Radical and non-radical mechanisms for alkane oxidations by hydrogen peroxide-trifluoroacetic acid

D. M. Camaioni, J. T. Bays, W. J. Shaw, John Linehan, J. C. Birnbaum

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

The oxidation of cyclohexane by the H2O2-trifluoroacetic acid system is revisited. Consistent with a previous report (Deno, N.; Messer, L. A. Chem. Comm. 1976, 1051), cyclohexanol forms initially but then esterifies to cyclohexyl trifluoroacetate. Small amounts of trans-1,2-cyclohexadiyl bis-(trifluoroacetate) also form. Although these products form irrespective of the presence or absence of O2, dual mechanisms are shown to operate. In the absence of O2, the dominant mechanism is a radical chain reaction that is propagated by CF3· abstracting H from C6H12 and SH2 displacement of C6H11· on CF3CO2OH. The intermediacy of C6H11· and CF3· is inferred from production of CHF3 and CO2 along with cyclohexyl trifluoroacetate, or CDF3 when cyclohexane-d12 is used. In the presence of O2, fluoroform and CO2 are suppressed, the reaction rate slows, and the rate law approaches second order (first order in peracid and in C6H12). Trapping of cyclohexyl radicals by quinoxaline is inefficient except at elevated (∼75°C) temperatures. Fluoroform and CO2, telltale evidence for the chain pathway, were not produced when quinoxaline was present in room temperature reactions. These observations suggest that a parallel, nonfree radical, oxenoid insertion mechanism dominates when O2 is present. A pathway is discussed in which a biradicaloid-zwiterionic transition state is attained by hydrogen transfer from alkane to peroxide oxygen with synchronous O-O bond scission.

Original languageEnglish
Pages (from-to)789-795
Number of pages7
JournalJournal of Organic Chemistry
Volume66
Issue number3
DOIs
Publication statusPublished - Feb 9 2001

Fingerprint

Trifluoroacetic Acid
Alkanes
Hydrogen Peroxide
Quinoxalines
Oxidation
Cyclohexanols
Peroxides
Reaction rates
Hydrogen
Oxygen
Temperature
fluoroform
Cyclohexane

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Radical and non-radical mechanisms for alkane oxidations by hydrogen peroxide-trifluoroacetic acid. / Camaioni, D. M.; Bays, J. T.; Shaw, W. J.; Linehan, John; Birnbaum, J. C.

In: Journal of Organic Chemistry, Vol. 66, No. 3, 09.02.2001, p. 789-795.

Research output: Contribution to journalArticle

Camaioni, D. M. ; Bays, J. T. ; Shaw, W. J. ; Linehan, John ; Birnbaum, J. C. / Radical and non-radical mechanisms for alkane oxidations by hydrogen peroxide-trifluoroacetic acid. In: Journal of Organic Chemistry. 2001 ; Vol. 66, No. 3. pp. 789-795.
@article{41ff9729a0df432b842b0847627b0f86,
title = "Radical and non-radical mechanisms for alkane oxidations by hydrogen peroxide-trifluoroacetic acid",
abstract = "The oxidation of cyclohexane by the H2O2-trifluoroacetic acid system is revisited. Consistent with a previous report (Deno, N.; Messer, L. A. Chem. Comm. 1976, 1051), cyclohexanol forms initially but then esterifies to cyclohexyl trifluoroacetate. Small amounts of trans-1,2-cyclohexadiyl bis-(trifluoroacetate) also form. Although these products form irrespective of the presence or absence of O2, dual mechanisms are shown to operate. In the absence of O2, the dominant mechanism is a radical chain reaction that is propagated by CF3· abstracting H from C6H12 and SH2 displacement of C6H11· on CF3CO2OH. The intermediacy of C6H11· and CF3· is inferred from production of CHF3 and CO2 along with cyclohexyl trifluoroacetate, or CDF3 when cyclohexane-d12 is used. In the presence of O2, fluoroform and CO2 are suppressed, the reaction rate slows, and the rate law approaches second order (first order in peracid and in C6H12). Trapping of cyclohexyl radicals by quinoxaline is inefficient except at elevated (∼75°C) temperatures. Fluoroform and CO2, telltale evidence for the chain pathway, were not produced when quinoxaline was present in room temperature reactions. These observations suggest that a parallel, nonfree radical, oxenoid insertion mechanism dominates when O2 is present. A pathway is discussed in which a biradicaloid-zwiterionic transition state is attained by hydrogen transfer from alkane to peroxide oxygen with synchronous O-O bond scission.",
author = "Camaioni, {D. M.} and Bays, {J. T.} and Shaw, {W. J.} and John Linehan and Birnbaum, {J. C.}",
year = "2001",
month = "2",
day = "9",
doi = "10.1021/jo005617d",
language = "English",
volume = "66",
pages = "789--795",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "3",

