The Journal of Organic Chemistry
powder (82.5 mg, 65%); following Procedure D using N,N-
Page 6 of 8
J = 7.7 Hz, 1H), 7.41 (t, J = 4.8 Hz, 2H), 7.25 (c with CHCl3, t,
J = 8.4 Hz, 1H), 6.61 (d, J = 8.5 Hz, 2H), 4.84 (s, 2H), 4.50
(s, 4H), 3.76 – 3.28 (m, 12H), 3.24 (s, 3H), 2.29 – 1.93 (m,
4H), 1.93 – 1.44 (c with H2O, m, 8H); 13C{1H} NMR (101
MHz, CDCl3) δ 167.5, 163.9, 162.4, 153.3, 149.3, 138.8,
129.5, 124.9, 113.3, 106.2, 67.7, 65.8, 65.7, 63.4, 50.1, 39.3,
38.2, 26.9, 26.1, 21.5, 15.2; HRMS (m/z) Calc. for
1
2
3
4
5
6
7
8
dimethyloctylamine (32 μL, 0.187 mmol) the target product
was obtained as white powder (118 mg, 93%). mp 251-253 C;
1H NMR (400 MHz, CDCl3) δ 11.27 (s, 1H), 9.36 (t, 2H), 8.34
(d, J = 7.8 Hz, 2H), 7.98 (c with DMF, t, J = 7.7 Hz, 1H), 7.38
(t, 2H), 7.27 (c with CHCl3, t, J = 8.4 Hz, 1H), 6.63 (d, J = 8.5
Hz, 2H), 4.79 (s, 2H), 4.51 (s, 4H), 3.48 (qd, J = 13.5, 7.3 Hz,
10H), 3.17 (s, 6H), 1.91–1.54 (c with H2O, m, 10H), 1.38–1.06
(m, 10H), 0.86 (t, J = 6.9 Hz, 3H); 13C{1H} NMR (101 MHz,
CDCl3) δ 167.3, 163.9, 161.8, 153.3, 149.4, 138.7, 129.6,
124.9, 113.3, 106.1, 67.7, 66.9, 63.3, 51.8, 39.3, 38.2, 31.5,
28.9, 28.9, 27.0, 26.0, 25.9, 22.8, 22.5, 14.0; HRMS (m/z)
+
C32H44N7O7 [M]+: 638.3301, found: 638.3302. These data
correspond to product obtained according to the Procedure D.
N,N‐dimethyl‐N‐[({4,11,17,24‐tetraoxo‐2,26‐dioxa‐5,10,18,23,
32‐pentaazatricyclo[25.3.1.112,16]dotriaconta‐1(31),12(32),
13,15,27,29‐hexaen‐31‐yl}carbamoyl)methyl]anilinium chlo-
ride (23). Following Procedure D using N,N-dimethylaniline
(22 μL, 0.187 mmol) the target product was obtained as white
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
+
Calc. for C37H56N7O7 [M]+: 710.4241, found: 710.4222. The-
se data correspond to product obtained according to the Proce-
dure D.
