Abstract
Trichloroisocyanuric acid was used as an effective oxidizing
agent for the oxidation of urazoles and bis-urazoles to their corresponding
triazolinediones under both heterogeneous and also solvent free
conditions with excellent yields at room temperature.
Keywords
trichloroisocyanuric - urazoles - bis-urazoles - triazolinediones - solvent free conditions
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23 Chemicals were purchased from Fluka,
Merck, Riedel-deHaën AG and Aldrich chemical companies.
Yields refer to isolated pure products. The oxidation products were characterized
by comparison of their spectral (IR, UV, 1 H NMR,
and 13 C NMR) and physical data with
the authentic samples. All urazoles and bis-urazoles were synthesized according
to our previously reported procedures.
[1 ]
[4 ]
[5 ]
[10 ]
[11 ]
[21 ]
24 Oxidation of 4-cyclohexyl urazole(1e ) to 4-cyclohexyl-1,2,4-triazoline-3,5-dione(2e ) with trichloroisocyanuric acid, a typical
procedure. A mixture of compound 1e
(0.366
g, 2.0 mmol) and trichloroisocyanuric acid (0.232 g, 1.0 mmol) was
shaken at r.t. for 0.25 h and dichloromethane (20 mL) was added
to the resulting mixture then filtered. Dichloromethane was removed
by water bath (40-50 °C)
[25 ]
under simple distillation.
The yield was 0.35 g (98%) of crystalline red solid (2e ), mp 95-98 °C [Lit
[8 ]
mp 95-96 °C]. 1 H
NMR (FT-90 MHz, CDCl3 /TMS): δ = 3.90
(quintet, 1 H, J = 12
Hz), 1.82-1.26 (m, 10 H). 13 C
NMR (FT-22.5 MHz, CDCl3 /TMS): δ = 158.77,
53.93, 28.72, 24.96, 24.28.
25 These compounds are sensitive to the
light, heat, alcohols, ethers, transition metals and any nucleophiles.
Also they are very volatile so that, if temperature rises over than
50 °C in the course of removing of CH2 Cl2 ,
some of TADs are removed with solvent simultaneously.
Therefore, the temperature must be controlled and dichloromethane
is the best solvent for this purpose.
26 For running the oxidation reaction
under heterogeneous conditions please see ref. 14.