(78 mg, 75%) as a yellow solid, mp 222–223 ◦C. dH (270 MHz,
CDCl3) 8.30 (d, 2H, J 9 Hz), 7.92 (dd, 2H, J 9, 8 Hz), 7.82
(d, 2H, J 8 Hz), 3.62 (s, 6H, Me), 1.9–0.5 (m, 16 H, 8 ×
CH2); dC (68 MHz, CDCl3) 174.9 (CO), 143.8 (Ar), 142.1 (Ar),
140.8 (Ar), 130.8 (Ar), 130.6 (Ar), 129.7 (Ar), 37.6, 33.1, 27.9,
26.7, 25.0; mmax/cm−1 (KBr) 2928, 1661, 1641, 1529, 1483, 1448,
1412, 1379; m/z (FAB) 405.2272 (M + H+, C24H29N4O2 requires
405.2291).
(d, 2H, J 8.5 Hz, Ar H-4,9), 7.63 (dd, 2H, J 8.5, 7.5 Hz,
Ar H-3,8), 7.01 (d, 2H, J 7.6 Hz, Ar H-2,7), 4.92–4.84 (m,
2H, NCHHCH2), 3.57 (dq, 2H, J 14, 7 Hz, NCHHCH3),
3.31 (m, 4H, NCHHCH2 and NCHHCH3), 1.43 (t, 6H, J
7.0 Hz, CH3), 1.37–1.12 (m, 4H, NCH2CH2), 0.99–0.76 (m, 4H,
NCH2CH2CH2), 0.58–0.48 (m, 2H, NCH2CH2CH2CH), 0.48–
0.39 (m, 2H, NCH2CH2CH2CH2CH), 0.27–0.16 (m, 2H,
NCH2CH2CH2CH), −0.24–(−0.35) (m, 2H, NCH2CH2CH2-
CH2CH); dC (101 MHz, CDCl3, assignments supported by
1
DEPT and H–13C correlation) 147.2 (Ar quaternary), 141.4
(R,R)-2,13-Bis[(2-methoxy-2-phenyl)ethyl]-2,13-diaza-1(1,6)-
(phenazina)cyclotridecaphane-3,12-diones (27c and 27cꢀ)
(Ar quaternary), 137.3 (Ar quaternary), 129.7 (Ar CH), 121.2
(Ar CH), 115.9 (Ar CH), 51.0 (CH2CH2N), 45.3 (CH3CH2N),
28.6 (NCH2CH2CH2CH2C), 26.8 (NCH2CH2CH2C), 25.3
(NCH2CH2CH2), 23.3 (NCH2CH2), 12.8 (CH3CH2); mmax/cm−1
(KBr) 2924, 2851, 1528, 1477, 1458, 1321, 1267, 1101, 800,
739; m/z (FAB) 404.2925 (M+, C26H36N4 requires 404.2940);
HPLC, tR/min [Daicel Chiralpak OT (+), hexane–propan-2-ol
(9 : 1), 1.0 ml min−1, detector 297 nm, T = 12 ◦C] 5.9
and 6.5.
A solution of sebacoyl chloride (54 ll, 0.253 mmol) in
dichloromethane (15 ml) was added dropwise at room tem-
perature over 12 h to a stirred mixture of (R,R)-1,6-bis[(2-
methoxy-2-phenyl)ethylamino)]phenazine (25c) (120 mg, 0.251
mmol), dichloromethane (10 ml), and pyridine (40 ll, 0.508
mmol). Evaporation of the solvent and separation by flash
chromatography (40% ethyl acetate in petroleum ether) gave first
27c (69 mg, 43%) and then 27cꢀ (18 mg, 11%), both as yellow
solids.