powder (36 mg, 30%); following Procedure
E N,N-
ethylbis(propan‐2‐yl)[({4,11,17,24‐tetraoxo‐2,26‐dioxa‐5,10,
18,23,32‐pentaazatricyclo[25.3.1.112,16]dotriaconta‐1(31),12
(32),13,15,27,29‐hexaen‐31‐yl}carbamoyl)methyl]azanium
chloride (20). Following Procedure E using DIPEA (148 μL,
0.85 mmol) the target product was obtained as white powder
(63.8 mg, 52%), following Procedure D using DIPEA (30 μL,
0.187 mmol) the target product was obtained as white powder
dimethylaniline (148 μL, 0.85 mmol) the target product was
obtained as white powder (82.8 mg, 69%). mp 126-128 C; H
1
NMR (400 MHz, CDCl3) δ 11.36 (s, 1H), 9.30 (s, 2H), 8.29
(d, J = 7.5 Hz, 2H), 7.95 (t, J = 7.5 Hz, 1H), 7.72 (d, 2H), 7.55
(s, 2H), 7.44 (s, 1H), 7.15 (d, J = 8.2 Hz, 1H), 6.50 (d, J = 8.3
Hz, 2H), 5.36 (s, 2H), 4.41 (s, 4H), 3.70 (s, 6H), 3.60 – 3.25 (c
with Et2O, m, 8H), 1.91 – 1.50 (c with Et2O, m, 8H); 13C{1H}
NMR (101 MHz, CDCl3) δ 167.6, 164.0, 161.5, 153.1, 149.4,
145.6, 138.6, 131.1, 130.8, 129.3, 124.9, 119.6, 113.3, 105.9,
67.6, 65.8, 56.1, 39.4, 38.3, 26.9, 26.0; HRMS (m/z) Calc. for
1
(46.4 mg, 38%). mp 205-207 C; H NMR (400 MHz, CDCl3)
δ 11.40 (s, 1H), 9.46 (s, 2H), 8.33 (d, J = 7.6 Hz, 2H), 7.98 (s,
1H), 7.34 (t, 2H), 7.27 (c with CHCl3, 1H), 6.63 (d, J = 9.2 Hz,
2H), 4.57 (m, 6H), 4.13 (q, 2H), 3.76 – 3.23 (m, 10H), 2.01 –
1.21 (m, 23H); 13C{1H} NMR (101 MHz, CDCl3) δ 167.60,
164.0, 163.2, 153.5, 149.33, 138.5, 129.4, 124.7, 113.7, 106.2,
67.6, 65.1, 55.4, 54.3, 49.4, 39.3, 38.3, 26.9, 26.1, 19.0, 18.9,
+
C35H44N7O7 [M]+: 674.3302, found: 674.3321. These data
correspond to product obtained according to the Procedure E.
4‐(dimethylamino)‐1‐[({4,11,17,24‐tetraoxo‐2,26‐dioxa‐5,10,
18,23,32‐pentaazatricyclo[25.3.1.112,16]dotriaconta‐1(31),12
(32),13,15,27,29‐hexaen‐31‐yl}carbamoyl)methyl]pyridin‐1‐
ium chloride (24). Following Procedure C using DMAP (83
mg, 0.68 mmol) the target product was obtained as white
powder (83 mg, 69%); following Procedure D using DMAP
(22.8 mg, 0.187 mmol) the target product was obtained as
+
10.4; HRMS (m/z) Calc. for C35H52N7O7 [M]+: 682.3928,
found: 682.3912. These data correspond to product obtained
according to the Procedure E.
4‐methyl‐4‐[({4,11,17,24‐tetraoxo‐2,26‐dioxa‐5,10,18,23,32‐
pentaazatricyclo[25.3.1.112,16]dotriaconta‐1(31),12(32),13,15,
27,29‐hexaen‐31‐yl}carbamoyl)methyl]morpholin‐4‐ium chlo-
ride (21). Following Procedure C using N-methylmorpholine
(75 μL, 0.68 mmol) the target product was obtained as white
powder (89 mg, 76%); following Procedure D using N-
methylmorpholine (21 μL, 0.187 mmol) the target product was
obtained as white powder (206 mg, 90%). mp 247 C (decom-
1
white powder (110 mg, 91%). mp 163-165 C; H NMR (400
MHz, CDCl3) δ 10.80 (s, 1H), 9.54 (s, 2H), 8.25 (d, J = 7.8
Hz, 2H), 8.08 (d, J = 7.2 Hz, 2H), 7.90 (t, J = 7.7 Hz, 1H),
