Photoisomerization of Bicyclo[3.1.1]heptan-2-ones in Methanol: Chemical Transformations of 'Verbanones'

1975 ◽  
Vol 53 (11) ◽  
pp. 1657-1669 ◽  
Author(s):  
Alex G. Fallis
Keyword(s):  
Carbonyl Group ◽  
Alkyl Radical ◽  
Membered Ring ◽  
Chemical Transformations ◽  
Photochemical Behavior ◽  
Unsaturated Aldehydes ◽  
Cyclopropyl Ketones

The products (predominantly unsaturated aldehydes) from photolysis in methanol of a series of 6,6-dimethylbicyclo[3.1.1]heptan-2-ones are reported. These results are rationalized on the basis of stereochemical interactions and the apparent preference for cleavage to occur adjacent to the less highly substituted α-carbon but more stable alkyl radical. It is concluded that the photochemical behavior of α-cyclobutyl ketones displays a closer parallel to the α-cyclopropyl ketones than previously recognized and that cleavage will occur preferentially on the side of the carbonyl group remote from the four-membered ring whenever possible. The synthetic steps involved in the preparation of the ketones from 'pinene' precursors are described.

ChemInform Abstract: 3a-Azaazulenones Containing a Carbonyl Group in the 5-Membered Ring.

ChemInform ◽  
1988 ◽  
Vol 19 (9) ◽  
Author(s):  
W. FLITSCH ◽  
R. A. JONES ◽  
M. HOHENHORST
Keyword(s):  
Carbonyl Group ◽  
Membered Ring

13C n.m.r. studies. IX. Carbonyl carbon shieldings of some cyclopropyl ketones

1967 ◽  
Vol 45 (3) ◽  
pp. 225-231 ◽  
Author(s):  
D. H. Marr ◽  
J. B. Stothers
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Primary Objective ◽  
Membered Ring ◽  
Carbonyl Carbon ◽  
Nuclear Magnetic Resonance Spectra ◽  
Carbonyl Grouping ◽  
Cyclopropyl Ketones ◽  
Derivatives Of ◽  
Related Compounds

The 15.1 Mc/s 13C nuclear magnetic resonance spectra of 15 aliphatic and alicyclic ketones having a three-membered ring alpha to the carbonyl group have been obtained and the shieldings of their carbonyl carbon nuclei are reported. A number of derivatives of bicyclo-[4.1.0]heptan-2-one, bicyclo[3.1.0]hexan-2-one, spiro[2.5]octan-4-one, and spiro[2.4]heptan-4-one have been included. The primary objective was to investigate the question of conjugation of the cyclopropyl ring with a carbonyl grouping, since we had shown previously that 13C shieldings of carbonyl carbons are significantly affected by conjugative interactions. The 13C data for several related compounds were obtained to aid in our assessment of the cyclopropyl results. Some evidence of cyclopropyl conjugation is presented.

Cyanoethylations and Michael additions. II. The synthesis of allylic cyclohexenols by γ-cyanoethylation of α,β-unsaturated aldehydes and ketones. Part II

1970 ◽  
Vol 48 (18) ◽  
pp. 2819-2838 ◽  
Author(s):  
Ch. R. Engel ◽  
J. Lessard
Keyword(s):  
Membered Ring ◽  
Detailed Report ◽  
Michael Additions ◽  
Unsaturated Aldehydes ◽  
Single Operation ◽  
Aldehydes And Ketones ◽  
High Yields

The detailed report of the first cyclo-γ-cyanoethylation of an α,β-unsaturated carbonyl system, 3β-acetoxy-5α-pregn-17-en-21-al, is given. This reaction, which proceeds in high yields, gives rise, in a single operation, to products with an additional functionalized six-membered ring, primarily to allylic α′-cyanohexenols.

Untersuchungen zur Chemie von Isoindolen und Isoindoleninen, XXXX. 3-Hydroximino-1-alkyl(aryl)-isoindoline und 3-Hydroxylamino-1-alkyl(aryl)-1Hisoindole - Modellverbindungen für Struktur- und Reaktivitätsuntersuchungen - / Studies on the Chemistry of Isoindoles and Isoindolenines, XXXX. 3-Hydroximino-1-alkyl(aryl)-isoindolines and 3-Hydroxylamino-1-alkyl(aryl)-1Hisoindoles - Model Compounds for Investigations of Structure and Reactivity -

1996 ◽  
Vol 51 (12) ◽  
pp. 1791-1810 ◽  
Author(s):  
Andrea Clemens ◽  
Richard P. Kreher ◽  
Johannes Preut
Keyword(s):  
Crystal Structure ◽  
Structure Determination ◽  
Membered Ring ◽  
Crystal Structure Determination ◽  
Chemical Transformations ◽  
Model Compounds ◽  
Alkyl Aryl ◽  
Spectroscopic Investigations

3-Hydroximino-isoindolines and 3-hydroxylamino-1 H-isoindoles with substituents at the five membered ring have been prepared by condensation of substituted 3-alkoxy-1 H-isoindoles with hydroxylamine and O-/N -substituted hydroxylamines. Constitution and configuration of semi-cyclic amidoximes were derived from spectroscopic investigations and deduced on the basis of orientating chemical transformations. These results have been established by a crystal structure determination of a representative 3-hydroximino-isoindoline.

3a-Azaazulenones containing a carbonyl group in the 5-membered ring

1987 ◽  
Vol 28 (38) ◽  
pp. 4397-4398 ◽  
Author(s):  
Wilhelm Flitsch ◽  
R.Alan Jones ◽  
Manfred Hohenhorst
Keyword(s):  
Carbonyl Group ◽  
Membered Ring

Silaheterocyclen, VII. Reaktionen des Dichlorneopentylsilaethens mit Aldehyden / Silaheterocycles, VII. Reactions of Dichloroneopentylsilene with Aldehydes

1990 ◽  
Vol 45 (6) ◽  
pp. 909-920 ◽  
Author(s):  
Norbert Auner ◽  
Claudia Seidenschwarz
Keyword(s):  
Carbonyl Group ◽  
Aromatic Aldehydes ◽  
Product Formation ◽  
Membered Ring ◽  
Coupling Reactions ◽  
Zwitterionic Intermediate

Dichloroneopentylsilene, Cl2Si=CHCH2Bu' (1), is produced from vinyltrichlorosilane (2) and LiBu' in n-pentane at —78 °C. The reactions of 1 with aromatic aldehydes like benzaldehyde and the 4-methoxy- or 4-fluoro-substituted derivatives, naphthalene-1- and -2- and 9-anthracenecarbaldehyde, furfurale and its S-analogous thiophene carbaldehyde yield 1,2-silaoxetanes by [2+2] cycloaddition with the carbonyl group. The same is true for the reactions of 1 with pivaline-, butyr- and acetaldehyde. The silaoxetanes cannot be isolated; the formation of dichlorovinylsiloxanes and the olefinic compounds R—CH=CH —CH2Bu′suggests that the cycloreversion of the Si—O four-membered ring competes with an intramolecular isomerization, evidently via formation of a zwitterionic intermediate . The product formation by coupling reactions of lithiated aldehydes and 2 is excluded by performing analogous reactions with the chlorosilanes Me2SiCl(R) (R = Cl, Me, Vi).

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