Nitrofuroxans(furazans) through diazotization
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 2, February, 2012
475
stirred for 20 min and cooled to 0—2 C. Concentrated HCl
(0.45 mL, 4.3 mmol) was added dropwise over 2 h to the resultꢀ
ing mixture at the same temperature with stirring, which was
continued for another 30 min, then the mixture was left to stand
for 16 h at ~20 C. After that, the reaction mixture was diluted
with water (5 mL) and extracted with CH2Cl2 (3×2 mL). The
solvent was evaporated in vacuo, the residue was stirred with
water (3 mL) for 30 min for the separation of DMSO, and the
water was decanted. The product was dissolved in CH2Cl2
(4 mL), dried with MgSO4, and the solvent was evaporated on
a rotary evaporator at 20 C.
References
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The yield of 8b was 160 mg (67%), m.p. 95—96 C (CCl4)
(Ref. 6: 97—97.5 C); 14N NMR (CDCl3), : –34.46 (Ref. 8:
–34.78, CDCl3).
The yield of 10a was 130 mg (88%), b.p. 52 C (14 Torr)
20
20
(Ref. 3: 58.8 C, 18 Torr); nD 1.4555 (Ref. 3: nD 1.4549);
14N NMR (CDCl3), : –33.69 (Ref. 9: –32.4, acetoneꢀd6).
The yield of 10b was 134 mg (61%), m.p. 40—41 C (C6H14
(Ref. 6: 39 C); 14N NMR (CDCl3), : –33.92.
)
In the trial with 4ꢀaminoꢀ3ꢀmethylfuroxan 1a, evaporation
of CH2Cl2 gave a suspension of crystals in an oil. It was stirred
for 30 min with CH2Cl2 (0.3 mL), the crystals were filtered off,
washed on the filter twice with small amount of CH2Cl2, and
dried. The yield of triazene 9a was 22 mg (16%). The filtrate was
concentrated and the residue was recrystallized from MeOH to
obtain 8a 52 mg (31%), m.p. 66—67 C (MeOH), (Ref. 7: 67 C);
14N NMR (CDCl3), : –34.03 (Ref. 10: –31.84, acetoneꢀd6).
1,3ꢀBis(4ꢀmethylfuroxanꢀ3ꢀyl)triazꢀ2ꢀene (9a), m.p.
185—187 C. IR, /cm–1: 3839, 3291, 3228, 3068, 1688, 1556,
1305, 1182, 1016, 856, 587. 1H NMR (DMSOꢀd6), : 2.12 (s, 6 H,
2 Me); 10.11 (s, 1 H, NH). 13C NMR (DMSOꢀd6), : 8.32 (Me),
110.52 (C(3) in furox. rings); 150.50, 152.35 (C(4) in furox. rings).
MS, m/z (Irel (%)): 241 [M]+ (7), 225 [M – O]+ (3), 224
[M – O – 1]+ (10), 210 [M – NO – 1]+ (13), 196 [M – NO2 + 1]+
(9), 180 [M – 2 NO + 1]+ (15), 173 (22), 165 [M – NO – NO2]+
(33), 150 (30), 142 (methylfuroxanyltriazene) (58), 127 (methylꢀ
furoxanyldiazene) (30), 85 (72), 69 (100). Found (%): C, 29.61;
H, 2.80; N, 40.22. C6H7N7O4. Calculated (%): C, 29.88; H, 2.93;
N, 40.66.
Received July 11, 2011;
in revised form November 14, 2011