ChemInform Abstract: PHOTOINDUCED TRANSFORMATIONS. PART 74. REPLACEMENT OF A CARBONYL GROUP OF CYCLIC KETONES BY A SULFUR OR A NITROGEN ATOM. A NEW METHOD FOR TRANSFORMATION OF STEROIDAL KETONES INTO THIA- OR AZASTEROIDS

1985 ◽  
Vol 16 (24) ◽  
Author(s):  
H. SUGINOME ◽  
S. YAMADA
Keyword(s):  
Nitrogen Atom ◽  
Carbonyl Group ◽  
New Method ◽  
Cyclic Ketones

Mechanism of interference with the Jaffé reaction for creatinine.

1987 ◽  
Vol 33 (7) ◽  
pp. 1129-1132 ◽  
Author(s):  
M H Kroll ◽  
N A Roach ◽  
B Poe ◽  
R J Elin
Keyword(s):  
Carbonyl Group ◽  
Equilibrium Constants ◽  
Molar Absorptivity ◽  
Reaction Products ◽  
Cyclic Ketones ◽  
Common Structure ◽  
Aliphatic Ketones ◽  
Rate Of Reaction ◽  
The Common

Abstract We investigated the mechanism of the Jaffé reaction for determination of creatinine by studying the spectrophotometric, kinetic, and equilibrium properties of the reaction of picrate with creatinine and with cyclic and aliphatic ketones. Absorbance spectra for the reaction products of picrate with all the ketones were superimposable with that of creatinine (Amax, 490 nm). Cyclic ketones not containing nitrogen had a molar absorptivity less than half that of creatinine and equilibrium constants approximately 0.01 that of creatinine. Aliphatic ketones, except for benzylacetone, had molar absorptivities similar to that of creatinine, but all of these compounds had equilibrium constants approximately a tenth or less that of creatinine. The common structure for all of the compounds reacting with picrate is the carbonyl group. The variable magnitude of interference for aliphatic and cyclic ketones is ascribable to the different rate constants, molar absorptivities, and equilibrium constants as compared with creatinine. Structures adjacent to the carbonyl group significantly affect the absorptivity and equilibrium constant, but steric hindrance is the major factor affecting the rate of reaction. We postulate that the carbonyl group is required for the Jaffé reaction, and we suggest a mechanism for the reaction.

Sur l'aptitude à l'extension du noyau pipéridique en fonction de la substitution de l'atome d'azote: réaction du diazométhane avec quelques pipéridones-4 et désamination nitreuse des aminométhyl-alcools correspondants

1971 ◽  
Vol 49 (19) ◽  
pp. 3075-3085 ◽  
Author(s):  
H. Favre ◽  
Z. Hamlet ◽  
R. Lanthier ◽  
M. Ménard
Keyword(s):  
Nitrogen Atom ◽  
Carbonyl Group ◽  
Nitrous Acid ◽  
Ring Expansion ◽  
Nucleophilic Attack ◽  
Electronic Effects ◽  
Field Effects ◽  
Benzoyl Group ◽  
La Substitution

Aptitude to ring expansion in the piperidine series, measured by the ratio of ring expanded ketone to epoxide, varies considerably according to the nitrogen atom substituent. This ratio is essentially the same in the case of the reaction of diazomethane on 4-piperidones and the nitrous acid deamination of the corresponding aminoalcohols. The values of the ratio are 0.01–0.1 for a phenylsulfonyl group, of the order 0.3–0.6 for a benzoyl group and slightly greater than 1 for a benzyl group. Electronic effects (inductive and field effects) are the cause of these differences. Parallels between the two reactions indicate that nucleophilic attack of diazomethane on the carbonyl group can lead to the ring expanded ketone and the epoxide.

STUDIES ON LIGNIN AND RELATED COMPOUNDS.: VIII. A KINETIC STUDY OF THE ACTION OF SULPHUROUS ACID ON LIGNIN AND RELATED COMPOUNDS

1931 ◽  
Vol 5 (1) ◽  
pp. 1-47 ◽  
Author(s):  
Charles A. Sankey ◽  
Harold Hibbert
Keyword(s):  
Carbonyl Group ◽  
Addition Product ◽  
Heterocyclic Ring ◽  
Acid Group ◽  
Cyclic Ketones ◽  
Reactive Group ◽  
Experimental Conditions ◽  
Commercial Process ◽  
The Stability ◽  
Related Compounds

Electrical conductivity measurements have been made over the temperature range 18–145 °C. of reaction mixtures of sulphurous acid and a large number of type compounds, and data obtained on the stability of the resulting sulphonic acids and the mobility of the equilibria involved. The compounds investigated include saturated and unsaturated aldehydes; saturated, unsaturated and cyclic ketones; phenols; substances in which an ethylene linkage is the only reactive group; furane derivatives; and substances containing pyrone rings.The results are discussed from the standpoints of structure and reaction mechanism. The sulphonic acids of nuclear aldehydes, saturated ketones and cylic ketones are typically unstable. With compounds containing an ethylene linkage conjugated with a carbonyl group, addition normally takes place in the 1:4 positions and is followed by hydrogen migration. Where an ethylene linkage is the only reactive group present, addition proceeds only very slowly and at high temperatures. The difficulty of effecting a reaction between sulphurous acid and phenols in their tautomeric alicyclic forms is indicated by the non-reactivity of resorcinol, and the formation of only a small percentage of an extremely unstable derivative by phloroglucinol. Furfuryl alcohol and glucal are shown to form oxonium derivatives which serve as intermediates for the entry of the sulphonic acid group into the ring system.Conductivity-temperature curves for lignosulphonic acids from various sources indicate that the products are sulphonic acids of the —C = C—type. Other evidence points to an oxonium addition product with a ring oxygen as being a probable intermediate in the formation of the final and more stable lignosulphonic acid. The relation of such a mechanism to the experimental conditions employed in the commercial process of the manufacture of sulphite pulp is indicated.The formation of lignosulphonic acids through tautomerization of a phenolic nucleus is highly improbable. Also for such formation a carbonyl group does not necessarily have to be present. Strong additional evidence is presented for the presence of a heterocyclic ring containing oxygen and for an ethylene linkage in the lignin molecule. The latter is indicated to be in the same ring system as the oxygen atom.

