Beilstein J. Org. Chem. 2012, 8, 120–128.
Ar(CH2)2CH(CH3)2), 1.54 (m, 4H, ArCH2CH2CH(CH3)2),
0.97 (d, J = 6.6 Hz, 12H, Ar(CH2)2CH(CH3)2); 13C NMR
(CDCl3, 125 MHz) δ 146.44 (C3 and C6), 133.43 (C4 and C5),
115.60 and 115.11 (C1, C2 and CN), 39.91 (C'2), 32.38 (C'1),
27.87 (C'3), 22.33 (C′4); HRMS–EI (70 eV) m/z: [M−CH3]+
calcd for C17H21N2, 253.1704; found, 253.1696 (100); Anal.
calcd for C18H24N2: C, 80.55; H, 9.01; N, 10.44; found: C,
79.90; H, 8.95; N, 10.30.
Supporting Information
Synthesis, analytical and spectroscopic details for the
alcohols, alkyl iodides, phthalonitriles 6b–6d and 6f and
phthalocyanines 7b–7d and 7f.
Supporting Information File 1
Experimental details.
3,6-Bis(4-methylpentyl)phthalonitrile (6d), 3,6-bis(5-methyl-
hexyl)phthalonitrile (6c), 3,6-bis(6-methylheptyl)phthalonitrile
(6b) and 3,6-bis((S)-3,7-dimethyloctyl)phthalonitrile (6f) were
We thank the EPSRC for a studentship (DJT) and the Royal
Thai Government for a DPST scholarship (SN). We also thank
James Cattle (supported by a Nuffield Foundation Studentship)
for the optical microscopy images.
1,4,8,11,15,18,22,25-Octa(3-methylbutyl)phthalo-
cyanine (7e)
To a flame-dried flask, under an argon atmosphere, lithium
metal (0.013 g, 1.86 mmol) was added to a solution of 3,6-
bis(3-methylbutyl)phthalonitrile (1.0 g, 3.73 mmol) dissolved in
freshly distilled pentanol (10 mL) under reflux. Upon comple-
tion of the addition, the reaction mixture turned dark green and
was stirred under reflux for 4 h. The mixture was allowed to
cool to rt and acetone (5 mL) was added. Excess pentanol was
removed in vacuo and the resultant dark green oil, which crys-
tallised on standing, was purified by chromatography on silica
gel with 10% DCM/hexane as eluent (Rf ~ 0.30) to afford the
title compound [24] as fine blue-green needles, which were re-
crystallised from 1:1 THF/acetone (0.81 g, 81%). mp
282–284 °C; DSC (°C, J·g−1): Cr 284.1 (40) I 189.9 (−43); IR
(neat): 3303 (N–H), 2954 (C–H), 2931 (C–H), 2864 (C–H)
cm−1; 1H NMR (CDCl3, 500 MHz) δ 7.86 (s, 8H,
C2,3,9,10,16,17,23,24H), 4.46 (t, J = 7.5 Hz, 16H,
5 ArCH2CH2CH(CH3)2), 1.91 (dt, J = 6.8 Hz and 8.1 Hz, 16H,
ArCH2CH2CH(CH3)2), 1.79 (m, J = 6.6 Hz, 8H,
Ar(CH2)2CH(CH3)2), 0.99 (d, J = 6.6 Hz, 48H,
Ar(CH2)2CH(CH3)2); 13C NMR (CDCl3, 75 MHz) δ 139.5
(C1,4,8,11,15,22,25), 131.2 (C2,3,9,10,16,17,23,24), 40.4 (C'2),
30.9 (C'1), 27.9 (C'3), 23.4 (C'4); HRMS–ES+ m/z: [M]+ calcd
for C72H98N8, 1074.7909; found 1074.7857 (100%), 1075.7900
(75%) [M + 1]+, 1076.7934 (30%) [M + 2]+.
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