Aqueous-Phase Oxidation of N-Substituted N-PhosphonomethylGlycines into Glyphosate with Hydrogen Peroxide in the Presence of Carbon-Supported Gold Catalysts

Standard

Aqueous-Phase Oxidation of N-Substituted N-PhosphonomethylGlycines into Glyphosate with Hydrogen Peroxide in the Presence of Carbon-Supported Gold Catalysts. / Pyrjaev, Pavel A.; Yushchenko, Dmitry Yu; Moroz, Boris L. et al.

In: ChemistrySelect, Vol. 4, No. 36, 30.09.2019, p. 10756-10764.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{4fb8fd1a95bb4e94b1eb10ec1413d1f0,

title = "Aqueous-Phase Oxidation of N-Substituted N-PhosphonomethylGlycines into Glyphosate with Hydrogen Peroxide in the Presence of Carbon-Supported Gold Catalysts",

abstract = "The catalytic performance of carbon-supported gold nanoparticles has been studied for the oxidative dealkylation of a series of N-substituted N-phosphonomethyl glycines into N-phosphonomethyl glycine (“glyphosate”) using dilute (0.11 m) aqueous H2O2 solution as oxidant. It was shown that the electron-donating inductive (+I) effect of the hydrocarbon substituent at the nitrogen atom greatly influences both the substrate reactivity and product distribution. Gold nanoparticles of 1.5-2.5 nm in diameter synthesized by “cationic adsorption” technique on the mesoporous Sibunit carbons, which are pre-oxidized with HNO3 and containing a lot of surface acidic groups, were found to catalyze the formation of glyphosate from N-isopropyl-N-phosphonomethyl glycine at 70 °C with selectivity up to 94% at 98% substrate conversion. Oxidation of other substrates containing the substituents with a weaker +I effect than that of iPr group resulted a large amount of undesirable N-decarboxymethylation product in addition to glyphosate. Considering the literature data and our own experimental results, assumptions about the reaction mechanism and causes of the observed trends are made.",

keywords = "glyphosate synthesis, gold, N-substituted glyphosates, oxidation, supported catalysts, SURFACE-PROPERTIES, SELECTIVE OXIDATION, H2O2, NANOPARTICLES, ACTIVATED CARBON, AMINES, KINETICS, AU/AL2O3, GENERATION, AU/CARBON",

author = "Pyrjaev, {Pavel A.} and Yushchenko, {Dmitry Yu} and Moroz, {Boris L.} and Pai, {Zinaida P.} and Bukhtiyarov, {Valerii I.}",

note = "Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2019",

month = sep,

day = "30",

doi = "10.1002/slct.201902625",

language = "English",

volume = "4",

pages = "10756--10764",

journal = "ChemistrySelect",

issn = "2365-6549",

publisher = "Wiley-Blackwell",

number = "36",

}

RIS

TY - JOUR

T1 - Aqueous-Phase Oxidation of N-Substituted N-PhosphonomethylGlycines into Glyphosate with Hydrogen Peroxide in the Presence of Carbon-Supported Gold Catalysts

AU - Pyrjaev, Pavel A.

AU - Yushchenko, Dmitry Yu

AU - Moroz, Boris L.

AU - Pai, Zinaida P.

AU - Bukhtiyarov, Valerii I.

PY - 2019/9/30

Y1 - 2019/9/30

N2 - The catalytic performance of carbon-supported gold nanoparticles has been studied for the oxidative dealkylation of a series of N-substituted N-phosphonomethyl glycines into N-phosphonomethyl glycine (“glyphosate”) using dilute (0.11 m) aqueous H2O2 solution as oxidant. It was shown that the electron-donating inductive (+I) effect of the hydrocarbon substituent at the nitrogen atom greatly influences both the substrate reactivity and product distribution. Gold nanoparticles of 1.5-2.5 nm in diameter synthesized by “cationic adsorption” technique on the mesoporous Sibunit carbons, which are pre-oxidized with HNO3 and containing a lot of surface acidic groups, were found to catalyze the formation of glyphosate from N-isopropyl-N-phosphonomethyl glycine at 70 °C with selectivity up to 94% at 98% substrate conversion. Oxidation of other substrates containing the substituents with a weaker +I effect than that of iPr group resulted a large amount of undesirable N-decarboxymethylation product in addition to glyphosate. Considering the literature data and our own experimental results, assumptions about the reaction mechanism and causes of the observed trends are made.

AB - The catalytic performance of carbon-supported gold nanoparticles has been studied for the oxidative dealkylation of a series of N-substituted N-phosphonomethyl glycines into N-phosphonomethyl glycine (“glyphosate”) using dilute (0.11 m) aqueous H2O2 solution as oxidant. It was shown that the electron-donating inductive (+I) effect of the hydrocarbon substituent at the nitrogen atom greatly influences both the substrate reactivity and product distribution. Gold nanoparticles of 1.5-2.5 nm in diameter synthesized by “cationic adsorption” technique on the mesoporous Sibunit carbons, which are pre-oxidized with HNO3 and containing a lot of surface acidic groups, were found to catalyze the formation of glyphosate from N-isopropyl-N-phosphonomethyl glycine at 70 °C with selectivity up to 94% at 98% substrate conversion. Oxidation of other substrates containing the substituents with a weaker +I effect than that of iPr group resulted a large amount of undesirable N-decarboxymethylation product in addition to glyphosate. Considering the literature data and our own experimental results, assumptions about the reaction mechanism and causes of the observed trends are made.

KW - glyphosate synthesis

KW - gold

KW - N-substituted glyphosates

KW - oxidation

KW - supported catalysts

KW - SURFACE-PROPERTIES

KW - SELECTIVE OXIDATION

KW - H2O2

KW - NANOPARTICLES

KW - ACTIVATED CARBON

KW - AMINES

KW - KINETICS

KW - AU/AL2O3

KW - GENERATION

KW - AU/CARBON

UR - http://www.scopus.com/inward/record.url?scp=85073226179&partnerID=8YFLogxK

U2 - 10.1002/slct.201902625

DO - 10.1002/slct.201902625

M3 - Article

AN - SCOPUS:85073226179

VL - 4

SP - 10756

EP - 10764

JO - ChemistrySelect

JF - ChemistrySelect

SN - 2365-6549

IS - 36

ER -

ID: 21856343