COMPARISON OF ELECTRONIC EFFECTS OF b-ARYL SUBSTITUENTS ON OPTICAL AND ELECTROCHEMICAL PROPERTIES
9
1H, pyrrole-b). HRMS (ESI): m/z 711.2350 (calcd. for
[M + H]+ 711.2377). UV-vis (CH2Cl2): lmax, nm (log e)
396 (4.85), 583 (4.56).
a purple solid (18.0 mg, 61%). According to similar
procedures, 4a, 4b, 4d, 4e were prepared from 2Zn and
the corresponding arylboronic acids.
3c. (Rf = 0.44 in hexane/AcOEt = 5/1) mp > 300°C.
1H NMR (700 MHz; CDCl3): dH, ppm 1.49 (t, J = 7.0 Hz,
3H, -CO2CH2CH3), 1.81 (s, 6H, ortho-Me), 1.84 (s, 6H,
ortho-Me) 2.61 (s, 3H, para-Me), 2.63 (s, 3H, para-Me),
4.49 (q, J = 7.0 Hz, 2H, -CO2CH2CH3), 7.27 (s, 2H,
Mes-meta), 7.29 (s, 2H, Mes-meta), 8.38 (d, J = 8.4 Hz,
2H, phenyl), 8.77 (d, J = 4.9 Hz, 1H, pyrrole-b), 8.78
(d, J = 4.9 Hz, 1H, pyrrole-b), 8.79 (d, J = 4.9 Hz, 1H,
pyrrole-b), 8.88 (d, J = 8.4 Hz, 2H, phenyl), 8.94 (s, 1H,
pyrrole-b), 9.149 (d, J = 4.9 Hz, 1H, pyrrole-b), 9.153
(d, J = 4.9 Hz, 1H, pyrrole-b), 9.19 (d, J = 4.9 Hz, 1H,
pyrrole-b). HRMS (ESI): m/z 753.2474 (calcd. for [M +
H]+ 753.2482). UV-vis (CH2Cl2): lmax, nm (log e) 399
(503), 585 (4.77).
3d. (Rf = 0.48 in hexane/AcOEt = 5/1) mp > 300°C.
1H NMR (700 MHz; CD2Cl2): dH, ppm 1.81 (s, 6H,
ortho-Me), 1.83 (s, 6H, ortho-Me) 2.62 (s, 3H, para-Me),
2.63 (s, 3H, para-Me), 7.30 (s, 2H, Mes-meta), 7.31 (s,
2H, Mes-meta), 8.01 (d, J = 8.4 Hz, 2H, phenyl), 8.78
(d, J = 4.9 Hz, 1H, pyrrole-b), 8.786 (d, J = 4.9 Hz, 1H,
pyrrole-b), 8.787 (d, J = 4.9 Hz, 1H, pyrrole-b), 8.986 (d,
J = 8.4 Hz, 2H, phenyl), 8.987 (s, 1H, pyrrole-b), 9.137
(d, J = 4.9 Hz, 1H, pyrrole-b), 9.142 (d, J = 4.9 Hz, 1H,
pyrrole-b), 9.19 (d, J = 4.9 Hz, 1H, pyrrole-b). HRMS
(ESI): m/z 706.2215 (calcd. for [M + H]+ 706.2224).
UV-vis (CH2Cl2): lmax, nm (log e) 400 (4.97), 587 (4.74).
