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Formation of CH3CH2OCH3+˙ and ˙CH2+OHCH2CH3 from ionized 2-ethoxyethanol and theoretical and experimental studies of the reactions of ˙CH2+OHCH2CH3

✍ Scribed by David J. McAdoo; Charles E. Hudson; V. M. Sadagopa Ramanujam; M. George

Publisher
John Wiley and Sons
Year
1993
Tongue
English
Weight
640 KB
Volume
28
Category
Article
ISSN
1076-5174

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✦ Synopsis

It is concluded that C3H80+' formed by dissociation of ionized 2ethoxyethanol ( ) is a mixture of CH,CH,OCHl' (7) and 'GH,+OHCH,CH, (2). Formation of 7 and CH3CH2+0HCH3 ( ) is attributed to dissociations of species formed by the hydrogen transfers [ CH,CH20CH2+ 'CH,OHI + [CH,CH,OCHi' CH,Ol -+ [CH,CH,+OHCH, HCO]. Production of 7 competes weakly with dissociation to CH,CH,+OCH, (13) and to 12. The low abundance of 7 is attributed to the simple dissociation 8 + 13 being both energetically and entropically favored, and a second H-transfer to give 12 being energetically favored. The threshold for forming 7 is 45 kJ mol-' above that for dissociation directly to 13, so formation of 7 is the first ion-neutral complex-mediated elimination found to have a threshold above that for the competing simple dissociation. The low abundance of 7 also demonstrates that ion-neutral complexes can be intermediates without obviously revealing their presence by direct dissociation. Experimental results suggest that 2 isomerizes to CH,CH2CHz0H+' (5) and then dissociates by eliminating water. Ab initio results support the feasibility of 2 + CH,+OHCH,CH,' (1) and 2 + 5. However, experimental observations suggest that 2 + 1 does not occur. This is attributed to strong competition from dissociation and isomerization to 5. The transition state for 2 + 5 resembles [ CH,CH, CH,OHI +., and a cyclic transition state for 2 + 5 is ruled out. When the ethyl-oxygen bond in 2 is simply lengthened, the charge is initially concentrated on ethyl, but it switches to CH,OH in a curve crossing at an apparent transition state for C -0 bond breaking.

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