HBr catalyzed photoisomerization of allyl halides

Abell, Paul I.; Adolf, Paul K.

doi:10.1016/0021-9614(69)90062-7

Cited by 19 publications

(7 citation statements)

References 7 publications

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“…However, the substitution product ( Z )-3 is not usually the more stable isomer and cannot be a thermodynamic product; 1-chloropropene ( 3a ) is slightly more stable in the ( Z ) configuration than in the ( E ) form, and the ( E ) isomer becomes progressively more stable as the β-alkyl group of 1-chloro-1-alkene 3 becomes bulkier ,10a Therefore, our failure to observe the products of a nucleophilic substitution reaction of chloride ion with the ( Z ) isomer of 1 does not affect our earlier conclusion that nucleophilic substitution reactions at the vinylic carbon of 1 occur with inversion of configuration.…”

Section: Discussionmentioning

confidence: 67%

In-Plane Vinylic S_N2 Substitution and Intramolecular β Elimination of β-Alkylvinyl(chloro)-λ³-iodanes

et al. 1998

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The reactions of four (E)-β-alkylvinyl(phenyl)iodonium salts with chloride ion were examined in acetonitrile and in several other solvents at 25 °C. The β-methyl-, β-octyl-, and β-isopropyl-substituted iodonium salts undergo competitive bimolecular nucleophilic substitution to form the corresponding (Z)-1-chloro-1-alkene with inversion of configuration at the vinylic carbon and elimination to form the 1-alkyne. The β-tert-butyl-substituted iodonium salt affords only the products of the elimination reaction. The UV absorption spectra of the reactants show the rapid coversion of chloride and iodonium ions to an equilibrium mixture of the corresponding chloro-λ3-iodane, with an association constant of 5600−7600 mol-1 dm3. A kinetic analysis shows that most of the substitution and elimination products form from reaction of the λ3-iodane. Evidence is presented that the substitution reaction proceeds by a concerted bimolecular SN2 mechanism and that the elimination reaction proceeds by a unimolecular reaction mechanism with intramolecular transfer of the β-proton to the leaving group.

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Section: Discussionmentioning

confidence: 67%

In-Plane Vinylic S_N2 Substitution and Intramolecular β Elimination of β-Alkylvinyl(chloro)-λ³-iodanes

et al. 1998

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“…We are aware of two works reporting these equilibria. , Although the enthalpies of the Z/E isomerization of 1-propenes are consistent, the enthalpies of isomerization of 3-fluoropropene differ by 8 kJ·mol –1 . This cannot be explained by their temperature difference.…”

Section: Resultsmentioning

confidence: 95%

Critical Evaluation of the Enthalpies of Formation for Fluorinated Compounds Using Experimental Data and High-Level Ab Initio Calculations

Paulechka

Kazakov

2019

J. Chem. Eng. Data

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The ab initio method for the prediction of the enthalpies of formation for CHON-containing organic compounds proposed earlier (Paulechka, E.; Kazakov, A. J. Chem. Theory Comput. 2018, 14, 5920−5932) has been extended to their fluorinated derivatives. A single experimental Δ f H°m is typically available for compounds in this scope. Thus, a priori evaluation of the data quality was found to be inefficient despite all available experimental data for C 1 −C 3 hydrofluorocarbons and 34 data points for medium-sized organofluorine compounds being considered. The training set was derived by analyzing the consistency of the experimental and predicted values and the removal of outliers. Significant issues with the experimental data, including inconsistency across different laboratories, were identified, and potential causes for these problems were discussed. A conservative estimate of uncertainty for the experimental Δ f H°m of organofluorine compounds was proposed.

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“…1965, 610-1. 8 Hiñe, J. "Structural Effects on Equilibria in Organic Chemistry"; Wiley-Interscience: New York, 1975, p 66. h Taken to be the same as for X = .…”

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confidence: 99%

Structural effects on rates and equilibriums. 26. Effects of 57 substituents on the stabilities of carbon-carbon double bonds

Hine¹,

Skoglund²

1982

J. Org. Chem.

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l-Phenyl-3-o -toly 1-1-propanol. A slurry of 5.90 g (155 mmol) of LiAlH4 in 200 mL of ether was added dropwise to a stirred solution of 35.44 g (155 mmol) of 2-methylchalcone in 250 mL of ether. After 3 hat reflux, the solution was quenched with water and then 5% HC1 until it was acidic. The brine-washed, dried (MgS04) ether layer was concentrated and distilled to give 31.0 g (88%) of the alcohol: bp 155 °C (0.25 mmHg); IR (film) 3350

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HBr catalyzed photoisomerization of allyl halides

Cited by 19 publications

References 7 publications

In-Plane Vinylic S_N2 Substitution and Intramolecular β Elimination of β-Alkylvinyl(chloro)-λ³-iodanes

In-Plane Vinylic S_N2 Substitution and Intramolecular β Elimination of β-Alkylvinyl(chloro)-λ³-iodanes

Critical Evaluation of the Enthalpies of Formation for Fluorinated Compounds Using Experimental Data and High-Level Ab Initio Calculations

Structural effects on rates and equilibriums. 26. Effects of 57 substituents on the stabilities of carbon-carbon double bonds

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HBr catalyzed photoisomerization of allyl halides

Cited by 19 publications

References 7 publications

In-Plane Vinylic SN2 Substitution and Intramolecular β Elimination of β-Alkylvinyl(chloro)-λ3-iodanes

In-Plane Vinylic SN2 Substitution and Intramolecular β Elimination of β-Alkylvinyl(chloro)-λ3-iodanes

Critical Evaluation of the Enthalpies of Formation for Fluorinated Compounds Using Experimental Data and High-Level Ab Initio Calculations

Structural effects on rates and equilibriums. 26. Effects of 57 substituents on the stabilities of carbon-carbon double bonds

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In-Plane Vinylic S_N2 Substitution and Intramolecular β Elimination of β-Alkylvinyl(chloro)-λ³-iodanes

In-Plane Vinylic S_N2 Substitution and Intramolecular β Elimination of β-Alkylvinyl(chloro)-λ³-iodanes