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E. G. Sakellariou et al. / Tetrahedron 59 (2003) 9083–9090
The suspension was heated at 508C for 3 h, allowed to cool
to 258C and left standing for another 16 h. After rotary
evaporation, CH2Cl2 was added to the residue and the
resulting suspension was washed with H2O (3£15 mL) and
dried (Na2SO4). Rotary evaporation and chromatography
(EtOAc/hexanes 3:1) gave dinitrile 5 (2.1 g, 87%), a
mixture of E and Z isomers, as a clear amber oil: Rf 0.25
(EtOAc/hexanes 3:1); IR (neat) 1581, 1562, 1496,
graphed (CHCl3/MeOH 9:1) to give the Zn-pz 9 (7.6 mg,
71%) as an amorphous blue solid: Rf 0.3 (CHCl3/MeOH
9:1); IR (CH2Cl2) 1685, 1637, 1463, 1265 cm21; UV–vis
(CH2Cl2) lmax (log 1) 345 (4.76), 609 (4.47) nm; 13C NMR
(75 MHz, CDCl3) d 15.1, 15.2, 15.3, 25.9, 26.3, 28.5, 28.6,
28.7, 51.6, 57.3, 60.7, 70.0, 70.2, 70.4, 70.6, 70.7, 71.3,
126.9, 128.6, 128.8, 129.0, 137.6, 141.0, 143.0, 143.3,
144.1, 155.5, 157.2, 157.3; MS (FAB) m/z 1191 [M22H]þ;
HRMS (FAB) calcd for C64H91N10O8Zn: [MþH]þ,
1191.6313; found: [MþH]þ, 1191.6279.
1
1349 cm21; H NMR (300 MHz, CDCl3) d 1.27–1.88 (m,
12H), 3.21–3.28 (m, 4H), 3.46–3.68 (m, 28H), 3.83–3.91
(m, 4H), 4.28 (s, 2H), 4.39 (s, 2H), 4.61–4.64 (m, 2H),
7.16–7.34 (m, 10H); 13C NMR (67.5 MHz, CDCl3) d 19.4,
25.3, 30.5, 50.5, 52.7, 55.8, 58.6, 62.1, 65.9, 66.5, 68.8,
69.2, 70.4, 70.48, 70.53, 70.7, 98.8, 114.0, 115.0, 116.6,
119.3, 127.7, 128.3, 128.5, 128.6, 128.7, 136.2, 136.8; MS
(CI, NH3) m/z 808 [Mþz]; HRMS (CI, NH3) m/z calcd for
C44H64N4O10: [Mþz], 808.4622; found: [Mþz], 808.4682.
Anal. calcd for C44H64N4O10: C, 65.32; H, 7.97; N, 6.93;
Found: C, 65.02; H, 7.65; N, 7.21.
4.3.6. 4,5-Di-(benzyl-(11-tetrahydropyranyloxy-3,6,9-
trioxaundecyl)amino)-9,10,14,15,19,20-hexapropyl-4,5-
dioxo-4,5-seco-porphyrazinatozinc(II) (11). KMnO4
(12.6 mg, 80 mmol) was added to pz 9 (5 mg, 8 mmol) in
CH2Cl2 (10 mL). After 45 min at 208C, the blue solution
was filtered (Celite), and the solids washed with CH2Cl2.
Rotary evaporation and chromatography (EtOAc/MeOH
19:1) gave the zinc-seco-pz 11 (9 mg, 92%) as an intense
amorphous blue solid: Rf 0.4 (EtOAc/MeOH 19:1); IR
(CH2Cl2) 1728, 1638, 1463, 1215 cm21; UV–vis (CH2Cl2)
4.3.4. 4,5-Di-(benzyl-(11-tetrahydropyranyloxy-3,6,9-
trioxaundecyl)amino)-9,10,14,15,19,20-hexapropylpor-
phyrazine (8). Propanol (5 mL), Mg (16.3 mg, 0.7 mmol)
and I2 (two small crystals) were heated to reflux for 24 h
under N2. The suspension was cooled to 208C and
dipropylmaleonitrile 6 (140.7 mg, 0.87 mmol) followed by
dinitrile 5 (103.7 mg, 0.13 mmol) were added and the
mixture further heated to reflux under N2 for 60 h. The deep
blue suspension was allowed to cool, filtered (Celite), and
the solids washed with CH2Cl2. Rotary evaporation and
chromatography (hexanes/EtOAc 7:3; EtOAc) gave the
Mg-pz 7 (56.2 mg, 34%) as a blue solid: Rf 0.7 (EtOAc);
UV–vis (CH2Cl2) lmax 239, 345, 612 nm; MS (FAB) m/z
1320 [Mþz]; HRMS (FAB) calcd for C74H107MgN10O10:
[MþH]þ, 1319.8022; found: [MþH]þ, 1319.7967. This
compound was used without further purification. Glacial
AcOH (12 drops) was added to pz 7 (22.5 mg, 17 mmol) in
CHCl3 (6 mL) and MeOH (1.5 mL) and, after 1 h at 208C,
conc. HCl (four drops) was added. After 2.5 h, the mixture
was neutralized with aqueous NaOH (1 M) and the aqueous
layer extracted with CHCl3 (2£10 mL). Rotary evaporation
and chromatography gave pz 8 (17.4 mg, 91%) as an
amorphous purple solid: Rf 0.14 (EtOAc); IR (CH2Cl2)
1728, 1567, 1455 cm21; UV–vis (CH2Cl2) lmax (log 1) 339
l
max 338, 354, 565, 654 nm; 13C NMR (75 MHz, pyridine-
d5) d 25.4, 25.6, 25.8, 28.1, 28.2, 28.4, 29.4, 29.7, 54.8, 61.3,
70.4, 70.5, 70.6, 73.5, 127.1, 127.7, 128.8, 139.2, 141.3,
142.5, 145.0, 154.9, 156.0, 157.3, 170.2; MS (FAB) m/z
1223 [Mþz], 912 [M2COCH2PhNCH2(CH2O–CH2)3
CH2OH]þ; HRMS (FAB) calc for C64H91N10O10Zn:
[MþH]þ, 1223.6211; found: [MþH]þ, 1223.6215.
