摘要:

Electronic and Raman spectra of adrenalin–copper(II) complexes and copper catalyzed compounds have been studied. Adrenalin reacts with copper(II) ion at pH 9.2 and higher to produce a very short lived violet free radical, a brown adrenochrome, a yellow conjugated salt, indolyl-indoquinone, and melanin. Results indicate that copper does not form complexes with adrenalin in basic solution. Between pH 6.5 and 8.5 adrenalin transforms into adrenochrome in presence of copper. The adrenochrome in 1.5 Nhydrochloric acid produces the conjugate salt that is produced in the solution of high pH. At low pHvalues, between pH 4.0 to 5.5, adrenalin forms a brown complex with copper(II). Copper is entirely chelated to the phenolic groups of the amines. The complex in 1.5 Nhydrochloric acid produces a black polymeric pigment.

ISSN:0008-4042    

DOI:10.1139/v76-548

出版商:NRC Research Press    

年代:1976

数据来源: NRC

摘要:

Two different 2% cross-linked divinylbenzene–styrene copolymers incorporating 1,3-diol groups were prepared. The symmetrical dialdehydes terephthalaldehyde ando-phthalaldehyde were attached to these polymers through acetal formation, showing that even hinderedo-aromatic dialdehydes can be monoblocked by the use of polymer supports. The free aldehyde group of polymer-bound terephthalaldehyde reacted with Wittig reagents to give 1-p-formylphenyl-4-phenyl-1,3-butadiene andp-formylstilbene. Similarly, polymer-boundo-phthalaldehyde gaveo-formylstilbenes. Polymer-bound 1,3- and 1,2-diols did not form acetals of aliphatic dialdehydes and formed ketals of symmetrical diketones in very low yield.

ISSN:0008-4042    

DOI:10.1139/v76-549

出版商:NRC Research Press    

年代:1976

数据来源: NRC

摘要:

Heating 5,5-dimethylcyclohex-2-en-1-one,1, with manganic acetate in acetic acid yields 6-acetoxy-5,5-dimethylcyclohex-2-en-1-one,2, as the only isolated product. Reaction of 3-methylcyclohex-2-en-1-one (3) or (+)-pulegone (5) under similar conditions yields the analogous 6-acetoxy-3-methylcyclohex-2-en-1-one(4) andcis- (6) andtrans-2-acetoxypulegone (7) respectively.

ISSN:0008-4042    

DOI:10.1139/v76-550

出版商:NRC Research Press    

年代:1976

数据来源: NRC

摘要:

The use of molecular oxygen as a spin trap in rigid glassy hydrocarbon media at 77 K is investigated. By slight warming of the matrix, oxygen is found to effectively scavenge the isolated alkyl radicals produced by γ-irradiation to give RO2•, but does not react with radical pairs lying in the ionization tracks. The yield of scavengable radicals in 3MP is determined and compared to the findings of other workers. The butyl radical yields for γ-irradiated 1.0 mol l−1butyl chlorides in 3MP are found to be:t-BuCl, 5.8;i-BuCl, 5.1; 2-BuCl, 4.9; and 1-BuCl, 2.2. Alkyl radicals cannot be recovered from either RO2or BuO2by uv photolysis due to solvent abstraction reactions, or because of photon induced reactions of the alkyl radicals. Photolysis of the butyl radicals themselves at 253.7 nm give rise to decomposition and solvent abstraction reactions.

ISSN:0008-4042    

DOI:10.1139/v76-551

出版商:NRC Research Press    

年代:1976

数据来源: NRC

摘要:

Various models for the interionic potential in the alkali metal chlorides have been examined. The parameters in these potentials have been determined by fitting the equilibrium, elastic and dielectric properties of each substance. The potentials are compared graphically with each other, with the theoretically derived potentials of Kim and Gordon (1,2) and with a potential derived earlier by Catlow, Diller, and Norgett (3) by fitting the properties of sixteen alkali halides simultaneously. Intrinsic defect properties of the four chlorides have been calculated from these potentials. The results show that while it is possible to derive adequate two-body potentials for these salts from fitting their bulk properties, it is concluded, as found earlier by Catlow, Diller, and Norgett (3), that such potentials need to have the anion–cation interaction hardened by neglecting completely the Van der Waals interaction between nearest neighbours. Inclusion of non-central forces does not improve the potential, as judged by the criterion of the results of defect calculations.

ISSN:0008-4042    

DOI:10.1139/v76-552

出版商:NRC Research Press    

年代:1976

数据来源: NRC

摘要:

The study of normal vibrations of 3-, 4-, or 5-monosubstituted isothiazole derivatives, assuming transferability of the valence force field of isothiazole, gives results which agree with the experimental data and which permit the assignment of the various vibrations.

ISSN:0008-4042    

DOI:10.1139/v76-553

出版商:NRC Research Press    

年代:1976

数据来源: NRC

摘要:

Enthalpies of transfer from the vapor to solution (ΔH(v → S)) in cyclohexane are similar for alkenes and the corresponding alkanes. The transfer from vapor to dimethylformamide is about 0.6 kcal/mol more exothermic for 1-alkenes, which results from the dipole-induced dipole interaction of the solvent dipole with the π system. When the ethylenic bond is hindered by large adjacent groups (trans-1,2-di-tert-butylethylene) to the approach of solvent dipoles, ΔH(v → DMF) becomes similar to that of the corresponding alkane (1,2-di-tert-butylethane). Similarly the interaction of di-tert-butyl ketone with DMF is 0.7 kcal/mol weaker than that of the less hindered isomer, 2-nonanone.

ISSN:0008-4042    

DOI:10.1139/v76-554

出版商:NRC Research Press    

年代:1976

数据来源: NRC

摘要:

The sulfoxide configurations of neothiobinupharidine α- and β-sulfoxides have been determined through a13C nmr investigation. The13C nmr sulfoxidation increments (ΔδC-i = δC–iS–O − δC–iS) for all carbons in 2,2,4,4-tetramethylthiolane sulfoxide have been determined, Sulfoxidation increments for the C-2 methyl groups, the indicator carbons, were found to be similar in sign and magnitude to the increments reported for methyl groups in penicillin sulfoxides, wherein methyl groupscisto the sulfoxide oxygen show larger sulfoxidation increments than do thetransmethyl groups. The sign and magnitude of the sulfoxidation increments for C-6 and C-8, the indicator carbons in the neothiobinupharidine sulfoxides, have been determined and compared with those of the model 2,2,4,4-tetramethylthiolane and those of the penicillins. The C-6 increments were −9.9 and −5.6 ppm respectively for the solid and liquid neothiobinupharidine sulfoxide. Therefore the solid sulfoxide is assigned the β-configuration and the liquid sulfoxide the α-configuration as a result of these studies.

ISSN:0008-4042    

DOI:10.1139/v76-555

出版商:NRC Research Press    

年代:1976

数据来源: NRC

摘要:

A practical total synthesis ofcis-jasmone (1) has been achieved in six steps and in an overall yield of 49% from levulinic acid.

ISSN:0008-4042    

DOI:10.1139/v76-556

出版商:NRC Research Press    

年代:1976

数据来源: NRC

摘要:

Heat of reaction and free energy of formation at 25 °C were determined from experimental equilibrium yields for the reactionin an aqueous solution.The values are 5045 and 1927 cal/mol respectively. Equilibrium constants for the reaction were determined over a temperature range from 20 to 193 °C.

ISSN:0008-4042    

DOI:10.1139/v76-557

出版商:NRC Research Press    

年代:1976

数据来源: NRC