The Peroxide- and Light-induced Additions of Alcohols to Olefins¹

The Kinetic Equations of Addition Processes by the Free-Radical Nonbranched-Chain Mechanism

“…R is an alkenyl radical (allyl or higher) [2,5,[17][18][19][20][21][22], 1-hydroxyalkenyl [5,17,18,23,24], or a similar functionalized low-reactive radical (inhibitor) [5,18];  3 R is a saturated reactive 1:1 adduct radical; R 0 A, R 0 B, and R 1 A are saturated molecules; R 2 B is an unsaturated molecule (alkene or its derivative); R 3 A and R 3 B are 1:1 adduct molecules; Prod designates the molecular products resulting from the dimerization or disproportionation of free radicals. The chain evolution (propagation and inhibition) stage of Scheme 1 include consecutive reactions 2 and 3, parallel (competing) reaction pairs 3 and 4, and consecutive-parallel reaction pair 2-4.…”

“…When reacting with alkenes not inclined to free-radical polymerization, the free radicals originating from inefficient saturated telogens, such as alcohols [17] and amines [18], usually add to the least substituted carbon atom at the double bond, primarily yielding a free 1:1 adduct radical. This radical accumulates an energy of 90-130 kJ mol -1 , which is released upon the transformation of the C=C bond to an ordinary bond (according to the data reported for the addition of nonbranched C 1 -C 4 alkyl radicals to propene and of similar C 1 and C 2 radicals to 1-butene in the gas phase under standard conditions [1][2][3][4]).…”

“…In this scheme, I is the initiator, for example, a peroxide [5,17,18,29,30] The chain evolution stage of Scheme 5 includes consecutive reactions 2, 3; 2, 3a; and 3a, 3b; parallel (competitive) reactions 3, 3a; 3, 3b; 3, 4 (or 4a); and 3a, 4 (or 4a); and consecutive-parallel reactions 2 and 4 (or 4a). Addition to alkenes is described by reactions 1-3, 4, and 5-7 and the corresponding rate equations (1)-(4a).…”

Kinetics of Nonbranched-Chain Processes of the Free-Radical Addition to Molecules of Alkenes, Formaldehyde, and Oxygen with Competing Reactions of Resulting 1:1 Adduct Radicals with Saturated and Unsaturated Components of the Binary Reaction System

“…In this scheme, I is an initiator (e.g., a peroxide [5,12,13] [20], alkyl [2,5], 1-hydroxyalkyl [5,6,17,[22][23][24], or a similar functionalized reactive addend radical [5];  2 R is an alkenyl radical (allyl or higher) [2,5,[17][18][19][20][21][22], 1-hydroxyalkenyl [5,17,18,23,24], or a similar functionalized low-reactive radical (inhibitor) [5,18]; derivative); R 3 A and R 3 B are 1:1 adduct molecules; Prod designates the molecular products resulting from the dimerization or disproportionation of free radicals. The chain evolution (propagation and inhibition) stage of Scheme 1 include consecutive reactions 2 and 3, parallel (competing) reaction pairs 3 and 4, and consecutiveparallel reaction pair 2-4.…”

“…In this scheme, I is the initiator, for example, a peroxide [5,17,18,29,30]; 0 R  is any reactive radical (initiator); A is an atom of hydrogen [2,5,6,17,18,[22][23][24][29][30][31][32] or halogen [2,5,[19][20][21]; B is an atom of hydrogen [5,[17][18][19][20][21]23,24,[29][30][31][32], halogen [22], or oxygen (in oxidation) [ [20], an alkyl [2,5,6,21], a 1-hydroxyalkyl [5,6,17,[22][23][24]29,32], or a similar functionalized radical [5]...…”