EPR AND ENDOR OF PERFLUOROALKYL RADICAL INTERMEDIATES IN THE REACTION BETWEEN PERFLUOROHYPOFLUORITES AND PERFLUOROALKENES

Author(s): CONTI, F; CORVAJA, C; CREMONESE, F; NAVARRINI, W; TORTELLI, V

Source: JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS

Volume: 91 Issue: 21 Pages: 3813-3820

DOI: 10.1039/ft9959103813 Published: NOV 7 1995

ABSTRACT:

EPR and ENDOR spectra of the reaction products of sterically hindered perfluoroalkenes with perfluoromethyl hypofluorite and with the perfluoroether hypofluorite X(CF2O)(n)(CF2CF2O)(m)CF2OF, where X is either OCF3 or a second hypofluorite group OCF2-OF, have been recorded. Tertiary and secondary free radicals are produced by the addition to the alkene double bond of a fluorine atom or of the partner radical formed by the homolysis of the hypofluorite O-F bond. Analysis of the spectra reveals that hyperfine splitting by F-19 nuclei in the gamma and delta positions, and even further from the radical centre, contribute spectra. The alpha- and beta-F-19 hyperfine splitting are discussed in relation to the radical structure and conformation. The beta-F-19 splittings are accounted for by the well known equation a(F)(beta) = B cos(2)(theta); different values of the constant B have to be used according to the number of beta-fluorine substituents bonded to the same alpha-carbon.

http://pubs.rsc.org/en/Content/ArticleLanding/1995/FT/ft9959103813#!divAbstract

RELATIVE RATE CONSTANTS FOR THE REACTIONS OF CF3OF WITH OLEFINS IN SOLUTION

Author(s):NAVARRINI, W; RUSSO, A; TORTELLI, V.

Source: JOURNAL OF ORGANIC CHEMISTRY

Volume: 60 Issue: 20 Pages: 6441-6443

DOI: 10.1021/jo00125a033 Published: OCT 6 1995

ABSTRACT:

The addition reactions of CF3OF to chloro fluoro olefins have been studied in solution at low temperature (-78, -105 degrees C), and their relative rate constants have been determined using the kinetic approach of competition reactions. The reactivity and regio- and stereoselectivity are consistent with a free radical chain-propagating reaction in which the alkenes are attacked by the CF3O. radical generated by homolitic cleavage of the O-F bond in the CF3OF molecule.

http://pubs.acs.org/doi/abs/10.1021/jo00125a033

THE REACTION OF CF3OOCF2OF WITH FLUOROOLEFINS

Author(s): RUSSO, A; MONTANARI, V; NAVARRINI, W; DESMARTEAU, DD.

Source: JOURNAL OF FLUORINE CHEMISTRY

Volume: 74 Issue: 1 Pages: 83-87

DOI: 10.1016/0022-1139(95)03243-7 Published: SEP 1995.

ABSTRACT

The reaction of fluoroxydifluoromethyl trifluoromethyl peroxide, CF3OOCF2OF (1), with fluoroolefins leads to the formation of novel fluorinated peroxides as major products. When 1 was added to 1,2-dichloro-1,2-difluoroethylene, CFCl=CFCl, under controlled conditions,the formation of 4,5-dichloro-2,2,4,5-tetrafluoro-1,3-dioxolane was also observed. A mechanism is proposed to rationalize these results.

http://www.sciencedirect.com/science/article/pii/0022113995032437

THE ADDITION OF TRIFLUOROMETHYLHYPOFLUORITE TO HEXAFLUOROPROPENE DIMERS

ABSTRACT:

The reaction of trifluomethylhypofluorite with the two anionic dimers of hexafluoropropene leads to the trifluoromethylether adducts in excellent yield. The radical intermediates of the reaction have been detected using the EPR technique.

http://www.sciencedirect.com/science/article/pii/004040399500553O

NOVEL MOLECULES AND INDUSTRIAL-PROCESSES INSPIRED BY CADY,G.H. RESEARCH ON HYPOFLUORITES

Author(s):DESMARTEAU, DD; NAVARRINI, W; ZEDDA, A; RUSSO, A; MONTANARI, V.

Source:JOURNAL OF FLUORINE CHEMISTRY

Volume: 71 Issue: 2 Pages: 169-170

DOI: 10.1016/0022-1139(94)06008-A Published: APR 1995

http://www.sciencedirect.com/science/article/pii/002211399406008A

A new approach to the synthesis of 2,2-difluoro-1,3-dioxolanes

Author(s):NAVARRINI, W;BRAGANTE, L;FONTANA, S;TORTELLI, V; ZEDDA, A.

Source:JOURNAL OF FLUORINE CHEMISTRY

Volume: 71 Issue: 1 Pages: 111-117

DOI: 10.1016/0022-1139(94)03167-X Published: MAR 1995

ABSTRACT:

A direct and versatile way to prepare halogenated 2,2-difluoro-1,3-dioxolanes through the addition of bis-(fluoroxy)difluoromethane (BDM) to halogenated alkenes (CF2=CFCF3, CF2=CFOCF2CF3, CF2=CHCF3, CF3CF=CFCF3, CFCl=CFCl, CFBr=CFBr, CCl2=CCl2, CHCl=CCl2, CHCl=CHCl, CH2=CHCl, CF2=CFCl, (CF3)(2)CFCF=CFCF3, CF2=CFBr, CF2=CF2) has been discovered.

http://www.sciencedirect.com/science/article/pii/002211399403167X