CYCLOHEXANONE-BENZIL

1931 ◽  
Vol 4 (3) ◽  
pp. 264-274 ◽  
Author(s):  
Charles F. H. Allen
Keyword(s):  
Free Radical ◽  
Chemical Property ◽  
Addition Product ◽  
Sodium Methylate ◽  
Reaction Products ◽  
Mineral Acids ◽  
Derivatives Of

In the presence of a small amount of sodium methylate, cyclohexanone and benzil form an addition product, which is a "semicyclic" 1:4-diketone. No derivatives of a bicyclic cyclo-heptane were found. Its most conspicuous chemical property is its sensitivity to mineral acids; among the reaction products is found a diphenyltetrahydrocumarone. Although the addition product exhibits the phenomenon of halochromism, the existence of a perchlorate is doubtful, and it did not form a free radical.

THE ADDITION OF CYANOACETAMIDE TO α-METHOXYBENZALACETOPHENONE

1934 ◽  
Vol 11 (3) ◽  
pp. 395-405 ◽  
Author(s):  
C. F. H. Allen ◽  
J. A. Scarrow
Keyword(s):  
Addition Product ◽  
Methoxyl Group ◽  
Pyridine Derivatives ◽  
Reaction Products ◽  
Alkaline Catalyst ◽  
Partial Degradation ◽  
Derivatives Of

When attempts were made to add substances of the type HA to α-methoxybenzalacetophenone in the presence of an alkaline catalyst, it was found that the components were largely recovered unchanged, except in the case of cyanoacetamide; the addition product from the latter is a hydropyridine. The hydropyridine gives two distinct series of reaction products; in the first, the substances are all pyridine derivatives and always contain a methoxyl group. In the second, partial degradation has taken place, giving rise to cyclic derivatives of a δ-ketonic acid.

Reactions of organotin compounds. IX. The reactions of tin hydrides with perfluorovinyl germanium and tin compounds

1968 ◽  
Vol 46 (12) ◽  
pp. 2165-2173 ◽  
Author(s):  
M. Akhtar ◽  
H. C. Clark
Keyword(s):  
Free Radical ◽  
Ultraviolet Irradiation ◽  
Spectroscopic Data ◽  
Addition Product ◽  
Tin Compounds ◽  
Radical Process ◽  
Organogermanium Compounds ◽  
The Stability ◽  
Derivatives Of ◽  
Free Radical Process

The formation of addition products (CH3)3MCFHCF2Sn(CH3)3 and (CH3)3MCF[Sn(CH3)3]CF2H where M = Ge or Sn has been observed in reactions involving the ultraviolet irradiation of (CH3)3MCF=CF2 with trimethyltin hydride. The former type of addition product is more stable than the latter, and the stability of both types decreases in the order M = Si, Ge, or Sn. Evidence is presented that decomposition occurs in all cases by a β-fiuorine elimination with the formation of fluorovinyl derivatives of M and trimethyltin fluoride. Similar reactions occur between (CH3)3GeCF=CF2 and dimethyltin dihydride and between (CH3)2Ge(CF=CF2)2 and dimethyltin dihydride or trimethyltin hydride. The evidence indicates that a free radical process is involved. Spectroscopic data are presented for new organogermanium compounds.

Cyclization and acid-catalyzed hydrolysis of O-benzoylbenzamidoximes

1986 ◽  
Vol 51 (12) ◽  
pp. 2786-2797
Author(s):  
František Grambal ◽  
Jan Lasovský
Keyword(s):  
Reaction Rate ◽  
Kinetic Isotope ◽  
Acid Base Equilibrium ◽  
Mineral Acids ◽  
Kinetics Of Formation ◽  
Acid Catalyzed ◽  
Ph Scale ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Derivatives Of

