Off-line tetramethylammonium hydroxide thermochemolysis of model compound aliphatic and aromatic carboxylic acids: Decarboxylation of some ortho- and/or para- substituted aromatic carboxylic acids

Tetramethylammonium hydroxide (TMAH) thermochemolysis was performed 'off-line' on a wide variety of aliphatic and aromatic carboxylic acids, as model compounds for moieties present in polymeric organic materials. Simple aliphatic carboxylic acids and some aromatic carboxylic acids afforded...

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Main Authors: Joll, Cynthia, Huynh, Tran, Heitz, Anna
Format: Journal Article
Published: Elsevier 2003
Subjects:
Online Access:http://hdl.handle.net/20.500.11937/32919
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author Joll, Cynthia
Huynh, Tran
Heitz, Anna
author_facet Joll, Cynthia
Huynh, Tran
Heitz, Anna
author_sort Joll, Cynthia
building Curtin Institutional Repository
collection Online Access
description Tetramethylammonium hydroxide (TMAH) thermochemolysis was performed 'off-line' on a wide variety of aliphatic and aromatic carboxylic acids, as model compounds for moieties present in polymeric organic materials. Simple aliphatic carboxylic acids and some aromatic carboxylic acids afforded only products of full or partial methylation. Aromatic carboxylic acids with ortho and/or para substituents which contain an unshared pair of electrons on the atom connected to the ring and which are activating to electrophilic aromatic substitution (e.g. phenoxide, hydroxy, methoxy, amino) exhibited varying degrees of decarboxylation under standard reaction conditions. Detailed reaction mechanisms to explain the formation of all key products are presented in this paper. The extent of the decarboxylation was found to be dependent upon the mole ratio of TMAH to which the model compound was exposed: a reduction in the mole ratio of TMAH to model compound reducing or eliminating the formation of decarboxylation products. These results indicate that interpretation of product mixtures from TMAH thermochemolysis of polymeric organic matter, in particular the heterogeneous humic substances, must be made with caution and the origins of hydroxy- and methoxy-benzene products must be considered to include hydroxy- and methoxy-benzoic acids.
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spelling curtin-20.500.11937-329192017-09-13T15:56:51Z Off-line tetramethylammonium hydroxide thermochemolysis of model compound aliphatic and aromatic carboxylic acids: Decarboxylation of some ortho- and/or para- substituted aromatic carboxylic acids Joll, Cynthia Huynh, Tran Heitz, Anna tetramethylammonium hydroxide (TMAH) reaction mechanisms thermally assisted hydrolysis and methylation benzoic acids gas chromatography -mass spectrometry (GC-MS) thermochemolysis pyrolysis -methylation humic substances decarboxylation carboxylic acids model compounds Tetramethylammonium hydroxide (TMAH) thermochemolysis was performed 'off-line' on a wide variety of aliphatic and aromatic carboxylic acids, as model compounds for moieties present in polymeric organic materials. Simple aliphatic carboxylic acids and some aromatic carboxylic acids afforded only products of full or partial methylation. Aromatic carboxylic acids with ortho and/or para substituents which contain an unshared pair of electrons on the atom connected to the ring and which are activating to electrophilic aromatic substitution (e.g. phenoxide, hydroxy, methoxy, amino) exhibited varying degrees of decarboxylation under standard reaction conditions. Detailed reaction mechanisms to explain the formation of all key products are presented in this paper. The extent of the decarboxylation was found to be dependent upon the mole ratio of TMAH to which the model compound was exposed: a reduction in the mole ratio of TMAH to model compound reducing or eliminating the formation of decarboxylation products. These results indicate that interpretation of product mixtures from TMAH thermochemolysis of polymeric organic matter, in particular the heterogeneous humic substances, must be made with caution and the origins of hydroxy- and methoxy-benzene products must be considered to include hydroxy- and methoxy-benzoic acids. 2003 Journal Article http://hdl.handle.net/20.500.11937/32919 10.1016/S0165-2370(02)00129-8 Elsevier restricted
spellingShingle tetramethylammonium hydroxide (TMAH)
reaction mechanisms
thermally assisted hydrolysis and methylation
benzoic acids
gas chromatography -mass spectrometry (GC-MS)
thermochemolysis
pyrolysis -methylation
humic substances
decarboxylation
carboxylic acids
model compounds
Joll, Cynthia
Huynh, Tran
Heitz, Anna
Off-line tetramethylammonium hydroxide thermochemolysis of model compound aliphatic and aromatic carboxylic acids: Decarboxylation of some ortho- and/or para- substituted aromatic carboxylic acids
title Off-line tetramethylammonium hydroxide thermochemolysis of model compound aliphatic and aromatic carboxylic acids: Decarboxylation of some ortho- and/or para- substituted aromatic carboxylic acids
title_full Off-line tetramethylammonium hydroxide thermochemolysis of model compound aliphatic and aromatic carboxylic acids: Decarboxylation of some ortho- and/or para- substituted aromatic carboxylic acids
title_fullStr Off-line tetramethylammonium hydroxide thermochemolysis of model compound aliphatic and aromatic carboxylic acids: Decarboxylation of some ortho- and/or para- substituted aromatic carboxylic acids
title_full_unstemmed Off-line tetramethylammonium hydroxide thermochemolysis of model compound aliphatic and aromatic carboxylic acids: Decarboxylation of some ortho- and/or para- substituted aromatic carboxylic acids
title_short Off-line tetramethylammonium hydroxide thermochemolysis of model compound aliphatic and aromatic carboxylic acids: Decarboxylation of some ortho- and/or para- substituted aromatic carboxylic acids
title_sort off-line tetramethylammonium hydroxide thermochemolysis of model compound aliphatic and aromatic carboxylic acids: decarboxylation of some ortho- and/or para- substituted aromatic carboxylic acids
topic tetramethylammonium hydroxide (TMAH)
reaction mechanisms
thermally assisted hydrolysis and methylation
benzoic acids
gas chromatography -mass spectrometry (GC-MS)
thermochemolysis
pyrolysis -methylation
humic substances
decarboxylation
carboxylic acids
model compounds
url http://hdl.handle.net/20.500.11937/32919