Reactions of organotin compounds. VIII. The reactions of tin hydrides with perfluorovinyl silicon compounds

1968 ◽  
Vol 46 (4) ◽  
pp. 633-642 ◽  
Author(s):  
M. Akhtar ◽  
H. C. Clark
Keyword(s):  
Free Radical ◽  
Ultraviolet Irradiation ◽  
Spectroscopic Data ◽  
Thermal Conditions ◽  
Organotin Compounds ◽  
Silicon Compounds ◽  
Radical Process ◽  
Free Radical Process

The reactions of trimethyltin hydride and dimethyltin dihydride with (CH3)3SiCF=CF2 and (CH3)2Si(CF=CF2)2 respectively have been investigated. Under thermal conditions, reaction led to organotin fluorides and fluorovinyl-silanes. However, under ultraviolet irradiation at 25°, addition products were isolated of which (CH3)3SiCFHCF2Sn(CH3)3 and (CH3)3SiCF[Sn(CH3)3]CF2H were fully characterized. Evidence is presented which shows that these addition products are formed by a free radical process and that their decomposition to organotin fluorides and fluorovinyl-silanes proceeds via a β-fluorine elimination. Spectroscopic data are presented for a number of new organo-silanes.

Reactions of organotin compounds. IX. The reactions of tin hydrides with perfluorovinyl germanium and tin compounds

1968 ◽  
Vol 46 (12) ◽  
pp. 2165-2173 ◽  
Author(s):  
M. Akhtar ◽  
H. C. Clark
Keyword(s):  
Free Radical ◽  
Ultraviolet Irradiation ◽  
Spectroscopic Data ◽  
Addition Product ◽  
Tin Compounds ◽  
Radical Process ◽  
Organogermanium Compounds ◽  
The Stability ◽  
Derivatives Of ◽  
Free Radical Process

The formation of addition products (CH3)3MCFHCF2Sn(CH3)3 and (CH3)3MCF[Sn(CH3)3]CF2H where M = Ge or Sn has been observed in reactions involving the ultraviolet irradiation of (CH3)3MCF=CF2 with trimethyltin hydride. The former type of addition product is more stable than the latter, and the stability of both types decreases in the order M = Si, Ge, or Sn. Evidence is presented that decomposition occurs in all cases by a β-fiuorine elimination with the formation of fluorovinyl derivatives of M and trimethyltin fluoride. Similar reactions occur between (CH3)3GeCF=CF2 and dimethyltin dihydride and between (CH3)2Ge(CF=CF2)2 and dimethyltin dihydride or trimethyltin hydride. The evidence indicates that a free radical process is involved. Spectroscopic data are presented for new organogermanium compounds.

Reactions of organotin compounds. X. Reactions of tin hydrides with CF2=CFRe(CO)5, CF3CF=CFRe(CO)5, and some fluorinated alkenes

1969 ◽  
Vol 47 (20) ◽  
pp. 3753-3758 ◽  
Author(s):  
M. Akhtar ◽  
H. C. Clark
Keyword(s):  
Ultraviolet Irradiation ◽  
Spectroscopic Data ◽  
Organotin Compounds ◽  
Vinyl Fluoride ◽  
New Compounds ◽  
Derivatives Of

Trimethyltin hydride reacts with CF2=CFRe(CO)5 under ultraviolet irradiation to give new fluorovinyl derivatives of —Re(CO)5. Similar products were obtained using dimethyltin dihydride, but no reaction occurred between trimethyltin hydride and CF3CF=CFRe(CO)5. The reactions of trifluoroethylene, 1,1-difluoroethylene, and vinyl fluoride with trimethyltin hydride have been studied, thus completing the sequence of such reactions with fluorinated ethylenes. While both possible addition products were obtained with trifluoroethylene, and also from the corresponding reaction with perfluoropropene, 1,1-difluoroethylene gave only (CH3)3SnCH2CF2H, and with vinyl fluoride only trimethyltin fluoride and ethylene were isolated. Possible explanations are proposed and spectroscopic data for the new compounds are presented.

Absolute rate constants for hydrocarbon autoxidation. 32. On the self-reaction of 1,1-diphenylethylperoxyl in solution

1982 ◽  
Vol 60 (20) ◽  
pp. 2566-2572 ◽  
Author(s):  
J. A. Howard ◽  
J. H. B. Chenier ◽  
T. Yamada
Keyword(s):  
Free Radical ◽  
Rate Constants ◽  
The Self ◽  
Absolute Rate ◽  
Radical Process ◽  
First Order ◽  
Hydroperoxide Decomposition ◽  
Solvent Cage ◽  
Induced Decomposition ◽  
Free Radical Process

The major products of the self-reaction of 1,1-diphenylethylperoxyl have been determined from product studies of the autoxidation of 1,1-diphenylethane, induced decomposition of 1,1-diphenylethyl hydroperoxide, and decomposition of 2,2,3,3-tetraphenylbutane under an atmosphere of oxygen. Overall self-reaction is a complex free-radical process involving the intermediacy of 1,1-diphenylethoxyl and 1-phenyl-1-phenoxyethoxyl which undergo H-atom abstraction, β-scission and, in the case of the former radical, rearrangement. Hydroperoxide decomposition under an atmosphere of 36O2 has shown that 1,1-diphenylethylperoxyl undergoes β-scission faster than α-cumylperoxyl at 303 K in solution. The values of the rate constants for self-reaction of Ph2C(Me)O2• relative to those for tert-butylperoxyl are, however, not affected by this reaction. Furthermore they are not affected to any appreciable extent by the efficiency with which Ph2C(Me)O•, formed in nonterminating self-reactions, escape from the solvent cage. They are influenced principally by the first-order rate of decomposition of Ph2C(Me)OOOOC(Me)Ph2.

Hydrogels based on pullulan derivatives crosslinked via a “living” free-radical process

2002 ◽  
Vol 203 (10-11) ◽  
pp. 1285-1291 ◽  
Author(s):  
Vittorio Crescenzi ◽  
Mariella Dentini ◽  
Debora Bontempo ◽  
Giancarlo Masci
Keyword(s):  
Free Radical ◽  
Radical Process ◽  
Free Radical Process

Oxidative addition to iridium(I). Free-radical process

1972 ◽  
Vol 94 (11) ◽  
pp. 4043-4044 ◽  
Author(s):  
John S. Bradley ◽  
Dan E. Connor ◽  
David Dolphin ◽  
Jay A. Labinger ◽  
John A. Osborn
Keyword(s):  
Free Radical ◽  
Oxidative Addition ◽  
Radical Process ◽  
Free Radical Process
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