Synthesis of methoxyꢀNNOꢀazoxyethene
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 6, June, 2003
1433
with a calibrated chromel—copel thermocouple. The yield of
compound 3 was determined using GLC with an LKhMꢀ8MD
chromatograph (column packed with 15% Carbowaxꢀ20М on
m/z (Irel (%)): 102 [M]+ (100), 87 [M – Me]+ (85), 58 (14), 57
[M – MeNO]+ (70), 46 (6), 45 [MeNO]+ (16), 43 (11), 42 (8),
41 (6), 40 (4), 32 (6), 31 (16), 30 (38), 29 (19), 28 (47), 27 (59).
Chromaton NꢀAW DMCS, N2 as the carrier gas, 30 mL min–1
,
The authors thank G. V. Lagodzinskaya and D. E.
Dmitriev for recording NMR spectra.
temperature of the column 150 °C, temperature of the evaporaꢀ
tor 200 °C), τ = 6.6 min, PhCN as the internal standard,
sp
τ
sp = 5.25 min.
References
1,1ꢀBis(methoxyꢀNNOꢀazoxy)ethane (4) was synthesized acꢀ
cording to a modified procedure.5 Nitrogen oxide17 was passed
through a solution of NaOH (98%, 245 g, 6 mol) and ethyl
methyl ketone (400 mL, 322 g, 4.47 mol, 2.23 equiv.) in MeOH
(2.5 L) with vigorous stirring and cooling with such a rate that
NO was completely absorbed, maintaining the temperature at
20—25 °C. A precipitate began to form after 20 min, and after
2 h the absorption of NO was sharply slowed down. The reaction
mixture was additionally stirred in an NO atmosphere for 3 h at
∼20 °C and neutralized by phenolphthalein with AcOH (5 mL).
The precipitate was filtered off, washed with MeOH (1 L) and
Et2O (1 L), and dried in air at the relative humidity not higher
than 60% (the product smeared at the humidity higher
than 70%). Thus obtained 1,1ꢀbis(nitrosohydroxylamino)ethane
disodium salt (490 g) was suspended without purification in DMF
(1 L), and Na2CO3 (53 g, 0.5 mol) was added. Then dimethyl
sulfate (560 mL, 5.8 mol) was gradually added with stirring and
cooling for 3.5 h, maintaining the temperature at 20—25 °C.
Plentiful gas evolution was observed, and the reaction mixture
darkened and homogenized, except for a minor precipitate of
Na2CO3. The mixture was additionally stirred for 0.5 h at 20 °C
and for 0.5 h at 50 °C, and the solvent was distilled off on a
rotary evaporator at 20—95 °C (8 Torr). In this distillation, the
target product was not distilled off (≤ 0.1%). Attention! The byꢀ
product, cancerogenic Nꢀnitrosodimethylamine, was distilled off
along with DMF. The residue was dissolved in water (1 L) and
extracted with CHCl3 (400 mL) for 15 h in a liquidꢀliquid exꢀ
tractor for the heavy organic phase. The extract (∼0.5 L) was
passed through a column packed with silica gel (100—160 µm,
100 g), washed with CHCl3 (250 mL), and evaporated in vacuo.
The residue was recrystallized from EtOH (200 mL). The yield
of the product was 118 g (16% based on ethyl methyl ketone),
m.p. 72—74 °C (cf. Ref. 5: m.p. 75—75.5 °C). After recrystalliꢀ
zation from an H2O—MeOH mixture, the product (92 g) was
obtained with m.p. 75—75.5 °C.
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MethoxyꢀNNOꢀazoxyethene (3). A 4ꢀL glass vessel containꢀ
ing compound 4 (7 g, 68.5 mmol, the maximum amount for
which the pressure of the pyrolysis products at 260 °C does not
exceed 1.5 atm) was evacuated with an oil pump (∼0.1 Torr),
sealed off and heated at 260 °C for 20 min, cooled, and opened.
The condensate was washed off with CHCl3 (30 mL). The solꢀ
vent was distilled off from the combined washings of five analoꢀ
gous experiments, and the residue was doubly distilled in vacuo.
The yield of the product was 10.6 g (53%), b.p. 66—68 °C
(8 Torr), nD20 1.4898, d420 1.111. UV, λmax/nm (ε): 250 (11170).
IR, ν/cm–1: 665, 745, 960, 1020, 1065, 1080, 1210, 1290 (N2O2),
1390 (N2O2), 1480 (N2O2), 1655 (C=C), 2845, 2960, 3000,
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1
3115, 3140. H NMR (without solvent, δ: 4.15 (s, 3 H, Me);
5.59 (d, 1 H, Hb, Ja,b = 7.5 Hz); 6.32 (d, 1 H, Hc, Ja,c = 15 Hz);
7.31 (dd, 1 H, Ha, Ja,b = 7.5 Hz, Ja,c = 15 Hz). 1H NMR
(CDCl3), δ: 4.02 (s, 3 H, Me); 5.37 (d, 1 H, Hb, Ja,b = 8 Hz);
6.25 (d, 1 H, Hc, Ja,c = 15 Hz); 6.93 (dd, 1 H, Ha, Ja,b = 8 Hz,
Ja,c = 15 Hz). 13C NMR, δ: 61.5 (CH3O); 113.6 (=CHN);
136.4 (CH2=). 14N NMR, δ, (∆ν1/2/Hz)): –66.8 (∼80). MS,
17. Yu. V. Karyakin and I. I. Angelov, Chistye khimicheskie
veshchestva [Pure Chemical Substances], Khimiya, Moscow,
1974, p. 24 (in Russian).
Received July 10, 2002;
in revised form March 13, 2003