A degradative sequence which has been used to determine the distribution of radioactivity in the pyrrolidine of nicotine involves, as one of the steps, the oxidation of NN-dimethylglycine with lead tetra-acetate; the formaldehyde produced in this reaction, formerly thought to originate entirely from C-2, has been shown to be derived in appreciable amounts from the N-methyl groups.
{"title":"Lead tetra-acetate oxidation of NN-dimethylglycine and its relevance to the biosynthesis of the pyrrolidine ring of nicotine","authors":"E. Leete","doi":"10.1039/C29710001524","DOIUrl":"https://doi.org/10.1039/C29710001524","url":null,"abstract":"A degradative sequence which has been used to determine the distribution of radioactivity in the pyrrolidine of nicotine involves, as one of the steps, the oxidation of NN-dimethylglycine with lead tetra-acetate; the formaldehyde produced in this reaction, formerly thought to originate entirely from C-2, has been shown to be derived in appreciable amounts from the N-methyl groups.","PeriodicalId":17278,"journal":{"name":"Journal of The Chemical Society D: Chemical Communications","volume":"72 1","pages":"1524-1525"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84175712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The Raman spectrum of crystalline titanium tetrachloride has been obtained at ca. 77K, and a factor group analysis of the fundamentals is presented in terms of the known space group C2h5.
在77K处获得了结晶四氯化钛的拉曼光谱，并根据已知空间群C2h5进行了基本面的因子群分析。
{"title":"Raman spectrum and factor group analysis of crystalline titanium tetrachloride","authors":"R. Clark, B. K. Hunter, C. J. Willis","doi":"10.1039/C29710000201","DOIUrl":"https://doi.org/10.1039/C29710000201","url":null,"abstract":"The Raman spectrum of crystalline titanium tetrachloride has been obtained at ca. 77K, and a factor group analysis of the fundamentals is presented in terms of the known space group C2h5.","PeriodicalId":17278,"journal":{"name":"Journal of The Chemical Society D: Chemical Communications","volume":"196 1","pages":"201-202"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77771252","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dynamic n.m.r. studies of tris-(2,6-dimethylheptane-3,5-dionato)aluminium(III), and bis(pentane-2,4-dionato)-(2,6-dimethylheptane-3,5-dionato)aluminium(III) give proof of the rapid enantiomerization of these complexes.
{"title":"Direct measurement of enantiomerization of labile aluminium(III)β-diketonates","authors":"Berardo Jurado, C. Springer","doi":"10.1039/C29710000085","DOIUrl":"https://doi.org/10.1039/C29710000085","url":null,"abstract":"Dynamic n.m.r. studies of tris-(2,6-dimethylheptane-3,5-dionato)aluminium(III), and bis(pentane-2,4-dionato)-(2,6-dimethylheptane-3,5-dionato)aluminium(III) give proof of the rapid enantiomerization of these complexes.","PeriodicalId":17278,"journal":{"name":"Journal of The Chemical Society D: Chemical Communications","volume":"10 1","pages":"85-87"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78085591","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In the series of tris-(2,2′-bipyridyl) complexes of chromium, the Cr–N stretching frequencies change very little by changing the oxidation state of chromium from III to 0, this unexpected result indicating that the strength of the Cr–N bond does not change appreciably over a wide change in the oxidation state of chromium.
{"title":"Effect of changing oxidation state on the metal–ligand vibrations of [Cr(2,2′-bipyridyl)3]n+ type complexes","authors":"J. Takemoto, B. Hutchinson, K. Nakamoto","doi":"10.1039/C29710001007","DOIUrl":"https://doi.org/10.1039/C29710001007","url":null,"abstract":"In the series of tris-(2,2′-bipyridyl) complexes of chromium, the Cr–N stretching frequencies change very little by changing the oxidation state of chromium from III to 0, this unexpected result indicating that the strength of the Cr–N bond does not change appreciably over a wide change in the oxidation state of chromium.","PeriodicalId":17278,"journal":{"name":"Journal of The Chemical Society D: Chemical Communications","volume":"21 1","pages":"1007-1008"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72851201","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The crystal structure of dioxygen–bis(diphenylethylphosphine)chlorocarbonyliridium(I) has been shown to consist of trans-trigonal bipyramidal molecules with an O–O distance of 1·461 (14)A.
{"title":"Oxygen–oxygen distances in synthetic oxygen carriers. The crystal and molecular structure of the oxygen adduct of bis(diphenylethylphosphine)chlorocarbonyliridium(I)","authors":"M. Weininger, I. Taylor, E. L. Amma","doi":"10.1039/C29710001172","DOIUrl":"https://doi.org/10.1039/C29710001172","url":null,"abstract":"The crystal structure of dioxygen–bis(diphenylethylphosphine)chlorocarbonyliridium(I) has been shown to consist of trans-trigonal bipyramidal molecules with an O–O distance of 1·461 (14)A.","PeriodicalId":17278,"journal":{"name":"Journal of The Chemical Society D: Chemical Communications","volume":"4 1","pages":"1172-1173"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72898723","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
M. Biollaz, W. Haefliger, E. Velarde, P. Crabbé, J. Fried
Zinc converts the 17α-ethynyl carbinol acetate (1) by a reductive process accompanied by rearrangement and elimination, into the allenyl steroid (2a), a useful intermediate for the preparation of the corticoid chain by osmylation, and of 17α-hydroxy-20-oxo-pregnanes by peracid oxidation.
