1556
P. J. Davis et al. / Tetrahedron Letters 52 (2011) 1553–1556
OEt
11a R1 = H, R2 = H, R3 = H
R3
R2
11b R1 = OMe, R2 = OMe, R3 = H
11c R1 = NO2, R2 = NO2, R3 = H
11d R1 = Cl, R2 = Cl, R3 = H
EtOH
1a-e
thermolysis or
photolysis
R1
11e R1 = H, R2 = Me, R3 = NO2
Scheme 4.
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Figure 2. Time course of reactions according to Scheme 4.
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Table 2
Reaction times and yields according to Scheme 4
Compound
Product
Reaction time (h) (Yield %)
Photolysis Thermolysis
1a
1b
1d
1e
11a
11b
11d
11e
72 (81)
24 (90)
48 (73)
72 (94)
4 (75)
1.5 (60)
3 (78)
5 (81)
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reaction of diphenyldiazomethane with ethanol has been mea-
sured to be À53.6 kcal molÀ1 34
.
These data indicate that substituted diaryldiazomethanes and
diazofluorenes, which are readily available, stable and storable sol-
ids, have decomposition temperatures dependent on substitution
pattern, and not less than 120 °C amongst the examples studied;
they are reactive with alcohols at elevated temperature in the ab-
sence of catalysts. Notable is the stability of systems containing
free hydroxy 3c and pyridyl 4a,b groups, and of diazofluorenones
generally (3 and 4).
Acknowledgements
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L.H. is grateful for CASE studentship support from the EPSRC
and GSK (Harlow). We gratefully acknowledge the use of the EPSRC
Chemical Database Service at Daresbury.44 Aman Karim was a vis-
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achi) and is grateful for receipt of funding from the IRSI Program
of the Higher Education Commission of Pakistan.
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Supplementary data
Supplementary data associated with this article can be found, in
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