DONOR ACCEPTOR TYPE FERROCENE SUBSTITUTED AZA-BODIPYS
727
Synthesis
Compound (3). Ferrocenylchalcone 1 (600.00 mg,
.89 mmol) was dissolved in ethanol 2.00 mL), after 5
min nitromethane (2.10 mL, 37.95 mmol) and KOH
22.00 mg, 0.37 mmol) were added. Then reaction mixture
(3507.00 mg, 45.56 mmol) was added to it, and the
reaction mixture was stirred for 48 h. The product was
filtered and washed with cold ethanol. Blue solid, yield
1
1
3% (122.00 mg). R = 0.15 (silica, DCM/hexane 1:4).
f
-1
IR: n, cm 3082.87, 1567.76, 1537.82, 1495.31, 1459.45.
(
1
H NMR (CDCl , 500 MHz): d, ppm 7.57 (d, J = 3.5 Hz,
3
was refluxed for 24 h. After this it was extracted with
ethylacetate and dried over anhydrous Na SO and solvent
2
2
H), 7.49 (d, J = 4.5 Hz, 2H), 7.18–7.2 (m, 2H), 6.81 (s,
2
4
13
H), 5.23 (s, 4H), 4.53 (s, 4H), 4.18 (s, 10 H). C NMR
was evaporated by using rotary evaporator under reduced
pressure. The desired product was purified by column
chromatographyonsilicagel, elutingwith8%ethylacetate/
(
1
6
CDCl , 127.5 MHz): d, ppm 149.18, 148.6 143.79,
3
37.52, 128.64, 128.07, 126.67, 112.32, 70.27, 69.98,
+
9.12. HRMS (ESI-Q-TOF): m/z C H N Fe S [M +
3
6
27
3
2 2
hexane. Orange solid, yield 44% (320.00 mg). R =
f
+
H] calcd. 678.0423, found 678.0421.
-1
0
.24 (silica, DCM/hexane 1:1.5). IR: n, cm 1679.65,
Compound (7). Compound 5 (657.00 mg, 0.98 mmol)
1
1593.74, 1544.31, 1280.51. H NMR (CDCl , 500 MHz):
3
was dissolved in dry DCM (0.70 mL) and dry
d, ppm 7.97 (d, J = 7 Hz, 2H), 7.6 (t, J = 7.5 Hz, 1H), 7.49
t, J = 7.5 Hz, 2H), 4.71 (dd, J = 4 Hz, J = 4.5 Hz, 2H),
.
DIEA (2.00 mL) were added after 5 min BF OEt
3
2
(
(1.90 mL, 15.39 mmol) was added and it was stirred for
4
3
1
8
.14 (s, 7H), 4.10–4.14 (m, 2H), 3.96–4.01 (m, 1H), 3.48–
24 h at room temperature. Reaction mixture was extracted
13
.49 (m, 2H). C NMR (CDCl , 127.5 MHz): d, ppm
3
with DCM and the solvent was evaporated by using rotary
evaporator. The desired product was purified by column
chromatography on silica gel eluting with 30% DCM/
97.47, 151.75, 136.64, 133.56, 128.8, 128.07, 88.23,
0.07, 68.80, 68.13, 68.07, 66.97, 52.34, 41.75, 33.65.
+
+
HRMS (ESI-Q-TOF): m/z C H FeNO [M + H] calcd.
20
20
3
hexane. Metallic green solid, yield 33% (232.00 mg). R =
f
388.0793, found 388.0819.
-1
0
1
5
6
.24 (silica, 35% DCM/hexane 1:3). IR: n, cm 1554.51,
Compound (4). Ferrocenylchalcone 2 (1910.00 mg,
.92 mmol) was dissolved in ethanol (5.90 mL), after
min nitromethane (6.30 mL, 118.26 mmol) and KOH
1
491.66, 1447.13, 1295.95, 1229.35. H NMR (CDCl ,
3
5
5
00 MHz): d, ppm 7.99–8.01 (m, 4H), 7.45–7.46 (m, 6H),
.69 (s, 2H), 5.29 (s, 1H), 5.26 (s, 4H), 4.73 (s, 4H), 4.23
(
66.40 mg, 1.18 mmol) were added. Then reaction
13
(
1
s, 9H). C NMR (CDCl , 127.5 MHz): d, ppm 157.21,
3
mixture was refluxed for 24 h. After this, it was extracted
with ethylacetate and dried over anhydrous Na SO and
46.78, 145.50, 132.35, 130.21, 129.21, 129.17, 129.14,
2
4
19
128.51, 116.61, 71.82, 71.03, 69.79, 53.44. F NMR
solvent was evaporated by using rotary evaporator under
reduced pressure. The desired product was purified by
column chromatography on silica gel eluting with 70%
DCM/hexane. Orange solid, yield 54% (1230.00 mg).
