8
J.-B. VERLHAC ET AL.
2 (500 mg, 0.7 mmole) in freshly distilled THF at 0°C,
250 mg of LiAlH4 was added in small portions. The
reaction mixture was stirred for 3 h at room temperature
and then hydrolyzed by slow addition of 6 mL of MeOH
at 0°C. Then, 15 mL of a saturated aqueous solution of
Rochelle’s salt (sodium and potassium tartrate) was added
and the product was extracted with CHCl3 (250 mL). The
organic phase was washed successively with the tartrate
solution and water. Drying over Na2SO4 and evaporation
afforded 3 as a violet powder (403 mg, 84%).1H NMR
(300 MHz, CDCl3): d, ppm 8.90 (d, J = 4.7 Hz, 4H), 8.89
(bs, 4H), 8.86 (d, J = 5.1 Hz, 4H), 8.25 (d, J = 8 Hz, 2H),
8.14 (d, J = 7.7 Hz, 6H), 7.79 (d, J = 8 Hz, 2H), 7.59 (d, J =
7.7 Hz, 6H), 5.11 (d, J = 5 Hz, 2H), 2.75 (s, 9H), 2.00 (t,
J = 5 Hz, 1H), -2.73 (s, 2H).
1H, CH=N), 7.61 (m, 10H), 7.46 (m, 14H), 7.32 (d, J =
9 Hz, 4H), 7.12 (d, J = 16.2 Hz, 2H), 7.10 (d, J = 16.2 Hz,
2H), 7.01 (d, J = 16.2 Hz, 4H), 6.93 (d, J = 9 Hz, 4H),
6.73 (d, J = 8.8 Hz), 6.68 (d, J = 8.8 Hz), 4.15 (t, J =
6.2 Hz), 3.77 (t, J = 6.2 Hz, 4H) 3.54 (d, JH-P = 10.2 Hz,
3H), 3.51 (m, 4H), 3.45 (m, 8H), 2.75 (bs, 9H), 2.02 (m,
8H), 1.64 (m, 16H), 1.42 (m, 8H), 1.24 (t, J = 7.7 Hz,
6H), 1.13 (m, 8H), 1.02 (t, J = 7.3 Hz, 12 H), 0.71 (t,
J = 7.3 Hz, 12H). 31P NMR (121.42 MHz, CDCl3): d,
ppm 64.29.
Compound 6. The Heck dissymmetrical coupling
was performed by mixing 2,7-diethenyl-9,9-dibutyl-9H-
fluorene (1.36 g, 4.11 mmole), 4-[2-[ethyl(4-iodophenyl)
amino]ethoxy]phenyl acetate (2 g, 4.70 mmole), 4-iodo-
N,N-dibutylaniline (1.55 g, 4.70 mmole), K2CO3 (1.45 g),
tetrabutylammonium bromide (2.78 g), triphenylphosphine
(237 mg) and Pd(OAc)2 (110 mg) in DMF (35 mL) under
an Ar atmosphere. The mixture was heated at 50°C under
Ar for 24 h. The DMF was removed by evaporation under
reduced pressure and the residue was chromatographed
on silica using an increasing gradient of petroleum ether/
CH2Cl2 (from 70/30 to 0/100) affording 1.25 g of a yellow-
green powder which was used directly for the deprotection
step. The compound was dissolved in a mixture of THF
(50 mL) and EtOH (25 mL) and 10 mL of 0.5 M NaOH was
added. The solution was stirred 20 min at room tempera-
ture and 0.5 M HCl aqueous solution (12 mL) was added.
The solution was taken up in diethyl ether and washed
with 10% NaHCO3 solution, dried and evaporated. The
residue was chromatographed on silica using a petroleum
ether/CH2Cl2 (40/60) mixture and afforded 6 as a yellow
powder (620 mg, 19% yield from the 2,7-diethenyl-9,9-
dibutyl-9H-fluorene precursor). By NMR the presence
of a small amount (ca. 10%) of minor isomers could be
5-(4-Formylphenyl)-10,15,20-tris(4-methylphenyl)
porphyrin (4). A suspension containing 340 mg of
alcohol 3 (0.5 mmoles) and 500 mg of MnO2 in 30 mL
of CH2Cl2 was refluxed for 4 h. The reaction could be
monitored by TLC on silica (eluent CHCl3). The crude
reaction mixture was filtered through a small silica pad,
eluting with CH2Cl2, evaporated to dryness and afforded
209 mg of aldehyde 4 (61% yield). 1H NMR (300 MHz,
CDCl3): d, ppm 10.42 (s, 1H), 8.94 (d, J = 4.7 Hz, 4H),
8.93 (bs, 4H), 8.80 (d, J = 4.7 Hz, 4H) 8.44 (d, J = 7.9 Hz,
2H), 8.31 (d, J = 7.9 Hz, 2H), 8.14 (d, J = 8.1 Hz, 6H),
7.60 (d, J = 8.1 Hz, 6H), 2.75 (s, 9H), -2.71 (s, 2H).