LYCOPODIUM ALKALOIDS: VIII. LYCOPODINE

1959 ◽  
Vol 37 (10) ◽  
pp. 1757-1763 ◽  
Author(s):  
D. B. MacLean ◽  
W. A. Harrison
Keyword(s):  
Nitrogen Atom ◽  
Carbonyl Group ◽  
Lycopodium Alkaloids

Information pertaining to the position of the carbonyl group relative to the nitrogen atom and to the size of one of the nitrogen rings in lycopodine has been obtained through a study of the reactions of α- and β-cyanobromolycopodine.

IONIZATION OF ORGANIC COMPOUNDS IN ACID I. ALIPHATIC KETONES

1960 ◽  
Vol 38 (11) ◽  
pp. 2109-2116 ◽  
Author(s):  
H. J. Campbell ◽  
J. T. Edward
Keyword(s):  
Sulphuric Acid ◽  
Carbonyl Group ◽  
Absorption Spectra ◽  
Organic Compounds ◽  
Acid Strength ◽  
Medium Effect ◽  
Ring Size ◽  
Cyclic Ketones ◽  
Aliphatic Ketones ◽  
Weak Peak

The changes in the ultraviolet absorption spectra of aliphatic ketones in aqueous sulphuric acid have been followed as the acid strength is increased from 0 to 98%. With increase in strength up to 65% the weak peak at about 270 mμ is shifted to shorter wavelengths by a medium effect. However, with further increase in acid strength the peak disappears altogether because of protonation of the carbonyl group. The pKBH+ values of several ketones have been calculated from the spectrophotometric results to be about −7. The pKBH+ values of cyclic ketones vary systematically with ring size. The significance of the present work to recent studies on the rate of enolization of acetone is discussed.

LYCOPODIUM ALKALOIDS: IV. REACTIONS OF α-CYANOBROMOLYCOPODINE AND ITS DERIVATIVES

1956 ◽  
Vol 34 (11) ◽  
pp. 1519-1527 ◽  
Author(s):  
L. R. C. Barclay ◽  
David B. MacLean
Keyword(s):  
Nitrogen Atom ◽  
Carbonyl Group ◽  
Lycopodium Alkaloids ◽  
Hydrolysis Of ◽  
Methylene Group

The hydrogenolysis and hydrolysis of α-cyanobromolycopodine to the secondary tricyclic base, α-des-dihydrolycopodine, is reported. The latter compound was converted to the methiodide in poor yield so that further degradations of the molecule through this derivative were not feasible. Hydride reductions of α-cyanobromolycopodine and some of its derivatives are recorded. The presence of a methylene group adjacent to the carbonyl group in lycopodine has been proved. Evidence is presented which suggests that the carbonyl group and the nitrogen atom are relatively close to one another in the molecule.

Umsetzungen von 2-chlor- und 2-organoaminosubstituierten 5.6-Benzo-1,3-dimethyl-1,3,2-diazaphosphorinan-4-onen mit Aziden / Reactions of 2-Chloro- and 2-Organoamino-Substituted 5.6-Benzo-1,3-dimethyl-1,3,2-diazaphosphorinane-4-ones with Azides

1994 ◽  
Vol 49 (2) ◽  
pp. 171-175 ◽  
Author(s):  
Ion Neda ◽  
Thomas Kaukorat ◽  
Reinhard Schmutzler
Keyword(s):  
Nmr Spectroscopy ◽  
Nitrogen Atom ◽  
Ir Spectroscopy ◽  
Carbonyl Group ◽  
Related Compound ◽  
Phosphorus Pentachloride ◽  
Trimethylsilyl Azide

The reaction of 5,6-benzo-2-chloro-1,3-dimethyl-1,3,2-diazaphosphorinane-4-one (1) with trimethylsilyl azide led to the substituted cyclotriphosphazene (3). A monomeric reaction product was not observed by NMR spectroscopy. The diazaphosphorinane 2, with the 2-chloroethyl substituent bonded to the nitrogen atom in a-position to the carbonyl group, did not react with trimethylsilyl azide. An attempt to prepare 3 from N,N'-dimethylanthranilamide 5 and hexachlorocyclotriphosphazene 4 failed, as did the attempt to react 5 with phosphorus pentachloride. The reaction of 5,6-benzo-2-{bis(2-chloroethyl)amino}-1,3-dimethyl- 1.3.2-diazaphosphorinane-4-one (7) and of the related compound 9, bearing only one 2-chloroethyl substituent, with 4-nitrobenzoyl azide furnished, in a normal Staudinger fashion, the monomeric products 8 and 10. In the case of 10, intramolecular P=O···H interaction was demonstrated by IR spectroscopy.

Electroorganic chemistry. 68. A new method of 1,4-transposition of a carbonyl group

1983 ◽  
Vol 48 (11) ◽  
pp. 1939-1940 ◽  
Author(s):  
Tatsuya Shono ◽  
Shigenori Kashimura
Keyword(s):  
Carbonyl Group ◽  
New Method
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