SPECIAL TOPIC
Nonsymmetrical 4,4¢-Bis(1,2,3-triazolium) Salts
2741
flux for 12 h. The volatiles were removed under reduced pressure
and the crude product was purified by precipitation with Et2O or by
column chromatography (silica gel; CH2Cl2–MeOH, 9:1).
1-Benzyl-1¢-(4-tert-butylbenzyl)-3-methyl-4,4¢-bis(1H-1,2,3-tri-
azol)-3-ium Tetrafluoroborate (5f)
Yield: 93%; white foam; mp 45–48 °C (Et2O).
IR: 3135, 2962, 1458 (triazole), 1046 (BF4) cm–1.
1,1¢-Dibenzyl-3-methyl-4,4¢-bis(1H-1,2,3-triazol)-3-ium Iodide
(5a)
Yield: 81%; white crystals; mp 140–142 °C (CH2Cl2/MeOH).
IR: 3436 (≡C–H), 3034, 1629, 1454 (triazole) cm–1.
1H NMR (500 MHz, CDCl3): d = 10.07 (s, 1 H), 9.26 (s, 1 H), 7.66–
7.25 (m, 10 H), 5.90 (s, 2 H), 5.61 (s, 2 H), 4.57 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 134.3, 133.5, 131.3, 130.8, 129.9,
129.5, 129.3, 129.0, 128.9, 128.8, 128.3, 127.2, 57.7, 54.5, 40.9.
1H NMR (500 MHz, CDCl3): d = 8.98 (s, 1 H), 8.66 (s, 1 H), 7.57–
7.25 (m, 9 H), 5.73 (s, 2 H), 5.55 (s, 2 H), 4.56 (s, 3 H), 1.28 (s,
9 H).
13C NMR (125 MHz, CDCl3): d = 152.1, 134.8, 131.7, 131.1, 130.8,
130.1, 129.5, 128.2, 128.2, 126.7, 126.1, 57.9, 54.4, 40.5, 34.6,
31.2.
1-Benzyl-1¢-(4-tert-butylbenzyl)-3-ethyl-4,4¢-bis(1H-1,2,3-triaz-
ol)-3-ium Tetrafluoroborate (5g)
Yield: 75%; oil.
IR: 3136, 2963, 1738, 1458 (triazole), 1047 (BF4) cm–1.
HRMS (ESI+): m/z [M-I]+ calcd for C19H19N6 : 331.1666; found:
+
331.1657.
3-Allyl-1,1¢-dibenzyl-3-methyl-4,4¢-bis(1H-1,2,3-triazol)-3-ium
1H NMR (500 MHz, CDCl3): d = 9.07 (s, 1 H), 8.70 (s, 1 H), 7.59–
7.24 (m, 9 H), 5.57 (s, 2 H), 5.32 (s, 2 H), 5.05 (q, J = 7.3Hz, 2 H),
1.68 (t, J = 7.3 Hz, 3 H), 1.30 (s, 9 H).
13C NMR (125 MHz, CDCl3): d = 152.1, 134.0, 131.7, 131.1, 130.7,
130.0, 129.5, 129.4, 128.3, 128.2, 126.8, 126.1, 57.9, 54.4, 49.5,
34.8, 31.1, 14.4.
Bromide (5c)
Yield: 84%; oil.
IR: 3403 (≡C–H), 3033, 2188, 1625 (C=C), 1456 (triazole) cm–1.
1H NMR (500 MHz, CDCl3): d = 10.60 (s, 1 H), 9.41 (s, 1 H), 7.68–
7.21 (m, 9 H), 6.04 (ddt, J = 16.5, 10.2, 6.2 Hz, 1 H), 5.94 (s, 2 H),
5.63 (d, J = 6.2 Hz, 2 H), 5.61 (s, 2 H), 5.42–5.35 (m, 2 H), 5.27 (s,
1 H).
13C NMR (125 MHz, CDCl3): d = 133.7, 133.5, 131.6, 131.1, 129.9,
129.6, 129.4, 129.3, 129.0, 128.8, 128.3, 128.1, 127.6, 122.8, 57.7,
55.7, 54.5.
1-Benzyl-3-methyl-1¢-phenyl-4,4¢-bis(1H-1,2,3-triazol)-3-ium
Tetrafluoroborate (5h)
Yield: 83%; white crystals; mp 183–185 °C (CH2Cl2–MeOH).
IR: 3163, 3128, 1644, 1595, 1457 (triazole), 1022 (BF4) cm–1.
1H NMR (500 MHz, CDCl3): d = 9.33 (s, 1 H), 9.24 (s, 1 H), 7.91–
4-(1,2,3-Triazol-4-yl)-(3-methyl-1,2,3-triazol-3-ium) Tetrafluo-
roborates 5; General Procedure
7.81 (m, 2 H), 7.64–7.44 (m, 7 H), 5.78 (s, 2 H), 4.69 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 135.9, 134.6, 132.2, 130.8, 130.3,
130.0, 129.8, 129.7, 129.5, 128.9, 125.0, 120.6, 58.2, 40.7.