}

TY - JOUR

T1 - Radical and non-radical mechanisms for alkane oxidations by hydrogen peroxide-trifluoroacetic acid

AU - Camaioni, D. M.

AU - Bays, J. T.

AU - Shaw, W. J.

AU - Linehan, John

AU - Birnbaum, J. C.

PY - 2001/2/9

Y1 - 2001/2/9

N2 - The oxidation of cyclohexane by the H2O2-trifluoroacetic acid system is revisited. Consistent with a previous report (Deno, N.; Messer, L. A. Chem. Comm. 1976, 1051), cyclohexanol forms initially but then esterifies to cyclohexyl trifluoroacetate. Small amounts of trans-1,2-cyclohexadiyl bis-(trifluoroacetate) also form. Although these products form irrespective of the presence or absence of O2, dual mechanisms are shown to operate. In the absence of O2, the dominant mechanism is a radical chain reaction that is propagated by CF3· abstracting H from C6H12 and SH2 displacement of C6H11· on CF3CO2OH. The intermediacy of C6H11· and CF3· is inferred from production of CHF3 and CO2 along with cyclohexyl trifluoroacetate, or CDF3 when cyclohexane-d12 is used. In the presence of O2, fluoroform and CO2 are suppressed, the reaction rate slows, and the rate law approaches second order (first order in peracid and in C6H12). Trapping of cyclohexyl radicals by quinoxaline is inefficient except at elevated (∼75°C) temperatures. Fluoroform and CO2, telltale evidence for the chain pathway, were not produced when quinoxaline was present in room temperature reactions. These observations suggest that a parallel, nonfree radical, oxenoid insertion mechanism dominates when O2 is present. A pathway is discussed in which a biradicaloid-zwiterionic transition state is attained by hydrogen transfer from alkane to peroxide oxygen with synchronous O-O bond scission.

AB - The oxidation of cyclohexane by the H2O2-trifluoroacetic acid system is revisited. Consistent with a previous report (Deno, N.; Messer, L. A. Chem. Comm. 1976, 1051), cyclohexanol forms initially but then esterifies to cyclohexyl trifluoroacetate. Small amounts of trans-1,2-cyclohexadiyl bis-(trifluoroacetate) also form. Although these products form irrespective of the presence or absence of O2, dual mechanisms are shown to operate. In the absence of O2, the dominant mechanism is a radical chain reaction that is propagated by CF3· abstracting H from C6H12 and SH2 displacement of C6H11· on CF3CO2OH. The intermediacy of C6H11· and CF3· is inferred from production of CHF3 and CO2 along with cyclohexyl trifluoroacetate, or CDF3 when cyclohexane-d12 is used. In the presence of O2, fluoroform and CO2 are suppressed, the reaction rate slows, and the rate law approaches second order (first order in peracid and in C6H12). Trapping of cyclohexyl radicals by quinoxaline is inefficient except at elevated (∼75°C) temperatures. Fluoroform and CO2, telltale evidence for the chain pathway, were not produced when quinoxaline was present in room temperature reactions. These observations suggest that a parallel, nonfree radical, oxenoid insertion mechanism dominates when O2 is present. A pathway is discussed in which a biradicaloid-zwiterionic transition state is attained by hydrogen transfer from alkane to peroxide oxygen with synchronous O-O bond scission.

UR - http://www.scopus.com/inward/record.url?scp=0035830560&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035830560&partnerID=8YFLogxK

U2 - 10.1021/jo005617d

DO - 10.1021/jo005617d

M3 - Article

VL - 66

SP - 789

EP - 795

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 3

ER -