Experimental and computational study on the reactivity of amino substituents
607
aqueous layer was extracted with EtOAc (4 9 150 cm3).
The combined organic layers were washed with NaHCO3
solution and water. Evaporation and chromatography
(dichloromethane:methanol 10:1) afforded 147 mg (13%)
6 as a brown oil. Rf = 0.19 (ethyl acetate:methanol 5:1);
MS (ESI): m/z = 317 (M - H-), 341 (M?Na?).
(m, 12H, 6 CH2CH2F) ppm; 19F NMR (376 MHz, pyridine-
d5): d = -140.99 (m), -141.04 (m), -141.21 (m) ppm; MS
(MALDI): m/z = 1307.592 (M?H?).
[1,4,8,11,15,18,22,25-Octakis(4-fluorobutoxy)phthalocy-
anato]zinc(II) (9, C64H72F8N8O8Zn) was isolated as a side-
product. Rf = 0.32 (dichloromethane:methanol 10:1); UV–
Vis (dichloromethane:methanol 1:1): kmax (log e) = 328
3,6-Bis(4-fluorobutoxy)benzene-1,2-dicarbonitrile
(7, C16H18F2N2O2)
1
(4.86), 663 (4.74), 738 (5.36), 822 (4.23) nm; H NMR
(400 MHz, pyridine-d5): d = 7.83 (s, 8H, H-2, H-3, H-9,
H-10, H-16, H-17, H-23, H-24), 5.08 (t, 16H, 3J = 6.5 Hz, 8
To a well-stirred slurry of 0.808 g 2,3-dicyanohydroquinone
(5.04 mmol) and 0.484 g NaH (60% dispersion in mineral
oil, 10.08 mmol) in 25 cm3 dimethylformamide cooled to
0 °C, 1.562 g 4-bromo-1-fluorobutane (10.08 mmol) was
added after 1.5 h. The solution was heated at 50 °C for 24 h.
The reaction contents were poured into 65 cm3 water, and
the suspension was vigorously stirred. The resulting white-
cream solid was filtered and next suspended in 100 cm3
methanol keeping under reflux. The filtration of the white
solid afforded 1.447 g (92%) 7. M.p.: 179–183 °C;
Rf = 0.82 (tetrahydrofuran:methanol 1:1); UV (methanol):
kmax (log e) = 226 (4.18), 350 (3.51) nm; 1H NMR
(300 MHz, DMSO-d6): d = 7.62 (s, 2H, H-4, H-5), 4.51
(dt, 4H, 2JHF = 47.5 Hz, 3J = 5.5 Hz, 2 CH2F), 4.20 (t, 4H,
3J = 6.0 Hz, 2 CH2O), 1.74–1.85 (m, 8H, 2 CH2CH2) ppm;
13C NMR (75 MHz, DMSO-d6): d = 154.8, 120.6, 113.5,
2
OCH2), 4.62 (dt, 16H, JHF = 47.5 Hz, 3J = 6.0 Hz, 8
CH2F), 2.38 (p, 3J = 7.0 Hz, 16H, 8 OCH2CH2), 2.15 (dp,
16H, 3JHF = 25.5 Hz, 3J = 7.0 Hz, 8 CH2CH2F) ppm; 19
F
NMR (376 MHz, pyridine-d5): d = -139.97 (m) ppm; 13
C
NMR (100 MHz, pyridine-d5): d = 153.24, 151.97, 128.65,
119.43, 84.4 (d, JCF = 163.0 Hz), 72.16, 27.8 (d,
1
3
2JCF = 20.0 Hz), 26.2 (d, JCF = 5.0 Hz) ppm; MS
(MALDI): m/z = 1 297.572 (M?H?).
