1778 J . Org. Chem., Vol. 65, No. 6, 2000
Bellec et al.
Trifluoroacetic anhydride (140 µL, 0.99 mmol) was slowly
added to the amide (98 mg, 0.38 mmol) in pyridine (4 mL) at
-30 °C over 1 h, and the solution was allowed to warm to room
temperature over 2 h. Rotary evaporation and chromatography
(5:1 hexane/EtOAc) afforded dinitrile 5a (83 mg, 97%) as white
crystals: Rf 0.31 (5:1 hexane/EtOAc); mp 102-103 °C (hexane);
18H), 1.45 (s, 18H), -1.78 (s, 2H); 13C NMR (CDCl3, 75 MHz)
δ 151.5, 151.4, 151.3, 141.3, 140.9, 138.7, 133.4, 133.2, 131.6,
131.4, 125.8, 100.8, 63.4, 35.5, 35.45, 35.42, 32.2, 29.5, 25.7,
19.0; HRMS (FAB) calcd for C86H98N8O4 (M + 2H)+, 1306.7711,
found (M + 2H)+, 1306.7748. Anal. Calcd for C86H96N8O4: C,
79.11; H, 7.41; N, 8.58. Found: C, 79.08; H, 7.59; N, 8.46.
Zn [p z(OR)2(t-bu tylp h en yl)6] (9c). Porphyrazine 9b (33
mg, 0.025 mmol), anhydrous Zn(OAc)2 (45 mg, 0.25 mmol),
PhCl (10 mL) and DMF (5 mL) were heated at 110 °C under
N2 for 24 h. The mixture was rotary evaporated, and metha-
nolic HCl (5%) (15 mL) was added to the residue. The resultant
solid was filtered off, washed with MeOH, and dried under
vacuum to afford Zn-porphyrazine 9c (30 mg, 89%) as a green
solid: Rf 0.33 (3:1 hexane/EtOAc); mp >350 °C (MeOH); IR
(neat) νmax 1648, 1470, 1364, 1203, 1104 cm-1; UV-vis (CH2-
Cl2, log ꢀ) λmax 359 (4.89), 432 (4.30), 466 (4.26), 625 (4.81),
640 (4.88) nm; 1H NMR (CDCl3, 300 MHz) δ 8.44-8.12 (m,
8H), 7.91-7.82 (m, 4H), 7.77-7.52 (m, 12H), 4.54-4.42 (m,
2H), 4.05-3.80 (m, 2H), 2.65-2.53 (m, 4H), 2.19-2.00 (m, 4H),
1.95-1.85 (m, 4H), 1.54 (s, 18H), 1.53 (s, 18H), 1.50 (s, 18H);
13C NMR (CDCl3, 75 MHz) δ 158.2, 157.2, 156.9, 150.8, 150.7,
149.7, 141.8, 133.2, 132.2, 132.1, 125.5, 100.3, 63.1, 35.4, 32.6,
29.4, 25.9, 18.8; HRMS (FAB) calcd for C86H96N8O4Zn (M +
2H)+, 1368.6846, found (M + 2H)+, 1368.6848. Anal. Calcd for
[R]24 -349.9° (c ) 1.0, CHCl3); IR (CDCl3) νmax 2235, 1630,
D
1165 cm-1; 1H NMR (CDCl3, 300 MHz) δ 3.38 (s, 6H), 1.55 (s,
6H); 13C NMR (CDCl3, 75 MHz) δ 121.7, 111.4, 101.2, 50.2,
16.6; MS (CI) 242 (M + NH4)+. Anal. Calcd for C10H12N2O4:
C, 53.57; H, 5.39; N, 12.49. Found: C, 53.89; H, 5.10; N, 12.46.
(6R,7R)-1,8,13,16-Tetr a oxa d isp ir o[5.0.5.4]h exa d ec-14-
en e-14,15-d in itr ile (5b). Dinitrile 5b (28 mg, 77%) was
prepared from 4b (48 mg, 0.14 mmol) via the corresponding
amide [mp 282-283 °C; [R]24 -16.0° (c ) 1.0, MeOH); IR
D
(KBr, DRIFTS) νmax 3321, 3168, 1697, 1681, 1657, 1171 cm-1
;
1H NMR (CD3OD, 300 MHz) δ 3.88-3.69 (m, 4H), 2.07-1.92
(m, 4H), 1.84-1.73 (m, 4H), 1.68-1.62 (m, 4H); 13C NMR (CD3-
OD, 75 MHz) δ 165.4, 130.9, 96.4, 62.0, 27.4, 24.4, 17.7; HRMS
(CI) calcd for C14H21N2O6 (M + H)+, 313.1400, found (M + H)+,
313.1420] by an identical procedure to that used in the
preparation of dinitrile 5a : Rf 0.25 (6:1 hexane/EtOAc); mp
172-173 °C; [R]24 -25.4° (c ) 1.0, CHCl3); IR (CHCl3) νmax
D
2234, 1633 cm-1; 1H NMR (CDCl3, 300 MHz) δ 3.86-3.67 (m,
4H), 2.07-1.59 (m, 12H); 13C NMR (CDCl3, 75 MHz) δ 121.6,
111.6, 99.2, 63.1, 27.5, 24.1, 17.5; HRMS (CI) calcd for
C14H20N3O4 (M + NH4)+, 294.1454, found (M + NH4)+, 294.1440.
