T. Fricke et al. · Synthesis and Structural of Bis-Urea Phenazines
943
(s, 3 H), 8.00 (m, 2 H), 8.56 (m, 2 H). Ð 13C NMR ene (10 ml) were added 0.1 ml (0.9 mmol) of n-
(62 MHz, DMSO-d6): δ = 18.0 (+), 30.6 (+), 37.2 butyl isocyanate (6) and 0.1 ml (1.2 mmol) of pyri-
(Cquat), 126.4 (+), 126.7 (+), 127.6 (+), 128.8 (+), dine. The reaction mixture was refluxed for 16 h
133.5 (Cquart), 134.9 (Cquat), 139.4 (Cquat), 140.3 and evaporated in vacuo to dryness. CC (Rf = 0.3;
(Cquat), 143.8 (Cquat), 144.3 (Cquat), 145.5 (Cquat), toluene/ethyl acetate 4:1) gave 15 (37 mg, 55%),
153.5 (Cquat). Ð MS (EI); m/z (%): 340 (100) [M]+, as an orange solid, m.p. 147 ∞C. Ð IR (KBr): ν =
˜
325 (96) [MÐCH3]+, 208 (28) [MÐNO2 + H]+. Ð 3328 cmÐ1, 2925, 1646, 1573. Ð UV/vis (CH3CN):
C17H16N4O4 (340.34): calcd. C 60.00, H 4.74, λmax (lg ε) = 353 nm (6.313), 370 (6.471), 476
1
N 16.46; found C 59.81, H 4.96, N 16.20. Ð 2.) (Rf = (6.601). Ð H NMR (400 MHz, D6-DMSO): δ =
3
0.7, toluene) 60 mg (30%) of 9-tert-butyl-1-methyl- 0.93 (t, J = 7.3 Hz, 6 H), 1.38 (m, 4 H), 1.51 (m,
2,6-dinitro-phenazine (12), as a yellow solid, m.p. 4 H), 1.68 (s, 9 H), 2.75 (s, 3 H), 3.22 (m, 4 H), 6.75
224 ∞C. Ð IR (KBr): ν = 2961 cmÐ1, 1532, 1357, (m, 2 H), 7.68 (m, 2 H), 8.39 (m, 2 H), 9.40 (s, 1 H),
˜
1
806. Ð UV/vis (CH3CN): λmax (lg ε) = 202 nm 9.45 (s, 1 H). Ð H NMR (250 MHz, CDCl3): δ =
1
(5.747), 252 (5.648), 366 (4.996). Ð H NMR (400 0.63 (bs, 6 H), 0.85 (m, 4 H), 1.33 (s, 9 H), 1.68 (s,
MHz, DMSO-d6): δ = 1.75 (s, 9 H), 3.08 (s, 3 H), 3 H), 2.35 (bs, 4 H), 3.17 (bs, 4 H), 6.86 (bs, 3 H),
3
3
8.00 (d, J = 7.9 Hz, 1 H), 8.26 (dd, J = 9.5 Hz, 7.19 (bs, 1 H), 8.04 (bs, 1 H), 8.24 (bs, 1 H), 9.32
4J = 0.7 Hz, 1 H), 8.39 (d, J = 9.5 Hz, 1 H), 8.56 (s, 1 H), 9.48 (bs, 1 H). Ð 13C NMR (100 MHz, D6-
3
(d, 3J = 7.9 Hz, 1 H). Ð 13C NMR (100 MHz, DMSO): δ = 13.7 (+), 16.9 (+), 19.6 (Ð), 30.8 (+),
DMSO-d6): δ = 13.5 (+), 30.7 (+), 37.3 (Cquat), 31.8 (Ð), 35.7 (Cquat), 38.8 (Ð), 112.5 (+), 112.8 (+),
126.2 (+), 126.6 (+), 126.7 (+), 128.4 (+), 133.8 127.2 (Cquat), 127.7 (+), 130.5 (+), 130.6 (Cquat),
(Cquat), 135.8 (Cquat), 140.0 (Cquat), 140.7 (Cquat), 132.0 (Cquat), 134.1 (Cquat), 134.7 (Cquat), 138.2
142.2 (Cquat), 145.7 (Cquat), 149.4 (Cquat), 153.4 (Cquat), 140.1 (Cquat), 141.0 (Cquat), 154.6 (Cquat),
(Cquat). Ð MS (EI); m/z (%): 340 (100) [M]+, 325 154.7 (Cquat). Ð MS (CI); m/z (%): 957 (50)
(88) [MÐCH3]+, 295 (14) [MÐNO2 + H]+. Ð [2·M + H]+, 479 (100) [M + H]+, 335 (24) [MÐn-
HRMS: C17H16N4O4 (340.1172); [M]+ = 340.1169 BuNH + H]+, 380 (41) [MÐn-BuNHCO + H]+. Ð
+/- 0.8 ppm.