Compound 5. 5 mL of a 0.18 M solution of
phosphorodichloridothioic hydrazide, 1-methyl-(MMH-
PSCl2) in CHCl3 was added to a solution of 4 (324 mg,
0.47 mmole) in dry dichloromethane (50 mL), and let
24 h at room temperature. Concentration to a final
volume of 15 mL and precipitation with petroleum
ether afforded a green precipitate which was collected
by filtration. A rapid filtration on a 10 cm silica pad was
carried out, eluting with CH2Cl2 and a trace amount of
Et3N and thus afforded 310 mg of a violet powder after
evaporation (yield 78%). The product was used without
1
detected. mp 65–67°C. H NMR (300 MHz, CDCl3):
d, ppm 7.65 (d, J = 8.1 Hz, 2H), 7.46 (m, 8H), 7.13 (d,
J = 16.2 Hz, 2H), 7.03 (d, J = 16.2 Hz, 1H), 7.01 (d,
J = 16.2 Hz, 1H), 6.81 (m, 6H), 6.78 (d, J = 8.1 Hz, 2H),
6.68 (d, J = 8.1 Hz, 2H), 4.50 (s, 1H), 4.13 (t, J = 6.1 Hz,
2H), 3.77 (t, J = 6.1 Hz, 2H), 3.55 (q, J = 7.0 Hz, 2H),
3.34 (t, J = 6.9 Hz, 4H), 2.05 (m, 4H), 1.64 (m, 4H), 1.41
(m, 4H), 1.27 (t, J = 7.0 Hz, 3H), 1.14 (m, 4H), 1.01 (t,
J = 7.2 Hz, 6H), 0.73 (t, J = 7.3 Hz, 6H), 0.71 (m, 4H). 13C
NMR (100 MHz, CDCl3): d, ppm 153.16, 151.68, 149.88,
140.28, 140.06, 137.32, 137.06, 128.92, 128.32, 128.02,
127.92, 126.66, 125.94, 125.23, 125.01, 124.63, 120.44,
120.34, 119.82, 116.31, 115.83, 112.11, 111.94, 66.36,
55.03, 51.05, 50.02, 45.94, 40.69, 29.77, 26.21, 23.39,
20.62, 14.28, 14.08, 12.64. Anal. calcd. for C55H68N2O2;
C: 83.71, H: 8.69, N: 3.55%. Found C: 83.45, H: 8.39, N:
3.41. HRMS (FD): m/z calcd. for C55H68N2O2 788.5281.
Found 788.5255.
1
further purification for the next reaction step. H NMR
(300 MHz, CDCl3): d, ppm 8.93–8.88 (AB system,
J = 4.7 Hz, 4H), 8.91 (bs, 4H), 8.32 (d, J = 8.3 Hz, 2H),
8.16 (d, J = 8.3 Hz, 2H), 8.14 (d, J = 8 Hz, 6H), 8.07
(d, J = 2.4 Hz, 1H), 7.60 (d, J = 8 Hz, 6H), 3.70 (d,
J = 13.9 Hz, 3H), 2.75 (s, 9H), -2.70 (s, 2H). 31P NMR
(121.4 MHz, CDCl3): d, ppm 63.38.
Triad 1. Cs2CO3 (300 mg, 0.92 mmole) was added
to a mixture of compound 5 (100 mg, 0.12 mmole) and
compound 6 (200 mg, 0.25 mmole) in 10 mL of dry
THF. The reaction mixture was heated for 5 h at 60°C
and the solvent was evaporated. Column chromatography
on neutral alumina (grade IV) with CH2Cl2 afforded
compound 1 as a brown powder, 235 mg. Yield 83%.
Anal. calcd. for C159H173N10O4PS.H2O; C: 81.22, H: 7.42,
N: 5.96, S: 1.36%. Found C: 81.43, H: 7.19, N: 5.71, S:
1.39. MS (MALDI-TOF): m/z 2351.3 (calcd. for [M +
Compound 8.
A commercial vinylmagnesium
bromide solution (25 mL, 1 M in THF) was slowly added
under argon to a degazed mixture of 2,7-diiodo-9,9-
dibutyl-9H-fluorene (4 g, 7.54 mmole) and PdCl2dppf
(246 mg, 302 mmole) in dry THF (50 mL) at room
1
H]+ 2351.3). H NMR (300 MHz, CDCl3): d, ppm 8.94
(m, 8H), 8.31 (d, J = 8.1 Hz, 2H), 8.15 (m, 8H), 8.03 (bs,
Copyright © 2016 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2016; 20: 8–11