Anal. Calcd for C14H16N2O4: C, 60.85; H, 5.84; N, 10.14.
Found: C, 60.92; H, 5.91; N, 10.00.
C
86H94N8O4Zn: C, 75.45; H, 6.92; N, 8.18. Found: C, 75.36; H,
6.95; N, 7.94.
Ni[p z(OR)2(t-bu tylp h en yl)6] (9d ). Porphyrazine 9d (29
mg, 85%) was prepared from porphyrazine 9b (33 mg, 0.025
mmol) by a procedure identical to that used in the preparation
of complex 9c and was obtained as a green solid: Rf 0.59 (3:1
hexane/EtOAc); mp 250-251 °C (MeOH); IR (neat) νmax 1675,
1460, 1377, 1215, 1104 cm-1; UV-vis (CH2Cl2, log ꢀ) λmax 342
H2[p z(OR)2P r 6] (7b). A small crystal of iodine, Mg (5.0 mg,
0.21 mmol), and n-BuOH (4 mL) were heated to reflux for 3 h
and allowed to cool to room temperature when dinitriles 5a
(41 mg, 0.18 mmol) and 6 (240 mg, 1.48 mmol) were added
neat under N2. The mixture was heated under reflux for 14 h,
after which the cooled solution was diluted with CH2Cl2 (5 mL)
and filtered through Celite. Rotary evaporation and chroma-
tography (4:1 hexane/EtOAc) gave Mg-porphyrazine 7a (79
mg, 60%). Demetalation was effected by stirring complex 7a
(77 mg, 0.11 mmol) in AcOH (2 mL) for 10 min at room
temperature. This solution was poured onto ice (ca. 30 g),
neutralized with 1 M NaOH, and filtered. The solid material
was taken up in CH2Cl2 (10 mL), extracted with H2O (2 mL),
dried (MgSO4), rotary evaporated, and chromatographed (8:1
hexane:EtOAc) to give porphyrazine 7b (53 mg, 0.074 mmol,
41% overall) as a deep purple solid: Rf 0.46 (8:1 hexane/
EtOAc); mp 201-204 °C; IR (neat) νmax 3305, 1622, 1487, 1379,
1153 cm-1; UV-vis (CH2Cl2, log ꢀ) λmax 341 (5.09), 557 (4.74),
627 (4.99) nm; 1H NMR (CDCl3, 300 MHz) δ 4.09-3.95 (m,
8H), 3.91-3.86 (m, 4H), 3.60 (s, 6H), 2.43-2.32 (m, 12H), 2.13
(s, 6H), 1.33-1.25 (m, 18H), -2.56 (s, 2H); 13C NMR (CDCl3,
75 MHz) δ 160.2, 148.9, 148.3, 144.8, 142.2, 138.5, 101.9, 49.7,
28.3, 28.2, 27.9, 25.6, 25.4, 18.0, 14.8, 14.6; HRMS (FAB) calcd
for C40H57N8O4 (M + H)+, 713.4503, found (M + H)+, 713.4492.
H2[p z(OR)2(t-bu tylp h en yl)6] (9b). A small crystal of
iodine, Mg (100 mg, 4.1 mmol), and n-BuOH (40 mL) were
heated to reflux for 5h under N2 and then cooled to room
temperature when dinitrile 5b (380 mg, 1.38 mmol) and
pyrroline 8 (3.6 g, 10 mmol) were added and the mixture
heated to reflux for 24 h. Rotary evaporation gave the crude
magnesium porphyrazine 9a : FAB-MS 1327 (M + H)+. This
was allowed to react with AcOH (10 mL) in CH2Cl2 (40 mL)
overnight at room temperature. The solution was poured onto
ice (100 mL), and the metal-free porphyrazine 9b was ex-
tracted with CH2Cl2, followed by Et2O. The combined extracts
were washed with H2O and dried (MgSO4). Rotary evaporation
and chromatography (3:1 hexane/EtOAc) followed by precipita-
tion in MeOH gave porphyrazine 9b (380 mg, 21%) as a green
solid: Rf 0.58 (3:1 hexane/EtOAc); mp 246-247 °C (MeOH);
IR (neat) νmax 3292, 1633, 1484, 1362, 1188, 1106 cm-1; UV-
vis (CH2Cl2, log ꢀ) λmax 362 (4.87), 458 (4.50), 610 (4.61), 652
1
(4.87), 446 (4.51), 614 (4.75), 632 (4.78) nm; H NMR (CDCl3,
300 MHz) δ 8.31 (d, 4H, J ) 8.6), 8.22 (d, 4H, J ) 8.6), 8.16
(d, 4H, J ) 8.2), 7.66 (d, 4H, J ) 8.2), 7.49 (d, 4H, J ) 8.9),
7.45 (d, 4H, J ) 8.9), 4.33-4.20 (m, 2H), 3.76 (d, 2H, J ) 9.9),
2.65-2.48 (m, 4H), 2.18-2.00 (m, 4H), 1.90-1.77 (m, 4H), 1.53
(s, 18H), 1.44 (s, 18H), 1.41 (s, 18H); 13C NMR (CDCl3, 75 MHz)
δ 151.3, 151.1, 151.0, 149.8, 149.5, 142.7, 142.2, 141.9, 138.8,
133.3, 133.1, 132.9, 131.5, 131.4, 131.3, 125.7, 100.9, 63.4, 35.5,
35.3, 32.2, 32.17, 32.1, 29.4, 25.8, 18.9; HRMS (FAB) calcd for
C86H95N8NiO4 (M + H)+, 1361.6830, found (M + H)+, 1361.6842.
