The chemical activation of nitrous oxide (N2O) can be achieved by organocalcium, organosodium, and organolithium compounds. Grignard reagents, on the other hand, are believed to be inert. We demonstrate that this generalization is not correct. Some aliphatic Grignard reagents undergo a rapid conversion when subjected to an atmosphere of N2O. Hydrazones are the main reaction products.
Tskhovrebov, Alexander G.,Solari, Euro,Scopelliti, Rosario,Severin, Kay
supporting information
p. 2405 - 2408
(2014/06/10)
A kinetic study of the reaction between CH3 radicals and azoisopropane; reactions of the radicals CH3, (CH3)2 CN = NCH(CH3)2 and (CH3)2CH NN(CH3)CH(CH3)2
The reaction of CH3 generated from di-tert-butyl peroxide with azoisopropane (AIP) in the temperature range 395-450 K was investigated by product analysis. The regioselectivity of CH3 with the carbon and nitrogen radical centres of (CH3)2 CN=NCH(CH3)2 was determined: CH3 + (CH3)2CN=NCH(CH3)2 → (CH3)3CN=NCH(CH3)2 (18) → (CH3)2C=NN(CH3)CH(CH3)2 (19) k18/k19 = 1.95 ± 0.24. The Arrhenius parameters of the H-abstraction and decomposition reactions CH3 + AIP → CH4 + (CH3)2CN=NCH(CH3)2 (3) (CH3)2CHNN(CH3)CH(CH3)2 → 2- CH7 + (CH3)2CHN=NCH3 (23) relative to the combinations 2 CH3 → C2H6 (13) 2 (CH3)2CHNN(CH3)CH(CH3)2 → (CH3)2CHN(CH3)N(CH(CH3)2)N(CH(CH3)2)N(CH3)CH(CH3)2 (26) were determined: log[(k3/, k13/(1/2)) / mol(-1/2) dm(3/2)s(-1/2)] = (3.1 ± 0.3) - (30.6 ± 2.4) kJ mol-1/θ log[k23 (φ k26/(1/2))- 1/mol(1/2)dm(-3/2)s(-1/2)] = (8.8 ± 0.5) - (110.0 ± 6.5) kJ mol-1/θ where θ = RT In 10 and φ is the cross-combination ratio of CH3 and (CH3)2CHNN(CH3)CH(CH3)2.
Kiraly,Goergenyi,Seres
p. 591 - 609
(2007/10/03)
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