Kinetics and mechanism of thermal gas-phase elimination of β-substituted carboxylic acids

Al-Awadi, Sameera; Abdallah, Mariam R.; Dib, Hicham H.; Ibrahim, Maher R.; Al‐Awadi, Nouria A.; El‐Dusouqui, Osman M. E.

doi:10.1016/j.tet.2005.04.031

Cited by 19 publications

(18 citation statements)

References 15 publications

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“…calcd for C6 H 7 NO: C 66.04, H 6.47, N 12.84; found C 66.15, H 6. 70, 18 : White crystal, m.p. 57-58 ℃ (lit.…”

mentioning

confidence: 99%

Triphenylphosphine‐Catalyzed Michael Addition of Alcohols to Acrylic Compounds

Liu¹,

Jiang²,

Wang³

2007

Chin. J. Chem.

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A facile triphenylphosphine-catalyzed Michael addition of alcohols to acrylic compounds was described. The reaction was carried out in open air at refluxing temperature in the presence of 10 mol% PPh 3 . Michael addition of saturated and unsaturated alcohols to acrylonitrile or acrylates has been examined. The reaction gave β-alkoxy derivatives with isolated yields of 5%-79%. PPh 3 is cheaper and more stable than those trialkylphosphines previously used for the similar reactions, and the products can be easily separated from the reaction mixture via distillation.

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“…calcd for C6 H 7 NO: C 66.04, H 6.47, N 12.84; found C 66.15, H 6. 70, 18 : White crystal, m.p. 57-58 ℃ (lit.…”

mentioning

confidence: 99%

Triphenylphosphine‐Catalyzed Michael Addition of Alcohols to Acrylic Compounds

Liu¹,

Jiang²,

Wang³

2007

Chin. J. Chem.

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“…Although it is not significant, it is of interest here to note that the results of the theoretScheme 4 Gas-phase elimination of 1a-c and the rate constant at 600 K. ical ab initio calculations show gas-phase thermodynamic stabilities of the arene fragments to be in order of PhNH 2 > PhCH 3 ∼ = PhOH > PhSH [4], so the thermodynamic stability of PhCH 3 in the gas-phase elimination reaction compensates the lower polarity of the (C X) bond in compound 3. It is worth mentioning that the rate constant of the gas-phase elimination reaction of 3-anilino-1-propanol at 600 K is 5.95 × 10 −5 .…”

Section: -Phenyl-1-butanol (3)mentioning

confidence: 91%

“…Phenoxy-2-methyl-2-butanol (1c). To a solution of CH 3 MgI (freshly prepared from 1.0 g Mg and 2.5 mL CH 3 I in 40 mL dry ether) was added methyl 3-phenoxypropionate [4] (1.8 g, 10 mmol) in dry ether (20 mL) portionwise at room temperature with stirring under nitrogen atmosphere. The reaction mixture was heated under reflux for 24 h. After cooling at room temperature, the mixture was quenched with saturated aqueous ammonium chloride solution and the ethereal layer was separated and the aqueous layer was further extracted with ether (3 × 50 mL).…”

Section: -Phenoxy-2-butanol (1b)mentioning

confidence: 99%

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Gas‐phase pyrolytic reaction of 3‐phenoxy and 3‐phenylsulfanyl‐1‐propanol derivatives: Kinetic and mechanistic study

Dib

Ibrahim

Al‐Awadi

et al. 2007

Int J of Chemical Kinetics

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3-Phenoxy-1-propanols 1a-c and 3-phenylsulfanyl-1-propanols 2a-c containing primary, secondary, and tertiary alcohols were prepared and subjected to gas-phase pyrolysis in a static reaction system. Pyrolysis of 4-phenyl-1-butanol 3, 2-methyl-3-phenyl-1-propanol 4, and 2-methyl-3-phenylpropanoic acid 5 was also studied, and results were compared with those obtained for compounds 1-3. The pyrolytic reactions were homogeneous and followed a first-order rate equation. Analysis of the pyrolysate showed the products to be phenol (from 1a to 1c), thiophenol (from 2a to 2c), and toluene (from 3 to 5) and carbonyl compounds. The kinetic results and product analysis of each of the nine investigated compounds are rationalized in terms of a plausible transition state for the elimination pathway. C 2007 Wiley Periodicals, Inc. Int J Chem Kinet 40: [51][52][53][54][55][56][57][58] 2008

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“…The α‐ and β‐( N ‐arylamino) propanoic acids, carboxylic acids, and 3‐amino propyl alcohols are all important materia medicas in medicine, and they also have very broad applications in many other fields 1–4. Al‐Awadi and coworkers have reported that the gas‐phase pyrolysis mechanisms of these compounds are similar 5–8. For example, the pyrolysate of 2‐ N ‐arylaminopropanoic acid showed the elimination products to be CO, CH 3 CHO, and aniline, while the pyrolysate of 3‐ N ‐arylaminopropanoic acid revealed the formation of acylic acid on aniline 6.…”

Section: Introductionmentioning

confidence: 99%

Gas‐phase pyrolysis mechanisms of 3‐anilino‐1‐propanol: Density functional theory study

Zhao

Tang

Wei

et al. 2008

Int J of Quantum Chemistry

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ABSTRACT:The gas-phase pyrolytic decomposition mechanisms of 3-anilino-1-propanol with the products of aniline, ethylene, and formaldehyde or N-methyl aniline and aldehyde were studied by density functional theory. The geometries of the reactant, transition states, and intermediates were optimized at the B3LYP/6-31G (d, p) level. Vibration analysis was carried out to confirm the transition state structures, and the intrinsic reaction coordinate method was performed to search the minimum energy path. Four possible reaction channels are shown, including two concerted reactions of direct pyrolytic decomposition and two indirect channels in which the reactant first becomes a ring-like intermediate, followed by concerted pyrogenation. One of the concerted reactions in the direct pyrolytic decomposition has the lowest activation barrier among all the four channels, and so, it occurs more often than others. The results appear to be consistent with the experimental outcomes.

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Kinetics and mechanism of thermal gas-phase elimination of β-substituted carboxylic acids

Cited by 19 publications

References 15 publications

Triphenylphosphine‐Catalyzed Michael Addition of Alcohols to Acrylic Compounds

Triphenylphosphine‐Catalyzed Michael Addition of Alcohols to Acrylic Compounds

Gas‐phase pyrolytic reaction of 3‐phenoxy and 3‐phenylsulfanyl‐1‐propanol derivatives: Kinetic and mechanistic study

Gas‐phase pyrolysis mechanisms of 3‐anilino‐1‐propanol: Density functional theory study

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