MOLECULAR REARRANGEMENTS IN THE REACTIONS OF OXYGEN ATOMS WITH OLEFINS

1958 ◽  
Vol 36 (4) ◽  
pp. 623-634 ◽  
Author(s):  
R. J. Cvetanović
Keyword(s):  
Double Bond ◽  
Carbon Atom ◽  
Internal Migration ◽  
Degrees Of Freedom ◽  
Large Fraction ◽  
Heats Of Reaction ◽  
Trans Butene ◽  
Pressure Independent ◽  
Olefinic Double Bond ◽  
Oxygen Atoms

Reactions of oxygen atoms with propylene, butene-1, iso-butene, cis-butene-2, trans-butene-2, cis-pentene-2, and tetramethyl ethylene have been studied at room temperature and at pressures between 50 and 600 mm. The following generalizations can be made. The oxygen atom adds predominantly to the "less-substituted" carbon atom of the olefinic double bond to form a short-lived biradical which rapidly rearranges into isomeric epoxy and carbonyl compounds. Rearrangements involve migration of radicals (including H atoms) from the carbon atom to which oxygen is attached to the other carbon atom of the original double bond. Partly inhibited rotation around the original double bond also takes place. Migration of H atoms is exclusively internal. Migration of larger radicals, such as CH3, is only partly internal: a large fraction of these radicals become completely detached from the rest of the molecule and the particular carbonyl compound is produced both by radical combination and by internal migration. The fragmentation resulting from the splitting off of a migrating radical is pressure independent. The final addition products formed are "hot" as a result of high heats of reaction and undergo decomposition if the excess energy is not removed by collisions. This second type of fragmentation is, therefore, pressure dependent. It is very extensive in the case of ethylene and appears to be completely suppressed in the investigated pressure range in the case of more complex olefins (possessing a greater number of degrees of freedom) such as butenes and higher homologues. Propylene exhibits an intermediate behavior. For orientation of addition of oxygen atoms a carbon atom of an olefinic double bond to which CH3 is attached is "less substituted" than a corresponding carbon atom to which C2H5 is attached.

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".

17O nuclear magnetic resonance:mutual effect between two β oxygen atoms and α,β double bond effect on 17O chemical shift

Tetrahedron ◽  
1980 ◽  
Vol 36 (23) ◽  
pp. 3431-3435 ◽  
Author(s):  
Jean-Pirre Kintzinger ◽  
Claude Delseth ◽  
T.Thanh-tâm nguyên
Keyword(s):  
Double Bond ◽  
Chemical Shift ◽  
Bond Effect ◽  
Nuclear Magnetic ◽  
Oxygen Atoms

ChemInform Abstract: Electroreduction of the Activated Olefinic Double Bond in Some 2-Aryl-1(2-acetylamino-1,3,4-thiadiazol-5-yl)-propionitrile Derivatives

ChemInform ◽  
1987 ◽  
Vol 18 (23) ◽  
Author(s):  
M. ABDEL AZZEM ◽  
M. M. M. RAMIZ ◽  
E. A. GHALI ◽  
H. M. FAHMY ◽  
M. R. H. ELMOGHAYAR
Keyword(s):  
Double Bond ◽  
Olefinic Double Bond

REACTION OF OXYGEN ATOMS WITH BUTADIENE

1960 ◽  
Vol 38 (11) ◽  
pp. 2187-2195 ◽  
Author(s):  
R. J. Cvetanović ◽  
L. C. Doyle
Keyword(s):  
Pressure Dependence ◽  
Rate Constants ◽  
Room Temperature ◽  
Relative Rate ◽  
Excess Energy ◽  
General Mechanism ◽  
Arrhenius Parameters ◽  
Heats Of Reaction ◽  
Relative Rate Constants ◽  
Oxygen Atoms

Reaction of oxygen atoms with 1,3-butadiene has been investigated at room temperature. It is found that it conforms to the general mechanism established previously for the analogous reactions of monoolefins. Only 1,2-addition occurs, and the addition products, butadiene monoxide and 3-butenal, possess excess energy when formed as a result of high heats of reaction. The pressure dependence of the formation of the addition products yields the values of the "lifetimes" of the initially produced "hot" molecules. The relative rate constants have been determined at 25 and 127 °C and from these the relative values of the Arrhenius parameters have been calculated.

Oxydation du cyclohexène par le nitrate cérique d'ammonium

1974 ◽  
Vol 52 (18) ◽  
pp. 3201-3205 ◽  
Author(s):  
Claude Briguet ◽  
Christian Freppel ◽  
Jean-Claude Richer ◽  
Miklos Zador
Keyword(s):  
Double Bond ◽  
Ammonium Nitrate ◽  
Ceric Ammonium Nitrate ◽  
Olefinic Double Bond

The oxidation of cyclohexene by ceric ammonium nitrate has been studied. In anhydrous DMSO the reaction leads to cyclohexene-3-nitrate, while in acetonitrile N-(cyclohexene-2-yl) acetamide is formed. Hydroxylated products are formed in the presence of water. The results obtained are explained in terms of the formation of an intermediate arising from the addition of the radical NO3• to the olefinic double bond. [Journal translation]

Electrochemical Heterodifunctionalization of α-CF3 Alkenes to Access α-Trifluoromethyl-β-sulfonyl Tertiary Alcohols

2021 ◽  
Author(s):  
Zhi-Peng Ye ◽  
Jie Gao ◽  
Xin-Yu Duan ◽  
Jianping Guan ◽  
Fang Liu ◽  
...  
Keyword(s):  
Double Bond ◽  
Hydroxyl Group ◽  
Tertiary Alcohols ◽  
Olefinic Double Bond

An unprecedented electrochemical heterodifunctionalization of α-CF3 alkenes with benzenesulfonyl hydrazides was accomplished in this work, wherein a β-sulfonyl and a α-hydroxyl group were simultaneously incorporated across the olefinic double bond...

