摘要:

AbstractPhenyl anda‐naphthylp‐toluenesulfonates as well as phenyl methanesulfonate were found to undergo photochemical rearrangement upon irradiation with light from a high pressure mercury arc lamp. In the case of phenylp‐toluenesulfonate,o‐ andp‐hydroxyphenyl‐p‐tolylsulfone and phenol were identified as products originating from a photo

ISSN:0165-0513    

DOI:10.1002/recl.19660850502

出版商:WILEY‐VCH Verlag    

年代:1966

数据来源: WILEY

摘要:

AbstractStraight‐chain aliphatic aldehydes of at least three carbon atoms can be catalytically in methanol solutions of copper‐pyridine complexes and triethylamine by oxygen at 40 °C. In this oxidation the carbon atoms, starting with the carbon atom, are successively split off as methyl formate or formic acid, until the aldehyde is degraded to acetaldehyde, which is not reactive. The reaction probably proceeds via α‐ketoaldehydes.The oxidation of aliphatic ketones with the same catalyst system has been inves

ISSN:0165-0513    

DOI:10.1002/recl.19660850503

出版商:WILEY‐VCH Verlag    

年代:1966

数据来源: WILEY

摘要:

AbstractFrom kinetic and stoichiometric data the following mechanism is derived for the oxidative steps of the degradation of saturated aldehydes and ketones with oxygen, catalysed by copper‐pyridine complexes in the presence of triethylamine, described in the previous paper.The aldehyde (ketone) is deprotonated by methoxide ions, formed from methanol and triethylamine. The enolate ion co‐ordinates with cupric ion and pyridine to a complex which does not decompose spontaneously. This complex, however, is reactive toward oxygen, yielding ana‐hydroperoxide anion of the carbonyl compound, which decomposes via ionic reactions. The complex is also reactive towards triphenylphosphine, yielding a cuprous phosphine complex and presumably an enolate radical. The dimers of such radicals have been isolated.At high concentrations of oxygen the overall reaction rate is controlled by the rate of formation of the copper‐enolate complex or, if the copper concentration is sufficiently high, by the deprotonation step. In the absence of oxygen the same reactions control the rate of the reaction with triphenylph

ISSN:0165-0513    

DOI:10.1002/recl.19660850504

出版商:WILEY‐VCH Verlag    

年代:1966

数据来源: WILEY

ISSN:0165-0513    

DOI:10.1002/recl.19660850505

出版商:WILEY‐VCH Verlag    

年代:1966

数据来源: WILEY

摘要:

AbstractThe reaction of 1,4‐di‐tert.butylbenzene in carbon tetrachloride with bromine and with iron as catalyst yields 1,4‐di‐tert.butyl‐2‐bromobenzene, 1‐tert.butyl‐3‐bromobenzene, 1‐tert.butyl‐4‐bromobenzene, and 1‐tert.butyl‐3,4‐dibromobenzene. Besides these compounds, 1‐tert.butyl‐2,4‐dibromobenzene and 1‐tert.‐butyl‐2,5‐dibromobenzene

ISSN:0165-0513    

DOI:10.1002/recl.19660850506

出版商:WILEY‐VCH Verlag    

年代:1966

数据来源: WILEY

摘要:

AbstractThe conformation of several 2‐substituted 1,3‐dithianes is studied by means of dipole moments and NMR spectra. The value of the dipole moments of all compounds having only hydrocarbon substituents is 2.0 ± 0.1 D., indicating that in all these compounds the six‐membered ring is in the same conformation. From the dipole moments of the 1,3‐dithianes studied it may be concluded that in solution the dithiane ring has the same geometry (chair conformation) as that found by X‐ray analysis of 2‐phenyl‐1,3‐dithiane2. The NMR spectra of 2‐methyl‐2‐phenyl‐, 2,2‐diphenyl‐ and 2‐p‐chlorophenyl‐2‐methyl‐1,3‐dithiane show that a phenyl group at atom 2 in axial position gives rise to two absorption peaks, one due to theorthoprotons and one to themeta(andpara) protons. The same effect is seen with the axial phenyl group in α‐trithiobenzaldehyde. The protons of an equatorial phenyl substituent give o

ISSN:0165-0513    

DOI:10.1002/recl.19660850507

出版商:WILEY‐VCH Verlag    

年代:1966

数据来源: WILEY

ISSN:0165-0513    

DOI:10.1002/recl.19660850508

出版商:WILEY‐VCH Verlag    

年代:1966

数据来源: WILEY

ISSN:0165-0513    

DOI:10.1002/recl.19660850509

出版商:WILEY‐VCH Verlag    

年代:1966

数据来源: WILEY

摘要:

AbstractTo some of the quinolizine derivatives described earlier (1and2) we have been able to assign acisortransstructure on the strength of a stereoselective synthesis. Infrared spectral data and differences in the rate of dehydrogenation, combined with a study of the conformations possible, allowed such assignment for other compounds in this series.

ISSN:0165-0513    

DOI:10.1002/recl.19660850510

出版商:WILEY‐VCH Verlag    

年代:1966

数据来源: WILEY

摘要:

AbstractExperimental data on fluid phase equilibria in the system polyethylene‐supercritical ethylene have been analyzed thermodynamically. The behaviour of the system can be treated as a case of partial miscibility. A quantitative description of this behaviour can be given with the Flory‐Huggins polymer solution theory. A mathematical expression has been derived for the pressure‐temperature projections at constant polymer concentration. Its form resembles a reduced equation of state. An empirical relation was found for the cloud‐point curve, which accounts for its maximum and two inflexions. The expressions obtained permit of extrapolating the experimental data into temperature regions investigated by other authors. The comparison indicates that the different sets of data are con

ISSN:0165-0513    

DOI:10.1002/recl.19660850511

出版商:WILEY‐VCH Verlag    

年代:1966

数据来源: WILEY