Catalytic efficiency and stability of tertiary amines in oxidation of methyl 4-deoxy-β-L-threo-hex-4-enopyranosiduronic acid by hypochlorous acid

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Catalytic efficiency and stability of tertiary amines in oxidation of methyl 4-deoxy-β-L-threo-hex-4-enopyranosiduronic acid by hypochlorous acid. / Afsahi, Ghazaleh; Bertinetto, Carlo; Hummel, Michael; Kesari, Kavindra Kumar; Vuorinen, Tapani.

In: Molecular Catalysis, Vol. 474, 110413, 01.09.2019.

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@article{febf3e62c2c34ebe94a57ebc6900194b,
title = "Catalytic efficiency and stability of tertiary amines in oxidation of methyl 4-deoxy-β-L-threo-hex-4-enopyranosiduronic acid by hypochlorous acid",
abstract = "Tertiary amines efficiently catalyze oxidation of unsaturated organic substances by hypochlorous acid (HOCl). However, the quaternary chloroammonium cation, formed spontaneously as the reactive species, often undergoes parallel self-decomposition that increases the catalyst dosage required. Thus, an otherwise potential industrial catalyst, 1,4-diazabicyclo[2.2.2]octane (DABCO), decomposes in a few seconds in the presence of HOCl. In this paper, we show that substituting one of the amino groups of DABCO with an alkyl group, in this case with carboxymethyl group, fully stabilizes the polycyclic chloroammonium cation towards self-decomposition. The catalytic efficiency of N-carboxymethyl-1,4-diazabicyclo[2.2.2]octane was similar to, or only slightly lower than that of DABCO, under mild acid conditions (pH 3-6). Although we studied oxidation of methyl 4-deoxy-β-L-threo-hex-4-enopyranosiduronic acid only, the main conclusions on the effect N-alkylation on the catalyst stability and activity should be transferable to catalytic conversion of any other substrate by HOCl.",
keywords = "4-deoxy-β-L-threo-hex-4-enopyranosiduronic acid, Catalyst, Chemometry, Hypochlorous acid, Kinetic model, N-carboxymethyl-1,4-diazabicyclo[2.2.2]octane",
author = "Ghazaleh Afsahi and Carlo Bertinetto and Michael Hummel and Kesari, {Kavindra Kumar} and Tapani Vuorinen",
year = "2019",
month = "9",
day = "1",
doi = "10.1016/j.mcat.2019.110413",
language = "English",
volume = "474",
journal = "Molecular Catalysis",
issn = "2468-8274",
publisher = "Elsevier BV",

}

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TY - JOUR

T1 - Catalytic efficiency and stability of tertiary amines in oxidation of methyl 4-deoxy-β-L-threo-hex-4-enopyranosiduronic acid by hypochlorous acid

AU - Afsahi, Ghazaleh

AU - Bertinetto, Carlo

AU - Hummel, Michael

AU - Kesari, Kavindra Kumar

AU - Vuorinen, Tapani

PY - 2019/9/1

Y1 - 2019/9/1

N2 - Tertiary amines efficiently catalyze oxidation of unsaturated organic substances by hypochlorous acid (HOCl). However, the quaternary chloroammonium cation, formed spontaneously as the reactive species, often undergoes parallel self-decomposition that increases the catalyst dosage required. Thus, an otherwise potential industrial catalyst, 1,4-diazabicyclo[2.2.2]octane (DABCO), decomposes in a few seconds in the presence of HOCl. In this paper, we show that substituting one of the amino groups of DABCO with an alkyl group, in this case with carboxymethyl group, fully stabilizes the polycyclic chloroammonium cation towards self-decomposition. The catalytic efficiency of N-carboxymethyl-1,4-diazabicyclo[2.2.2]octane was similar to, or only slightly lower than that of DABCO, under mild acid conditions (pH 3-6). Although we studied oxidation of methyl 4-deoxy-β-L-threo-hex-4-enopyranosiduronic acid only, the main conclusions on the effect N-alkylation on the catalyst stability and activity should be transferable to catalytic conversion of any other substrate by HOCl.

AB - Tertiary amines efficiently catalyze oxidation of unsaturated organic substances by hypochlorous acid (HOCl). However, the quaternary chloroammonium cation, formed spontaneously as the reactive species, often undergoes parallel self-decomposition that increases the catalyst dosage required. Thus, an otherwise potential industrial catalyst, 1,4-diazabicyclo[2.2.2]octane (DABCO), decomposes in a few seconds in the presence of HOCl. In this paper, we show that substituting one of the amino groups of DABCO with an alkyl group, in this case with carboxymethyl group, fully stabilizes the polycyclic chloroammonium cation towards self-decomposition. The catalytic efficiency of N-carboxymethyl-1,4-diazabicyclo[2.2.2]octane was similar to, or only slightly lower than that of DABCO, under mild acid conditions (pH 3-6). Although we studied oxidation of methyl 4-deoxy-β-L-threo-hex-4-enopyranosiduronic acid only, the main conclusions on the effect N-alkylation on the catalyst stability and activity should be transferable to catalytic conversion of any other substrate by HOCl.

KW - 4-deoxy-β-L-threo-hex-4-enopyranosiduronic acid

KW - Catalyst

KW - Chemometry

KW - Hypochlorous acid

KW - Kinetic model

KW - N-carboxymethyl-1,4-diazabicyclo[2.2.2]octane

UR - http://www.scopus.com/inward/record.url?scp=85066124081&partnerID=8YFLogxK

U2 - 10.1016/j.mcat.2019.110413

DO - 10.1016/j.mcat.2019.110413

M3 - Article

VL - 474

JO - Molecular Catalysis

JF - Molecular Catalysis

SN - 2468-8274

M1 - 110413

ER -

ID: 34480179