3e. (Rf = 0.47 in hexane/AcOEt = 5/1) mp > 300°C; 1H
NMR (700 MHz; CDCl3): dH, ppm 1.81 (s, 6H, ortho-Me),
1.83 (s, 6H, ortho-Me) 2.61 (s, 3H, para-Me), 2.64 (s,
3H, para-Me), 7.27 (s, 2H, Mes-meta), 7.29 (s, 2H, Mes-
meta), 7.36 (dd, J = 3.5, 4.9 Hz, 1H, thienyl-b), 7.69 (dd,
J = 1.4, 4.9 Hz, 1H, thienyl-a), 8.47 (dd, J = 1.4, 3.5 Hz,
1H, thienyl-b 8.73 (d, J = 4.9 Hz, 1H, pyrrole-b), 8.760 (s,
1H, pyrrole-b), 8.761 (d, J = 4.9 Hz, 1H, pyrrole-b), 8.77
(d, J = 4.9 Hz, 1H, pyrrole-b), 9.118 (d, J = 4.9 Hz, 1H,
pyrrole-b), 9.122 (d, J = 4.9 Hz, 1H, pyrrole-b), 9.21 (d,
J = 4.9 Hz, 1H, pyrrole-b). HRMS (ESI): m/z 687.1821
(calcd. for [M + H]+ 687.1835). UV-vis (CH2Cl2): lmax, nm
(log e) 398 (4.89), 587 (4.55).
4a. (Rf = 0.13 in CH2Cl2/AcOEt = 100/1) mp > 300°C.
1H NMR (700 MHz; CDCl3/CD3OD): dH, ppm 1.86 (s,
6H, ortho-Me), 1.88 (s, 6H, ortho-Me), 2.65 (s, 3H,
para-Me), 2.67 (s, 3H, para-Me), 7.31 (s, 2H, Mes-meta),
7.33 (s, 2H, Mes-meta), 7.58 (t, J = 7.0 Hz, 1H, phenyl),
7.76 (pseudo-t, J = 7.0 Hz, 2H, phenyl), 8.81–8.82 (m,
3H, pyrrole-b), 8.85 (d, J = 7.0 Hz, 2H, phenyl), 8.88
(s, 1H, pyrrole-b), 9.16 (d, J = 4.2 Hz, 1H, pyrrole-b),
9.17 (d, J = 4.2 Hz, 1H, pyrrole-b), 9.26 (d, J = 4.2 Hz,
1H, pyrrole-b). HRMS (ESI): m/z 686.2197 (calcd. for
[M + H]+ 687.2209). UV-vis (CH2Cl2): lmax, nm (log e)
402 (5.02), 593 (4.86).
4b. (Rf = 0.77 in CH2Cl2/MeOH = 50/1) mp > 300°C.
1H NMR (700 MHz; CD2Cl2, 2 mM): dH, ppm 1.85 (s, 6H,
ortho-Me), 1.87 (s, 6H, ortho-Me), 2.65 (s, 3H, para-Me),
2.66 (s, 3H, para-Me), 4.02 (s, 3H, OMe), 7.309 (s, 2H,
Mes-meta), 7.310 (d, J = 8.4 Hz, 2H, phenyl), 7.32 (s, 2H,
Mes-meta), 8.87–8.89 (m, 4H, pyrrole-b), 8.99 (d, J =
8.4 Hz, 2H, phenyl), 9.29 (d, J = 4.2 Hz, 1H, pyrrole-b),
9.30 (d, J = 4.2 Hz, 1H, pyrrole-b), 9.35 (d, J = 4.2 Hz,
1H, pyrrole-b). HRMS (ESI): m/z 717.2300 (calcd. for
[M + H]+ 717.2315). UV-vis (CH2Cl2): lmax, nm (log e)
400 (5.03), 597 (4.82).
4c. (Rf = 0.48 in CH2Cl2/AcOEt = 20/1) mp > 300°C.
