Acid Catalyzed Rearrangements of Structurally Constrained Tricarbonyl(trans-pentadienyl)iron Cations

1974 ◽  
Vol 52 (11) ◽  
pp. 2085-2097 ◽  
Author(s):  
C. R. Jablonski ◽  
T. S. Sorensen
Keyword(s):  
Positive Charge ◽  
Strong Acid ◽  
Order Process ◽  
Iron Cation ◽  
Acid Media ◽  
First Order ◽  
Bond Rotation ◽  
Carbonium Ions ◽  
Acid Catalyzed ◽  
Secondary Ion

Both the tricarbonyl(1,4-dimethylene-cis, cis, trans, cis-hexa-1,3-dienyl)iron (secondary) and the tricarbonyl(1,4-dimethylene-5-methyl-cis, cis, trans-hexa-1,3-dienyl)iron (tertiary) cations, which cannot convert to a 5h-cis pentadienyl system via a simple bond rotation, can be prepared at low temperature in strong acid media from their related alcohol complexes. The secondary as well as the tertiary ions rearrange to give the thermodynamically more stable tricarbonyl-(1-alkylcyclohexa-1,3-dienyl)iron cation via an acid catalyzed pseudo first order process. The rate of rearrangement of the secondary ion is much faster than that of the tertiary ion indicating a substantial amount of residual positive charge on the exocyclic (β) carbon in the complexed trans-pentadienyl carbonium ions.

Acid-catalyzed cyclization reactions. XII. Rearrangement of N-acylaziridines in strong acid media

1976 ◽  
Vol 41 (11) ◽  
pp. 1895-1899 ◽  
Author(s):  
Samuel P. McManus ◽  
Richard A. Hearn ◽  
Charles U. Pittman
Keyword(s):  
Strong Acid ◽  
Cyclization Reactions ◽  
Acid Media ◽  
Acid Catalyzed

Styrene hydration and stilbene isomerization in strong acid media. An excess acidity analysis

1999 ◽  
Vol 77 (5-6) ◽  
pp. 709-718 ◽  
Author(s):  
Robin A Cox
Keyword(s):  
Proton Transfer ◽  
Transition State ◽  
Positive Charge ◽  
Isotope Effects ◽  
Activation Parameters ◽  
Strong Acid ◽  
Analysis Data ◽  
The Other ◽  
Acid Media ◽  
Solvent Isotope

Rate constants obtained for the hydration of some ring-substituted styrenes, YC6H4CR=CH2 (R = H, CH3, CF3) (1-3), and for the isomerization of some cis-stilbenes substituted in both rings, YC6H4CH=CHC6H4Z (4), in aqueous H2SO4, D2SO4, and HClO4 media at 25°C and, in some cases, at other temperatures, have been subjected to an excess acidity analysis. Data obtained by different groups and in different media for the same substrates agree very well. The m‡ values obtained show that all the substrates react via the A-SE2 mechanism, rate-determining proton transfer to carbon; the transition state is late, with the proton transfer being about three-quarters complete. The reactivities of 1-3 in the aqueous standard state are obtained by extrapolation; they are 1:103:10-7, respectively. The stilbenes are relatively unreactive; log k0 values for compounds with substituents in the ring adjacent to the developing positive charge show a good correlation with σ+ with a large negative ρ+ value, but those for compounds with substituents in the other ring correlate with σ with a small negative ρ. Extrapolated log k0 values for 1 and 3 show a good correlation with σ+, but those for 2 correlate with neither σ+ nor σ, because the α-CH3 group twists the molecule and reduces the resonance interaction of ring substituents with the developing positive charge. On the other hand, this effect is not seen in 3, when the strongly deactivating α-CF3 group is present, meaning that the transition state is forced to be planar in this case. The activation parameters, solvent isotope effects, and excess acidity slope parameters m‡m* obtained in the analysis are tabulated and discussed. The parameters obtained for the parent styrenes 1 are very similar to those previously obtained for the phenylacetylenes YC6H4Ctriple bondCH, meaning that reactions with vinyl cation intermediates and reactions with benzyl cation intermediates can be quite similar. Key words: styrenes, stilbenes, hydration, excess acidity, LFER, mechanism.

Isobutane from acid-catalyzed dehydration of butanols

1970 ◽  
Vol 48 (22) ◽  
pp. 3545-3548 ◽  
Author(s):  
John Warkentin ◽  
Kenneth E. Hine
Keyword(s):  
Acid Solution ◽  
Hydride Transfer ◽  
Strong Acid ◽  
Isomeric Butanols ◽  
Carbonium Ions ◽  
Acid Catalyzed

Dehydration of the four isomeric butanols by strong acid at about 160° gives a C4-fraction containing isobutane as well as the isomeric butenes. Isobutane probably arises by hydride transfer, from one or more donors including the substrate alcohol and hydrocarbons formed from it in the medium, to one or more carbonium ions including the t-butyl cation. Materials which react with 2,4-dinitrophenylhydrazine reagent to form 2,4-dinitrophenylhydrazones can be swept out of the hot acid solution with a stream of nitrogen.

