摘要:

AbstractTransiodinationoccurs when reacting iodobenzenes with other halogeno‐or with alkylbenzene derivatives in the presence of aluminium bromide at room temperature.Isomer equilibriaamong iodobenzenes resemble those for the corresponding bromides1.Di‐ and tri‐substitutedbromo‐ and iodo‐benzenes show equilibrium patterns agreeing with those computed on the basis of addivitity, using patterns for monosubstituted halogenobenzenes. Results are discussed in terms of partial equilibrium factors1, believed to be mainly governed by electrostatic and steric interactions.Results ofdirect brominations(AlBr3catalyst, no solvent) indicate that for halogeno‐ and alkylbenzenes the main difference between the isomer ratios observed and those at equilibrium consists in the large proportions ofmeta(or 1, 3, 5) isomer found in the

ISSN:0165-0513    

DOI:10.1002/recl.19670860202

出版商:WILEY‐VCH Verlag    

年代:1967

数据来源: WILEY

摘要:

AbstractTrienes of the type R(R′)CCCCH2(R and R′ are H or alkyl) have been prepared in good to excellent yields from 1,4‐dichloro‐2‐alkynes, R(R′)C(Cl)CCCH2Cl, and zinc dust or sodium iodide in dimethyl sulfoxide.The dichloro compounds were obtained from the corresponding 1,4‐dihydroxy‐2‐alkynes and thionyl chloride.The 1,4‐diols were synthesized from propargyl alcohol; the adduct of this alcohol and 2,3‐dihydropyran, , was coupled with an aldehyde RCHO or a ketone RR′CO (R and R′ are alkyl) under Grignard conditions. The resulting products R(R′)C(OH)CCCH2OT.H.P. (T.H.P. = tetrahydropyranyl) were treated with a catalytic amount ofp‐toluenesulfonic acid in an excess of methanol, furnishing the diols R(R′)C(OH)CCCH2OH (R = H and R′ = alkyl or R and R′ are both alkyl) in good overall yields.Reaction of the cumulenes with equivalent amounts of alkali amide in liquid ammonia followed by hydrolysis of the reaction mixtures afforded the isomeric 3,1‐enynes, R(R′)CCHCCH, in good yields. Buta‐1,2,3‐triene, CH2CCCH2, and hexa‐1,2,3‐triene, CH3CH2CHCCCH2, were isomerized by sodium methoxide in liquid ammonia to the enynes vinylacetylene, HCCCHCH2, and hex‐2‐en‐4‐yne, CH3CHCHCCCH3, respectively. In the case of buta‐1,2,3‐triene also a considerable quantity of the 1,4‐adduct of methanol, 1‐methoxy‐2‐butyne, CH3CCCH2OCH3, was isolated.The addition of ethanethiol to buta‐1,2,3‐triene and hexa‐1,2,3‐triene proceeded readily, yielding mixtures of isomeric adducts, C2H5SCH2CHCCH2and C2H5SCH2CCCH3, in the first case, and C2H5CH(SC2H5)CHCCH2, C2H5CH(SC2H5)CCCH3and C2H5SCH2CHCCHC2H5, in the second case. These compounds lost et

ISSN:0165-0513    

DOI:10.1002/recl.19670860203

出版商:WILEY‐VCH Verlag    

年代:1967

数据来源: WILEY

摘要:

AbstractVapour phase thermolysis at 485°C of methallyl acetate and the allyl esters of benzoic, phenylacetic and trifluoroacetic acid proceeds by radical mechanisms analogous to that proposed for allyl acetate1. Rates of primary allyl‐oxygen homolysis appear to depend only slightly on the nature of the acyl moiety.The induced radical decomposition proceeds mainly by addition to ester, followed by β‐elimination, polymerization being unimportant under the present experimental conditions.An explanation is offered for the fact that allyl(ic) esters of aromatic acids ‐ in contrast to those of aliphatic acids ‐ produce a substantial amount of carboxylic acid in addition to the main oxygen‐containing product, car

ISSN:0165-0513    

DOI:10.1002/recl.19670860204

出版商:WILEY‐VCH Verlag    

年代:1967

数据来源: WILEY

摘要:

AbstractAn X‐ray diffraction study of a disulfide dioxide has shown the compound to be a thiolsulfonate rather than a disulfoxid

ISSN:0165-0513    

DOI:10.1002/recl.19670860205

出版商:WILEY‐VCH Verlag    

年代:1967

数据来源: WILEY

摘要:

AbstractThe addition of dichlorocarbene to propadiene has been investigated. The reaction between propadiene and dichlorocarbene obtained from chloroform and potassiumt‐butoxide leads to tarry products. When generated by thermal decomposition of sodium trichloroacetate, the dichlorocarbene reacts with propadiene, yielding 1,1‐dichloro‐2‐methylenecyclopropane (II). The structure of this compound was established by means of infrared and NMR spectroscopy and confirmed by chemica

ISSN:0165-0513    

DOI:10.1002/recl.19670860206

出版商:WILEY‐VCH Verlag    

年代:1967

数据来源: WILEY

摘要:

AbstractIn contrast to the addition of nitrosyl chloride to olefins, yielding chloronitroso addition products, the reaction of propadiene and nitrosyl chloride leads to the formation of 1,3‐dichloroacetone. The reaction sequence involved is discusse

ISSN:0165-0513    

DOI:10.1002/recl.19670860207

出版商:WILEY‐VCH Verlag    

年代:1967

数据来源: WILEY

摘要:

AbstractThe structure of bicyclo [2,1,1] hexane has been investigated by means of electron diffraction of the vapour. In the discussion of the results presented here, emphasis is on the ambiguities connected with the analysis of molecules containing many nearly equal interatomic distances.

ISSN:0165-0513    

DOI:10.1002/recl.19670860208

出版商:WILEY‐VCH Verlag    

年代:1967

数据来源: WILEY

摘要:

AbstractBoth 3‐ and 4‐bromoquinoline when reacted with potassium amide in liquid ammonia, are converted into a mixture of 3‐ and 4‐aminoquinoline probablyvia3,4‐quinolyne as an intermediate.2‐Bromoquinoline yields together with 2‐aminoquinoline, 2‐methylquinazoline as the result of a ring transformation.The mechanisms of the reaction

ISSN:0165-0513    

DOI:10.1002/recl.19670860209

出版商:WILEY‐VCH Verlag    

年代:1967

数据来源: WILEY

摘要:

AbstractVinyl acetate reacts with palladium acetate to produce 1,4‐diacetoxy‐1,3‐butadiene. In addition, 1,1,4,4‐tetraacetoxybutane and 1,1,4‐triacetoxy‐2‐butene are formed. When using palladium chloride in combination with lithium acetate no oxidative coupling takes place: vinyl acetate is then converted into acetaldehyde + acetic anhydride. The mechanism of this novel oxidative coupling reaction

ISSN:0165-0513    

DOI:10.1002/recl.19670860210

出版商:WILEY‐VCH Verlag    

年代:1967

数据来源: WILEY

摘要:

AbstractThe infrared spectra of several complexes of diphenylsulfoxide (DPSO) are reported. Only one SO stretching frequency has been found, at lower wavenumbers than in DPSO itself, indicating that all DPSO's are coordinated to the metal ion. The asymmetric stretching frequencies of CIO⊖and BF4⊖have been observed as unusually sharp absorp

ISSN:0165-0513    

DOI:10.1002/recl.19670860211

出版商:WILEY‐VCH Verlag    

年代:1967

数据来源: WILEY