,N-dialkylguanidines, the action of ethyl acetate on the free bases gave monoacetyl derivatives. Acetic anhydride with the acetate salts gave diacetyl derivatives with monoalkylguanidines, acetamido-1,3,5-triazines with N,N-dialkylguanidines, and unstable di- and tri-acetyl derivatives with N,N′-dialkyl-guanidines. The assignment of symmetrical structures to the mono- and tri-acetyl derivatives and an asymmetrical structure to the diacetyl derivatives was supported by nuclear magnetic resonance spectra. The ultraviolet spectra of the monoacetyl derivatives exhibited one peak in the region 230–235 mµ whilst the diacetyl derivatives showed two peaks in the regions 220–230 mµ and 253–263 mµ. Some comments are made on the infrared spectra of these compounds.

ISSN:0008-4042    

DOI:10.1139/v61-126

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

The preparation of two solid paramagnetic forms, one light green and the other buffcolored, of bis-N-methyl-5-chloro-salicylaldimine nickel (II) is reported. Their magnetic and spectral properties are correlated with those of solutions of the originally diamagnetic complex, and it is concluded that in both of these species and also in some of the solutions association of the complex occurs. On this basis a general explanation of the properties of bis-N-alkyl-salicylaldimine nickel (II) complexes is given.

ISSN:0008-4042    

DOI:10.1139/v61-127

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

A careful re-examination of the arylation (P. Brassard and P. L'Écuyer. Can. J. Chem.36, 814(1958)). reaction with chlorobenzoquinone has revealed in its products the presence of all the three possible disubstituted isomeric quinones. Arylation using diazotizedp-nitro-aniline has resulted in the isolation of the three new isomeric quinones, whose structures are assigned, based on chemical and spectral evidences. Mechanistic implications in the arylation and halogenation of benzoquinones are discussed.

ISSN:0008-4042    

DOI:10.1139/v61-128

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

It is shown that the rare earth ion Yb3+is very resistant towards ordinary thermal exchange when it is complexed with the chelating agent EDTA in aqueous solution. However, when the complexed rare earth atom, as the 1.8-h Yb-177, emits a beta-particle, the daughter atom Lu-177 escapes readily from the chelate structure. Nuclear recoil arising from the beta-particle emission is shown not to be the cause of the escape of the daughter atom. It is suggested that the observed lability of the daughter atom is a result of a high degree of chemical reactivity of the chelate ion arising from the sudden change in atomic number of the central metal ion of the chelate structure.

ISSN:0008-4042    

DOI:10.1139/v61-129

出版商:NRC Research Press    

年代:1961

数据来源: NRC

摘要:

2,4- and 3,4-Dichlorobenzylcyanamides dimerize on standing to 1-cyano-1,3-di-(2,4-di-chlorobenzyl)-guanidine and 1-cyano-1,3-di-(3,4-dichlorobenzyl)-guanidine respectively. Apart from dicyandiamide itself, no other cyanamide dimers appear to have been described. The dinners on heating are converted into the corresponding trisubstituted isomelamines. 1-Cyano-1,3-di-(3,4-dichlorobenzyl)-guanidine condenses with 4-nitrobenzylcyanamide to form 1,3-di-(3,4-dichlorobenzyl)-5-(4-nitrobenzyl)-isomelamine. No dimers were obtained from the 4-chloro-, 4-bromo-, 4-nitro-, or 4-methyl-benzylcyanamides.

ISSN:0008-4042    

DOI:10.1139/v61-130

出版商:NRC Research Press    

年代:1961

数据来源: NRC