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VERESHCHAGIN et al.
triazole). Found, %: C 61.14; H 4.60; N 19.48.
C22H20O4N6. Calculated, %: C 61.11; H 4.63; N 19.44.
propargyl oxalate (VIIIc) and 4.8 g (36 mmol) of benzyl
azide in 15 ml of ethanol. Yield 0.62 g (11%), mp 167
1
170°C (EtOH). IR spectrum, cm : 3130 (CH of
Bis[(1-cyanomethyl-1,2,3-triazol-4-yl)methyl]
terephthalate (IXa). A mixture of 2 g (8 mmol) of
propargyl terephthalate (VIIIa) and 1.47 g (18 mmol) of
azidoacetonitrile (I) in 15 ml of ethanol was heated at
reflux and stirring for 1820 h. The separated precipitate
was filtered off, and washed with cold ethanol. Yield
1
triazole), 1745 (OCO), 1590 (Ph). H NMR spectrum,
d, ppm: 5.37 s (4H, 2CH2Ph), 5.6 s (2H, 2CH2OCO),
7.37.5 m (10H, 2Ph), 8.3 s (2H, 2CH of triazole). Found,
%: C 60.74; H 4.54; N 19.71. C22H20O4N6. Calculated,
%: C 61.11; H 4.63; N 19.44.
1
0.9 g (27%), mp 132°C (EtOH). IR spectrum, cm : 3125
Bis[(1-benzyl-1,2,3-triazol-4-yl)methyl] malonate
(IXf) was obtained from a mixture of 2 g (11 mmol) of
propargyl malonate (VIIIb) and 2.93 g (22 mmol) of
benzyl azide in 15 ml of ethanol. Yield 1.88 g (38%) of
(CH of triazole ring), 1720 (OCO), 1230, 1100, 1050
(triazole ring). 13C NMR spectrum, d, ppm: 36.6 (2C,
CH2 at CN), 57.3 (2C, CH2 at OCO), 114.1 (2C, 2CN),
125.2 (2C, 2CH of triazole), 128.9 and 132.6 (C1,2 arom),
141.6 (2C, 2CCH2 of triazole), 164.0 (2C, 2OCO).
Found, %: C 53.17; H 3.47; N 27.61. C18H14O4N8.
Calculated, %: C 53.20; H 3.45; N 27.59.
1
noncrystallizable oil.. IR spectrum, cm : 3125 (CH of
triazole), 1745 (OCO), 1590 (Ph).
Bis{[1-(tetrazol-5-ylmethyl)-1,2,3-triazol-4-
yl]methyl} terephthalate (Xa). A mixture of 0.97 g
(4 mmol) of ester VIIIa and 1 g (8.5 mmol) of azide II
in 10 ml of ethanol was heated at reflux for 10.5 h. The
separated precipitate was filtered off and washed with
cold ethanol. We obtained 0.8 g (41%) of light crystals
Likewise were synthesized compounds IXbf.
Bis[(1-cyanomethyl-1,2,3-triazol-4-yl)methyl]
malonate (IXb) was obtained from a mixture of 3 g
(17 mmol) of propargyl malonate (VIIIb) and 3 g (37
mmol) of azidoacetonitrile (I) in 20 ml of ethanol. Yield
1
of mp 239°C (EtOH). IR spectrum, cm : 3120 (CH of
1
triazole), 1710 (OCO). 13C NMR spectrum, d, ppm: 42.2
(2C, 2CH2N), 57.5 (2C, 2CH2OCO), 125.3 (2C, 2CH of
triazole), 129.0 and 132.7 (C1,2 arom), 141.1 (2C, 2C
CH2O of triazole), 152.9 (2C, 2NCN of tetrazole ring),
164.1 (2C, 2OCO). Found, %: C 43.65; H 3.38; N 39.98.
C18H16O4N14. Calculated, %: C 43.90; H 3.25; N 39.84.
1.29 g (23%), mp 170172°C (EtOH). IR spectrum, cm :
1
3130 (CH of triazole), 1725 (OCO). H NMR spectrum,
d, ppm: 5.25 s (4H, 2CH2CN), 5.9 s (4H, 2CH2OCO),
3.65 s [2H, CH2(COO)2], 8.3 s (2H, 2CH of triazole).
Found, %: C 45.87; H 3.44; N 32.02. C13H12O4N8.
Calculated, %: C 45.35; H 3.49; N 32.56.
Bis[(1-cyanomethyl-1,2,3-triazol-4-yl)methyl
oxalate (IXc) was obtained from a mixture of 3 g
(18 mmol) of propargyl oxalate (VIIIc) and 3.3 g
(39 mmol) of azidoacetonitrile (I) in 20 ml of ethanol.
Yield 2.06 g (35%), mp 197199°C (EtOH). IR spectrum,
Bis{[1-(tetrazol-5-ylmethyl)-1,2,3-triazol-4-yl]-
methyl} oxalate (Xb). A suspension of 0.8 g (12 mmol)
of sodium azide and 0.64 g (12 mmol) of ammonium
chloride was dissolved at stirring and heating to 9095°C
in 7 ml of DMF, then the solution was cooled, and 2 g
(6 mmol) of compound IXc was added. The reaction
mixture was stirred for 25 h at 120°C. The precipitate
was filtered off, the filtrate was evaporated in a vacuum.
The concentrated water solution was washed with ether,
poured into 30 ml of cold water, acidified with
hydrochloric acid to pH 2, the separated precipitate was
filtered off and washed with ethanol. Yield 0.68 g (27%),
1
cm : 3130 (CH of triazole), 1745 (OCO). 1H NMR
spectrum, d, ppm: 5.4 s (4H, 2CH2CN), 5.85 s (4H,
2CH2OCO), 8.4 s (2H, 2CH of triazole). Found, %:
C 43.94; H 3.05; N 33.15. C12H10O4N8. Calculated, %:
C 43.64; H 3.03; N 33.94.
Bis[(1-benzyl-1,2,3-triazol-4-yl)methyl] tere-
phthalate (IXd) was obtained from a mixture of 1 g
(4.1 mmol) of propargyl terephthalate (VIIIa) and
1.09 g (8.3 mmol) of benzyl azide in 10 ml of ethanol.
Yield 0.83 g (39.7%), mp 170172°C (EtOH), sparingly
1
mp 210°C (subl.). IR spectrum, cm : 3110 (CH of
1
triazole), 1710 (OCO). H NMR spectrum, d, ppm: 5.7
dC (4H, 2CH2 between heterocycles), 5.8 dC (4H,
2CH2O), 8.4 dC (2H, CH of triazole). Found, %: C 34.64;
H 3.94; N 47.17. C12H12O4N14. Calculated, %: C 34.62;
H 2.88; N 47.12.
1
soluble in organic solvents.. IR spectrum, cm : 3130
(CH of triazole), 1710 (OCO), 1590 (Ph). Found, %:
C 66.62; H 4.75; N 16.05. C28H24O4N6. Calculated, %:
C 66.14; H 4.72; N 16.54.
Polycycloaddition of diazides VIa and XI to
diacetylene compounds VIIIac. A mixture of 8 mmol
of diacetylene compound VIIIac and 8 mmol of diazide
Bis[(1-benzyl-1,2,3-triazol-4-yl)methyl] oxalate
(IXe) was obtained from a mixture of 3 g (18 mmol) of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004