{"title":"A two-step synthesis of the pregnane and corticoid side-chains","authors":"M. Biollaz, W. Haefliger, E. Velarde, P. Crabbé, J. Fried","doi":"10.1039/C29710001322","DOIUrl":"https://doi.org/10.1039/C29710001322","url":null,"abstract":"Zinc converts the 17α-ethynyl carbinol acetate (1) by a reductive process accompanied by rearrangement and elimination, into the allenyl steroid (2a), a useful intermediate for the preparation of the corticoid chain by osmylation, and of 17α-hydroxy-20-oxo-pregnanes by peracid oxidation.","PeriodicalId":17278,"journal":{"name":"Journal of The Chemical Society D: Chemical Communications","volume":"24 1","pages":"1322-1323"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73401494","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Several NN-diethyl-1-naphthylalkylamines and NN-diethyl-9-anthrylalkylamines exhibit intramolecular exciplex formation and as a result reactions typical of the hydrocarbon singlet states, e.g. hydrogen abstraction from tertiary amines and dimerisation, are quenched.
{"title":"Effect of intramolecular exciplex formation upon the photoreactivity of naphthylalkylamines and anthrylalkylamines","authors":"D. Brimage, R. Davidson","doi":"10.1039/C29710001385","DOIUrl":"https://doi.org/10.1039/C29710001385","url":null,"abstract":"Several NN-diethyl-1-naphthylalkylamines and NN-diethyl-9-anthrylalkylamines exhibit intramolecular exciplex formation and as a result reactions typical of the hydrocarbon singlet states, e.g. hydrogen abstraction from tertiary amines and dimerisation, are quenched.","PeriodicalId":17278,"journal":{"name":"Journal of The Chemical Society D: Chemical Communications","volume":"184 1","pages":"1385-1386"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76639154","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The reaction of carbanions of β-ketoesters and β-diketones with 1,4-dichloro-butan-2-one leads to epoxyannelation and annelated chlorohydrins.
β-酮酯和β-二酮的碳离子与1,4-二氯丁烷-2- 1反应，生成环氧环化反应和环化氯丙烷。
{"title":"Epoxyannelation with 1,4-dichloro-butan-2-one","authors":"S. Danishefsky, G. Koppel","doi":"10.1039/C29710000367","DOIUrl":"https://doi.org/10.1039/C29710000367","url":null,"abstract":"The reaction of carbanions of β-ketoesters and β-diketones with 1,4-dichloro-butan-2-one leads to epoxyannelation and annelated chlorohydrins.","PeriodicalId":17278,"journal":{"name":"Journal of The Chemical Society D: Chemical Communications","volume":"21 1","pages":"367-367"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76648465","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Paramagnetic shifts induced in the 13C n.m.r. spectrum of borneol by tris-(2,2,6,6-tetramethylheptanedionato)praseodymium, Pr(tmhd), have been used in a total assignment; these shifts and those induced by the corresponding europium and terbium complexes agree well with values calculated on the basis that their origin is of a pseudo-contact nature.
{"title":"A ready method of assignment for 13C nuclear magnetic resonance spectra: the complete assignment of the 13C spectrum of borneol","authors":"J. Briggs, F. A. Hart, G. P. Moss, E. W. Randall","doi":"10.1039/C29710000364","DOIUrl":"https://doi.org/10.1039/C29710000364","url":null,"abstract":"Paramagnetic shifts induced in the 13C n.m.r. spectrum of borneol by tris-(2,2,6,6-tetramethylheptanedionato)praseodymium, Pr(tmhd), have been used in a total assignment; these shifts and those induced by the corresponding europium and terbium complexes agree well with values calculated on the basis that their origin is of a pseudo-contact nature.","PeriodicalId":17278,"journal":{"name":"Journal of The Chemical Society D: Chemical Communications","volume":"258 1","pages":"364-365"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76692332","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The kinetics of the reactions of a series of alkylcobaloxime complexes with the mercury(II) ion, in which alkylmercury(II) ions are formed, suggests a bimolecular mechanism of electrophilic substitution.
{"title":"De-alkylation reactions of alkylcobaloxime complexes with mercury(II)","authors":"A. Adin, J. Espenson","doi":"10.1039/C29710000653","DOIUrl":"https://doi.org/10.1039/C29710000653","url":null,"abstract":"The kinetics of the reactions of a series of alkylcobaloxime complexes with the mercury(II) ion, in which alkylmercury(II) ions are formed, suggests a bimolecular mechanism of electrophilic substitution.","PeriodicalId":17278,"journal":{"name":"Journal of The Chemical Society D: Chemical Communications","volume":"25 1","pages":"653-654"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76741697","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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