1331. Pyrolysis studies. Part XVI. A mechanistic study of the pyrolysis of β-hydroxy-olefins

Smith, Grant Gill; Yates, Brian L.

doi:10.1039/jr9650007242

Cited by 35 publications

(21 citation statements)

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“…From the slope and intercept, where the limits are for one standard deviation. which is consistent with the analogous reaction [4] The AS# is -8.3 gibbs/mole, The group additivity rules of Benson et al [7] have been very successful in predicting AHrO and ASo for many molecules.…”

Section: Resultssupporting

confidence: 62%

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Pyrolysis of 4,4‐bisperfluoromethylbutene‐1,4 01 in the gas phase

Gordon¹

1972

Int J of Chemical Kinetics

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Pyrolysis of (CF3)2C(OH)CH2CH=CH2, the reverse of the reaction between perfluoroacetone and propene, has been studied in the gas phase between 475" and 598'K. Even at 573"K, the unimolecular reaction rate constant appears to be in its pressure-independent region at 20.0 torr pressure.The specific unimolecular rate constant is In a quartz vessel, the decomposition is homogeneous. It is noteworthy that in the temperature range of the study of the forward reaction (448" to 573"K), the percentage of back reaction in the times of the experiments varies from less than 0.1 to 1.5. Using group additivities and the above AHO, aHro of (CFa)&O is calculated to be -325.2 kcal/mole at 600°K and the average C-C bond is 42.0 kcal/mole.

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Section: Resultssupporting

confidence: 62%

“…In both types of pyrolysis involving more than one mole of product per mole of reactant, there is no evidence of back reaction. The pyrolysis of CH&H(OH)CH2CH=CHz is very analogous to the reaction reported in this paper [4].…”

Section: Introductionmentioning

confidence: 51%

Pyrolysis of 4,4‐bisperfluoromethylbutene‐1,4 01 in the gas phase

Gordon¹

1972

Int J of Chemical Kinetics

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“…Based on the results obtained, the corresponding mechanism has been proposed in which b-hydroxy alkenes decompose thermally to give a mixture of alkenes and carbonyl compounds, following a first-order homogeneous unimolecular reaction [3]. In this context, tertiary alcohols decompose more readily than secondary and primary alcohols [1].…”

Section: Introductionmentioning

confidence: 96%

“…The thermolysis of b-hydroxy alkenes and ketones in the gas phase has been previously studied both experimentally [1][2][3][4][5] and theoretically [6]. Based on the results obtained, the corresponding mechanism has been proposed in which b-hydroxy alkenes decompose thermally to give a mixture of alkenes and carbonyl compounds, following a first-order homogeneous unimolecular reaction [3].…”

Section: Introductionmentioning

confidence: 98%

Correlations between hardness, electrostatic interactions, and thermodynamic parameters in the decomposition reactions of 3-buten-1-ol, 3-methoxy-1-propene, and ethoxyethene

et al. 2014

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Decomposition of the three isomeric compounds, 3-buten-1-ol (1), 3-methoxy-1-propene (2), and ethoxyethene (3), at two different (300 and 550 K) temperatures has been investigated by means of ab initio molecular orbital theory (MP2/6-311?G**//B3LYP/6-311?G**), hybrid-density functional theory (B3LYP/6-311?G**), the complete basis set, nuclear magnetic resonance analysis, and the electrostatic model associated with the dipole-dipole interactions. All three levels of theory showed that the calculated Gibbs free energy differences between the transition and ground state structures (DG = ) increase from compound 1 to compound 3. The variations of the calculated DG = values can not be justified by the decrease of the calculated global hardness (g) differences between the ground and transition states structures (i.e., D[g(GS)-g(TS)]). Based on the synchronicity indices, the transition state structures of compounds 1-3 involve synchronous aromatic transition structures, but there is no significant difference between their calculated synchronicity indices. The optimized geometries for the transition state structures of the decomposition reactions of compounds 1-3 consist in chair-like six-membered rings. The variation of the calculated activation entropy (DS = ) values can not be justified by the decrease of D[g(GS)-g(TS)] parameter from compound 1 to compound 3. On the other hand, dipole moment differences between the ground and transition state structures [D(l TS -l GS )] decrease from compound 1 to compound 3. Therefore, the electrostatic model associated with the dipole-dipole interactions justifies the increase of the calculated DG = values from compound 1 to compound 3. The correlations between DG = , D[g(GS)-g(TS)], (DS = ), k(T), electrostatic model, and structural parameters have been investigated.

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“…The same type of "retro-ene" mechanism is operative in olefins [4], but-3-enols [ 5 ] , 3-enoic acids [6], alkylallyl ethers [7], etc., and consistent activation parameters have been observed with characteristically low intrinsic preexponential factors of -101*x5*0.5 resulting from a considerable loss of rotational entropy in the transition state relative to the ground state molecule4). It has been shown that the introduction of a vinyl group for R1 or R2 reduces the activation energy of the process by about G kcal mol-l, while alkyl-groups lead to a smaller but still significant rate enhance- ment.…”

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confidence: 99%

The Thermochemical Kinetics of Retro “‐Ene” Reactions of Molecules with the General Structure (Allyl)XYH in the Gas Phase. 8.. The Thermal Decomposition of Methylallylaniline in the Gas Phase

Egger

Vitins

1974

Helvetica Chimica Acta

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Summary. The thermal decomposition of N-methyl-N-allylanilinc in the gas phase over the temperature range 575 to 665 K appears to be a homogcueous radical chain reaction yielding ally1 and C6H,NCH, radicals in the primary step as is indicated by the numerous chain-terminating radical recombination products and the effect of diluents on the rate constants. From experiments carried out with excess of diluent, first order rate constants which can be identified with the rate determining chain initiating step, were calculated using the internal standard technique and found to fit the Arrhenius rclationship log (hisA1) = 13.75 5 0.43 -(48.50 & 1.23 kcal mol-l)/2.303 R T .Although the Arrhelzius parameters are slightly low, which is attributed to some loss of substrate by secondary reactions, they are in general agreement with prediction. The relevance of these results to the thermal behavior of allylamines and the nature of six-center transition states is discussed.

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1331. Pyrolysis studies. Part XVI. A mechanistic study of the pyrolysis of β-hydroxy-olefins

Cited by 35 publications

References 0 publications

Pyrolysis of 4,4‐bisperfluoromethylbutene‐1,4 01 in the gas phase

Pyrolysis of 4,4‐bisperfluoromethylbutene‐1,4 01 in the gas phase

Correlations between hardness, electrostatic interactions, and thermodynamic parameters in the decomposition reactions of 3-buten-1-ol, 3-methoxy-1-propene, and ethoxyethene

The Thermochemical Kinetics of Retro “‐Ene” Reactions of Molecules with the General Structure (Allyl)XYH in the Gas Phase. 8.. The Thermal Decomposition of Methylallylaniline in the Gas Phase

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