4.3.7. 2,3-Di-(4-(methoxycarbonyl)phenyl)maleonitrile
(14). Ester 12 (1.0 g, 4.4 mmol) and KCN (0.3 g,
4.6 mmol) in EtOH (10 mL) were heated at 608C for 24 h.
The mixture was cooled to 208C, filtered and rotary
evaporated. Chromatography (hexanes/EtOAc 7:3) gave
nitrile 13 (0.6 g, 76%) as a white solid mp 57–598C (lit.21
63–648C): Rf 0.4 (hexanes/EtOAc 7:3); 1H NMR
(270 MHz, CDCl3) d 3.84 (s, 2H), 3.95 (s, 3H), 7.44 (d,
J¼8.3 Hz, 2H), 8.08 (d, J¼8.3 Hz, 2H); 13C NMR (75 MHz,
CDCl3) d 24.1, 52.7, 117.5, 130.5, 130.8, 135.2, 166.8; MS
(CI) m/z 193 [MþNH4]þ. Crude nitrile 13 was used directly
without further purification. A slurry of nitrile 13 (0.95 g,
5.42 mmol), and I2 (1.37 g, 5.42 mmol) in Et2O and MeOH
(1:1; 28 mL) was heated at reflux for 1 h under N2. The
mixture was cooled to 208C, when methanolic NaOMe
(0.27 g of Na in 3.5 mL of MeOH) was added and reflux
continued for another 2 h. After rotary evaporation, the
crude mixture was redissolved in CH2Cl2, washed with H2O
(2£15 mL), and aqueous Na2S2O3 (2£15 mL), dried
(MgSO4) and rotary evaporated. Recrystallization from
CHCl3 and MeOH gave dinitrile 14 (0.6 g, 64%) as a white
solid mp 225–2278C: Rf 0.4 (hexanes/EtOAc 7:3); IR
1
(4.70), 571 (4.37), 640 (4.23) nm; H NMR (270 MHz,
pyridine-d5) d 21.44 (s, 2H), 1.18–1.43 (m, 18H),
2.26–2.52 (m, 12H), 3.43–3.64 (m, 28H), 3.81–4.13 (m,
16H), 5.91 (s, 4H), 6.16 (br s, 2H), 7.20–7.38 (m, 6H), 7.8
(d, 4H, J¼6.9 Hz); 13C NMR (75 MHz, CDCl3) d 15.0,
15.1, 25.8, 26.0, 28.5, 52.1, 57.3, 62.0, 70.5, 70.8, 72.6,
127.0, 128.6, 128.8, 136.4, 140.5, 142.4, 143.2, 143.3,
152.4, 155.0; MS (FAB) m/z 1129 [Mþz]; HRMS (FAB)
calcd for C64H93N10O8: [MþH]þ, 1129.7178; found:
[MþH]þ, 1129.7158. Anal. calcd for C64H92N10O8: C,
68.06; H, 8.20; N, 12.40; Found: C, 68.01; H, 8.19; N,
12.24.
1
(CH2Cl2) 1725, 1609, 1437, 1407, 1284 cm21; H NMR
(270 MHz, CDCl3) d 3.94 (s, 6H), 7.91 (d, J¼8.6 Hz, 4H),
8.20 (d, J¼8.6 Hz, 4H); 13C NMR (75 MHz, CDCl3) d 53.0,
116.3, 126.3, 129.2, 130.8, 133.5, 135.9, 166.1; MS (CI) m/z
364 [MþNH4]þ; HRMS (CI) calcd for C20H18N3O4:
[MþNH4]þ, 364.1297; found: [MþNH4]þ, 364.1308.
Anal. calcd for C20H14N2O4: C, 69.36; H, 4.07; N, 8.08;
Found: C, 69.34; H, 3.95; N, 7.89.
4.3.5. 4,5-Di-(benzyl-(11-tetrahydropyranyloxy-3,6,9-
trioxaundecyl)amino)-9,10,14,15,19,20-hexapropylpor-
phyrazinatozinc(II) (9). Pz 8 (10.1 mg, 9 mmol) and
anhydrous zinc acetate (2.4 mg, 13 mmol) in DMF (5 mL)
were heated at 1008C for 6 h under N2. The mixture was
allowed to cool to 208C, rotary evaporated and chromato-
4.3.8. 4,5,9,10,14,15,19,20-Octa-(4-(butyloxycarbonyl)-
phenyl)porphyrazine (16). Butanol (5 mL), Mg (8.8 mg,
0.36 mmol) and I2 (two small crystals) were heated to reflux