11
(
470.4 MHz, CDCl ): d, ppm -130.26 (q, 2F). B NMR (160
3
MHz, CDCl ): d, ppm 0.88 (t, 1B). HRMS (ESI-Q-TOF):
m/z C H N Fe BF [M] calcd. 713.1200, found 713.1210.
3
+
+
40
30
3
2
2
Compound(8).Compound6(100.00mg,0.147mmol)
was dissolved in dry DCM (0.10 mL) and dry DIEA
-
1
R = 0.22 (silica, DCM–hexane 1:1.5). IR: n, cm
f
1
1
5
4
4
3
1
6
657.61, 1543.23, 1518.89, 1282.61. H NMR (CDCl ,
3
(
0.30 mL) were added after 5 min BF .OEt (0.30 mL,
3 2
00 MHz): d, ppm 7.74 (d, J = 3 Hz, 1H), 7.66 (d, J =
.5 Hz, 1H), 7.13–7.15 (m, 1H ), 4.7 (d, J = 6 Hz, 2H),
.14 (s, 7H), 4.08–4.1 (m, 2H), 3.92–3.97 (m, 1H), 3.35–
.45 (m, 1H). C NMR (CDCl , 127.5 MHz): d, ppm
90.33, 143.82, 134.3, 132.27, 128.37, 87.95, 79.96,
8.85, 68.16, 68.09, 66.96, 42.34, 33.98. HRMS (ESI-
2
.32 mmol) was added and it was stirred for 24 h at
room temperature. Reaction mixture was extracted with
DCM and the solvent was evaporated by using rotary
evaporator. The desired product was purified by column
chromatography on silica gel eluting with 30% DCM/
1
3
3
hexane. Metallic green solid, yield 20% (21.00 mg). R =
+
+
f
Q-TOF): m/z C H FeNSO [M] calcd. 383.0279,
1
8
17
3
-1
0
1
5
5
4
1
1
1
.21 (silica, DCM/hexane 1:3). IR: n, cm 1505.8,
found 383.0304.
1
447.9, 1405.05, 1292.96, 1243.51. H NMR (CDCl ,
3
Compound(5).Compound3(1000.00mg,2.65mmol)
00 MHz): d, ppm 8.33 (d, J = 4 Hz, 2H), 7.58 (d, J =
Hz, 2H), 7.22–7.24 (m, 2H), 6.85 (s, 2H), 5.29 (s,
H), 5.25 (t, J = 1.5 Hz, 4H), 4.7–4.71 (m, 4H), 4.23 (s,
was dissolved in ethanol (20.00 mL) and NH OAc
4
(7169.00 mg, 92.75 mmol) was added to it, and the
reaction mixture was stirred for 48 h. The product was
filtered and washed with cold ethanol. Blue solid, yield
1
3
0H). C NMR (CDCl , 127.5 MHz): d, ppm 157.21,
3
46.78, 145.50, 132.35, 130.21, 129.21, 129.17, 129.14,
28.21, 116.61, 71.82, 71.03, 69.79, 53.44. F NMR
3
1% (550.00 mg). R = 0.18 (silica, DCM/hexane 1:4).
f
19
-1
IR: n, cm 3088.54, 1576.82, 1559.25, 1459.32, 1263.44.
1
1
(
(
470.4 MHz, CDCl ): d, ppm -136.91 (q, 2F). B NMR
1
3
H NMR (CDCl , 500 MHz): d, ppm 7.93 (d, J = 7.5 Hz,
3
160 MHz, CDCl ): d, ppm 1.13 (t, 1B). HRMS (ESI-Q-
3
4
6
H), 7.52 (d, J = 7.5 Hz, 4H), 7.45 (d, J = 7.5 Hz, 2 H),
13
+
+
TOF): m/z C H N Fe S BF [M + H] calcd. 725.0328,
36 26
3
2
2
2
.96 (s, 2 H), 5.52 (s, 4 H), 4.54 (s, 4 H), 4.19 (s, 10 H). C
found 726.0322.
NMR (CDCl , 127.5 MHz): d, ppm 154.5, 149.51, 144.15,
3
1
6
32.52, 129.66, 129.06, 126.36, 112.49, 70.27, 69.98,
+
9.16. HRMS (ESI-Q-TOF): m/z C H Fe N [M +
4
0
31
2
3
CONCLUSION
+
H] calcd. 666.1295, found 666.1302.
Compound (6). Compound 4 (500.00 mg, 1.30 mmol)
1,7-Diferrocenyl substituted aza-dipyrrins and aza-
BODIPYs having two phenyl or 2-thienyl groups at
was dissolved in ethanol (10.00 mL) and NH OAc
4
Copyright © 2016 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2016; 20: 727–729