Kinetics of formation of 1,2,4-oxadiazoles from 24 substitution derivatives of O-benzoylbenzamidoxime have been studied in sulphuric acid and aqueous ethanol media. It has been found that this medium requires introduction of the Hammett H0 function instead of the pH scale beginning as low as from 0.1% solutions of mineral acids. Effects of the acid concentration, ionic strength, and temperature on the reaction rate and on the kinetic isotope effect have been followed. From these dependences and from polar effects of substituents it was concluded that along with the cyclization to 1,2,4-oxadiazoles there proceeds hydrolysis to benzamidoxime and benzoic acid. The reaction is thermodynamically controlled by the acid-base equilibrium of the O-benzylated benzamidoximes.

scholarly journals Gasification Pathways and Reaction Mechanisms of Primary Alcohols in Supercritical Water

2019 ◽  
Author(s):  
Brian Pinkard ◽  
John Kramlich ◽  
Igor V. Novosselov
Keyword(s):  
Free Radical ◽  
Supercritical Water ◽  
Reaction Mechanisms ◽  
Radical Reaction ◽  
Water Environment ◽  
Waste To Energy ◽  
Reaction Pathways ◽  
Free Radical Reaction ◽  
Reaction Products ◽  
Primary Alcohols

<div> <p></p><p>Supercritical water gasification is a promising waste-to-energy technology with the ability to convert aqueous and/or heterogeneous organic feedstocks to high-value gaseous products. Reaction behavior of complex molecules in supercritical water can be inferred through knowledge of the reaction pathways of model compounds in supercritical water. In this study methanol, ethanol, and isopropyl alcohol are gasified in a continuous supercritical water reactor at temperatures between 500 and 560 °C, and for residence times between 3 and 8 s. <i>In situ</i> Raman spectroscopy is used to rapidly identify and quantify reaction products. The results suggest the dominance of chain-branching, free radical reaction mechanisms that are responsible for decomposing primary alcohols in the supercritical water environment. The presence of a catalytic surface is proposed to be highly significant for initiating radical reactions. Global reaction pathways are proposed, and mechanisms for free radical reaction initiation, propagation, and termination are discussed in light of these and previously published experimental results.</p><br><p></p></div>

scholarly journals Gasification Pathways and Reaction Mechanisms of Primary Alcohols in Supercritical Water

2019 ◽  
Author(s):  
Brian Pinkard ◽  
John Kramlich ◽  
Igor V. Novosselov
Keyword(s):  
Free Radical ◽  
Supercritical Water ◽  
Reaction Mechanisms ◽  
Radical Reaction ◽  
Water Environment ◽  
Waste To Energy ◽  
Reaction Pathways ◽  
Free Radical Reaction ◽  
Reaction Products ◽  
Primary Alcohols

<div> <p></p><p>Supercritical water gasification is a promising waste-to-energy technology with the ability to convert aqueous and/or heterogeneous organic feedstocks to high-value gaseous products. Reaction behavior of complex molecules in supercritical water can be inferred through knowledge of the reaction pathways of model compounds in supercritical water. In this study methanol, ethanol, and isopropyl alcohol are gasified in a continuous supercritical water reactor at temperatures between 500 and 560 °C, and for residence times between 3 and 8 s. <i>In situ</i> Raman spectroscopy is used to rapidly identify and quantify reaction products. The results suggest the dominance of chain-branching, free radical reaction mechanisms that are responsible for decomposing primary alcohols in the supercritical water environment. The presence of a catalytic surface is proposed to be highly significant for initiating radical reactions. Global reaction pathways are proposed, and mechanisms for free radical reaction initiation, propagation, and termination are discussed in light of these and previously published experimental results.</p><br><p></p></div>

Photoreaktionen von Dekacarbonyldirhenium mit Allen und unverzweigten Allenderivaten / Photoreactions of Decacarbonyldirhenium with Allene and Unbranched Derivatives of Allene

1995 ◽  
Vol 50 (4) ◽  
pp. 649-660 ◽  
Author(s):  
Cornelius G. Kreiter ◽  
Wolfgang Michels ◽  
Gerhard Heeb
Keyword(s):  
Nmr Spectra ◽  
Crystal And Molecular Structure ◽  
Reaction Products ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Oxidative Rearrangement ◽  
Dirhenium Complexes ◽  
Derivatives Of ◽  
By Products