General procedure for UV–Vis titrations
of tribenzoporphyrazine 8
CH3OH:CH2Cl2 (1:1) solution of known concentration of
porphyrazine 8 was subjected to UV–Vis titrations with
CH3OH:CH2Cl2 (1:1) solutions of varying concentrations
(0, 0.01, 0.1, 0.5, 1 molar equiv.) of PdCl2(C6H5CN)2.
Blank UV–Vis spectra (in the absence of metal salt) were
run for 8 to determine any solvent effect (of which there
were none). Blank UV–Vis spectra (in the absence of
tribenzoporphyrazine 8) were also run for the metal salt to
make sure that there was no significant absorbance in the
window of interest (300–850 nm).
1
102.8, 83.5 (d, JCF = 161.5 Hz), 69.3, 26.4 (d,
2JCF = 19.5 Hz), 24.3 ppm; MS (CI, NH3): m/z = 326
(M?NH4?); HRMS calcd for C16H22N3O2F2 326.1680,
found 326.1683.
1,4,8,11,15,18-Hexakis(4-fluorobutoxy)-22,23-bis[methyl-
(3-pyridylmethyl)amino]tribenzo[b,g,l]porphyrazinato-
zinc(II) (8, C66H72F6N12O6Zn)
To 2 cm3 pentanol 65 mg 6 (0.20 mmol), 414 mg 7
(1.43 mmol), 300 mg Zn(OAc)2 (1.63 mmol), and
0.244 cm3 1,8-diazabicyclo[5.4.0]undec-7-ene (1.63 mmol)
were added and heated under reflux for 23 h. Evaporation and
chromatography (dichloromethane:methanol 25:1–15:1)
afforded 25 mg greyish-blue 8 (9%) as a thin film. Further
purification by means of PTLC afforded 8 mg (3%).
Rf = 0.29 (dichloromethane:methanol 8:1); UV–Vis
(dichloromethane:methanol 1:1): kmax (log e) = 332 (4.24),
730 (4.36) nm; 1H NMR (400 MHz, pyridine-d5): d = 9.06
Acknowledgments This study was supported in part by Polish
Ministry of Science and Higher Education grant no. N405 031
32/2052. T.G. thanks Professor A.G.M. Barrett from Imperial College
London and Professor S. Sobiak from Poznan University of Medical
Sciences for supporting his studies. The authors thank Mrs B.
Kwiatkowska for excellent technical assistance. Z.D. thanks MSc A.
Maruszewski for preparation of input data for computational study.
Open Access This article is distributed under the terms of the
Creative Commons Attribution Noncommercial License which per-
mits any noncommercial use, distribution, and reproduction in any
medium, provided the original author(s) and source are credited.
4
(d, 2H, J = 2.0 Hz, 2 pyridine-20H), 8.52 (dd, 2H,
4
3J = 4.5 Hz, J = 1.5 Hz, 2 pyridine-60H), 7.89 (dt, 2H,
4
3J = 8.0 Hz, J = 2.0 Hz, 2 pyridine-40H), 7.87 (s, 2H,
References
18-H, 19-H), 7.84 (d, 2H, 3J = 8.5 Hz, 2 Ar–H), 7.67 (d, 2H,
3
3
3J = 8.5 Hz, 2 Ar–H), 7.07 (dd, 2H, J = 8.0, Hz, J =
1. Begland RW, Hartter DR, Jones FN, Sam DJ, Sheppard WA,
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2
(hidden m, 8H, 4 OCH2), 4.65 (dt, 4H, JHF = 47.5 Hz,
3J = 6.0 Hz, 2 CH2F), 4.63 (dt, 4H, JHF = 47.5 Hz,
2
3J = 6.0 Hz, 2 CH2F), 4.63 (t, 4H, J = 7.0 Hz, 2 OCH2),
3
2
3
4.58 (dt, 4H, JHF = 47.0 Hz, J = 6.0 Hz, 2 CH2F), 4.06
(s, 6H, 2 CH3), 2.46–2.32 (m, 12H, 6 OCH2CH2), 1.98–2.26
123