摘要:

AbstractA 1 : 1 CH2O/SO3product has been prepared from sulfur trioxide and trioxane or paraformaldehyde in 1,2‐dichloroethane, which was different from methylene sulfate (a 1 : 1 CH2O/SO3compound described in the literature).In contrast to methylene sulfate, the CH2O/SO3product reacts with 1‐dodecene in 1,2‐dichloroethane at 10°C. The main reaction leads mainly to organic sulfates. The structures of the sulfates indicate that the CH2O/SO3compound mainly reacts similar to a formaldehyde/(Lewis) acid complex (Prins‐type reaction). The major side‐reaction leads to sulfonates. This side‐reaction is similar to the reaction of 1‐dodecene with the dioxane/SO3complex. Other side‐reactions are acid‐catalysed isomerizations and addition of sulfonic acids and organic sulfates to 1‐dodecene to give alkyl alkanesulfonates

ISSN:0165-0513    

DOI:10.1002/recl.19720910402

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractCrystals of the title compounds are monoclinic. The lattice constants of the first compound (E) are: a = 16.33, b = 6.48, c = 6.96 Å and β = 91.03° at 20°C. Its space group is P21and Z = 2. The configuration follows from a three‐dimensional X‐ray analysis and turns out to be 1e,2e,3e,4e,5e,6e‐hexachloro‐1a‐phenylcyclohexane. The conformation is described by means of Newman projections. The sum of C‐Cl vectors is not zero and results in a calculated electric moment of 1.06 D, the experimental value being 1.65 D.The lattice constants of the second compound (A) are: a = 20.0, b = 10.8, c = 15.2 Å and β = 112.4° at 20°C. The space group is P21/c and Z = 8.The interpretation of the NMR spectrum of E agrees quite well with the X‐ray analysis. The configuration of A was established by combined NMR (100 and 220 MHz) and13CNMR techniques, its molecular structure being 1a,2a,3e,4e,5e,6e‐hexachlo

ISSN:0165-0513    

DOI:10.1002/recl.19720910403

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractThe infrared spectra of a number of linear alkynoic acids with 2‐5 triple bonds, many of them containing methylene interrupted triple bond sequences, are discussed. Compounds with an equal number of methylene groups between the carboxylic acid group and the first triple bond show great similarity in the 1180‐1350 cm−1region. This indicates that the bands in this region are predominantly determined by this part of the chain. The conclusion is in agreement with literature data concerning alkanoic and alkenoic

ISSN:0165-0513    

DOI:10.1002/recl.19720910404

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractCompounds D‐(CH2)n‐A (n = 1‐5) are studied, in which D = an aromatic group with low ionization potential (e.g.an electron donor) and A is mainly theN‐3,6‐dinitro‐1,8‐naphthalimide group. Especially for n = 1 and n = 3, interaction between D and A leads to the observation ofdiscrete intramolecular C(harge) T(ransfer) transitions in the electronic absorption spectra. For n = 1 this is explained by “homoconjugative” interaction, while for n = 3 the molecules probably adopt a folded conformation, a suggestion which is suppported by NMR data. For n = 2 close approach of D and A seems to be sterically excluded, while for n>3 the interaction between D and A rapidly diminishes. For the compound with D = 9‐anthryl and n = 3 steric interaction between theperi‐hydrogens of the anthryl group and the trimethylene chain seems to inhibit the molecule from adopting a folded conformation. For the compounds with D =p‐dimethylaminophenyl and n = 3 or 4 a double intramolecular CT transition is observed; a tentative explanation for t

ISSN:0165-0513    

DOI:10.1002/recl.19720910405

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractInfrared gas‐phase spectra and Raman liquid‐phase spectra are recorded ofcis‐ andtrans‐1‐bromopropene. A vibrational assignment is reported for both isomers.Some vibration‐rotational bands of the trans isomer can be analyzed in terms of Coriolis interaction; three Coriolis coupling constants are