Decacarbonyldirhenium (1) reacts upon UV irradiation with allene (2), 1,2-butadiene (3) and 2,3-pentadiene (4) preferentially by CO substitution and oxidative rearrangement to the corresponding enneacarbonyl-μ-η1:3-endiyl-dirhenium complexes 5, 9, and 15 and to the octacarbonyl-μ-η2:2-allene-dirhenium complexes 6, the stereoisomers 10, 11, and 16. At elevated temperature 5, 9, and 15 loose CO and yield by a reductive rearrangement also the complexes 6, 10, 11, and 16. In addition to these main products, depending upon the allene derivative used, various by-products are obtained.By-products of the reaction o f 1 with 2 are octacarbonyl-μ-η3:3-(2,3-dimethylene-buta-1,4- diyl)dirhenium (7) and μ-η2:2-allene-hexacarbonyl-μ-η1:3-1-propene-1,3-diyl-dirheniurn (8). The photo reaction of 1 with 3 yields, in addition to 9-11, tetracarbonyl-η3-(E-5-ethylidene- 4-methyl-2-cyclopenten-1-yl)rhenium (12) and tetracarbonyl-η3-(Z-5-ethyliden-4- methyl-2-cyclopenten-1-yl)rhenium (13) as a mixture of isomers. 1 and 4 form the by-products tetracarbonyl-η3-(EZ-3-penten-2-yl)rhenium (17), tetracarbonyl-η3-(EE-3-penten-2-yl)rhenium (18) and heptacarbonyl-μ-η1:2:1:2-(4,5-dimethyl-2,6-octadiene-3,6-diyl)dirhenium (19) with an unusually bridging and chelating ligand. The constitutions of the reaction products have been concluded from the IR and 1H NMR spectra. For 19 the crystal and molecular structure has been determined by X-ray diffraction analysis.

ÉTUDES SUR LA SYNTHÈSE DE L’HYDROXYPROLINE À PARTIR DE DÉRIVÉS DE L’ACIDE 2-AMINO-4-PENTÈNOÏQUE

1956 ◽  
Vol 34 (4) ◽  
pp. 502-514 ◽  
Author(s):  
Roger Gaudry ◽  
Louis Berlinguet ◽  
André Langis ◽  
Gérard Paris
Keyword(s):  
Double Bond ◽  
Acid Hydrolysis ◽  
Malonic Acid ◽  
Systematic Investigation ◽  
Carboxyl Group ◽  
Reaction Products ◽  
Pentanoic Acid ◽  
Copper Salts ◽  
Halogenation Reaction ◽  
Derivatives Of

A systematic investigation of the synthesis of 4-hydroxy-DL-proline and 2-amino-4-dihydroxyvaleric acid has been made, starting from the following derivatives of 2-amino-4-pentenoic acid: ethyl allylacetamidomalonate, ethyl allylacetamidocyanoacetate, 2-phthalimidopentenoic acid, allylacetamido-malonic acid, acetylallylglycine, 5-allylhydantoin, and 3-phenyl-5-allylhydantoin. Chlorine or bromine was added to the double bond of these compounds, and the reaction products were either derivatives of 5-halogenated-4-valerolactones or derivatives of 4,5-dihalogenated pentanoic acids, depending on whether the carboxyl group of the pentanoic acid was free or not when the halogenation reaction was carried out. Acid hydrolysis followed by treatment with barium hydroxide always gave mixtures, in different ratio, of 4-hydroxy-DL-proline and 2-amino-4,5-dihydroxyvaleric acid which were analyzed and isolated as the copper salts. In the case of 5-(2,3-dibromopropyl)hydantoin and 3-phenyl-5-(2,3-dibromopropyl)hydantoin, no cyclization could be obtained.

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