By H. Fischer (auth.), H. Fischer (eds.)
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Additional info for Carbon-Centered Radicals II
P. / add. ref. 330. 320. 2(25)kJ mol- ’ (Polyvinylacetate)’ *‘) + 2-t-butyl-2,2-bis-4-hydroxyphenylpropane(R-OH) f:BN as initiator in vinylacetate ‘vinylacetate k=51M-‘s-l 323 1 - products + R--i) 77Sim l/ 67 Sim 2 (Polyvinylacetate)’ 22) + 2,2’-I-butyl-2,2-bis-4hydroxyphenylpropane(R-OH) ---* R--6 + products + (R-OD) R-O + products-d, I$comp. 929) (Polyvinylacetate)’ 22) + 2,2’-t-butyl-6,6’-dimethyl-2,2-bis-p-hydroxyphenylpropane(R-OH)R-6 + (R-OD) + pcomp. BN as initiator in vinylacetate vinylacetate ) products + R--6 77 Sim l/ 67 Sim 2 k = 254M-'s-l 323 (Polyvinylacetate)’ 22) + 2,2’,6,6’-tetraethyl-2,2-bis-p-hydroxyphenylpropane(R-OH) + R-OH..
10’ M- ’ s- ’ referringto 2(4-CIC,H,),CH~CI, ‘) Radicalsfrom anedosine-5’-monophosphate + OH reaction. ‘) Measured via RSSR; absorption (RS + RS- F= RSSR;). 3, Radicals from cytidine-5’-monophosphate + 6H reaction. 3OM-*s-~. ‘) Radicals from dihydrothymine + i)H reaction. ‘) Radicals from glucoset OH reaction. ‘) Rate constant measured via RSSR: formation (RS $ RS- = RSSR;). 1 Absolute rate constants of displacement reactions 36 Reaction Radical generation Method Solvent TrKl [Ref. p. / add. ref.
Hydrogenbridging with monomervinylacetate(M). 29)k(Hx/k@) > 10 indicates tunneling. 9(26). *I) At least partially C-centered radical. BunifaEif/Asmus Ref. p. 2 Relative rate constants of displacement reactions Solvent TCKI (Thymine-OH’) 42) + CH,OH eH,OH + products Rad. of thymine + N,O + H,O RT PR, glc H2O (Uridine-OH’)44) + HSCH,CH(NH,)COOH Pulse rad. / add. ref. 10sM-‘s-‘45) (Uridine-S-monophosphate-OH’) 46) + HSCH,CH(NH,)COOH SCH,CH(NH,)COOH Pulse rad. 1 Radicals containing only C and H atoms eD, + CH,OH * CD,H + cH,OH + cD,cocD, --L CD, + CD,COCD, Phot.
Carbon-Centered Radicals II by H. Fischer (auth.), H. Fischer (eds.)