10
J. OSTAPKO ET AL.
R
R
R
R
R
N
H
N
H
N
N
N
N
H
N
H
N
R
R2
Br
9a,b
1, 3
Br
+
+
R2
R
R
N
H
N
H
N
N
N
N
H
N
H
N
R
R
2, 4
10a,b
Br
R2
Scheme 3. Synthesis of porphyrins functionalized with thiocarbamate (1, 2) and thioacetate (3, 4) groups. Reaction conditions:
NaS(CO)CH3 or NaS(CS)(NH3)2, acetone. 1, 2: R = phenyl, R2 = S(CS)(NH3)2; 3, 4: R = 4-methylphenyl, R2 = S(CO)CH3
1
(2,3-dichloro-5,6-dicyano-1,4-benzoquinone) (1.53 g,
6.74 mmol). After stirring for 20 min the solvent was
concentrated to approximately 100 mL. This solution
was filtered through silica pad in dichloromethane and
the solvent was evaporated. The residue was suspended in
hot methanol (150 mL) and filtered, giving crude mixture
of porphyrins as a deep purple solid. The material was
dissolvedinacetone(150mL)anddimethyldithiocarbamic
acid sodium salt was added. The TLC analysis (SiO2,
ethyl acetate:n-hexane 1:2) indicated the presence of at
least four porphyrin products. The products were isolated
by gradient chromatography column (SiO2). The first
fraction containing tetraphenylporphyrin was collected
in ethyl acetate:n-hexane 1:5, 0.25% triethylamine and
then eluent was changed to ethyl acetate:n-hexane 1:3,
0.25% triethylamine to isolate porphyrins 1 and 2. After
isolation each product was suspended in hot methanol
and filtrated, affording 1 (132 mg, 0.17 mmol) and 2 (66
mg, 0.07 mmol, 1.62%).
Porphyrins 3 and 4 were prepared by analogical
protocol using 4-methylphenyldipyrromethane 8 (2.13 g,
9.00 mmol) and potassium thioacetate (1.00 g, 8.80 mmol).
Compounds 3 and 4 were isolated in amounts of 286 mg
(0.37 mmol) and 423 mg (0.49 mmol, 8%), respectively.
1. mp > 300°C. 1H NMR (500 MHz; CDCl3; Me4Si):
d, ppm 8.85–8.80 (m, 8H), 8.20 (m, 6H), 8.15 (d, J =
8.00 Hz, 2H), 7.82 (d, J = 8.00 Hz, 2H), 7.90–7.30 (m,
9H), 4.48 (s, 2H), 3.62 (s, 3H), 3.45 (s, 3H), -2.78 (s, 2H).
13C NMR (126 MHz, CDCl3): d, ppm 195.46, 142.32,
142.12, 134.54, 134.42, 130.23, 127.74, 126.69, 122.35,
120.35, 120.26, 119.15, 84.88, 83.52, 45.50, 41.41,
27.98. UV-vis (CHCl3): lmax, nm (log e) 419 (5.50),
516 (4.18), 551 (3.86), 590 (3.68), 646 (5.52). MS: m/z
772.2554 (calcd. for [M + H]+ 772.2569).
2. mp > 300°C. H NMR (500 MHz; CDCl3; Me4Si):
d, ppm 8.85–8.80 (m, 8H), 8.20 (m, 4H), 8.14 (d, J =
7.90 Hz, 4H), 7.82 (d, J = 7.90 Hz, 4H), 7.80–7.73 (m, 6H),
4.48 (s, 4H), 3.63 (s, 6H), 3.46 (s, 6H), -2.80 (s, 2H). 13C
NMR (126 MHz, CDCl3): d, ppm 195.40, 142.22, 142.20,
142.01, 142.00, 134.50, 134.38, 130.22, 127.75, 126.68,
122.36, 122.34, 120.44, 120.36, 119.34, 119.25, 84.87,
83.46, 45.49, 41.44, 27.95. UV-vis (CHCl3): lmax, nm
(log e) 421 (5.38), 517 (4.25), 553 (4.00), 591 (3.79), 647
(3.67). MS: m/z 929.2590 (calcd. for [M+H]+ 929.2589).
3. mp > 300°C. 1H NMR (500 MHz; CDCl3; Me4Si):
d, ppm 8.87–8.77 (m, 8H), 7.55 (m, 6H), 7.79 (d,
J = 8.20, 2H), 7.93 (m, 6H), 8.15 (d, J = 8.20, 2H),
8.87–8.77 (m, 8H), 4.05 (s, 2H), 2.70 (s, 9H), 2.46 (s,
3H), -2.78 (s, 2H). 13C NMR (126 MHz, CDCl3): d,
ppm 194.15, 142.48, 139.23, 139.19, 137.37, 137.36,
134.48, 134.42, 130.12, 127.42, 122.14, 120.43,
120.27, 118.80, 85.19, 82.80, 30.29, 21.52, 18.81.
UV-vis (CHCl3): lmax, nm (log e) 421 (5.57), 517 (4.18),
553 (3.91), 592 (3.66), 647 (3.57). MS: m/z 768.2929
(calcd. for [M + H]+ 768.2923).
4. mp > 300°C. 1H NMR (500 MHz; CDCl3; Me4Si):
d, ppm 8.87–8.77 (m, 8H), 7.54 (d, J = 7.70 Hz, 4H), 7.79
(d, J = 8.05 Hz, 4H), 8.07 (d, J = 7.70, 4H), 8.13 (d, J =
8.05, 4H), 8.87–8.77 (m, 8H), 4.05 (s, 4H), 2.70 (s, 6H),
2.46 (s, 6H), -2.80 (s, 2H). 13C NMR (126 MHz, CDCl3):
d, ppm 194.14, 142.37, 142.32, 139.09, 139.05, 137.45,
137.43, 134.47, 134.41, 130.14, 127.44, 127.43, 122.23,
122.21, 120.64, 120.48, 119.16, 119.01, 85.25, 82.76,
30.28, 21.51, 18.80. UV-vis (CHCl3): lmax, nm (log e)
421 (5.71), 517 (4.26), 553 (4.02), 592 (3.76), 648 (3.66).
MS: m/z 867.2843 (calcd. for [M + H]+ 867.2827).
Gold nanoparticles synthesis. HAuCl4·H2O (9.92 mg,
49%Au) was added to a solution of dodecylamine (90 mg)
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 10–12