(R,pS)-(−)-/(R,pR)-(+)-2,5,8,11,14-Pentaoxa-1(1,6)-[5-(a-
methoxyphenylacetyl)-5,10-dihydrophenazina]-
cyclotetradecaphanes (31a and 31b)
The major product 27c had the following properties. mp 74–
◦
76 C, [a]2D7 +127 (c 0.5, CH2Cl2). dH (270 MHz, CDCl3) 8.19
(dd, 2H, J 8.8, 1.2 Hz, Ar), 8.04 (dd, 2H, J 7.0, 1.2 Hz, Ar),
7.91 (dd, 2H, J 8.8, 7.0 Hz, Ar H-3,8), 7.45–7.25 (m, 10H, m,
Ph), 4.93 (dd, 2H, J 9.8, 2.4 Hz, OCH), 4.73 (dd, 2H, J 14.0,
2.4 Hz, NCH2), 3.52 (dd, 2H, J 14.3, 9.8 Hz, NCH2), 3.35 (s, 6H,
OCH3), 1.9–1.7 (m, 4H, chain), 1.5–1.3 (m, 2H, chain), 1.2–1.0
(m, 2H, chain), 0.85–0.55 (m, 4H, chain), 0.1–0.0 (m, 2H, chain),
−0.6–(−0.8) (m, 2H, chain), dC (68 MHz, CDCl3) 175.3 (CO),
143.7 (Ar), 141.9 (Ar), 140.0 (Ar), 131.2 (Ar), 130.9 (Ar), 130.4
(Ar), 128.7 (Ar), 128.0 (Ar), 126.9 (Ar), 112.5 (Ar), 82.9 (CH),
57.7, 57.3, 33.4, 27.9, 27.1, 24.9; mmax/cm−1 (KBr) 2924, 1660,
1529, 1107, 750; m/z (FAB) 667.3245 (M + Na+, C40H44N4O4Na
requires 667.3260).
rac-2,5,8,11,14-Pentaoxa-1(1,6)-(phenazina)cyclotetradecaphane
(14) (124 mg, 0.336 mmol) and 10% Pd/C (240 mg) were stirred
in dry, oxygen-free CH2Cl2 (2 ml) under a hydrogen balloon
at room temperature until the yellow solution had become
colourless (30 min). Then the mixture was filtered through
celite under nitrogen and the celite was rinsed with CH2Cl2
(4 ml). The solvent was evaporated under vacuum and CH2Cl2
(1 ml) was added to the residue under nitrogen. (R)-a-Metho-
xyphenylacetyl chloride (155 mg, 0.84 mmol) and anhydrous
pyridine (68 ll, 0.84 mmol) were added and the mixture was
heated overnight at 40 ◦C. The solvent was evaporated and
the crude mixture was purified by flash chromatography on
silica which had previously been washed with 10% Et3N in
hexane. Elution with CHCl3–Et2O (9 : 1) gave (R,pS)-(−)-
2,5,8,11,14-pentaoxa-1(1,6)-[5-(a-methoxyphenylacetyl)-5,10-
dihydrophenazina]cyclotetradecaphane (31a) (42 mg, 24%)
and (R,pR)-(+)-2,5,8,11,14-pentaoxa-1(1,6)-[5-(a-methoxyphe-
nylacetyl)-5,10-dihydrophenazina]cyclotetradecaphane (31b)
The minor product, 27cꢀ had dH (270 MHz, CDCl3) 8.22 (dd,
2H, J 9, 1 Hz, Ar), 7.75 (dd, 2H, J 9,7 Hz, Ar), 7.33–7.45 (10H,
m, Ph), 6.11 (dd, 2H, J 7, 1 Hz, Ar), 4.80 (dd, 2H, J 8.5, 6 Hz,
PhCH), 4.57 (dd, 2H, J 14, 8 Hz, NCH2), 3.94 (dd, 2H, J 14,
5 Hz, CH2), 3.04 (s, 6H, OMe), 1.9–1.7 (m, 4H), 1.5–0.5 (m,
10H), 0.1–(−0.1) (m, 2H), −0.6–(−0.8) (m, 2H).
1
1,6-Bis(diethylamino)phenazine (28a)
(51 mg; contaminated with 10 mol% of 14 as judged by H
NMR) as pale yellow solids. Recrystallisation from heptane
gave spectroscopically pure 31b (14 mg, 8%).
Borane solution (1 M in THF; 5 ml, 5 mmol) was added
under nitrogen to 1,6-bis(N-ethylacetamido)phenazine (26a)
(149 mg, 0.425 mmol). The mixture was refluxed for 2 h, then
methanol (10 ml) was added and the mixture was refluxed
for a further 5 min. Evaporation of the solvent followed
by flash chromatography (CH2Cl2–EtOAc, 9 : 1) gave 1,6-
bis(diethylamino)phenazine (28a) (113 mg, 82%) as a red solid,
mp 55–56 ◦C. dH (270 MHz, CDCl3) 7.76 (dd, 2H, J 8.7, 1.2 Hz,
Ar), 7.61 (dd, 2H, J 8.7, 7.7 Hz, Ar), 7.01 (dd, 2H, J 7.7, 1.2 Hz,
Ar), 3.67 (q, 8H, J 7.1 Hz, CH2), 1.25 (t, 12H, J 7.1 Hz, CH3);
dC (68 MHz, CDCl3) 147.2 (Ar), 142.5 (Ar), 138.8 (Ar), 129.7
(Ar), 121.6 (Ar), 115.3 (Ar), 47.2 (CH2), 12.4 (CH3); mmax/cm−1
(KBr) 2970, 2928, 1607, 1530, 1484, 1265, 1209, 1094, 801; m/z
(FAB) 323.2250 (M + H+, C20H27N4 requires 323.2236).
