C.G. Sun et al. / Chinese Chemical Letters 22 (2011) 527–530
529
Table 2
Melting point, yields and MS–MS analysis results of compounds 1–3.
a
Compounds
Metal salts
FeCl
Mp (8C)
>250
Yield (%)
89
MS–MS m/z (%)
+
565.89 (35 eV, 75) [M+H] , 550.79 (5), 532.91 (20), 517.92 (35),
1
2
5
06.92 (45), 486.03 (25), 472.97 (100), 459.95 (95), 445.95 (35), 428.76 (5)
+
568.92 (35 eV, 30) [M+H] , 553.92 (10), 535.93 (20), 520.92 (25),
2
CoCl
2
ꢀ6H
2
O
>250
>250
92
91
5
09.92 (45), 475.95 (95), 461.93 (100), 448.90 (50), 422.86 (5)
+
564.93 (45 eV, 5) [M+H] , 498.96 (30), 484.98 (15), 471.99 (100),
3
MnCl
2
ꢀ4H
2
O
458.88 (50), 445.02 (25), 428.99 (3)
a
Isolated yields.
[()TD$FIG]
3
Fig. 1. UV–vis spectra of compounds 1–4 in CHCl .
In conclusion, we have demonstrated a convenient method for the first time syntheses of the three novel 2,7,12,18-
tetramethyl-13,17-di(3-disulfidepropyl)porphyrin metal. Easy procedure, new aim compounds and high yields
attained in almost short reaction times can be mentioned as advantages of this method. Currently, we are working on
the investigation of catalytic activity of these novel compounds. Further details and application in modified electrodes,
as catalysis for many important reactions will be presented in due course.
2
. Experimental
Melting points were determined on a XT4 micro hot-stage apparatus and are uncorrected. IR spectra were obtained
by a Perkin-Elmer 681 instrument with KBr optics. LC–MS/MS (ESI) mass spectra were recorded on a Finnigan TSQ
1
Quantum ultra AM mass spectrometer. H NMR was recorded on a Bruker 500 MHz spectrometers in CDCl with
3
tetramethylsilane (TMS) as an internal standard. Elemental analysis was conducted on an PE-2004 (Perkin-Elmer)
elemental analyzer. The UV–vis spectra were measured by a Shimadzu UV-240 spectrophotometer.
Synthesis of 2,7,12,18-tetramethyl-13,17-di(3-bromicpropyl)porphyrin (5). A solution of compound 6 (0.4 g,
0
condition of stirring for 4 h. After completion, the reaction mixture was washed with water, extracted with CH Cl .
.83 mmol) in 40 mL of dichloromethane was treated at 39 8C with 0.4 mL of PBr in 5 mL of CH Cl under the
3
2
2
2
2
The solution was concentrated and purified by silica gel chromatography (10:1, CH Cl /EtOAc) to give 0.41 g
2
2
1
(
82.8%) of 5 as clear. mp: >250 8C. H NMR (500 MHz, CDCl ): d 3.86 (s, 2H), 2.85–2.88 (t, 4H, J = 11.5 Hz), 3.71–
3
+
.76 (s, 12H), 3.79–3.84 (t, 4H, J = 9.5 Hz), 4.29 (m, 4H), 9.12 (s, 2H), 10.08–10.24 (s, 4H); ESI -MS (40 eV, m/z):
3
+
+
+
+
06.85 [M+H] , 526.90 [M+H–HBr] , 499.0 [M+H–CH CH –HBr] , 485.96 [M+H–CH CH CH Br] ; Anal. Calcd.
6
for C H N Br : C, 59.95; H, 4.86; N, 9.65. Found: C, 59.78; H, 4.74; N, 9.76.
2
2
2
2
2
2
8
32
4
2
Synthesis of 2,7,12,18-tetramethyl-13,17-di(3-disulfidepropyl)porphyrin (4). To a solution of thiourea (0.6 g,
.9 mmol) in ethanol (50 mL) were added a solution of compound 5 (0.5 g, 0.83 mmol) in CHCl (25 mL). The
7
mixture was stirred magnetically under reflux condition for 8 h. The process of reaction was monitored by TLC until
3
the compound 5 was consumed. Then, the saturated Na CO solution was added to the mixture until the pH was 9.0.
2
3