7.42 (s, 2H), 7.20 (t, J = 8.4 Hz, 1H), 6.58 (d, J = 8.4, 2H),
6.53 (d, J = 6.8, 2H), 5.49 (s, 2H), 4.46 (s, 4H), 3.71 – 3.33
(m, 8H), 3.20 (s, 6H), 2.11 – 1.43 (m, 8H); 13C{1H} NMR
(101 MHz, CDCl3) δ 167.7, 164.6, 164.0, 153.5, 149.4, 142.4,
138.4, 129.1, 124.6, 114.1, 107.2, 106.5, 100.0 , 67.9, 58.5,
40.4, 39.3, 38.1, 27.0, 26.1; HRMS (m/z) Calc. for
1
position); H NMR (500 MHz, CD2Cl2:DMSO-d6 3:1) δ 10.83
(s, 1H), 9.50 (t, J = 6.1 Hz, 2H), 8.22 (d, J = 1.8 Hz, 1H), 8.20
(s, 1H), 8.16 (dd, J = 8.9, 6.3 Hz, 1H), 7.97 (t, J = 5.6 Hz, 2H),
7.24 (t, J = 8.5 Hz, 1H), 6.72 (d, J = 8.5 Hz, 2H), 4.70 (s, 2H),
4.55 (s, 4H), 3.89–3.64 (m, J = 26.4 Hz, 4H), 3.56 – 3.40 (m,
4H), 3.30 (c with multiplet 3.38–3.15, s, 3H) 3.38–3.15 (c with
H2O, m, 8H), 1.72–1.40 (m, 8H); 13C{1H} NMR (126 MHz,
CD2Cl2:DMSO-d6 3:1) δ 167.0 , 162.8, 148.9, 124.2, 105.6,
67.4, 60.2, 59.6, 39.9, 39.8, 39.6, 39.4, 37.6, 26.7, 26.3;
+
C34H43N8O7 [M]+: 675.3255, found: 675.3242. These data
correspond to product obtained according to the Procedure D.
1‐[({4,11,17,24‐tetraoxo‐2,26‐dioxa‐5,10,18,23,32‐pentaazatri
cyclo[25.3.1.112,16]dotriaconta‐1(31),12(32),13,15,27,29‐hexa
en‐31‐yl}carbamoyl)methyl]pyridin‐1‐ium chloride (25). Fol-
lowing Procedure C using pyridine (55 μL, 0.68 mmol) the
target product was obtained as white powder (91 mg, 80 %);
following Procedure D using pyridine (15 μmL, 0.187 mmol)
the target product was obtained as white powder (102 mg,
90%). mp 265-268 C; 1H NMR (400 MHz, CDCl3) δ 11.15 (s,
1H), 9.52 (s, 2H), 9.04 (s, 2H), 8.42 (s, 1H), 8.26 (d, J = 7.1
Hz, 2H), 7.90 (d, J = 5.4 Hz, 3H), 7.47 (s, 2H), 7.21 (c with
CHCl3, s, 1H), 6.59 (d, J = 7.9 Hz, 2H), 6.12 (s, 2H), 4.48 (s,
4H), 3.54 (m, 8H), 1.83 (m, 8H); 13C{1H} NMR (126 MHz,
DMSO-d6) δ 167.2, 163.4, 162.8, 153.1, 148.8, 146.1, 145.7,
139.3, 128.1, 127.4, 124.2, 113.7, 105.8, 67.5, 61.7, 38.8,
+
HRMS (m/z) Calc. for C32H44N7O8 [M]+: 654.3251, found:
654.3271. These data correspond to product obtained accord-
ing to the Procedure D.
1‐methyl‐1‐[({4,11,17,24‐tetraoxo‐2,26‐dioxa‐5,10,18,23,32‐
pentaazatricyclo[25.3.1.112,16]dotriaconta‐1(31),12(32),13,15,
27,29‐hexaen‐31‐yl}carbamoyl)methyl]pyrrolidin‐1‐ium chlo-
ride (22). Following Procedure C using N-methylpyrrolidine
(71 μL, 0.68 mmol) the target product was obtained as white
powder (90.5 mg, 79%); following Procedure D using N-
methylpyrrolidine (19 μL, 0.187 mmol) the target product was
obtained as white powder (113 mg, 99%). mp 278 C (decom-
position); 1H NMR (400 MHz, CDCl3) δ 11.11 (s, 1H), 9.40 (t,
J = 5.6 Hz, 2H), 8.33 (d, J = 7.8 Hz, 2H), 7.99 (c with DMF, t,
+
37.6, 26.5, 26.3; HRMS (m/z) Calc. for C32H38N7O7
[M]+:632.2833, found: 632.2834. These data correspond to
product obtained according to the Procedure D.
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