The effect of polymeric and model imidazolium halides on the rate of hydrolysis of 4-acetoxy-3-nitrobenzoic acid

1985 ◽  
Vol 50 (4) ◽  
pp. 845-853 ◽  
Author(s):  
Miloslav Šorm ◽  
Miloslav Procházka ◽  
Jaroslav Kálal
Keyword(s):  
Catalyst Concentration ◽  
Low Molecular Weight ◽  
Imidazolium Chloride ◽  
First Order ◽  
Nitrobenzoic Acid ◽  
Rate Of Hydrolysis ◽  
Acid Catalyzed ◽  
Hydrolysis Of ◽  
Ethanol In Water ◽  
Direct Attack

The course of hydrolysis of an ester, 4-acetoxy-3-nitrobenzoic acid catalyzed with poly(1-methyl-3-allylimidazolium bromide) (IIa), poly[l-methyl-3-(2-propinyl)imidazolium chloride] (IIb) and poly[l-methyl-3-(2-methacryloyloxyethyl)imidazolium bromide] (IIc) in a 28.5% aqueous ethanol was investigated as a function of pH and compared with low-molecular weight models, viz., l-methyl-3-alkylimidazolium bromides (the alkyl group being methyl, propyl, and hexyl, resp). Polymers IIb, IIc possessed a higher activity at pH above 9, while the models were more active at a lower pH with a maximum at pH 7.67. The catalytic activity at the higher pH is attributed to an attack by the OH- group, while at the lower pH it is assigned to a direct attack of water on the substrate. The rate of hydrolysis of 4-acetoxy-3-nitrobenzoic acid is proportional to the catalyst concentration [IIc] and proceeds as a first-order reaction. The hydrolysis depends on the composition of the solvent and was highest at 28.5% (vol.) of ethanol in water. The hydrolysis of a neutral ester, 4-nitrophenyl acetate, was not accelerated by IIc.

Strong acid-catalyzed electrophilic ring expansion of oxetanes and sulfoxonium ylides

2021 ◽  
Vol 510 ◽  
pp. 111687
Author(s):  
Wenhao Yuan ◽  
Wenlai Xie ◽  
Jiaxi Xu
Keyword(s):  
Strong Acid ◽  
Ring Expansion ◽  
Acid Catalyzed

A kinetic standard for precise calibration of spectrophotometer cell temperature.

1981 ◽  
Vol 27 (5) ◽  
pp. 753-755 ◽  
Author(s):  
P A Adams ◽  
M C Berman
Keyword(s):  
Temperature Dependence ◽  
Rate Constants ◽  
Cell Temperature ◽  
First Order ◽  
Order Rate ◽  
Acid Catalyzed ◽  
Pseudo First Order ◽  
Hydrolysis Of

Abstract We describe a simple, highly reproducible kinetic technique for precisely measuring temperature in spectrophotometric systems having reaction cells that are inaccessible to conventional temperature probes. The method is based on the temperature dependence of pseudo-first-order rate constants for the acid-catalyzed hydrolysis of N-o-tolyl-D-glucosylamine. Temperatures of reaction cuvette contents are measured with a precision of +/- 0.05 degrees C (1 SD).

Rearrangement of 1-acylaziridines to oxazolinium cations in strong acid media

1970 ◽  
Vol 35 (4) ◽  
pp. 1187-1190 ◽  
Author(s):  
Charles U. Pittman ◽  
Samuel P. McManus
Keyword(s):  
Strong Acid ◽  
Acid Media

scholarly journals REGENERATION OF VISUAL PURPLE IN SOLUTION

1939 ◽  
Vol 23 (1) ◽  
pp. 21-39 ◽  
Author(s):  
Aurin M. Chase ◽  
Emil L. Smith
Keyword(s):  
Order Process ◽  
First Order ◽  
Color Changes ◽  
Violet Light ◽  
Frog Retina ◽  
Significant Difference ◽  
Kinetics Of ◽  
Photosensitive Substance ◽  
Subsequent Regeneration

1. Measurements of visual purple regeneration in solution have been made by a procedure which minimized distortion of the results by other color changes so that density changes caused by the regenerating substance alone are obtained. 2. Bleaching a visual purple solution with blue and violet light causes a greater subsequent regeneration than does an equivalent bleaching with light which lacks blue and violet. This is due to a photosensitive substance which has a gradually increasing effective absorption toward the shorter wavelengths. It is uncertain whether this substance is a product of visual purple bleaching or is present in the solution before illumination. 3. The regeneration of visual purple measured at 560 mµ is maximal at about pH 6.7 and decreases markedly at more acid and more alkaline pH's. 4. The absorption spectrum of the regenerating material shows only a concentration change during the course of regeneration, but has a higher absorption at the shorter wavelengths than has visual purple before illumination. 5. Visual purple extractions made at various temperatures show no significant difference in per cent of regeneration. 6. The kinetics of regeneration is usually that of a first order process. Successive regenerations in the same solution have the same velocity constant but form smaller total amounts of regenerated substance. 7. In vivo, the frog retina shows no additional oxygen consumption while visual purple is regenerating.

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