Dimethyl formamide was catalytically synthesized from dimethyl amine, carbon dioxide and hydrogen in the presence of palladium(II) chloride and bases in the methyl cellosolve.
The photochemical primary processes of ethylene oxide in the vacuum ultraviolet region have been studied with emphasis on the dependence on energy. It has been found that the decomposition into methyl and formyl radicals is the main process while the decomposition into ethylene and oxygen atoms is also important at shorter wavelengths. 1470 Å1744 Å1783 ∼ 1845 ÅC2H4O+ h ν→ CH3+CHO(CO+H)111(I)→ O+C2H4(C2H2+H2)0.70.10.1(II)→ H2+(CH2CO)0.10.1···(III)→ CH3CHO0.2······(IV)→ CH2+HCHO0.2······(V)The formation of excited ethylene in Process (II) which decomposes into acetylene and hydrogen has been suggested.
Kinetical studies were made at 167°C on the decomposition of methanol induced by methoxy radicals, by pyrolyzing a small amount of dimethyl peroxide in methanol. A considerable amount of ethylene glycol was found. The following mechanism was proposed, and the kinetical equations derived therefrom could express the most part of the reaction quantitatively: CH3OOCH3 →2CH3O,CH3O+CH3OH→CH3OH+CH2OH, (a)CH3O →CH2OH,CH3O+CH2OH→CH3OH+HCHO,2CH3O →CH3OH+HCHO,CH3O+HCHO →CH3OH+CHO, (b)CH3O+CHO →CH3OH+CO or 2CHO→HCHO+CO,2CH2OH →CH2OH−CH2OH.The dissociation rate constant of dimethyl peroxide is represented by 4.1×1015 exp (—36.9 kcal/RT) sec—1, and the activation heat of (a) is 3.0∼4.3 kcal higher than that of (b).
Publication costs assisted by the Institute for Chemical Research Chemically activated 1-buten-l-yl radicals were generated by the addition of ethyl radicals produced by the photolysis of diethyl ketone to acetylene at 75 and 123°. The unimolecular rate constant for the isomerization of the excited 1-buten-l-yl to l-buten-4-yl radicals through 1,4-hydrogen atom migration was measured. In addition, it was found that the l-buten-4-yl formed can isomerize to methylallyl radicals via 1,2-H atom shift. The average rate constants for isomerization were found to be 1.00 X 109 and 1.05 X 109 sec-1 for 1-buten-l-yl and 3.47 X 107 and 6.20 X 107 sec-1 for l-buten-4-yl radicals at 75 and 123°, respectively. The best agreement between the rate constants as calculated by the RRKM theory and the experimental results was found when the threshold energies, Eq, were chosen as 17.1 and 33.0 kcal/mol for 1,4and 1,2-H atom shifts, respectively. It is shown that these values satisfy the expression, Eq = \> + Est where Eab is the activation energy for a bimolecular H atom abstraction and Es is the ring strain energy.
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