Imenes derived from methylsulphonyl‐acetonitrile: (Properties of the sulphonyl group XLIII)

Dijkstra, R.; Backer, H. J.

doi:10.1002/recl.19540730710

Cited by 16 publications

(2 citation statements)

References 9 publications

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“…Materials. Compound 3 was prepared according to the literature procedure . Cyano- N- phenylketenimine 13 and its precursor, 3-methylthio-3-(phenylamino)acrylonitrile, were prepared according to ref .…”

Section: Methodsmentioning

confidence: 99%

Linear Ketenimines. Variable Structures of C,C-Dicyanoketenimines and C,C-Bis-sulfonylketenimines

2002

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C,C-dicyanoketenimines 10a-c were generated by flash vacuum thermolysis of ketene N,S-acetals 9a-c or by thermal or photochemical decomposition of alpha-azido-beta-cyanocinnamonitrile 11. In the latter reaction, 3,3-dicyano-2-phenyl-1-azirine 12 is also formed. IR spectroscopy of the keteniminines isolated in Ar matrixes or as neat films, NMR spectroscopy of 10c, and theoretical calculations (B3LYP/6-31G) demonstrate that these ketenimines have variable geometry, being essentially linear along the CCN-R framework in polar media (neat films and solution), but in the gas phase or Ar matrix they are bent, as is usual for ketenimines. Experiments and calculations agree that a single CN substituent as in 13 is not enough to enforce linearity, and sulfonyl groups are less effective that cyano groups in causing linearity. C,C-bis(methylsulfonyl)ketenimines 4-5 and a C-cyano-C-(methylsulfonyl)ketenimine 15 are not linear. The compound p-O2NC6H4N=C=C(COOMe)2 previously reported in the literature is probably somewhat linearized along the CCNR moiety. A computational survey (B3LYP/6-31G) of the inversion barrier at nitrogen indicates that electronegative C-substituents dramatically lower the barrier; this is also true of N-acyl substituents. Increasing polarity causes lower barriers. Although N-alkylbis(methylsulfonyl)ketenimines are not calculated to be linear, the barriers are so low that crystal lattice forces can induce planarity in N-methylbis(methylsulfonyl)ketenimine 3.

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Section: Methodsmentioning

confidence: 99%

Linear Ketenimines. Variable Structures of C,C-Dicyanoketenimines and C,C-Bis-sulfonylketenimines

2002

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“…They are further employed for [2 + 2]-cycloaddition reactions or for the synthesis of five- and six-membered ring systems . Dijkstra and Backer reported on Lewis-acid-catalyzed electrophilic substitution reactions of arenes using ketenimines to obtain aromatic imine derivatives . Ketenimines may be transformed into metal organic species by deprotonation.…”

Section: Introductionmentioning

confidence: 99%

Hydroalumination of Ketenimines and Subsequent Reactions with Heterocumulenes: Synthesis of Unsaturated Amide Derivatives and 1,3-Diimines

et al. 2015

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The series of differently substituted ketenimines 1 was hydroluminated using di-iso-butyl aluminum hydride. For the sterically congested ketenimine 1a, preferred hydroalumination of the C═N-bond was proven by X-ray crystallography (compound 5a). In situ treatment of the hydroaluminated ketenimines 5 with various heterocumulenes like carbodiimides, isocycanates, isothiocyanates and ketenimines as electrophiles and subsequent hydrolytic workup resulted in novel enamine derived amide species in case of N-attack (sterically less hindered ketenimines) under formation of a new C-N-bond or in 1,3-diimines by C-C-bond-formation in case of bulky substituents at the ketenimine-nitrogen atom. Furthermore, domino reactions with more than 1 equiv of the electrophile or by subsequent addition of two different electrophiles are possible and lead to polyfunctional amide derivatives of the biuret type which are otherwise not easily accessible.

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Synthese und Reaktionen der Ketenimine

Krow

1971

Angewandte Chemie

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Imenes derived from methylsulphonyl‐acetonitrile: (Properties of the sulphonyl group XLIII)

Cited by 16 publications

References 9 publications

Linear Ketenimines. Variable Structures of C,C-Dicyanoketenimines and C,C-Bis-sulfonylketenimines

Linear Ketenimines. Variable Structures of C,C-Dicyanoketenimines and C,C-Bis-sulfonylketenimines

Hydroalumination of Ketenimines and Subsequent Reactions with Heterocumulenes: Synthesis of Unsaturated Amide Derivatives and 1,3-Diimines

Synthese und Reaktionen der Ketenimine

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