26
G. Kaplan, G. Drake, K. Tollison, L. Hall and T. Hawkins
Vol. 42
with several aliquots (50 ml total) of diethyl ether. The mother
liquor was concentrated by distillation under reduced pressure
resulting in a second crop of crystals that were collected by filtra-
tion, washed with diethyl ether combined with first crop and
dried under high vacuum, resulting in a good yield 4.99 g (93%)
of 1-amino-3-methyl-1,2,3-triazolium iodide (3a) , mp 146 °C
CH -CH ), 18.7 (CH -CH CH -CH ), 30.5 (CH -CH CH -
2 3 2 2- 2 3 2 2- 2
CH ), 52.5 (CH -CH CH -CH ), 126.8 (C-5), 130.6 (C-4).
3
2
2-
2
3
Anal. Calcd. for C H N Br: C, 32.59; H, 5.93; N, 25.34.
6
13 4
Found: C, 32.50; H, 6.21; N, 25.08.
1-n-Propyl-(1H)-1,2,3-triazole (4a).
1
dec; H nmr (DMSO-d ): δ 4.2 (s, 3H, CH ), 8.2 (s, 2H, NH ),
1-Amino-3-n-propyl-1,2,3-triazolium bromide (3c) 1.56 g (7.5
mmoles) was dissolved and stirred vigorously in 10 ml of water in
a 50 ml round-bottomed flask, cooled in the ice-bath. Hydrochloric
acid (37%), 1.56 g (7.5 mmoles) was added slowly to the vigor-
ously stirred triazolium solution followed by the slow, drop-wise
6
3
2
13
8.6 (s, 1H, triazolyl C5-H), 8.7 (s, 1H, triazolyl C4-H); C nmr
(DMSO-d ): δ 39.7 (CH ), 126.8 (C-5), 131.5 (C-4).
6
3
Anal. Calcd. for C H N I: C, 15.94; H, 3.12; N, 24.79. Found:
3
7 4
C, 16.22; H, 3.20; N, 24.66.
addition of NaNO 0.556 g (8.1 mmoles) dissolved in 1 ml of water
2
1-Amino-3-ethyl-1,2,3-triazolium Bromide (3b).
to the acidic solution of 3-amino-1-n-propyl-1,2,3-triazolium bro-
mide (3c). After addition was completed the reaction mixture was
removed from the ice bath, stirred for 1 hour at room temperature
In a manner similar to that for the methyl iodide salt cited above,
1-amino-1,2,3-triazole (2) 2.00 g (3.8 mmoles) was reacted with
ethyl bromide (12.05 g, 110.5 mmoles) at 45 °C, resulting in a
good yield 3.82 g (83 %) of 1-amino-3-ethyl-1,2,3-triazolium bro-
and rendered alkaline by addition of Na CO 4.5 g (42.4 mmol).
2
3,
The reaction mixture was extracted twice by 30 ml of ethyl acetate,
the extracts combined, dried over magnesium sulfate, and the ethyl
acetate carefully distilled off under reduced pressure, yielding 0.72
1
mide (3b), mp 117-118 °C; DSC onset 149 °C; H nmr (DMSO-
d ): δ 1.4 (m, 3H, CH ), 4.5 (m, 2H, CH ), 8.4 (s, 2H, NH ), 8.7(s,
6
3
2
2
13
1H, triazolyl C5-H), 8.9 (s, 1H, triazolyl C4-H); C nmr (DMSO-
-1
g (87%) of 1-n-propyl-1,2,3-triazole (4a), bp 42 °C (3.2x10
d ): δ 14.1 (CH ), 48.4 (CH ), 126.7 (C-5), 130.2 (C-4)
+
1
6
3
2
Torr); Mass m/e=111(M ); H nmr (DMSO-d ): δ 0.8 (t, 3H, CH
6
2-
Anal. Calcd. for C H N Br: C, 24.88; H, 4.70; N, 29.02.
4
9 4
CH -CH ), 1.8 (m, 2H, CH CH -CH ), 4.3 (t, 2H, CH CH -
2
3
2-
2
3
2-
2
C
Found: C, 24.56; H, 4.97; N, 28.90.
13
CH ), 7.7 (d, 1H, triazolyl C-5H), 8.1 (d, 1H, triazolyl C4-H);
3
nmr (DMSO-d ): δ 10.7 (CH CH -CH ), 23.2 (CH CH -CH ),
6
2-
2
3
2-
2
3
1-Amino-3-n-propyl-1,2,3-triazolium Bromide (3c).
50.6 (CH CH -CH ), 124.5 (C-5), 133.1 (C-4).
2-
2
3
In the same manner as above 1-amino-1,2,3-triazole (2) 2.00 g
(23.8 mmoles) was reacted with n-propyl bromide 13.60 g (110.6
mmoles) at 60 °C, resulting in a good yield 4.43 gm (90%) of 1-
Anal. Calcd. for C H N : C, 54.03; H, 8.16; N, 37.81. Found:
5
9 3
C, 53.63; H, 8.31; N, 37.74.
1-(2-Propenyl)(1H)-1,2,3-triazole (4b).
amino-3-n-propyl-1,2,3-triazolium bromide (3c), mp 128-129 °C;
1
DSC onset 135 °C; H nmr (DMSO-d ): δ 0.8 (t, 3H, CH -CH -
6
2
2
In the same manner as cited for the preceding 1-n-propyl-
1,2,3-triazole (4a), 1-amino-3-(2-propenyl)-1,2,3-triazolium bro-
mide (3d) 0.611 g (2.98 mmoles) was diazotized and upon
workup yielded an excellent yield 0.292 g (90%) of 1-(2-allyl)-
CH ), 1.8 (m, 2H, CH -CH -CH ), 4.5 (t, 2H, CH -CH -CH ), 8.4
3
2
2
3
2
2
3
(s, 2H, NH ), 8.7 (s, 1H, triazolyl C5-H), 9.0 (s, 1H, triazolyl C4-
2
13
H); C nmr (DMSO-d ): δ 10.3 (CH -CH -CH ), 22.2 (CH -CH -
6
2
2
3
2
2
CH ), 54.2 (CH -CH -CH ), 126.8 (C-5), 130.5(C-4).