HRMS: C27H38N6O2 (478.3056); [M]+ = 478.3058
ð 0.8 ppm.
4-tert-Butyl-6-methyl-phenazine-1,9-diamine (14)
1-Butyl-3-{6-[(3-butyl-ureido)-methyl]pyridine-2-
ylmethyl}-urea (17)
To a solution of 13 (50 mg, 0.15 mmol) in EtOAc
(10 ml) was added Pd/C (10%, 30 mg, 0.03 mmol)
and hydrogen pressure of 106 Pa was applied for
16 h. The catalyst was filtered off, the filtrate evap-
orated in vacuo and the red solid residue was puri-
fied by CC (Rf = 0.9, EtOAc) to yield 40 mg (97%)
To a solution of pyridine-2,6-dinitrile (16)
(260 mg, 2.0 mmol) in 10 ml of THF were added
25 ml (25 mmol, 1 M) of BH3 ·THF. The reaction
mixture was stirred for 16 h at r.t., excess of bo-
rane was destroyed by careful addition of metha-
nol and the mixture was evaporated to dryness in
vacuo. The residue was recrystallized from 30 ml
of HCl saturated ethanol, filtered and dried to
yield 340 mg (1.4 mmol) pyridine-1,6-methylene-
diamine. The compound was allowed to react with
0.3 ml (3.2 mmol) of n-butyl isocyanate (6) and
1.0 ml (7.0 mmol) of NEt3 in 30 ml of THF for 16 h
under reflux. The reaction mixture was evaporated
to dryness and recrystallization from ethanol gave
17 (170 mg, 25%; Rf = 0.2, CH2Cl2/MeOH, 20:2),
of 14 as a red solid, m.p. 59 ∞C. Ð IR (KBr): ν =
˜
3446 cmÐ1, 2926, 1625, 1494. Ð UV/vis (CH3CN):
λmax (lg ε) = 237 nm (4.765), 291 (5.441), 514
1
(4.145). Ð H NMR (250 MHz, CDCl3): δ = 1.73
3
(s, 9 H), 2.80 (s, 3 H), 4.93 (bs, 4 H), 6.79 (d, J =
3
7.5 Hz, 1 H), 6.82 (d, J = 7.8 Hz, 1 H), 7.38 (d,
3
3J = 7.5 Hz, 1 H), 7.49 (d, J = 7.8 Hz, 1 H). Ð 13C
NMR (62 MHz, CDCl3): δ = 17.5 (+), 31.1 (+),
36.0 (Cquat), 107.6 (+), 108.0 (+), 126.0 (Cquat),
127.0 (+), 129.7 (+), 131.7 (Cquat), 133.1 (Cquat),
137.0 (Cquat), 141.3 (Cquat), 141.5 (Cquat), 141.9
(Cquat), 142.4 (Cquat). Ð MS (EI); m/z (%): 280
(38) [M]+, 265 (60) [MÐCH3]+, 237 (100). Ð
HRMS: C17H20N4 (280.1688); [M]+ = 280.1686 ð
0.6 ppm.
as a white solid, m.p. 183 ∞C. Ð IR (KBr): ν =
˜
3326 cmÐ1, 2927, 1627, 1459. Ð UV/vis (MeOH):
λmax (lg ε)
= 264 nm (4.107). Ð
1H NMR
3
(400 MHz, D6-DMSO): δ = 0.87 (t, J = 7.2 Hz,
6 H), 1.27 (m, 4 H), 1.35 (m, 4 H), 3.00 (m, 4 H),
4.26 (d, 3J = 5.9 Hz, 4 H), 6.09 (t, 3J = 5.7 Hz, 2 H),
1-Butyl-3-[6-tert-butyl-9-(3-butyl-ureido)-4-methyl-
phenazine-1-yl]-urea (15)
6.38 (t, 3J = 5.9 Hz, 2 H), 7.10 (d, 3J = 7.7 Hz, 2 H),
3
To a solution of 4-tert-butyl-6-methyl-phena- 7.71 (t, J = 7.7 Hz, 1 H). Ð 13C NMR (62 MHz,
zine-1,9-diamine (14) (40 mg, 0.14 mmol) in tolu- D6-DMSO): δ = 13.7 (+), 19.5 (Ð), 32.1 (Ð), 32.1
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