Anal. Calcd for C86H94N8NiO4: C, 75.82; H, 6.95; N, 8.22.
Found: C, 75.59; H, 6.82; N, 8.08.
Cu [p z(OR)2(t-bu tylp h en yl)6] (9e). Porphyrazine 9e (30
mg, 85%), prepared from porphyrazine 9b (33 mg, 0.026 mmol)
by a procedure identical to that used in the preparation of
complex 9d , was obtained as a green solid: Rf 0.51 (3:1 hexane/
EtOAc); mp 253-254 °C (MeOH); IR (neat) νmax 1656, 1488,
1374, 1213, 1104 cm-1; UV-vis (CH2Cl2, log ꢀ) λmax 357 (5.03),
456 (4.56), 615 (4.95), 634 (5.03) nm; HRMS (FAB) calcd for
C
86H96CuN8O4 (M + 2H)+, 1367.6851, found (M + 2H)+,
1367.6872. Anal. Calcd for C86H94CuN8O4: C, 75.55; H, 6.93;
N, 8.20. Found: C, 75.73; H, 7.09; N, 8.14.
H2[p z(OTBDMS)2P r 6] (10c). t-BuMe2SiO3SCF3 (0.20 mL,
0.83 mmol) was added to porphyrazine 7b (32 mg, 0.045 mmol)
in CH2Cl2 (10 mL) at -78 °C, and the solution was allowed to
warm to room temperature during 18 h. Et3N (0.5 mL) was
added, and the stirring was continued for a further 3 h. Rotary
evaporation and chromatography (1:99 EtOAc/hexane) fol-
lowed by extraction of the solid residue with Me2CO (2 × 20
mL) gave porphyrazine 10c (29 mg, 79%) as a green solid: Rf
0.12 (1:99 EtOAc/hexane); mp 178-181 °C; IR (neat) νmax 1645,
1486, 1363, 1172 cm-1; UV-vis (CH2Cl2, log ꢀ) λmax 342 (4.90),
558 (4.56), 601 (4.01), 629 (4.80), 657 (3.85), 761 (3.08) nm; 1H
NMR (CDCl3, 300 MHz) δ 4.01 (t, 8H, J ) 7.8), 3.89 (t, 4H, J
) 7.5), 2.44-2.27 (m, 12H), 1.38 (s, 18H), 1.36-1.26 (m, 18H),
0.56 (s, 12H), -2.45 (s, 2H); 13C NMR (CDCl3, 75 MHz) δ 159.5,
153.2, 148.9, 148.7, 144.6, 142.5, 142.3, 141.6, 28.3, 28.1, 26.1,
25.9, 25.6, 18.8, 14.8, -3.5; HRMS (FAB) calcd for C46H75N8O2-
Si2 (M + H)+, 827.5552, found (M + H)+, 827.5545.
1
(4.64), 675 (4.60) nm; H NMR (CDCl3, 300 MHz) δ 8.41 (d,
4H, J ) 8.2), 8.36 (d, 4H, J ) 8.2), 8.30 (d, 4H, J ) 8.2), 7.69
(d, 4H, J ) 8.2), 7.56 (d, 4H, J ) 8.2), 7.52 (d, 4H, J ) 8.2),
4.35-4.20 (m, 2H), 3.76 (d, 2H, J ) 10.2), 2.70-2.50 (m, 4H),
2.20-2.00 (m, 4H), 1.90-1.75 (m, 4H), 1.54 (s, 18H), 1.49 (s,
Ni[p z(OH)2(t-b u t ylp h en yl)6] (11d ). Trifluoroacetic acid
and H2O (19:1) (1 mL) were added to porphyrazine 9d (10 mg,
7.3 µmol) under N2 when the solution turned purple im-
mediately. The mixture was stirred overnight at room tem-