α-Amido Trifluoromethyl Xanthates: A New Class of RAFT/MADIX Agents

Mathias Destarac; Juliette Ruchmann-Sternchuss; Eric Van Gramberen; Xavier Vila; Samir Z. Zard

doi:10.3390/molecules29102174

α-Amido Trifluoromethyl Xanthates: A New Class of RAFT/MADIX Agents

Mathias Destarac
, Juliette Ruchmann-Sternchuss
, Eric Van Gramberen
, Xavier Vila
, Samir Z. Zard

Université Paul-Sabatier
Rhodia Recherches
Laboratoire de Synthèse Organique

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

1 Citation (Scopus)

Abstract

Xanthates have long been described as poor RAFT/MADIX agents for styrene polymerization. Through the determination of chain transfer constants to xanthates, this work demonstrated beneficial capto-dative substituent effects for the leaving group of a new series of α-amido trifluoromethyl xanthates, with the best effect observed with trifluoroacetyl group. The previously observed Z-group activation with a O-trifluoroethyl group compared to the O-ethyl counterpart was quantitatively established with C_ex = 2.7 (3–4 fold increase) using the SEC peak resolution method. This study further confirmed the advantageous incorporation of trifluoromethyl substituents to activate xanthates in radical chain transfer processes and contributed to identify the most reactive xanthate reported to date for RAFT/MADIX polymerization of styrene.

Original language	English
Article number	2174
Journal	Molecules
Volume	29
Issue number	10
DOIs	https://doi.org/10.3390/molecules29102174
Publication status	Published - 1 May 2024
Externally published	Yes

Keywords

MADIX polymerization
RAFT polymerization
reactivity
xanthate

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title = "α-Amido Trifluoromethyl Xanthates: A New Class of RAFT/MADIX Agents",

abstract = "Xanthates have long been described as poor RAFT/MADIX agents for styrene polymerization. Through the determination of chain transfer constants to xanthates, this work demonstrated beneficial capto-dative substituent effects for the leaving group of a new series of α-amido trifluoromethyl xanthates, with the best effect observed with trifluoroacetyl group. The previously observed Z-group activation with a O-trifluoroethyl group compared to the O-ethyl counterpart was quantitatively established with Cex = 2.7 (3–4 fold increase) using the SEC peak resolution method. This study further confirmed the advantageous incorporation of trifluoromethyl substituents to activate xanthates in radical chain transfer processes and contributed to identify the most reactive xanthate reported to date for RAFT/MADIX polymerization of styrene.",

keywords = "MADIX polymerization, RAFT polymerization, reactivity, xanthate",

author = "Mathias Destarac and Juliette Ruchmann-Sternchuss and \{Van Gramberen\}, Eric and Xavier Vila and Zard, \{Samir Z.\}",

note = "Publisher Copyright: {\textcopyright} 2024 by the authors.",

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doi = "10.3390/molecules29102174",

language = "English",

volume = "29",

journal = "Molecules",

issn = "1420-3049",

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TY - JOUR

T1 - α-Amido Trifluoromethyl Xanthates

T2 - A New Class of RAFT/MADIX Agents

AU - Destarac, Mathias

AU - Ruchmann-Sternchuss, Juliette

AU - Van Gramberen, Eric

AU - Vila, Xavier

AU - Zard, Samir Z.

PY - 2024/5/1

Y1 - 2024/5/1

N2 - Xanthates have long been described as poor RAFT/MADIX agents for styrene polymerization. Through the determination of chain transfer constants to xanthates, this work demonstrated beneficial capto-dative substituent effects for the leaving group of a new series of α-amido trifluoromethyl xanthates, with the best effect observed with trifluoroacetyl group. The previously observed Z-group activation with a O-trifluoroethyl group compared to the O-ethyl counterpart was quantitatively established with Cex = 2.7 (3–4 fold increase) using the SEC peak resolution method. This study further confirmed the advantageous incorporation of trifluoromethyl substituents to activate xanthates in radical chain transfer processes and contributed to identify the most reactive xanthate reported to date for RAFT/MADIX polymerization of styrene.

AB - Xanthates have long been described as poor RAFT/MADIX agents for styrene polymerization. Through the determination of chain transfer constants to xanthates, this work demonstrated beneficial capto-dative substituent effects for the leaving group of a new series of α-amido trifluoromethyl xanthates, with the best effect observed with trifluoroacetyl group. The previously observed Z-group activation with a O-trifluoroethyl group compared to the O-ethyl counterpart was quantitatively established with Cex = 2.7 (3–4 fold increase) using the SEC peak resolution method. This study further confirmed the advantageous incorporation of trifluoromethyl substituents to activate xanthates in radical chain transfer processes and contributed to identify the most reactive xanthate reported to date for RAFT/MADIX polymerization of styrene.

KW - MADIX polymerization

KW - RAFT polymerization

KW - reactivity

KW - xanthate

U2 - 10.3390/molecules29102174

DO - 10.3390/molecules29102174

M3 - Article

AN - SCOPUS:85194258074

SN - 1420-3049

VL - 29

JO - Molecules

JF - Molecules

IS - 10

M1 - 2174

ER -

α-Amido Trifluoromethyl Xanthates: A New Class of RAFT/MADIX Agents

Abstract

Keywords

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