7
4
A. V. Gulevskaya et al.
LETTER
2
-Amino-1,3,5-triazine (4a): white solid; mp >206 °C
0.91 (t, J = 7.1 Hz, 3 H, CH CH CH CH CH ). 13C NMR
2
2
2
2
3
3
a
1
(
sublimation) (Lit. 226 °C). H NMR (400 MHz, CDCl ):
(100 MHz, CDCl ): d = 166.3, 165.5, 164.6, 41.0, 29.0, 28.9,
3
3
1
+
d = 8.60 (s, 2 H, H-4, H-6), 5.34 (br s, 2 H, NH ). H NMR
22.4, 14.0. HRMS (ESI): m/z [M + H] calcd for C H N :
2
8
15
4
(
400 MHz, DMSO-d ): d = 8.45 (s, 2 H, H-4, H-6), 7.52 (br
167.1297; found: 167.1303.
2-(Piperidin-1-yl)-1,3,5-triazine (4f): white solid; mp 43–
6
13
s, 2 H, NH ). C NMR (100 MHz, CDCl ): d = 165.9, 165.7.
HRMS (ESI): m/z [M + H] calcd for C H N : 97.0514;
2
3
+
3a
1
44 °C (Lit. 43–44 °C). H NMR (400 MHz, CDCl ): d =
3
5
4
3
found: 97.0511.
8.49 (s, 2 H, H-4, H-6), 3.81 (m, 4 H, a-CH of piperidinyl),
2
1
3
2-Methylamino-1,3,5-triazine (4b): white solid; mp 109–
1.70 (m, 6 H, b-CH and g-CH of piperidinyl). C NMR
2 2
10 °C (Lit.3 109–110 °C). H NMR (400 MHz, CDCl ):
a
1
(100 MHz, CDCl ): d = 165.6, 162.7, 44.3, 25.7, 24.6.
1
3
3
+
d = 8.61 (s, 1 H, H-4 or H-6), 8.48 (s, 1 H, H-6 or H-4), 5.65
HRMS (ESI): m/z [M + H] calcd for C H N : 165.1140;
8
13
4
1
3
(br s, 1 H, NH ), 3.04 (d, J = 5.1 Hz, 3 H, CH ). C NMR
found: 165.1134.
2-(Morpholin-1-yl)-1,3,5-triazine (4g): white solid; mp
2
3
(
100 MHz, CDCl ): d = 166.3, 165.5, 165.1. HRMS (ESI):
3
+
3c
1
m/z [M + H] calcd for C H N : 111.0671; found: 111.0667.
108–110 °C (Lit. 106–108 °C). H NMR (400 MHz,
4
7
4
2
-Isopropylamino-1,3,5-triazine (4c): white solid; mp 73–
CDCl ): d = 8.54 (s, 2 H, H-4, H-6), 3.87 [m, 4 H, O(CH ) ],
3
2 2
1
13
7
4 °C. H NMR (400 MHz, CDCl ): d = 8.57 (s, 1 H, H-4 or
3.75 [m, 4 H, N(CH ) ]. C NMR (100 MHz, CDCl ): d =
2 2 3
+
3
H-6), 8.47 (s, 1 H, H-6 or H-4), 5.51 (br s, 1 H, NH), 4.20 [m,
165.7, 163.2, 66.6, 43.5. HRMS (ESI): m/z [M + H] calcd
1
3
1
H, CH(CH ) ], 1.26 [d, J = 6.5 Hz, 6 H, CH(CH ) ].
C
for C H N O: 167.0933; found: 167.0931. (b) Firouzabadi,
3
2
3 2
7
11
4
NMR (100 MHz, CDCl ): d = 166.3, 165.6, 163.8, 42.8,
H.; Vessal, B.; Naderi, M. Tetrahedron Lett. 1982, 23, 1847.
(9) Earlier several research groups reported that H NMR
3
+
1
2
1
2
6
8
2.5. HRMS (ESI): m/z [M + H] calcd for C H N :
6
11
4
39.0984; found: 139.0990.
spectroscopy is an effective diagnostic tool for the detection
H
-Butylamino-1,3,5-triazine (4d): white solid; mp 61–
of covalent s adducts because their formation is
3 °C (Lit.3 61–62 °C). H NMR (400 MHz, CDCl ): d =
a
1
characterized by an upfield shift of all proton signals in
comparison with the same signals in the substrate. The signal
of the proton bound to carbon which undergoes nucleophilic
attack is shifted the most (Dd = 3.5–4.0 ppm), due to the
3
.58 (s, 1 H, H-4 or H-6), 8.46 (s, 1 H, H-6 orH-4), 6.29 (br
s, 1 H, NH), 3.44 (dt, J = 5.9, 7.1 Hz, 2 H, CH CH CH CH ),
2
2
2
3
1
.60 (m, 2 H, CH CH CH CH ), 1.41 (m, 2 H,
2
2
2
3
2
CH CH CH CH ), 0.95 (t, J = 7.3 Hz, 3 H,
rehybridization of this carbon atom from sp in the substrate
2
2
2
3
1
3
H
CH CH CH CH ). H NMR (400 MHz, DMSO-d ): d = 8.56
to sp in the s adduct (see ref. 4).
2
2
2
3
6
(
6
d, J = 1.3 Hz, 1 H, H-4 or H-6), 8.47 (d, J = 1.3 Hz, 1 H, H-
or H-4), 8.11 (br s, 1 H, NH), 3.33 (dt, J = 6.0, 7.1 Hz, 2 H,
CH CH CH CH ), 1.55 (m, 2 H, CH CH CH CH ), 1.36 (m,
(10) When NH is used as the nucleophile, the reaction can also
3
occur via an alternative ANRORC-mechanism: ring-closure
of 6 can give 5 in which the exocyclic nitrogen (originating
from the ammonia nucleophile) has been incorporated in the
ring and the original ring nitrogen is transformed into the
exocyclic amino group. For a review on this topic, see: Van
der Plas, H. C. Tetrahedron 1985, 41, 237.
2
2
2
3
2
2
2
3
2
H, CH CH CH CH ), 0.94 (t, J = 7.3 Hz, 3 H,
2 2 2 3
1
3
CH CH CH CH ). C NMR (100 MHz, CDCl ): d = 166.3,
2
2
2
3
3
165.5, 164.6, 40.7, 31.3, 20.0, 13.7. HRMS (ESI): m/z [M +
+
H] calcd for C H N : 153.1140; found: 153.1140.
7
13
4
2
-Amylamino-1,3,5-triazine (4e): white solid; mp 47–
(11) For the calculation method of the activation barrier, see:
Aganov, A. V.; Klochkov, V. V.; Samitov, Y. Russ. Chem.
Rev. 1985, 54, 931.
1
49 °C. H NMR (400 MHz, CDCl ): d = 8.58 (s, 1 H, H-4 or
3
H-6), 8.48 (s, 1 H, H-6 or H-4), 6.25 (br s, 1 H, NH), 3.44 (dt,
J = 5.9, 7.1 Hz, 2 H, CH CH CH CH CH ), 1.62 (m, 2 H,
(12) Willner, I.; Rosengaus, J.; Eichen, Y. J. Phys. Org. Chem.
1993, 6, 29.
2
2
2
2
3
CH CH CH CH CH ), 1.36 (m, 4 H, CH CH CH CH CH ),
2
2
2
2
3
2
2
2
2
3
Synlett 2007, No. 1, 71–74 © Thieme Stuttgart · New York