Electron spin resonance spectra from ultraviolet irradiation in an adamantane matrix. Primary process for aliphatic amines

1971 ◽  
Vol 93 (8) ◽  
pp. 2062-2063 ◽  
Author(s):  
David H. Volman ◽  
T. Richerzhagen
Keyword(s):  
Electron Spin Resonance ◽  
Electron Spin ◽  
Ultraviolet Irradiation ◽  
Aliphatic Amines ◽  
Primary Process ◽  
Spin Resonance

Electron Spin Resonance Studies of the Radiolysis of Aliphatic Amines Adsorbed on Silica Gel

1971 ◽  
Vol 49 (11) ◽  
pp. 1880-1887 ◽  
Author(s):  
P. Wardman ◽  
D. R. Smith
Keyword(s):  
Electron Spin Resonance ◽  
Silica Gel ◽  
Electron Spin ◽  
Active Site ◽  
Cation Radical ◽  
Aliphatic Amines ◽  
Polycrystalline Solid ◽  
Spin Resonance ◽  
Butyl Amine ◽  
Surface Active

Several aliphatic amines have been adsorben in sub-monolayer amounts on silica gel and γ-irradiated at 77 °K. The electron spin resonance (e.s.r.) spectra of the radicals trapped on the surface at 77 °K were similar, in most cases, to the spectra obtained after irradiating the corresponding polycrystalline solid amine at 77 °K. Methyl-, ethyl-, n-propyl, and n-butylamines all gave [Formula: see text] radicals, and dimethylamine gave [Formula: see text] radicals. The radical cation [Formula: see text] was observed in the case of trimethylamine. Adsorbed methoxy-amine and t-butyl amine have also been studied and the cation-radical of the latter tentatively identified. The results are discussed in terms of reaction of the adsorbed amine with a surface active site.

Electron Spin Resonance Studies of the Radiolysis of Aliphatic Amines at 77 °K

1971 ◽  
Vol 49 (11) ◽  
pp. 1869-1879 ◽  
Author(s):  
P. Wardman ◽  
D. R. Smith
Keyword(s):  
Electron Spin Resonance ◽  
Electron Spin ◽  
Aliphatic Amines ◽  
Methyl Ethyl ◽  
Alkyl Radicals ◽  
Restricted Rotation ◽  
Parallel Component ◽  
Alkyl Groups ◽  
Spin Resonance ◽  
Butyl Amine

Several frozen aliphatic amines have been γ-irradiated at 77 °K and the electron spin resonance (e.s.r.) spectra of the trapped radicals obtained at 77 °K and on warming. Radiolysis of methyl, ethyl and isopropyl amines produces predominantly alkylamino [Formula: see text] radicals. The proton hyperfine (h.f.) couplings of [Formula: see text] radicals are 10–30% larger than those in the corresponding isoelectronic alkyl radicals and the parallel component of the 14N coupling is about 35 G. Restricted rotation of alkyl groups occurs at 77 °K in some cases. On warming from 77 °K, the [Formula: see text] radicals generally abstract from the solvent or isomerize to produce radicals of the aminoalkyl type (e.g. RĊHNH2). The alkyl proton h.f. splittings of these latter radicals are 20–40% lower than in the corresponding alkyl radicals, and the observed 14N coupling was [Formula: see text] in ĊH2NR2 and [Formula: see text] in (CH3)2ĊNH2 and CH3ĊHNH2. The amino proton couplings in the aminoalkyl radicals were not resolved. Irradiated dimethylamine produces both (CH3)2N and CH2N(CH3) radicals, but (CH3)2N disappears on warming. Only ĊH2N(CH3)2 was observed after irradiation of (CH3)3N at 77 °K. Solid methoxyamine (giving CH3ONH) and tert-butyl-amine were also studied.

Sign in / Sign up

Export Citation Format

Share Document