cm3 molecule-1 s-1 (19)] and 2-ethoxyethanol [14.5 × 10-12
cm3 molecule-1 s-1 (6)].
(2) ECETOC Technical Report 64; The Toxicology of Glycol Ethers
and its Relevance to Man; ECETOC: Brussels, 1995.
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As shown in Scheme 1, ethyl formate can be formed
from the photooxidation of ethoxyacetaldehyde via two
routes, and a preliminary investigation of the photooxi-
dation of ethoxyacetaldehyde was undertaken. The mea-
sured yields of ethyl formate in presence of high initial
mixing ratios of NO and NO2 respectively were combined
and give an estimated yield of 48 ( 20% by neglecting the
influence of the NO/ NO2 ratio. This approximation was
necessary since the variations of the NO/ NO2 ratios during
the experiments were unknown.. The overall yield of ethyl
formate formed from 2-ethoxyethanol is thus significantly
affected by this secondary channel. An estimate of the
ethyl formate yield formed as a primary product from
2-ethoxyethanol via alkoxy radical 5 was derived by
subtracting the calculated secondary formation from the
total observed formation of ethyl formate and resulted in
a value of ∼34 ( 10%. The given uncertainty brackets both
sets of conditions, i.e., high and low ratios of NO/ NO2.
Finally, the distribution of major products from the
photooxidation of 2-ethoxyethanol may be compared with
the SAR predictions of Atkinson (20) with respect of the
reactivity of the different reaction sites in 2-ethoxyethanol
toward the initial OH attack. The SARpredicts the following
fractions of the total reactivity of the groups in CH3CH2-
OCH2CH2OH, starting on the left-hand side of the mol-
ecule: 0.8% for the primary carbon group; 36%, 44%, and
18% for the secondary carbon groups; and 0.8% for the
hydroxy group. In the present study, only products from
attack on the secondary carbon groups were observed. The
sum of the corrected yields of 2-methyl-1,3-dioxolane,
ethylene glycol monoformate, and ethylene glycol monoac-
etate yields 47 ( 8% and indicates the importance of OH
abstraction at the first secondary carbon group. The
corrected primary yield of ethyl formate represents the
abstraction from the second CH2 group that was estimated
above to be 34 ( 10%. The corrected yield of ethoxyac-
etaldehyde was found to be 24 ( 13%, which corresponds
to the OH attack at the third CH2 group. Thus, the observed
product distributions are in reasonable agreement with the
SAR predictions.
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Acknowledgments
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The authors thank the Schweizerische Nationalfonds zur
Fo¨ rderung der wissenschaftlichen Forschung for financial
support and Dr. C. Geel of Dow Europe, Horgen, Switzer-
land, for supplying technical information on glycol ethers.
Received for review April 16, 1996. Revised manuscript re-
ceived June 14, 1996. Accepted June 17, 1996.X
ES960348N
Literature Cited
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X Abstract published in Advance ACS Abstracts, September 15, 1996.
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