1H NMR (700 MHz; CDCl3, 1 mM): dH, ppm 1.14 (t, J =
6.7 Hz, 3H, -CO2CH2CH3), 1.85 (s, 6H, ortho-Me), 1.87
(s, 6H, ortho-Me), 2.65 (s, 3H, para-Me), 2.67 (s, 3H,
para-Me), 4.50 (q, J = 6.7 Hz, 2H, -CO2CH2CH3), 7.31
(s, 2H, Mes-meta), 7.34 (s, 2H, Mes-meta), 8.42 (d, J =
8.0 Hz, 2H, phenyl), 8.89–8.90 (m, 3H, pyrrole-b), 9.06
(s, 1H, pyrrole-b), 9.09 (d, J = 8.0 Hz, 2H, phenyl), 9.30
(d, J = 4.2 Hz, 1H, pyrrole-b), 9.31 (d, J = 4.2 Hz, 1H,
pyrrole-b), 9.35 (d, J = 4.2 Hz, 1H, pyrrole-b). HRMS
(ESI): m/z 759.2409 (calcd. for [M + H]+ 759.2420).
UV-vis (CH2Cl2): lmax, nm (log e) 406 (5.06), 596 (4.87).
4d. (Rf = 0.58 in CH2Cl2/AcOEt/pyridine = 100/1/1)
1
mp 248°C (decomposed). H NMR (700 MHz; CD2Cl2/
CD3OD): dH, ppm 1.85 (s, 6H, ortho-Me), 1.88 (s, 6H,
ortho-Me), 2.64 (s, 3H, para-Me), 2.65 (s, 3H, para-Me),
7.13 (t, J = 7.4 Hz, 2H, phenyl-para), 7.28 (d, J = 7.4 Hz,
4H, phenyl-ortho), 7.33 (s, 2H, Mes-meta), 7.34 (s, 2H,
Mes-meta), 7.37 (pseudo-t, J = 7.4 Hz, 4H, phenyl-meta),
7.42 (d, J = 8.8 Hz, 2H, phenylene), 8.77 (d, J = 4.2 Hz,
1H, pyrrole-b), 8.78 (d, J = 4.2 Hz, 1H, pyrrole-b), 8.79
(d, J = 4.2 Hz, 1H, pyrrole-b), 8.81 (s, 1H, pyrrole-b),
8.84 (d, J = 8.8 Hz, 2H, phenylene), 9.15 (d, J = 4.2 Hz,
1H, pyrrole-b), 9.17 (d, J = 4.2 Hz, 1H, pyrrole-b), 9.22
(d, J = 4.2 Hz, 1H, pyrrole-b). HRMS (ESI): m/z 854.2931
3-Aryl-5,15-diaza-10,20-dimesitylporphinato-
zinc(II) (4). Typical procedure: A mixture of 2Zn
(26.9 mg, 0.039 mmol), Pd(OAc)2 (1.6 mg, 0.007 mmol),
2-biphenyldicyclohexylphosphine (5.5 mg, 0.016 mmol),
K2CO3 (15.7 mg, 0.114 mmol), 4-(ethoxycarbonyl)
phenylboronic acid (37.6 mg, 0.194 mmol), 1,4-dioxane
(6 mL), and distilled water (0.6 mL) was heated at 80°C.
After 1.5 h, CH2Cl2, pyridine, and water were added, and
thecombinedorganicextractswereseparated,washedwith
brine several times, dried over Na2SO4, and concentrated
under reduced pressure to leave a solid residue, which
was then chromatographed on silica gel using CH2Cl2/
AcOEt/pyridine as eluents. The green fraction (Rf = 0.48
in CH2Cl2/AcOEt = 100/5) was collected, concentrated,
and recrystallized from CH2Cl2/MeOH to give 4c as
(calcd. for [M + H]+ 854.2944). UV-vis (CH2Cl2): lmax
nm (log e) 304 (4.71), 401 (5.25), 603 (4.88).
,
4e. (Rf = 0.36 in CH2Cl2/AcOEt = 100/1) mp 281–
1
282°C (decomposed). H NMR (700 MHz; CD2Cl2/
CD3OD): dH, ppm 1.85 (s, 6H, ortho-Me), 1.98 (s, 6H,
ortho-Me), 2.60 (s, 3H, para-Me), 2.63 (s, 3H, para-Me),
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 9–11