The (R,pS)-(−)-diastereoisomer 31a had the following prop-
◦
erties. Rf 0.04 (CHCl3–Et2O, 9 : 1), mp >230 C, [a]2D0 −114 (c
1, CH2Cl2); dH (400 MHz, CDCl3) 7.5–6.2 (m, 12H, Ar + NH),
5.29 (br s, 1H, MeOCH), 4.5–4.2 (m, 4H, ArOCH2), 3.7–2.5
(m, 15H); dC (101 MHz, CDCl3, assignment by DEPT) 171.1
=
(br, C O), 153.6 (Ar C quat), 146.7 (Ar C quat), 146.2 (Ar C
quat), 144.1 (Ar C quat), 143.4 (Ar C quat), 136.2 (Ar C quat),
131.8 (Ar C quat), 128.4 (Ar CH), 128.0 (Ar), 127.9 (Ar), 127.7
(Ar), 127.4 (Ar), 127.1 (Ar CH), 120.0 (Ar CH), 119.3 (Ar CH),
114.6 (Ar CH), 112.3 (Ar CH), 108.5 (Ar CH), 80.3 (OCH),
72.7 (CH2), 72.65 (CH2), 71.8 (CH2), 71.2 (CH2), 70.8 (CH2),
70.7 (CH2), 70.1 (CH2), 57.1 (CH3); mmax/cm−1 (film) 3400 (br,
+
=
N–H), 1679 (C O); m/z (ESI) 521.2287 (M + H , C29H33N2O7
requires 521.2282).
2,13-Diethyl-2,13-diaza-1(1,6)-(phenazina)cyclotridecaphane
(29a)
The (R,pR)-(+)-diastereoisomer 31b had the fo◦llowing prop-
erties. Rf 0.14 (CHCl3–Et2O, 9 : 1), mp 182–184 C (heptane),
[a]2D6 +42 (c 0.25, CH2Cl2). dH (400 MHz, CDCl3) 7.39 (m, 1H,
Ar), 7.2–7.0 (m, 4H, Ar), 6.9–6.7 (m, 5H, Ar), 6.31 (m, 2H, Ar
and NH), 5.28 (s, 1H, MeOCH), 4.5–4.2 (m, 4H, ArOCH2), 3.8–
3.5 (m, 4H, ArOCH2CH2), 3.47 (s, 3H, CH3O), 3.2–2.5 (m, 8H,
ArOCH2CH2OCH2CH2O); dC (101 MHz, CDCl3, assignment
Borane solution (1 M in THF; 10 ml, 10 mmol) was added to
2,13-diethyl-2,13-diaza-1(1,6)-(phenazina)cyclotridecaphane-
3,12-dione (27a) (184 mg, 0.425 mmol) under nitrogen. The
mixture was refluxed for 5 h, then methanol (20 ml) was added
and the mixture was refluxed for a further 15 min. Evaporation
of the solvent followed by flash chromatography (CHCl3) gave
2,13-diethyl-2,13-diaza-1(1,6)-(phenazina)cyclotridecaphane
(29a) (103 mg, 60%) as a red solid, mp 123–125 ◦C, dH
(400 MHz, CDCl3, assignments supported by COSY) 7.82
=
by DEPT) 171.1 (C O), 153.6 (Ar C quat), 146.2 (Ar C quat),
144.1 (Ar C quat), 136.2 (Ar C quat), 131.9 (Ar C quat), 128.1
(Ar), 127.9 (Ar), 127.8 (Ar), 127.5 (Ar), 127.3 (Ar), 120.0 (Ar
CH), 119.6 (Ar CH), 117.7 (Ar CH), 114.4 (Ar CH), 112.6 (Ar
2 8 4 0
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 2 8 3 2 – 2 8 4 1