-1
3
2
2
3
1,2,3-triazole (4b), bp 40 °C (2.2x10 Torr); Mass
Anal. Calcd. for C H N Br: C, 29.00; H, 5.35; N, 27.06.
+
1
5
11 4
m/e=109(M ); H nmr (DMSO-d ): δ 5.0(m, 2H, CH -
6
2
Found: C, 29.11; H, 5.32; N, 26.82.
CH=CH ), 5.2(m, 2H, CH -CH=CH ), 6.0 (m, 1H, CH -
2
2
2
2
CH=CH ), 7.7 (s, 1H, triazolyl C5-H), 8.0 (s, 1H, triazolyl C4-
1-Amino-3-(2-propenyl)-1,2,3-triazolium Bromide (3d).
2
13
H); C nmr (DMSO-d ): δ 51.4 (CH -CH=CH ), 118.5 (CH -
6
2
2
2
In the aforementioned method, 1-amino-1,2,3-triazole (2) 5.00
g (59.5 mmoles) was reacted with allyl bromide 35.00 g (289
mmoles) at 20 °C, and upon work-up resulted in a decent yield
9.03 g (75%) of 1-amino-3-(2-propenyl)-1,2,3-triazolium bro-
CH=CH ), 124.7 (C-5), 132.8 (CH -CH=CH ), 133.4 (C-4)
2
2
2
Anal. Calcd. for C H N : C, 55.03; H, 6.47; N, 38.50. Found:
5
7 3
C, 55.41; H, 6.53; N, 38.23.
1
mide (3d), mp 100-101 °C; DSC onset 135 °C; H nmr (DMSO-
1-n-Butyl-(1H)-1,2,3-triazole (4c).
d ): δ 5.2 (d, 2H, CH -CH=CH ), 5.4 (t, 2H, CH -CH=CH ), 6.0
6
2
2
2
2
Using the method described above, 1-amino-3-n-butyl-1,2,3-
triazolium bromide (3e) (1.62 g, 7.3 mmoles) was diazotized
resulting in an excellent yield 0.848 g (93%) of 1-n-butyl-1,2,3-
(m, 1H, CH -CH=CH ), 8.4 (s, 2H, NH ), 8.710 (s, 1H, triazolyl
2
2
2
13
C5-H), 8.9 (s, 1H, triazolyl C4-H); C nmr (DMSO-d ): δ 54.7
6
(CH -CH=CH ), 121.5 (CH -CH=CH ), 126.8 (C-5), 130.1
2
2
2
2
-2
+
triazole (4c), bp 58 °C (3.9x10 Torr) ; Mass m/e=125(M ),
(CH -CH=CH ), 130.7 (C-4).
2
2
1
96(M- HN-N), 68(M-C H ); H nmr (DMSO-d ): δ 0.8 (m, 3H,
4
9
6
Anal. Calcd. for C H N Br: C, 29.29; H, 4.42; N, 27.32.
5
9 4
CH -CH -CH -CH ), 1.2 (m, 2H, CH -CH -CH -CH ), 1.8 (m,
2
2
2
3
2
2
2
3
Found: C, 29.51; H, 4.42; N, 27.41.
2H, CH -CH -CH -CH ), 4.3 (m, 2H, CH -CH -CH -CH ), 7.7
2
2
2
3
2
2
2
3
13
1-Amino-3-n-butyl-1,2,3-triazolium Bromide (3e).
(s, 1H, triazolyl CH), 8.1 (s, 1H, triazolyl CH); C nmr (DMSO-
d ): δ 13.2 (CH -CH -CH -CH ), 19.0 (CH -CH -CH -CH ),
6
2
2
2
3
2
2
2
3
Using the same method as previously mentioned, 1-amino-
1,2,3-triazole (2) 2.00 g (23.8 mmoles) was reacted with n-butyl
bromide (16.01 g, 116.8 mmoles) at 60 °C. Upon work-up, 4.12 g
31.8 (CH -CH -CH -CH ), 48.8 (CH -CH -CH -CH ), 124.5
2
2
2
3
2
2
2
3
(C-5), 133.1 (C-4).
Anal. Calcd. for C H N : C, 57.57; H, 8.86; N, 33.57. Found:
6
11 3
(78%) of 1-amino-3-n-butyl-1,2,3-triazolium bromide (3e) was
C, 57.31; H, 9.11; N, 33.49.
1
yielded, mp 131-132 °C DCS onset 145 °C; H nmr (DMSO-d ):
6
δ 0.8 (m, 3H, CH -CH CH -CH ), 1.2 (m, 2H, CH -CH CH -
2
2-
2
3
2
2-
2
Acknowledgments.
CH ), 1.8 (m, 2H, CH -CH CH -CH ), 4.5 (m, 2H, CH -CH
3
2
2-
2
3
2
2-
The authors would like to thank Michael Berman (AFOSR)
and Michael Huggins (AFRL/PRS) as well as Ronald Channell
CH -CH ), 8.4(s, 2H, NH ), 8.7 (s, 1H, triazolyl C5-H), 8.9 (s,
2
3
2
13
1H, triazolyl C4-H); C nmr (DMSO-d ): δ 13.2 (CH -CH
6
2
2-