Über Lichtreaktionen IX. Umsetzungen photochemisch erzeugter Carbene

Kirmse, Wolfgang; Horner, L.; Hoffmann, Hinrich

doi:10.1002/jlac.19586140104

Cited by 131 publications

(40 citation statements)

References 13 publications

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“…Consequently, the formation of 6 is rationalised by the abstraction of a hydrogen aton1 by the carbene 13 from the solvent t o give an intermediate radical. The radical appears to be sufficiently stable t o give the dimer in confornlity with most of the diarylcarbenes (18). It may therefore be inferred that the reactions of carbene 13 are similar to those of arylcarbenes.…”

Section: Fortnation Of Procl~rctsmentioning

confidence: 93%

Thermolysis of the sodium salt of tricarbonyl(acetophenone)chromium p-tosylhydrazone

Ashraf¹

1976

Can. J. Chem.

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MUHAMMAD ASHRAF. Can. J. Chern. 54,448 (1976). Thermolysis of the sodium salt of tricarbonyl(acetophenone)chromium p-tosylhydrazone was carried out at 116-118 "C in pyridine, both in the presence and absence of 1,l-diphenylethylene and cyclohexene. The products, separated by column chromatography, were shown by analyses to be acetophenone azine, symmetrical and unsymmetrical tricarbonyl(acetophenone azine)chromium complexes, and a diastereomeric mixture of liexacarbonyl(2,3-dip1ienylbutane)-dichromium and 1-tricarbonyl(plienyl)chromium-l-methyl-2,2-diphenylcyclopropane. The formation of these compounds has been rationalised by the combination of a diazo intermediate and tricarbonyl(methylphenylcarbene)chromiurn. Their stereochemistry has been discussed in the light of various spectroscopic results.MUHAMMAD ASHRAF. Can. J. Chem. 54,448 (1976). On a effectui la thermolyse du sel de sodium de la p-tosylhydrazone du tricarbonyle acitophCnone chrome; cette reaction a Ct C effectuie ii 116-118 "C dans la pyridine en presence et en l'absence de diphinyl-1,1 Cthylkne et de cyclohexkne. On a montrC que les produits, siparks par chromatographie sur colonne, sont l'azine de l'acCtophCnone, les complexes symetriques et non-symitriques du tricarbonyle(ac6tophCnone azine)chrome et un melange diastCrCoisomke d'hexacarbonyl(diphCny1-2,3 butane)dichrome et du tricarbonyl(p1iCnyl)chrome-1 methyl-1 diphCnyl-2,2 cyclopropane. On a rationnalisi la formation de ces composes par une combinaison des intermediaires diazo avec le tricarbonyl(mCthylphCnylcarbkne)chrorne. On a discutC de leur stCrCochirnie B la lumihe des divers rCsultats spectroscopiques.[Traduit par le journal] Introduction Pyrolysis (2) and photolysis (3) of hydrazone salts are well known methods for the generation of carbenes. But it appears that a carbene bearing a tricarbonylchron~ium moiety in the aromatic portion has not been studied so far. It was, therefore, decided to investigate the pyrolytic decomposition of the sodium salt of tricarbonyl(acetophenone)chronlium y-tosylhydrazone, 1, in order to generate tricarbonyl(methylpheny1carbene)-chromium, to study the effect of the tricarbonylchromium group on the spin state of this carbene and the stereochemistry of various products obtained. This was accomplished by the thermal deconlposition of 1 in pyridine at 116-118 "C both in the presence and absence of external unsaturated system, e.g., 1,l-diphenylethylene ( 2 ) and cyclohexene.

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Section: Fortnation Of Procl~rctsmentioning

confidence: 93%

Thermolysis of the sodium salt of tricarbonyl(acetophenone)chromium p-tosylhydrazone

Ashraf¹

1976

Can. J. Chem.

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“…The crude product on column chromatography on silica gel gave 9-cyclohexylfluorene in a 30% yield; m.p. 113°C [8]. The NMR spectrum gave the C-9H as a doublet at 3.96 ppm (3j = 3 Hz).…”

Section: Introduction 2 Materials and Methodsmentioning

confidence: 99%

Diazofluorene — A new reagent for fluorescent photochemical labelling of membrane hydrophobic core

Anjaneyulu

Lala

1982

FEBS Letters

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“…Recently, the first example of dioxirane formation from the ozonolysis of an alkene (Scheme 5) was reported by Kopecky et al 50 . The ozonolysis of (Z)-1,2-dimethoxy-1,2-diphenylethene (17) in CD 2 Cl 2 at Ϫ 20°C resulted in the formation of dioxirane 19, which was characterized by a typical 13 C NMR absorption at ␦ 109·1 ppm. The addition of excess 17 to a solution of 19 led to the stereospecific conversion of the alkene into the corresponding oxirane.…”

Section: Effect Of -Donating Substituentsmentioning

confidence: 99%

“…The oxides can also be generated by the reaction of carbenes and 3 O 2 [Scheme 1 (ii), path c] 13 or by the oxidation of diazo compounds with singlet oxygen,…”

Section: Photooxidation Of Diazo Compoundsmentioning

confidence: 99%

Novel aspects of carbonyl oxide chemistry

Ishiguro

Nojima

Sawaki

1997

J. Phys. Org. Chem.

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The structural and chemical properties of 1,3-dipolar peroxidic species (X-O-O) such as ozone (X = O) and carbonyl oxides (X = R 2 C) depend significantly on the nature of X. Although cyclic O 3 is thermodynamically unstable, dioxiranes, cyclic isomers of carbonyl oxides, are isolable and have been fully characterized. In contrast to the well known electrophilic nature of ozone, carbonyl oxides usually act as a nucleophilic oxygen transfer agent, but their reactivity could be altered by substituents. It is expected that the chemistry of R 2 C-O 2 species will provide a good starting point for a better understanding of dioxygen complexes (X-O 2 ) with various Xs. Interesting aspects of carbonyl oxide chemistry are discussed, including methods of generation, cyclization to dioxiranes and the nature of their oxygen transfer activities.

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Über Lichtreaktionen IX. Umsetzungen photochemisch erzeugter Carbene

Abstract: Aus Diphenyldiazomethan im Licht gebildetes Diphenylcarben vermag CH-

Cited by 131 publications

References 13 publications

Thermolysis of the sodium salt of tricarbonyl(acetophenone)chromium p-tosylhydrazone

Thermolysis of the sodium salt of tricarbonyl(acetophenone)chromium p-tosylhydrazone

Diazofluorene — A new reagent for fluorescent photochemical labelling of membrane hydrophobic core

Novel aspects of carbonyl oxide chemistry

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