Radical reactions of p-Nitrobenzylidene dichloride with lithium 2-nitropropan-2-ide. Consecutive SRN1 and ERC1 reactions

1976 ◽  
Vol 29 (12) ◽  
pp. 2631 ◽  
Author(s):  
DJ Freeman ◽  
RK Norris
Keyword(s):  
Radical Anion ◽  
Anion Radical ◽  
Lithium Salt ◽  
Substituent Effects ◽  
Radical Reactions ◽  
Elimination Reaction ◽  
Radical Chain ◽  
Radical Processes

The reaction of p-nitrobenzylidene dichloride with the lithium salt of 2-nitropropane gives initially the monosubstituted compound, p- NO2C6H4CH(Cl)CMe2NO2, by a radical-anion radical chain, SRN1 process. This compound then undergoes a radical-anion radical chain elimination reaction giving the styrene, p-NO2C6H4CH=CMe2, and the dimer of 2- nitropropane, Me2C(NO2)CMe2NO2. This latter reaction, which is designated ?ERC1?, also occurs in competition with an E2 reaction in the reaction of the methanesulphonate, p-NO2C6H4CH(OMs)CMe2NO2, with the 2- nitropropan-2-ide ion giving the above styrene and the enol methanesulphonate, p-NO2C6H4C(OMs)=CMe2, respectively. Catalytic, inhibition, and substituent effects are used to confirm the operation of these radical processes.

The ERC1 reaction: A radical anion — radical chain elimination process.

1975 ◽  
Vol 16 (28) ◽  
pp. 2375-2378 ◽  
Author(s):  
Diana J. Girdler ◽  
Robert K. Norris
Keyword(s):  
Radical Anion ◽  
Anion Radical ◽  
Radical Chain ◽  
Elimination Process

Radical reactions of p-nitrobenzylidene halides with aci-nitronate ions

1978 ◽  
Vol 31 (11) ◽  
pp. 2477 ◽  
Author(s):  
DJ Freeman ◽  
RK Norris ◽  
SK Woolfenden
Keyword(s):  
Nitrous Acid ◽  
Catalytic Effect ◽  
Lithium Salt ◽  
Phase Transfer ◽  
Hydrogen Bromide ◽  
Radical Reactions ◽  
Radical Process ◽  
Tetrabutylammonium Salt ◽  
Effect Of Oxygen ◽  
Radical Processes

The radical SRN1 and subsequent ERC1 reactions of p-nitrobenzylidene dibromide (2b) and bromide chloride (2c) with the lithium salt (1a) and the tetrabutylammonium salt (1b) (under phase-transfer conditions) of 2-nitropropane are discussed and compared with the reactions of the dichloride (2a). The SRN1 and ERC1 sequence occurs in rapid succession in the reaction of (2b), in contrast to the reactions of (2a) and (2c) which give isolable amounts of the SRN1 product, p-NO2C6H4CH(Cl)-CMe2NO2 (3a). The monobromide p-NO2C6H4CH(Br)CMe2NO2 (3b) cannot be detected in the SRN1-ERC1 sequence leading from (2b) to β,β-dimethyl-p-nitrostyrene (5). The ERC1 reaction of the monobromide (3b) is also studied and shown to take place more slowly than the combined SRN1-ERC1 sequence for (2b). ��� The phase-transfer technique is shown to be a convenient method for the preparation of C-alkylated derivatives like (3a), but not (3b), in both-the o- and p-nitrobenzylic systems. The dibromide p- NO2C6H4CH(Br)CMe2Br (7) was shown to undergo competitive ERC1 and E2(H) reactions with (1a) to give the styrene (5) and p-NO2C6H4C(Br)=CMe2 (8) respectively. Iodide ion reacts with (7) to give the styrene (5) by an E2(Br) mechanism at a rate which is several orders of magnitude slower than the radical process. Alkoxide ions gave E2(H) reactions on dibromide (7) and monochloride (3a) with elimination of the elements of hydrogen bromide and nitrous acid respectively. The catalytic effect of white light, the inhibitive effect of oxygen and p-dinitrobenzene, and the effect of concentration on the radical processes are discussed.

Radical Chain Reduction via Carbon Dioxide Radical Anion (CO2•–)

2021 ◽  
Author(s):  
Cecilia M. Hendy ◽  
Gavin C. Smith ◽  
Zihao Xu ◽  
Tianquan Lian ◽  
Nathan T. Jui
Keyword(s):  
Carbon Dioxide ◽  
Radical Anion ◽  
Radical Chain

A Fluorine 1,2-Migration via Aryl Cation/Radical/Radical Anion/Radical Sequence

2013 ◽  
Vol 15 (15) ◽  
pp. 3926-3929 ◽  
Author(s):  
Luca Pretali ◽  
Daniele Dondi ◽  
Mila D’Angelantonio ◽  
Ilse Manet ◽  
Elisa Fasani ◽  
...  
Keyword(s):  
Radical Anion ◽  
Anion Radical ◽  
Cation Radical

scholarly journals Mechanisms of the Electrohydrodimerization of Activated Olefins. V. Substituted Benzylidene Meldrum's Acid Anion Radical Reactions in the Presence of Acetic Acid.

1982 ◽  
Vol 36b ◽  
pp. 260-262 ◽  
Author(s):  
Paul Margaretha ◽  
Vernon D. Parker ◽  
S.-O. Lawesson ◽  
Toshiaki Nishida ◽  
Curt R. Enzell ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Anion Radical ◽  
Radical Reactions ◽  
Meldrum's Acid ◽  
Acid Anion ◽  
Meldrum’S Acid ◽  
Activated Olefins
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