Kinetics of the HBr‐catalyzed photoisomerization of the allyl halides

Abell, Paul I.; Adolf, Paul K.

doi:10.1002/kin.550010602

Cited by 3 publications

(2 citation statements)

References 13 publications

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“…2 + PhCH= CH2 CH2CH2CH -Ph (10) 3 + Cu2+ Due to the very high values of kx and k2, reactions 1 and 2 are suitable for kinetic studies only with very reactive substrates. Also the rate of reaction 3 is influenced by the medium, as it strictly depends on the monomer-dimer equilibrium13 (eq 4).…”

Section: Rch2ch2 + Cucl2mentioning

confidence: 99%

Nucleophilic character of alkyl radicals. 18. Absolute rate constants for the addition of primary alkyl radicals to conjugated olefins and 1,4-benzoquinone

Citterio¹,

Arnoldi²,

Minisci³

1979

J. Org. Chem.

116

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The rate constants for the addition of the 5-hexenyl radical to styrene, -methylstyrene, butadiene, acrylic monomers, methyl vinyl ketone, and 1,4-benzoquinone were measured from 16 to 69 °C. The importance of polar effects, due to the nucleophilic character of the alkyl radical in olefin addition, is emphasized. The inhibition of chain processes by quinone is discussed in terms of the high rate constant (2.0 X 107 L mol"1 s'1 at 69 °C) of the alkyl radical addition to 1,4-benzoquinone.

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Section: Rch2ch2 + Cucl2mentioning

confidence: 99%

Nucleophilic character of alkyl radicals. 18. Absolute rate constants for the addition of primary alkyl radicals to conjugated olefins and 1,4-benzoquinone

Citterio¹,

Arnoldi²,

Minisci³

1979

J. Org. Chem.

116

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“…activation energy of the secondary fragmentation processes, reactions (3) and (7), are approximately equal to 50.4 kcal mole-l [12,13].' This value is probably the actual value f 3 kcal mole-'.…”

Section: 1mentioning

confidence: 97%

The vacuum UV photolysis of various C₄ and C₅ olefins: The energy content of the α‐ and β‐methallyl fragments

Collin

Deslauriers

1980

Int J of Chemical Kinetics

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Abstract111 recent puhlicatiuiis I r o m this lahoratory. we have shown that the tragnientatiuii ol' photoexcited olel'inic moleculeh in the vacuum 1IV region leads mainly hi the cleavage ot'a ( ' 'I'he ally1 fragment hear> auav part 01 the excess energy ul the photoii. A t low pressure, this excited radical is capable t i t undergoing further decomposition. F r o m the pressure eftect. we were able to measure the Iir5t order rate constant for this secondary trapmentation. In this paper we shall use HRKM ( alculations in order to get a hetter idea un how the energy is distributed among the p r i m a r y l r a g m r n t x In cabes where cr. and 3 meLhallyl radicals were involved. the results show that iiii i i n p i r t a n t part ot'the excess energy is l w a t e t l in the methallyl fragment in t h e 7.1 a n d 7.6 r\' photolysis uf :]-methyl 1 butene. '-methyl. I -hutene. a i i d ( i.\-?-pentene.( * hind located in the 13 pusition r e l a t i t c t o the doublr bond

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Kinetics of the I₂‐catalyzed isomerization of allyl chloride to cis‐ and trans‐1‐chloro‐1‐propene. The stabilization energy of the chloroallyl radical

Alfassi

Golden

Benson

1973

Int J of Chemical Kinetics

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The I 2-catalyzed isomerization of allyl chloride to cis-and tmns-1 -chloro-l-propene was measured in a static system in the temperature range 225-329°C. Propylene was found as a side product, mainly at thr lower temperatures. The rate constant for an abstraction of a hydrogen atom from allyl chloride by an iodine atom was found to obey the equationUsing this activation energy together with 1 rt 1 kcal/mole for the activation energy for the reaction of H I with alkyl radicals gives DHO (CH2CHCHCI-H) = 88.6 =t 1.1 kcal/mole, and 7.4 i 1.5 kcal/mole as the stabilization energy (SE) of the chloroallyl radical. Using the results of Abell and Adolf on allyl fluoride and allyl bromide, we conclude DHO (CHZCHCHF-H) = 88.6 f 1.1 and DH" (CHtCHCHBr-H) = 89.4 =k 1.1 kcal/ mole; the SE of the corresponding radicals are 7.4 i 2.2 and 7.8 i 1.5 kcal/mole. The bond dissociation energies of the C-H bonds in the allyl halides are similar to that of propene, while the SE values are about 2 kcal/mole less than in the allyl radical, resulting perhaps more from the stabilization of alkyl radicals by a-halogen atoms than from differences in the unsaturated systems.

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Kinetics of the HBr‐catalyzed photoisomerization of the allyl halides

Cited by 3 publications

References 13 publications

Nucleophilic character of alkyl radicals. 18. Absolute rate constants for the addition of primary alkyl radicals to conjugated olefins and 1,4-benzoquinone

Nucleophilic character of alkyl radicals. 18. Absolute rate constants for the addition of primary alkyl radicals to conjugated olefins and 1,4-benzoquinone

The vacuum UV photolysis of various C₄ and C₅ olefins: The energy content of the α‐ and β‐methallyl fragments

Kinetics of the I₂‐catalyzed isomerization of allyl chloride to cis‐ and trans‐1‐chloro‐1‐propene. The stabilization energy of the chloroallyl radical

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Kinetics of the HBr‐catalyzed photoisomerization of the allyl halides

Cited by 3 publications

References 13 publications

Nucleophilic character of alkyl radicals. 18. Absolute rate constants for the addition of primary alkyl radicals to conjugated olefins and 1,4-benzoquinone

Nucleophilic character of alkyl radicals. 18. Absolute rate constants for the addition of primary alkyl radicals to conjugated olefins and 1,4-benzoquinone

The vacuum UV photolysis of various C4 and C5 olefins: The energy content of the α‐ and β‐methallyl fragments

Kinetics of the I2‐catalyzed isomerization of allyl chloride to cis‐ and trans‐1‐chloro‐1‐propene. The stabilization energy of the chloroallyl radical

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The vacuum UV photolysis of various C₄ and C₅ olefins: The energy content of the α‐ and β‐methallyl fragments

Kinetics of the I₂‐catalyzed isomerization of allyl chloride to cis‐ and trans‐1‐chloro‐1‐propene. The stabilization energy of the chloroallyl radical