ChemInform Abstract: THE STRUCTURES OF TWO REACTION PRODUCTS OF DI-TERT.-BUTYLACETYLENE WITH DIIRON NONACARBONYL. A NEW IRON-IRON DOUBLE BOND

1975 ◽  
Vol 6 (51) ◽  
pp. no-no
Author(s):  
F. A. COTTON ◽  
J. D. JAMERSON ◽  
B. R. STULTS
Keyword(s):  
Double Bond ◽  
Reaction Products ◽  
Iron Iron

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.

The gaseous oxidation of 2-methyl-but-2-ene. I. Kinetic and analytical studies

1961 ◽  
Vol 262 (1310) ◽  
pp. 318-327 ◽  
Keyword(s):  
Double Bond ◽  
Methyl Alcohol ◽  
Initial Pressure ◽  
Pressure Increase ◽  
Reaction Products ◽  
Initial Attack ◽  
Primary Reaction ◽  
Slow Combustion ◽  
Propyl Ketone ◽  
Parallel Fashion

In the slow combustion of 2-methyl-but-2-ene at ca . 250 °C, an initial pressure decrease, which represents the formation of peroxidic intermediates, is followed by an autocatalytic pressure increase during which little olefin is consumed and the main processes are break ­ down and further oxidation of primary reaction products. Acetone and acetaldehyde are the principal early non-peroxidic products and these are formed initially in equivalent quantities and in closely parallel fashion. Methyl iso propyl ketone is produced in somewhat smaller amounts and methyl alcohol, which appears comparatively late in the reaction, probably arises from the oxidation of acetaldehyde. The results suggest that the predominant mode of initial attack of the olefin is addition of oxygen to the double bond followed by decomposition of the resulting cyclic peroxides, although some hydroperoxylation also occurs.

RELATIVE RATES OF REACTION OF OZONE WITH OLEFINS IN THE VAPOR PHASE

1960 ◽  
Vol 38 (7) ◽  
pp. 1053-1062 ◽  
Author(s):  
T. Vrbaski ◽  
R. J. Cvetanović
Keyword(s):  
Double Bond ◽  
Carbon Atom ◽  
Vapor Phase ◽  
Reaction Products ◽  
Initial Formation ◽  
Inhibiting Effect ◽  
Π Complex ◽  
Olefinic Double Bond

Relative rates of reaction of ozone with a number of olefins in the vapor phase have been determined by the use of the competitive method and GLC analysis of the reaction products. The results indicate a basic electrophilic trend onto which is superimposed a trend due to a partially inhibiting effect of the substituent groups, in particular of those on the more substituted carbon atom of the olefinic double bond. The results are discussed particularly in terms of a two-step addition process, involving an initial formation of an ozone–olefin π-complex and a slower rearrangement of the π-complex into the cyclic "initial ozonide".

Tetracarbonyldi-µ-2,2,5,5-tetramethylhex-3-yne-di-iron. A novel complex containing an iron–iron double bond

1971 ◽  
Vol 0 (12) ◽  
pp. 608-608 ◽  
Author(s):  
K. Nicholas ◽  
Linda S. Bray ◽  
Raymond E. Davis ◽  
R. Pettit
Keyword(s):  
Double Bond ◽  
Iron Iron ◽  
Novel Complex

scholarly journals The initial stages of the dehydrogenation and isomeric change of allyl alcohol

1926 ◽  
Vol 113 (764) ◽  
pp. 254-258 ◽  
Keyword(s):  
Carbon Monoxide ◽  
Elevated Temperature ◽  
Double Bond ◽  
Allyl Alcohol ◽  
Catalytic Decomposition ◽  
Unsaturated Alcohol ◽  
Reaction Products ◽  
Brass Tube ◽  
Saturated Aldehyde ◽  
Lower Temperature

The catalytic decomposition of allyl alcohol has been studied by Ipatiev, who passed the vapour through a brass tube filled with brass filings maintained at 600° C. He found hydrogen and acrolein, some propylene and carbon monoxide, with a little divinyl in the reaction products, showing that under these conditions of elevated temperature very little hydrogenation of the double bond of the unsaturated alcohol takes place. Sabatier and Senderensf used reduced copper as catalyst at temperatures varying from 180-300° C. They found that a yield of over 50 per cent, of propionaldehyde could be obtained and only a little acrolein and hydrogen. The lower temperature seems to favour the production of the saturated aldehyde. The observations of Moureu and Boismenu have shown that acrolein is very appreciably hydrogenated by copper at temperatures between 110 and 250° C. At 300° C. the destruction of the acrolein is very rapid. It is evident, therefore, that there are two reactions to be followed in the initial stages of the dehydrogenation of allyl alcohol by copper CH 2 ═ CH . CH 2 OH— ↗CH 3 . CH 2 . CHO ↘ CH 2 = CH. CHO + H 2 A detailed study was made of these two reactions to attempt to throw light on the state of the adsorbed molecules, and to consider in detail the mechanism of the two reactions and the connection between them.

scholarly journals Different pathways of the formation of highly oxidized multifunctional organic compounds (HOMs) from the gas-phase ozonolysis of <i>β</i>-caryophyllene

2016 ◽  
Vol 16 (15) ◽  
pp. 9831-9845 ◽  
Author(s):  
Stefanie Richters ◽  
Hartmut Herrmann ◽  
Torsten Berndt
Keyword(s):  
Double Bond ◽  
Gas Phase ◽  
Organic Compounds ◽  
Atmospheric Pressure ◽  
Reaction System ◽  
Peroxy Radical ◽  
Closed Shell ◽  
Atmospheric Conditions ◽  
Reaction Products ◽  
Product Analysis

Abstract. The gas-phase mechanism of the formation of highly oxidized multifunctional organic compounds (HOMs) from the ozonolysis of β-caryophyllene was investigated in a free-jet flow system at atmospheric pressure and a temperature of 295 ± 2 K. Reaction products, mainly highly oxidized RO2 radicals containing up to 14 oxygen atoms, were detected using chemical ionization – atmospheric pressure interface – time-of-flight mass spectrometry with nitrate and acetate ionization. These highly oxidized RO2 radicals react with NO, NO2, HO2 and other RO2 radicals under atmospheric conditions forming the first-generation HOM closed-shell products. Mechanistic information on the formation of the highly oxidized RO2 radicals is based on results obtained with isotopically labelled ozone (18O3) in the ozonolysis reaction and from hydrogen/deuterium (H/D) exchange experiments of acidic H atoms in the products. The experimental findings indicate that HOM formation in this reaction system is considerably influenced by the presence of a double bond in the RO2 radicals primarily formed from the β-caryophyllene ozonolysis. Three different reaction types for HOM formation can be proposed, allowing for an explanation of the detected main products: (i) the simple autoxidation, corresponding to the repetitive reaction sequence of intramolecular H-abstraction of a RO2 radical, RO2  →  QOOH, and subsequent O2 addition, next forming a peroxy radical, QOOH + O2  →  R′O2; (ii) an extended autoxidation mechanism additionally involving the internal reaction of a RO2 radical with a double bond forming most likely an endoperoxide and (iii) an extended autoxidation mechanism including CO2 elimination. The individual reaction steps of the reaction types (ii) and (iii) are uncertain at the moment. From the product analysis it can be followed that the simple autoxidation mechanism accounts only for about one-third of the formed HOMs. Time-dependent measurements showed that the HOM formation proceeds at a timescale of 3 s or less under the concentration regime applied here. The new reaction pathways represent an extension of the mechanistic understanding of HOM formation via autoxidation in the atmosphere, as recently discovered from laboratory investigations on monoterpene ozonolysis.

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