To a solution of the corresponding 4-ethynyl-3-alkyl-1H-1,2,3-tria-
zol-3-ium tetrafluroborate 6 (0.20 mmol), azide 7 (0.22 mmol) and
TBTA (0.002 mmol) in t-BuOH–THF (1:1, 2 mL) kept under a ni-
trogen atmosphere, was added a deoxygenated aqueous solution (1
mL) containing sodium ascorbate (0.08 mmol) and CuSO4·H2O
(0.04 mmol). The homogeneous solution was stirred for 4–5 h, then
the organic solvents were evaporated under reduced pressure and
aqueous 10% ammonia (3 mL) was added and the mixture was ex-
tracted with EtOAc (3 × 5 mL). The combined organic phases were
dried (Na2SO4) and the product was purified by column chromatog-
raphy (silica gel; CH2Cl2–MeOH, 9:1).
+
HRMS (ESI+): m/z [M]+ calcd for C18H17N6 : 317.1509; found:
317.1513.
1¢-[1-(Benzyloxycarbonyl)isopropyl]-1-(4-cyanophenyl)-3-
methyl-4,4¢-bis(1H-1,2,3-triazol)-3-ium Tetrafluoroborate (5i)
Yield: 80%; white crystals; mp 205–208 °C (CH2Cl2–MeOH).
IR: 3013, 2970, 2230 (C≡N), 1737 (C=O), 1457 (triazole), 1042
(BF4) cm–1.
1H NMR (500 MHz, DMSO-d6): d = 10.16 (s, 1 H), 9.26 (s, 1 H),
8.31 (s, 4 H), 7.46–7.23 (m, 5 H), 5.23 (s, 2 H), 4.64 (s, 3 H), 2.09
(s, 6 H).
1,1¢-Dibenzyl-3-methyl-4,4¢-bis(1H-1,2,3-triazol)-3-ium Tet-
rafluoroborate (5d)
Yield: 95%; oil.
IR: 3136, 1456 (triazole), 1029 (BF4) cm–1.
1H NMR (500 MHz, CDCl3): d = 9.00 (s, 1 H), 8.67 (s, 1 H), 7.55–
7.30 (m, 9 H), 5.71 (s, 2 H), 5.55 (d, J = 13.5 Hz, 2 H), 4.55 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 134.7, 133.7, 131.7, 131.0, 130.1,
129.5, 129.5, 129.1, 128.9, 128.4, 128.2, 126.8, 57.9, 54.6, 40.5.
13C NMR (125 MHz, CDCl3): d = 170.5, 137.5, 135.5, 135.3, 134.7,
131.0, 128.5, 128.3, 127.6, 127.0, 125.5, 122.3, 117.5, 114.4, 67.4,
65.4, 30.7, 25.0.
3-Ethyl-1-(4-cyanophenyl)-1¢-(2,3,4-tri-O-acetyl-a-L-fucosyl)-
4,4¢-bis(1H-1,2,3-triazol)-3-ium Tetrafluoroborate (5j)
Yield: 70%; white crystals; mp 190–192 °C (CH2Cl2); [a]D20 –50.5
(c 0.10, CH2Cl2).
1¢-Benzyl-1-(4-tert-butylbenzyl)-3-methyl-4,4¢-bis(1H-1,2,3-tri-
azol)-3-ium Tetrafluoroborate (5e)
Yield: 88%; white crystals; mp 137–139 °C (Et2O).
IR: 2961, 1738, 1455 (triazole), 1032 (BF4) cm–1.
1H NMR (500 MHz, CDCl3): d = 8.90 (s, 1 H), 8.65 (s, 1 H), 7.61–
7.22 (m, 9 H), 5.67 (s, 2 H), 5.54 (s, 2 H), 4.47 (s, 3 H), 1.30 (s,
9 H).
13C NMR (125 MHz, CDCl3): d = 153.3, 134.6, 133.9, 131.8, 129.2,
129.1, 128.9, 128.6, 128.4, 128.3, 127.2, 126.4, 57.5, 54.5, 40.4,
34.7, 31.1.
IR: 3137, 2991, 2235 (C≡N), 1744 (C=O), 1371 (triazole), 1215,
1061 (BF4) cm–1.
1H NMR (500 MHz, CDCl3): d = 9.61 (s, 1 H), 8.88 (s, 1 H), 8.22
(d, J = 8.9 Hz, 2 H), 7.95 (d, J = 8.8 Hz, 2 H), 6.40 (d, J = 5.9 Hz,
1 H), 6.10 (dd, J = 10.9, 3.4 Hz, 1 H), 5.67 (dd, J = 11.0, 5.9 Hz,
1 H), 5.55 (d, J = 2.9 Hz, 1 H), 5.32 (s, 1 H), 5.24 (q, J = 7.3 Hz,
2 H), 4.69 (q, J = 6.3 Hz, 1 H), 2.28 (s, 3 H), 2.06–2.01 (m, 3 H),
1.91 (s, 3 H), 1.85 (t, J = 7.3 Hz, 3 H), 1.25–1.19 (m, 4 H).
13C NMR (125 MHz, CDCl3): d = 170.5, 170.3, 169.8, 137.4, 134.4,
131.8, 130.5, 130.1, 127.2, 122.3, 116.9, 116.0, 83.6, 70.5, 69.9,
68.0, 65.9, 50.6, 20.7, 20.6, 20.2, 16.1, 14.6.
HRMS (ESI+): m/z [M]+ calcd for C23H27N6 : 387.2292; found:
+
387.2294.
Synthesis 2011, No. 17, 2737–2742 © Thieme Stuttgart · New York