Heterometallische Cluster durch ligandunterstützte Metallfragmentkondensation / Heterometallic Clusters by Ligand Assisted Metal Fragment Condensation

1991 ◽  
Vol 46 (9) ◽  
pp. 1169-1176 ◽  
Author(s):  
Wolfgang Rohde ◽  
Gert Fendesak
Keyword(s):  
Double Bond ◽  
Chelate Complexes ◽  
Heterometallic Clusters ◽  
X Ray ◽  
X Ray Crystallography ◽  
Inert Solvent ◽  
Fragment Condensation ◽  
Olefinic Double Bond ◽  
High Yields ◽  
Iron Fragment

Dicobalt complexes of 3-vinylpropargylic alcohol derivatives react with biscyclooctenetricarbonyliron to give new chelate complexes of the iron tricarbonyl fragment with the olefinic double bond and the alcohol oxygen atom bound to the iron fragment. These compounds react upon heating in an inert solvent to give FeCo-alkynyl cluster complexes in high yields. One of these compounds has been structurally characterized by X-ray crystallography.

scholarly journals Coordination of Sodium Cation to an Oxygen Function and Olefinic Double Bond to Form Molecular Adduct Ion in Fast Atom Bombardment Mass Spectrometry

2002 ◽  
Vol 50 (7) ◽  
pp. 935-940 ◽  
Author(s):  
Naoko Morisaki ◽  
Hisayoshi Kobayashi ◽  
Yumiko Yamamura ◽  
Masuo Morisaki ◽  
Kazuo Nagasawa ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Double Bond ◽  
Fast Atom Bombardment ◽  
Sodium Cation ◽  
Molecular Adduct ◽  
Olefinic Double Bond

Group 6 metal carbonyl complexes of tridentate olefinic tertiary diphosphines. Crystal and molecular structure of {(E)-1,3-Bis[2-(diphenylphosphino)phenyl]-propene}tricarbonyltungsten(0),W(CO)3 {(E)-o-Ph2PC6H4CH=CHC6H4PPh2-o}

1980 ◽  
Vol 33 (6) ◽  
pp. 1261 ◽  
Author(s):  
MA Bennett ◽  
S Corlett ◽  
GB Robertson ◽  
WL Steffen
Keyword(s):  
Molecular Structure ◽  
Double Bond ◽  
Crystal And Molecular Structure ◽  
Heavy Atom ◽  
Metal Carbonyl ◽  
Free Ligand ◽  
Spectroscopic Studies ◽  
Carbonyl Complexes ◽  
X Ray Diffraction ◽  
Olefinic Double Bond

The ligands (L) (E)-2,2'-bis(diphenylphosphino)stilbene, (E)-o-Ph2PC6H4CH=CHC6H4PPh2-o (bdps), (E)-1,3-bis[2-(diphenylphosphino)phenyl]propene, (E)-o-Ph2PC6H4CH=CHCH2C6H4PPh2-o (bdpp), and (E)-1,3-bis[2-(diphenylphosphino)phenyl]but-1-ene,( E)-o-Ph2PC6H4CH=CHCHMeC6- H4PPh2-o (bdpb), form complexes of general formula M(CO)3L (M = Cr, Mo, W). N.m.r. (1H, 13C and 31P) and i.r. data indicate that the metal atoms are octahedrally coordinated by mutually trans phosphorus atoms and the double bond of the olefinic tertiary diphosphines and by meridionally disposed carbonyl groups. Conformational isomers of the complexes of bdpb can be detected by n.m.r, spectroscopy, but there is no evidence for similar conformers in the corresponding complexes of bdps and bdpp. The crystal and molecular structure of W(CO)3(bdpp),0.5CH2C12 has been determined by single-crystal X-ray diffraction analysis. The crystals are triclinic, space group PI, with a 10.1 13(Z), b 13.820(2), c 14.512(3) A, α 76.24(1), β 88.08(1), γ 76.31(1)°. The structure, solved by the heavy-atom method and refined to a conventional R of 0.049 for 8418 diffractometer data, confirms the conclusions drawn from spectroscopic studies. The olefinic double bond of bdpp is attached symmetrically to the metal atom [W-C(olefin) 2.403(8), 2.387(9) Ǻ] and is roughly parallel to the P-W-P axis. The C=C bond length of 1.359(11) Ǻ is only slightly longer than that expected for the free ligand and is indicative of relatively weak metal-olefin back-bonding. Other important bond lengths are: W-P 2.450(2), 2.462(2) Ǻ and W-C(C0) 2.020(7), 2.024(7) Ǻ (CO trans to CO) and 1.971(7) Ǻ (CO trans to olefin).

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