ISSN:0165-0513    

DOI:10.1002/recl.19720910406

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractThe trialkyl‐silyl‐, ‐germyl‐ and ‐stannyl‐phosphines R3MPEt2react with β‐propiolactoneviathe cleavage of the alkyl‐oxygen bond of the lactone, leading to the trialkylmetal β‐diethylphosphinopropionates R3MOCOCH2CH2PEt2(M = Si, Ge, Sn). These reactions are accompanied by a strong polymerization of the β‐propiolactone.The germyl‐ and silyl‐phosphines cleave γ‐butyrolactone at a rather high temperature and in the presence of catalyst (ZnCl2). Only the acyl‐oxygen scission is observed in this case, with formation of the phosphorated kétoalkoxymetal derivatives R3MO(CH2)3COPEt2. Under the same conditions, the stannylphosphines decompose before reacting.In the case of the hydrosilylphosphines R2(H)SiPEt2, the kétoalkoxymetal derivative cyclises by intramolecular addition SiH/C=O with formation of 2‐sila‐1,3‐dioxepane with a phosphorated substituent:The same acyl‐oxygen cleavage is observed in the action of the metal‐IVbphosphines on succinic anhydride to lead to the kétoesters R3MOCO (CH2)2COPEt2(M = Si, Ge, Sn). The action of the hydro‐germyl‐ or ‐silyl‐phosphines R2(H)MPEt2leads, in a first phase, to the corresponding γ‐kétoesters R2(H)MOCOCH2CH2COPEt

ISSN:0165-0513    

DOI:10.1002/recl.19720910407

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractThe cyclo‐addition reaction of sulfines with 1,3‐dienes is described. In all cases studied six‐membered ring sulfoxides were formed (Schemes I, II and III). Sulfines with electron‐withdrawing substituents, such as dichlorosulfine, appeared to be very reactive dienophiles. The stereochemistry of the reaction was studied withZ‐ andE‐chloro‐phenylsulfine and 2,3‐dimethyl‐1,3‐butadiene. The results show that the stereochemical configuration of the starting sulfine is predominantly retained in the (

ISSN:0165-0513    

DOI:10.1002/recl.19720910408

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractThe method described byDe Lignyet al. for the estimation of activity coefficients of single ions, which originated from ideas ofAlfenaarandDe Ligny, Buckingham, HalliwellandNyburgandMuirhead‐GouldandLaidler, has been improved further.The modified method was applied successfully to the transfer of ions from water to methanol and methanol‐water mixtures.A similar method was used to estimate the standard partial molar enthalpy of transfer ΔH° of single ions, and from these data values for the standard partial molar entropy of transfer ΔS° were obtained.The differences between the standardrealpotentials of the chloride ion in methanol and methanol‐water mixtures, and in water have been determined byCaseandParsons. From these data, the corresponding differences for the standardchemicalpotentials and the surface potential of water, the surface potentials of methanol and methanol‐water mixtures, were

ISSN:0165-0513    

DOI:10.1002/recl.19720910409

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractThe vapour pressure of aluminium isopropoxide is measured statically at temperatures ranging from 80° to 126°. In the lower part of this range the compound is more volatile than is indicated by previous data. For the latent heat of vaporization a value of 11.5 ± 1.5 kcal/mole is calculated. This low value points to just small shifts in degree of association upon vaporizati

ISSN:0165-0513    

DOI:10.1002/recl.19720910410

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractSpecific interaction of aqueous solutions of cyclodextrin derivatives has been investigated with respect to the isomers hexane and 2,3‐dimethylbutane.Saturated vapour of hexane or 2,3‐dimethylbutane is equilibrated with aqueous solutions of different concentrations of cyclodextrin derivatives at 1, 10, 20, 30 and 40°. The solubilities of the hydrocarbons in these solutions and in water are measured gaschromatographically. It appears that linear interaction isotherms are formed, from which the degree of occupation of the cyclodextrin voids can be calculated, assuming for the present a 1 : 1 composition of the inclusion complex.The complex association constant has been calculated for the equilibrium: saturated vapour + cyclodextrin derivative ⇆ inclusion complex.Plots of the natural logarithms of the association constantsvs1/T show linear relationships. The standard molar values of the free enthalpy, enthalpy and entropy pertaining to the above‐mentioned equilibrium have been ca

ISSN:0165-0513    

DOI:10.1002/recl.19720910411

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY