Concise synthesis of [1,1′-biisoquinoline]-4,4′-diol via a protecting group strategy and its application for potential liquid-crystalline compounds

Article abstract of DOI:10.1002/hlca.200900085

The [1,1′-biisoquinoline]-4,4′-diol (4a), which was obtained as hydrochloride 4a·2 HCl in two steps starting from the methoxymethyl (MOM)-protected 1-chloroisoquinoline 8 (Scheme 3), opens access to further O-functionalized biisoquinoline derivatives. Com

Full text of DOI:10.1002/hlca.200900085

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Helvetica Chimica Acta – Vol. 92 (2009)
Concise Synthesis of [1,1’-Biisoquinoline]-4,4’-diol via a Protecting Group
Strategy and Its Application for Potential Liquid-Crystalline
Compounds
by Elisabeth Kapatsina, Markus Mateescu, Angelika Baro, Wolfgang Frey, and Sabine Laschat*
Institut fꢀr Organische Chemie der Universitꢁt Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart
(phone: þ 49-711-68564565; fax: þ 49-711-68564285; e-mail: sabine.laschat@oc.uni-stuttgart.de)
Dedicated to Prof. Helmut Schwarz on the occasion of his 65th birthday
The [1,1’-biisoquinoline]-4,4’-diol (4a), which was obtained as hydrochloride 4a · 2 HCl in two steps
starting from the methoxymethyl (MOM)-protected 1-chloroisoquinoline 8 (Scheme 3), opens access to
further O-functionalized biisoquinoline derivatives. Compound 4a · 2 HCl was esterified with 4-
(hexadecyloxy)benzoyl chloride (5b) to give the corresponding diester 3b (Scheme 4), which could
not be obtained by Ni-mediated homocoupling of 6b (Scheme 2). The ether derivative 2b was accessible
in good yield by reaction of 4a · 2 HCl with the respective alkyl bromide 9 under the conditions of
Williamson etherification (Scheme 4). Slightly modified conditions were applied to the esterification of
4a · 2 HCl with galloyl chlorides 10a – h as well as etherification of 4a · 2 HCl with 6-bromohexyl
tris(alkyloxy)benzoates 11b,d – h and [(6-bromohexyl)oxy]-substituted pentakis(alkyloxy)triphenylenes
14a – c (Scheme 5). Despite the bulky substituents, the respective target 1,1’-biisoquinolines 12, 13, and 15
were isolated in 14 – 86% yield (Table).
Introduction. – Biisoquinolines are highly attractive ligands for metal complexes
because of their strong structural resemblance with bipyridines [1] and BINOL-derived
ligands [2] (BINOL ¼ [1,1’-binaphthalene]-2,2’-diol). However, in contrast to the
latter, the chemistry of biisoquinolines has been explored to a much lesser extent. For
example, Kotora and co-workers reported a sequence of Sonogashira coupling of a,w-
diynes with 1-chloroisoquinolines followed by a Vollhardt cyclization and oxidation
with 3-chloroperbenzoic acid to give the corresponding bis-N-oxide, which was utilized
in an asymmetric allylsilane addition to aldehydes [3]. Knochel and co-workers
developed a Negishi coupling for 8,8’-biquinolines [4], while Hashim and Kappe
published a microwave-assisted Ni-catalyzed homocoupling to [4,4’-biquinolin]-2-ones
[5], and Blakemore et al. reported the enzymatic resolution of [8,8’-biquinoline]-7,7’-
diols [6]. Very recently, we described the convenient synthesis of 4,4’-bifunctionalized
1,1’-biisoquinolines 2 from 1-chloroisoquinolin-4-ol (1) via Williamson etherification
and Ni-mediated homocoupling (Scheme 1) [7].
The sequence 1 ! 2 proceeded well for alkyl substituents even with long chain
lengths, whereas (aryloxy)alkyl-substituted isoquinoline could still be coupled but with
dramatically decreased yields [7]. The Ni-mediated homocoupling of the correspond-
ing ester-functionalized isoquinoline to give 3, however, failed completely (Scheme 2).
Thus, in order to expand the scope of O-substituents in the 4,4’-positions of the 1,1’-
ꢂ 2009 Verlag Helvetica Chimica Acta AG, Zꢀrich

Helvetica Chimica Acta – Vol. 92 (2009)
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Scheme 1
Scheme 2
biisoquinoline, a more flexible approach is required. For this purpose, we envisioned
[1,1’-biisoquinoline]-4,4’-diol (4a) as the key subunit (Scheme 1), which might be
extended towards liquid-crystalline compounds (for reviews, see [8]). The results are
discussed below.
Results and Discussion. – Initial attempts to obtain [1,1’-biisoquinoline]-4,4’-diol
(4a) by deprotection of 4,4’-diethoxy-1,1’-biisoquinoline (2a, R ¼ Et) with HBr/AcOH
under reflux for 42 h according to the method of Fukuda et al. [9a] resulted in
incomplete ether cleavage. Deprotection with BBr3 and MeOH by using the procedure
of Finn and co-workers [9b] provided a violet solid, from which the desired product 4a
could not be isolated. The direct homocoupling of 1-chloroisoquinolin-4-ol (1) with
NiCl2 · 6 H2O, Ph3P, and Zn in DMF at 708 following a procedure of Bolm et al. [10] did
not yield any trace of 4a. It should be noted that Naumann and Langhals obtained the
homocoupling product from 3-bromoisoquinolin-4-ol under similar conditions in 27%

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Helvetica Chimica Acta – Vol. 92 (2009)
yield, whereas the 2-bromoquinolin-3-ol gave the homocoupling product only in trace
amounts [11].
With regard to the analogous pyridine-3-ol, only O-protected derivatives were used
for the Ni-mediated homocoupling [12]. Consequently, we prepared as potential
homocoupling precursors both the ester derivatives 6a,b and the allyl ether 7 from 1 by
standard esterification [13] with acid chlorides 5a,b in the presence of Et3N in Et2O and
by treatment with allyl bromide and NaH in DMF, respectively (Scheme 2). However,
neither the 1-chloroisoquinolin-4-yl carboxylates 6 nor the allyl protected isoquinoline
7 reacted under the usual Ni-mediated coupling conditions. Presumably, the ester and
allylic moiety interfere with the Ni complex.
Therefore, we introduced the methoxymethyl (MOM) protecting group in 1.
Whereas treatment of 1 with dimethoxymethane in the presence of P2O5 in CH2Cl2 or
acetone [14] at room temperature did not give any conversion due to the poor solubility
of the starting material in both solvents, the methoxymethylation with MOMCl and
K2CO3 in refluxing MeCN [13b] yielded product 8 in 47% (Scheme 3). The yield could
be further improved to 81% analogously to [13b], where MOMCl was generated in situ
from acetyl chloride, MeOH, and dimethoxymethane as described by Amato et al. [15].
Under the usual conditions, 8 was then coupled to give the 4,4’-MOM-protected
biisoquinoline 4b in 43% yield. Deprotection with conc. HCl in THF/i-PrOH at room
temperature [16] provided the dihydrochloride 4a · 2 HCl in 95% yield as a crystalline
solid1) [17].
Scheme 3
In preliminary attempts, we demonstrated that [1,1’-biisoquinoline]-4,4’-diol (4a ·
2 HCl) indeed may act as a precursor for further O-functionalization (Scheme 4). O-
Acylation of 4a · 2 HCl with 4-(hexadecyloxy)benzoyl chloride (5b) in the presence of
Et3N gave the target biisoquinoline diester 3b in 16% yield. Also ether derivative 2b,
which was isolated under the homocoupling conditions only in very poor yields of 4%
[7], was accessible in 50% yield from 4a · 2 HCl by Williamson etherification with the
respective bromide 9 and NaH in DMF at room temperature.
1
)
CCDC-701631 and 701632 contain the crystallographic data (excluding structural factors) of 4a and
those of 4,4’-diethoxy-1,1’-biisoquinoline (2a) [7]. These data can be obtained free of charge via
[17].

Helvetica Chimica Acta – Vol. 92 (2009)
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Scheme 4
Based on these results, we extended the method to the derivatization of 4a · 2 HCl
with mesogenic gallic acid (¼ 3,4,5-trihydroxybenzoic acid) derivatives 10 and 11 as
well as (alkyloxy)triphenylenes 14 with regard to liquid-crystalline compounds
(Scheme 5; Table). O-Acylation of 4a · 2 HCl with galloyl chlorides 10a – h (which
were easily obtained from the respective acids by chlorination with SOCl2 [18]) in the
presence of Et3N afforded the 1,1’-biisoquinolinediyl diesters 12a – h in 48 – 86% yield.
The alkylation reagents 11b,d – h were prepared by esterification of the galloyl
chlorides 10b,d – h with 6-bromohexan-1-ol in analogy to [19]. Bromides 11 and 4a ·
2 HCl were linked via the hexyloxy chains in the presence of K2CO3 in DMF at 1008
to give biisoquinolines 13b,d – h in yields between 18 and 77%. Under the same
Table. O-Functionalization of 4a · 2 HCl via Esterification and Etherification (for details, see Scheme 5)
Halide
R
R1
Product
Yield [%]
M.p. [8]
10a
10b
10c
10d
10e
10f
10g
10h
11b
11d
11e
11f
11g
11h
14a
14b
14c
Me(CH2)5
Me(CH2)7
Me(CH2)8
Me(CH2)9
Me(CH2)10
Me(CH2)11
Me(CH2)13
Me(CH2)15
Me(CH2)7
Me(CH2)9
Me(CH2)10
Me(CH2)11
Me(CH2)13
Me(CH2)15
Me(CH2)7
Me(CH2)7
Me(CH2)11
12a
12b
12c
12d
12e
12f
12g
12h
13b
13d
13e
13f
13g
13h
15a
15b
15c
63
74
69
84
86
49
51
48
77
32
18
21
60
36
69
31
14
94
76
79
81
85
88
82
82
34
69
32
52
58
67
101
69
66
Me
Me(CH2)7
Me(CH2)11

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Helvetica Chimica Acta – Vol. 92 (2009)
Scheme 5
conditions, O-alkylation of 4a· 2 HCl with 2-[(6-bromohexyl)oxy]-3,6,7,10,11-pentakis-
(alkyloxy)triphenylenes 14a – c gave a third series of biisoquinolines 15a – c bearing
pentakis(alkyloxy)triphenylene moieties in the substituents. Triphenylenes 14 were
accessible by trimerization of bis(alkyloxy)benzenes [20] to give the respective
pentakis(alkyloxy)triphenylen-2-ols, which were converted with 1,6-dibromohexane in
analogy to a method of Kumar et al. [21].
Conclusion. – A synthetic route to [1,1’-biisoquinoline]-4,4’-diol (4a) via protection
with in situ generated MOMCl solution followed by Ni-catalyzed homocoupling and
acidic deprotection could be established. Diol 4a, isolated as hydrochloride 4a · 2 HCl,
was found to be a key building block for O-alkylations and O-acylations resulting in a
series of 1,1’-biisoquinolines 2, 3, 12, 13, and 15 tethered to (alkyloxy)benzenes, gallic
acids, and triphenylenes. These substituents were chosen with regard to potential
mesogenic properties. The physical investigations are currently under way.
Generous financial support by the Deutsche Forschungsgemeinschaft, the Ministerium fꢀr
Wissenschaft, Forschung und Kunst des Landes Baden-Wꢀrttemberg (ꢃLandesgraduiertenꢄ fellowship

Helvetica Chimica Acta – Vol. 92 (2009)
2029
for E. K.), and the Fonds der Chemischen Industrie is gratefully acknowledged. We would like to thank
Robert Hoffmann for his experimental contribution.
Experimental Part
1. General. Commercial reagents were used without further purification unless otherwise indicated.
All solvents were distilled prior to use. Reactions were performed in oven-dried glassware. Flash
chromatography (FC): silica gel 60 (230 – 400 mesh; Fluka). M.p.: Bꢀchi SMP 20; uncorrected. IR
Spectra: Bruker-Vector-22-FT-IR spectrophotometer; ATR ¼ attenuated total reflection; in cmꢀ1
.
1H-
and 13C-NMR Spectra: Bruker-Avance-300 and -500 instrument; at 300 (1H) and 75 (13C) and 500 (1H)
and 125 MHz (13C), resp.; d in ppm, J in Hz; signal assignments are based on DEPT and COSY
experiments. MS and ESI-MS: Finnigan MAT 95, Varian MAT 711, and Bruker Daltonics micrOTOF_Q;
APCI ¼ atmospheric pressure chemical ionization; in m/z (rel. %). GC/MS: Thermo-Electron-
Corporation-Trace-DSQ apparatus with Macherey-Nagel-Optima-5-MS column (30 m ꢁ 0.25 mm).
2.1. 1-Chloroisoquinolin-4-yl Tetradecanoate (6a). To a suspension of 1 (718 mg, 4 mmol) in anh.
Et2O (40 ml), Et3N (0.62 ml, 446 mg, 4.4 mmol) was added dropwise followed by tetradecanoyl chloride
(5a; 1.0 ml, 1.08 g, 4.4 mmol) at 08. After stirring at r.t. for another 24 h, 1m aq. NaHCO3 (28 ml) was
added and the org. layer washed with H2O (28 ml). The combined aq. layer was extracted with Et2O (2 ꢁ
40 ml) and the extract dried (Na2SO4) and concentrated: 6a (1.46 g, 94%). Colorless solid. M.p. 758. FT-
IR (ATR): 2916s, 2849s, 1772m, 1471m, 1309m, 1258m, 1227m, 1119m, 1087s, 1021m, 963m, 913m, 772s,
744m, 717m, 641m. 1H-NMR (300 MHz, CDCl3): 0.88 (t, J ¼ 6.7, Me); 1.24 – 1.50 (m, 10 CH2); 1.80 – 1.90
(m, CH2); 2.75 (t, J ¼ 7.5, COOCH2); 7.70 – 7.87 (m, HꢀC(6), HꢀC(7), HꢀC(5) or HꢀC(8)); 8.17 (s,
HꢀC(3)); 8.33 – 8.37 (m, HꢀC(5) or HꢀC(8)). 13C-NMR (75 MHz, CDCl3): 14.1 (Me); 22.7, 25.0, 29.2,
29.3, 29.4, 29.5, 29.6, 29.7, 31.9 (CH2); 34.2 (COOCH2); 121.1, 126.8, 128.9, 131.5 (C(5), C(8), C(6),
C(7)); 127.5, 131.8 (C(4a), C(8a)); 134.2 (C(3)); 142.3, 148.1 (C(1), C(4)); 171.6 (C¼O). GC/EI-MS: 389
(1, Mþ), 354 (3, [M ꢀ Cl]þ), 211 (24, [C13H27CO]þ), 179 (100, [M þ H ꢀ C13H27CO]þ), 123 (10), 85 (20),
71 (36), 57 (34). Anal. calc. for C23H32ClNO2 (389.21): C 70.84, H 8.27, Cl 9.09, N 3.59 found: C 71.02, H
8.41, Cl 8.98, N 3.29.
2.2. 1-Chloroisoquinolin-4-yl 4-(Hexadecyloxy)benzoate (6b). As described for 6a, from 1 (359 mg,
2 mmol), 4-(hexadecyloxy)benzoyl chloride (5b, 914 mg, 2.4 mmol), and Et3N (0.33 ml, 240 mg,
2.4 mmol): 681 mg (65%) of 6b. Colorless solid. M.p. 1158. FT-IR (ATR): 2916s, 2850s, 1725s, 1604s,
1508m, 1468m, 1316m, 1257s, 1166s, 1152m, 1093s, 1039m, 1019m, 1001m, 958m, 901m, 844m, 760s, 721m,
691m, 675m, 640m. 1H-NMR (300 MHz, CDCl3): 0.88 (t, J ¼ 6.7, Me); 1.23 – 1.43 (m, 12 CH2); 1.44 – 1.54
(m, CH2); 1.80 – 1.89 (m, CH2); 4.08 (t, J ¼ 6.6, CH2O); 7.00 – 7.05 (m, HꢀC(3’), HꢀC(5’)); 7.71 – 7.81 (m,
HꢀC(6), HꢀC(7)); 7.91 – 7.95 (m, HꢀC(5) or HꢀC(8)); 8.22 – 8.27 (m, HꢀC(2’), HꢀC(6’)); 8.29 (s,
HꢀC(3)); 8.36 – 8.39 (m, HꢀC(5) or HꢀC(8)). 13C-NMR (75 MHz, CDCl3): 14.1 (Me); 22.7, 26.0, 29.1,
29.4, 29.57, 29.61, 29.67, 29.71, 31.9 (CH2); 68.5 (CH2O); 114.6 (C(3’), C(5’)); 120.3, 127.6, 132.1 (C(1’),
C(4a), C(8a)); 121.3, 126.7 (C(5), C(8)); 128.9, 131.5 (C(6), C(7)); 132.6 (C(2’), C(6’)); 134.5 (C(3));
142.7, 148.2 (C(1), C(4)); 164.1, 164.3 (C¼O, C(4’)). EI-MS (pos.): 523.3 (7, Mþ), 488.3 (1, [M ꢀ Cl]þ),
345.3 (100, [C16H33OC6H4CO]þ), 121.1 (35, [OHC6H4CO]þ), 43.3 (10). Anal. calc. for C32H42ClNO3
(523.28): C 73.33, H 8.08, Cl 6.76, N 2.67; found: C 73.42, H 8.04, Cl 6.77, N 2.58.
2.3. [1,1’-Biisoquinoline]-4,4’-diyl Bis(4-(Hexadecyloxy)benzoate (3b). As described for 6a, from
4a · 2 HCl (29 mg, 0.08 mmol), 5b (63 mg, 0.17 mmol), and Et3N (0.06 ml, 44 mg, 0.44 mmol).
Purification by dissolving in warm CH2Cl2 and precipitation with EtOH, yielded 13 mg (16%) of 3b.
Colorless solid. M.p. 1108. FT-IR (ATR): 1579m, 1561m, 1504m, 1447m, 1392m, 1311m, 1282m, 1158m,
1111m, 1079m, 1022m, 984m, 912s, 874m, 858m, 800m, 760s, 739s, 666m, 609s, 565m. 1H-NMR (300 MHz,
CDCl3): 0.86 – 0.90 (m, 2 Me); 1.24 – 1.41 (m, 24 CH2); 1.46 – 1.53, 1.82 – 1.91 (2m, 2 CH2); 4.10 (t, J ¼ 6.5,
2 CH2O); 7.50 – 7.08, 8.31 – 8.34 (2m, 8 H, HꢀC(2’), HꢀC(3’), HꢀC(5’), HꢀC(6’)); 7.53 – 7.59, 7.72 – 7.77
(2m, 4 H, HꢀC(6), HꢀC(7)); 7.93 – 7.96, 8.03 – 8.06 (2m, 4 H, HꢀC(5), HꢀC(8)); 8.71 (s, 2 H,
HꢀC(3)). 13C-NMR (125 MHz, CDCl3): 14.1 (Me); 22.7, 26.0, 29.1, 29.38, 29.39, 29.58, 29.62, 29.67, 29.71,
31.9 (CH2); 68.5 (CH2O); 114.6, 132.7 (C(2’), C(3’), C(5’), C(6’)); 120.6, 128.9, 131.2 (C(4a), C(8a),
C(1’)); 120.8, 127.6 (C(5), C(8)); 128.1, 130.8 (C(6), C(7)); 134.8 (C(3)); 143.0, 155.2, 164.0, 164.6 (C(1),

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Helvetica Chimica Acta – Vol. 92 (2009)
C(4), C(4’), C¼O). ESI-MS: 977.64 ([M þ H]þ), 858.42, 666.38, 617.38, 345.28. HR-ESI-MS (pos.):
977.6403 ([M þ H]þ, C64H84N2Oþ6 ; calc. 977.6402).
2.4. [1,1’-Biisoquinoline]-4,4’-diyl Bis[(3,4,5-tris(alkyloxy)benzoates 12a,c – f. The bis-benzoates
12a,c – f were prepared as described below for 12b,g,h. For yields and m.p.s. of 12a – h, see Table.
2.5. [1,1’-Biisoquinolin]-4,4’-diyl Bis[3,4,5-tris(octyloxy)benzoate] (12b). As described for 6a, from
4a · 2 HCl (50 mg, 0.138 mmol), 10b (160 mg, 0.304 mmol), and Et3N (1.0 ml, 726 mg, 7.21 mmol) in DMF
(2 ml). Purification by FC (SiO2, hexanes/AcOEt 20 :1 and 10 :1; Rf 0.28) yielded 129 mg (74%) of 12b.
Light yellow waxy solid. FT-IR (ATR): 3065w, 2954m, 2920s, 2852s, 1736s, 1623w, 1584s, 1429s, 1335s,
1
1193s, 1115s, 1095s, 752s. H-NMR (300 MHz, CDCl3): 0.87 – 0.93 (m, 6 Me); 1.26 – 1.43 (m, 24 CH2);
1.48 – 1.58 (m, 6 CH2); 1.76 – 1.92 (m, 6 CH2); 4.12 (t, J ¼ 6.5, 8 H, CH2OꢀC(3’’), CH2OꢀC(5’’)); 4.13 (t,
J ¼ 6.5, 4 H, CH2OꢀC(4’’)); 7.58 (ddd, J ¼ 8.5, 6.9, 1.2, 2 H, HꢀC(7)); 7.59 (s, 4 H, HꢀC(2’’), HꢀC(6’’));
7.76 (ddd, J ¼ 8.5, 6.9, 1.2, 2 H, HꢀC(6)); 7.95 (ddd, J ¼ 8.5, 1.2, 0.8, 2 HꢀC(8)); 8.03 (ddd, J ¼ 8.5, 1.2, 0.8,
2 H, HꢀC(5)); 8.69 (s, 2 H, HꢀC(3)). 13C-NMR (75 MHz, CDCl3): 14.1 (Me); 22.69, 22.72, 26.08, 26.12,
29.31, 29.33, 29.37, 29.40, 29.5, 30.4, 31.8, 31.9 (CH2); 69.4 (CH2O); 73.7 (CH2O); 108.9 (C(2’’), C(6’’));
120.9 (C(5)); 123.0 (C(1’’)); 127.6 (C(8)); 128.1 (C(7)); 129.0 (C(8a)); 130.9 (C(6)); 131.1 (C(4a)); 134.9
(C(3)); 143.1 (C(4)); 143.6 (C(4’’)); 153.2 (C(3’’), C(5’’)); 155.4 (C(1)); 164.8 (COO). APCI-MS: 1265.9
([M þ H]þ), 1145.9, 777.5 ([M þ 2 H ꢀ R]þ), 693.4 ([M þ H ꢀ R ꢀ C8H17]þ), 493.4. Anal. calc. for
C80H116N2O10 (1265.78): C 75.91, H 9.24, N 2.21; found: C 75.82, H 9.12, N 2.21.
2.6. [1,1’-Biisoquinoline]-4,4’-diyl Bis[3,4,5-tris(tetradecyloxy)benzoate] (12g). As described for 6a,
from 4a · 2 HCl (50 mg, 0.138 mmol), 10g (236 mg, 0.304 mmol), and Et3N (1.0 ml, 726 mg, 7.21 mmol) in
DMF (2 ml). Purification by FC (SiO2, hexanes/AcOEt 20 :1 and 10 :1; Rf 0.47, yielded 125 mg (51%) of
12g. FT-IR (ATR): 2920s, 2851s, 2185w, 1978w, 1732s, 1586s, 1430s, 1335s, 1194s, 1118s, 1056s, 758s.
1H-NMR (300 MHz, CDCl3): 0.86 – 0.91 (m, 6 Me); 1.26 – 1.43 (m, 60 CH2); 1.47 – 1.57 (m, 6 CH2); 1.76 –
1.92 (m, 6 CH2); 4.12 (t, J ¼ 6.5, 8 H, CH2OꢀC(3’’), CH2OꢀC(5’’)); 4.12 (t, J ¼ 6.5, 4 H, CH2OꢀC(4’’));
7.57 (ddd, J ¼ 8.5, 6.9, 1.2, 2 H, HꢀC(7)); 7.59 (s, 4 H, HꢀC(2’’), HꢀC(6’’)); 7.76 (ddd, J ¼ 8.5, 6.9, 1.2,
2 H, HꢀC(6)); 7.95 (ddd, J ¼ 8.5, 1.2, 0.8, 2 H, HꢀC(8)); 8.03 (ddd, J ¼ 8.5, 1.2, 0.8, 2 H, HꢀC(5)); 8.69
(s, 2 H, HꢀC(3)). 13C-NMR (75 MHz, CDCl3): 14.1, 14.2 (Me); 21.1, 22.7, 26.11, 26.13, 29.3, 29.38, 29.41,
29.43, 29.6, 29.67, 29.68, 29.73, 29.8, 30.4, 31.9 (CH2); 69.4 (CH2O); 73.7 (CH2O); 108.9 (C(2’’), C(6’’));
120.9 (C(5)); 122.9 (C(1’’)); 127.6 (C(8)); 128.2 (C(7)); 129.0 (C(8a)); 130.9 (C(6)); 131.2 (C(4a)); 134.8
(C(3)); 143.1 (C(4)); 143.6 (C(4’’)); 153.2 (C(3’’), C(5’’)); 155.3 (C(1)); 164.8 (COO). APCI-MS: 1895.4,
1771.4 ([M þ H]þ), 1729.5, 1550.2, 1431.2, 1387.2, 886.7, 741.7, 545.5, 351.3. Anal. calc. for C166H188N2O10
(1770.74): C 78.68, H 10.70, N 1.58; found: C 78.57, H 10.53, N 1.48.
2.7. [1,1’-Biisoquinoline]-4,4’-diyl Bis[3,4,5-tris(hexadecyloxy)benzoate] (12h). As described for 6a,
from 4a · 2 HCl (50 mg, 0.138 mmol), 10h (262 mg, 0.304 mmol), and Et3N (1.0 ml, 726 mg, 7.21 mmol) in
DMF (2 ml). Purification by FC (SiO2, hexanes/AcOEt 20 :1 and 10 :1; Rf 0.51, yielded 126 mg (48%) of
12h. Light yellow waxy solid. FT-IR (ATR): 2916s, 2849s, 1737s, 1587s, 1503s, 1467s, 1430s, 1385m, 1336s,
1199s, 1122s, 1096s, 751s, 720s. 1H-NMR (300 MHz, CDCl3): 0.86 – 0.91 (m, 6 Me); 1.26 – 1.43 (m,
72 CH2); 1.47 – 1.57 (m, 6 CH2); 1.76 – 1.92 (m, 6 CH2); 4.12 (t, J ¼ 6.5, 8 H, CH2OꢀC(3’’),
CH2OꢀC(5’’)); 4.12 (t, J ¼ 6.5, 4 H, CH2OꢀC(4’’)); 7.57 (ddd, J ¼ 8.5, 6.9, 1.2, 2 H, HꢀC(7)); 7.59 (s,
4 H, HꢀC(2’’), HꢀC(6’’)); 7.76 (ddd, J ¼ 8.5, 6.9, 1.2, 2 H, HꢀC(6)); 7.95 (ddd, J ¼ 8.5, 1.2, 0.8, 2 H,
HꢀC(8)); 8.03 (ddd, J ¼ 8.5, 1.2, 0.8, 2 H, HꢀC(5)); 8.69 (s, 2 H, HꢀC(3)). 13C-NMR (75 MHz, CDCl3):
14.1, 14.2 (Me); 22.7, 26.10, 26.14, 29.3, 29.38, 29.44, 29.6, 29.7, 29.8, 30.4, 31.9 (CH2); 69.4 (CH2O); 73.7
(CH2O); 108.9 (C(2’’), C(6’’)); 120.9 (C(5)); 122.9 (C(1’’)); 127.6 (C(8)); 128.2 (C(7)); 128.9 (C(8a));
131.0 (C(6)); 131.2 (C(4a)); 134.7 (C(3)); 143.1 (C(4)); 143.6 (C(4’’)); 153.2 (C(3’’), C(5’’)); 155.1 (C(1));
164.8 (COO). APCI-MS: 2063.6, 1939.6 ([M þ H]þ), 970.8, 825.8, 601.5, 379.3. Anal. calc. for
C128H212N2O10 (1939.06): C 79.28, H 11.02, N 1.44; found: C 79.08, H 10.80, N 1.42.
3.1. 1-Chloro-4-(prop-2-en-1-yloxy)isoquinoline (7). A soln. of 1 (718 mg, 4 mmol) in anh. DMF
(2 ml) was slowly added dropwise to a suspension of NaH (192 mg, 4.8 mmol) in anh. DMF (4 ml) at 08.
After stirring of the green soln. at r.t. for 1 h, 3-bromoprop-1-ene (0.7 ml, 968 mg, 8 mmol) was added at
08 (green ! reddish-brown). The mixture was stirred at r.t. for another 5 h. Then, H2O (20 ml) and
CH2Cl2 (60 ml) were added. The org. layer was dried (Na2SO4), the solvent evaporated, and the residue
purified by FC (SiO2, hexanes/AcOEt 6 :1, Rf 0.47): 7 (607 mg, 69%). Colorless solid. M.p. 948. IR
(ATR): 2916s, 2849m, 1735m, 1605m, 1579m, 1510m, 1469m, 1250s, 1168s, 1150m, 1127m, 1076s, 1038m,

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914m, 844m, 757s, 719m, 689m, 660m. H-NMR (300 MHz, CDCl3): 4.76 – 4.78 (m, CH2); 5.36 – 5.41,
5.49 – 5.57 (2m, CH¼CH2); 6.09 – 6.22 (m, CH¼CH2); 7.68 – 7.79 (m, HꢀC(6), HꢀC(7)); 7.81 (s,
HꢀC(3)); 8.25 – 8.28 (m, HꢀC(5), HꢀC(8)). 13C-NMR (125 MHz, CDCl3): 69.6 (CH2); 118.3
(CH¼CH2); 121.9, 126.0 (C(5), C(8)); 122.4 (C(3)); 127.0, 130.4 (C(4a), C(8a)); 128.8, 130.3 (C(6),
C(7)); 132.3 (CH¼CH2); 142.7, 149.4 (C(1), C(4)). EI-MS (pos.): 219.0 (44, Mþ), 184.1 (72, [M ꢀ Cl]þ),
150.0 (100). Anal. calc. for C12H10ClNO (219.67): C 65.61, H 4.59, N 6.31, Cl 16.14; found: C 65.52, H 4.63,
N 6.38, Cl 16.25.
3.2. 4,4’-Bis{{6-[4-(octyloxy)phenoxy]hexyl}oxy}-1,1’-biisoquinoline (2b). As described for 7, from
4a · 2 HCl (36 mg, 0.1 mmol) in anh. DMF (2 ml), NaH (18 mg, 0.44 mmol), and 1-[(6-bromohexyl)oxy]-
4-(octyloxy)benzene (9; 85 mg, 0.2 mmol) in anh. DMF (2 ml): 45 mg (50%) of 2b. Spectroscopic data:
in accordance with those in [7].
4. 1-Chloro-4-(methoxymethoxy)isoquinoline (8). Method A. K2CO3 (5.53 g, 40.0 mmol) was added
to a suspension of 1 (1.79 g, 10.0 mmol) in anh. MeCN (50 ml), and the mixture was heated under reflux
for 30 min. Then, MOMCl (1.2 ml, 1.21 g, 15.0 mmol) was added and the mixture heated under reflux for
another 12 h and filtered without cooling. The residue was washed with CH2Cl2 (3 ꢁ 20 ml) and the
combined filtrate concentrated. The residue was taken up in CH2Cl2 (60 ml), the soln. washed with 0.5n
aq. NaOH (2 ꢁ 25 ml) and H2O (2 ꢁ 25 ml) and dried (Na2SO4), the solvent evaporated, and the residue
purified by FC (SiO2, hexanes/AcOEt 5 :1, Rf 0.43); 8 (1.06 g, 47%). Yellowish solid.
Method B. A soln. of 1 (179 mg, 1 mmol) in anh. DMF (2 ml) was slowly added dropwise to a
suspension of NaH (44 mg, 1.1 mmol) in anh. DMF (1.5 ml) at 08, and the green mixture was stirred at r.t.
for 1 h. Then, a 6n soln. of MOMCl [14] (0.2 ml, 1 mmol) was added at 08 (green ! yellow). The mixture
was stirred at r.t. for another 3 h, and then H2O (10 ml) and CH2Cl2 (20 ml) were added. The org. layer
was dried (Na2SO4) and the solvent evaporated: 8 (182 mg, 81%). Yellowish solid. M.p. 668. FT-IR
(ATR): 1312m, 1285m, 1211m, 1174m, 1151m, 1082m, 936s, 876s, 760s, 741m. 1H-NMR (500 MHz,
CDCl3): 3.56 (s, Me); 5.40 (s, CH2); 7.68 (ddd, J ¼ 8.3, 6.9, 1.3, HꢀC(6) or HꢀC(7)); 7.75 (ddd, J ¼ 8.3,
6.9, 1.3, HꢀC(6) or HꢀC(7)); 8.07 (s, HꢀC(3)); 8.21 (ddd, J ¼ 8.3, 1.3, 0.8, HꢀC(5) or HꢀC(8)); 8.24
(ddd, J ¼ 8.3, 1.3, 0.8, HꢀC(5) or HꢀC(8)). 13C-NMR (63 MHz, CDCl3): 56.5 (Me); 95.3 (CH2); 121.7
(C(3)); 125.1, 126.2 (C(5), C(8)); 127.1, 130.7 (C(4a), C(8a)); 128.7, 130.5 (C(6), C(7)); 143.6, 148.3
(C(1), C(4)). EI-MS: 223 (28, Mþ), 193 (4, [C10H11ClNO]þ), 150 (10), 45 (100, [MeOCH2]þ). HR-ESI-
MS (pos.): 246.0299 ([M þ Na]þ, C11H10ClNaO2þ ; calc. 246.0298). Anal. calc. for C11H10ClNO2 (223.66):
C 59.07, H 4.51, Cl 15.85, N 6.26; found: C 59.16, H 4.54, Cl 15.76, N 6.01.
5. 4,4’-Bis(methoxymethoxy)-1,1’-biisoquinoline (4b). A soln. of NiCl2 · 6 H2O (808 mg, 3.40 mmol)
in degassed anh. DMF (15 ml) was heated at 708 (bath temp.), and Ph3P (3.56 g, 13.7 mmol) and Zn
(237 mg, 3.65 mmol) were added. The mixture became brown and was heated at 708 for 1 h. Then, a soln.
of 8 (525 mg, 2.79 mmol) in degassed anh. DMF (5 ml) was added and the mixture stirred at 708 for 4 h
(TLC control). After cooling to r.t., the mixture was quenched with 5% NH3 soln. (21 ml). The aq. layer
extracted with CH2Cl2/Et2O 2 :1 (3 ꢁ 25 ml), the combined org. phase concentrated, and the residue
taken up in CH2Cl2 (15 ml), washed with H2O (4 ꢁ 8 ml) and brine (1 ꢁ 10 ml), dried (Na2SO4), and
concentrated. The crude product was purified by FC (SiO2, hexanes/AcOEt 1:2; Rf (AcOEt) ¼ 0.54): 4b
(220 mg, 43%). M.p. 1358. FT-IR (ATR): 1579m, 1292m, 1279m, 1150s, 1085m, 1063s, 1018m, 960s, 928m,
902m, 861m, 773m, 687m. 1H-NMR (300 MHz, CDCl3): 3.62 (s, Me); 5.51 (s, CH2); 7.49 (ddd, J ¼ 8.4, 7.0,
1.3, HꢀC(6) or HꢀC(7)); 7.71 (ddd, J ¼ 8.4, 7.0, 1.3, HꢀC(6) or HꢀC(7)); 7.79 (ddd, J ¼ 8.4, 1.3, 0.7,
HꢀC(5) or HꢀC(8)); 8.33 (ddd, J ¼ 8.4, 1.3, 0.7, HꢀC(5) or HꢀC(8)); 8.48 (s, HꢀC(3)). 13C-NMR
(75 MHz, CDCl3): 56.5 (Me); 95.2 (CH2); 121.2, 127.0 (C(5), C(8)); 125.7 (C(3)); 127.6, 129.6 (C(6),
C(7)); 128.6, 129.3 (C(4a), C(8a)); 148.2, 151.7 (C(1), C(4)). GC/EI-MS: 376 (100, Mþ), 345 (12), 331
(94, [M ꢀ CH2OMe]þ), 315 (10), 301 (40, [M þ H ꢀ CH2OMe ꢀ OMe]þ), 287 (38, [M þ H –
2CH2OMe]þ), 270 (48), 258 (24), 242 (12), 229 (22), 214 (20), 207 (46), 191 (18), 176 (26), 150 (8),
130 (10), 115 (8), 78 (20, Phþ). HR-ESI-MS (pos.): 377.1499 ([M þ H]þ, C22H20N2Oþ4 ; calc. 377.1496).
6. [1,1’-Biisoquinoline]-4,4’-diol Hydrochloride (1:2) (4a · 2 HCl). Conc. HCl soln. (0.2 ml) was
added to a soln. of 4b (36 mg, 0.096 mmol) in THF/i-PrOH 1:1 (10 ml), and the mixture was stirred at r.t.
for 7 h. The solvent was evaporated: 4a · 2 HCl (33 mg, 95%). Yellow solid. M.p. > 2408. FT-IR (ATR):
2860m, 2324m, 1984m, 1581s, 1495m, 1454m, 1389s, 1358s, 1265m, 1084m, 842m, 771s, 716m, 584m.
1H-NMR (300 MHz, CD3OD): 7.70 – 7.73 (m, 2 H, HꢀC(5) or HꢀC(8)); 7.81 – 7.86, 8.05 – 8.10 (2m, 4 H,

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Helvetica Chimica Acta – Vol. 92 (2009)
HꢀC(6), HꢀC(7)); 8.26 (s, 2 H, HꢀC(3)); 8.60 – 8.63 (m, 2 H, HꢀC(5) or HꢀC(8)). 13C-NMR
(125 MHz, (D6)DMSO): 121.2 (C(3)); 122.1, 127.0 (C(5), C(8)); 130.2, 132.2 (C(6), C(7)); 128.1, 129.0
(C(4a), C(8a)); 141.5, 152.0 (C(1), C(4)). ESI-MS: 289.10 ([M þ H]þ), 311.08 ([M þ Na]þ). Anal. calc.
for C18H14Cl2N2O2 (361.23): C 59.85, H 3.91, Cl 19.63, N 7.76; found: C 59.71, H 4.05, Cl 19.39, N 7.63.
7.1. 6-Bromohexyl 3,4,5-Tris(alkyloxy)benzoates 11d – f. The benzoates 11d – f were prepared as
described below for 11b,g,h.
7.2. 6-Bromohexyl 3,4,5-Tris(octyloxy)benzoate (11b). In analogy to [19], 10b (877 mg, 1.67 mmol)
was added to a soln. of 6-bromohexan-1-ol (0.18 ml, 0.25 g, 1.41 mmol) and Et3N (0.5 ml, 0.37 g,
3.61 mmol) in CH2Cl2 (10 ml), and the mixture was stirred at r.t. for 2 h. The solvent was evaporated and
the residue purified by FC (SiO2, hexanes/AcOEt 40 :1; Rf 0.48): 11b (651 mg, 64%). M.p. 108. FT-IR
(ATR): 2923s, 2855s, 2366w, 2168w, 2003w, 1715s, 1586s, 1499m, 1465m, 1428s, 1381m, 1332s, 1212s, 1110s,
1043m, 1008m, 853m, 764s, 723m. 1H-NMR (300 MHz, CDCl3): 0.86 – 0.91 (m, 3 Me); 1.24 – 1.40 (m, 12
CH2); 1.43 – 1.54 (m, 10 H, CH2, 2 HꢀC(3’), 2 HꢀC(4’)); 1.70 – 1.94 (m, 10 H, CH2, 2 HꢀC(2’),
2 HꢀC(5’)); 3.42 (t, J ¼ 6.8, 2 HꢀC(6’)); 4.01 (2t, J ¼ 6.5, CH2OꢀC(3’’), CH2OꢀC(4’’), CH2OꢀC(5’’));
4.30 (t, J ¼ 6.7, 2 HꢀC(1’)); 7.24 (s, HꢀC(2’’), HꢀC(6’’)). 13C-NMR (75 MHz, CDCl3): 14.1 (Me); 22.7,
25.2, 26.06, 26.11, 26.9, 27.8, 28.6, 29.30, 29.33, 29.4, 29.5, 30.3, 31.8, 31.9, 32.6 (CH2, C(2’), C(3’), C(4’),
C(5’)); 33.6 (C(6’)); 64.8 (C(1’)); 69.2 (CH2O); 73.5 (CH2O); 108.0 (C(2’’), C(6’’)); 124.9 (C(1’’)); 142.4
(C(4’’)); 152.8 (C(3”), C(5’’)); 166.5 (COO). ESI-MS: 669.4 ([M þ H]þ), 507.4 ([M þ H ꢀ BrC6H13]þ),
395.3 ([M þ 2 H ꢀ BrC6H13 ꢀ C8H17]þ). HR-ESI-MS: 669.4080 and 671.4067 ([M þ H]þ, C37H65BrOþ5 ;
calc. 669.4088 and 671.4075).
7.3. 6-Bromohexyl 3,4,5-Tris(tetradecyloxy)benzoate (11g). As described for 11b, from 10g (1.04 g,
1.34 mmol), 6-bromohexan-1-ol (0.18 ml, 0.25 g, 1.41 mmol), and Et3N (0.5 ml, 0.37 g, 3.61 mmol):
497 mg (37%) of 11g. Rf 0.61 (hexanes/AcOEt 20 :1). M.p. 418. FT-IR (ATR): 2915s, 2849s, 2362w,
1703s, 1585m, 1466m, 1429s, 1346s, 1334s, 1255s, 1219s, 1121s, 994s, 767s, 725m, 651m. 1H-NMR
(300 MHz, CDCl3): 0.86 – 0.90 (m, 3 Me); 1.26 – 1.38 (m, 30 CH2); 1.43 – 1.54 (m, 10 H, CH2, 2 HꢀC(3’),
2 HꢀC(4’)); 1.69 – 1.94 (m, 10 H, CH2, 2 HꢀC(2’), 2 HꢀC(5’)); 3.42 (t, J ¼ 6.8, 2 HꢀC(6’)); 4.01 (2t, J ¼
6.5, CH2OꢀC(3’’), CH2OꢀC(4’’), CH2OꢀC(5’’)); 4.30 (t, J ¼ 6.7, 2 HꢀC(1’)); 7.24 (s, HꢀC(2’’),
HꢀC(6’’)). 13C-NMR (75 MHz, CDCl3): 14.1 (Me); 22.7, 25.3, 26.1, 27.8, 28.6, 29.36, 29.39, 29.43, 29.6,
29.66, 29.69, 29.73, 30.4, 32.0, 32.6 (CH2, C(2’), C(3’), C(4’), C(5’)); 33.6 (C(6’)); 64.8 (C(1’)); 69.2
(CH2O); 73.5 (CH2O); 108.1 (C(2’’), C(6’’)); 125.0 (C(1’’)); 142.5 (C(4’’)); 152.8 (C(3’’), C(5’’)); 166.5
(COO). (APCI)-MS: 923.7 ([M þ H]þ), 773.7, 759.7 ([M þ H ꢀ BrC6H13]þ), 727.5, 577.48, 563.5, 519.5,
367.3, 323.3. HR-APCI-MS: 921.6869 and 923.6867 ([M þ H]þ, C55H101BrO5þ ; calc. 921.6905 and
923.6899).
7.4. 6-Bromohexyl 3,4,5-Tris(hexadecyloxy)benzoate (11h). As described for 11b, from 10h (3.00 g,
3.48 mmol), 6-bromohexan-1-ol (0.18 ml, 0.25 g, 1.41 mmol), and Et3N (0.5 ml, 0.37 g, 3.61 mmol): 2.18 g
(62%) of 11h. Rf 0.52 (hexanes/AcOEt 20 :1). M.p. 468. FT-IR (ATR): 2916s, 2849s, 2169w, 1975w, 1707s,
1587m, 1502m, 1467s, 1429s, 1335s, 1219s, 1121s, 988m, 765m, 721s. 1H-NMR (300 MHz, CDCl3): 0.86 –
0.90 (m, 3 Me); 1.26 – 1.38 (m, 36 CH2); 1.43 – 1.54 (m, 10 H, CH2, 2 HꢀC(3’), 2 HꢀC(4’)); 1.69 – 1.94 (m,
10 H, CH2, 2 HꢀC(2’), 2 HꢀC(5’)); 3.42 (t, J ¼ 6.8, 2 HꢀC(6’)); 4.01 (2t, J ¼ 6.5, CH2OꢀC(3’’),
CH2OꢀC(4’’), CH2OꢀC(5’’)); 4.30 (t, J ¼ 6.7, 2 HꢀC(1’)); 7.24 (s, HꢀC(2’’), HꢀC(6’’)). 13C-NMR
(75 MHz, CDCl3): 14.1 (Me); 22.7, 25.2, 26.08, 26.11, 27.8, 28.6, 29.3, 29.40, 29.43, 29.6, 29.67, 29.69, 29.74,
30.3, 32.0 (CH2, C(2’), C(3’), C(4’), C(5’)); 33.6 (C(6’)); 64.8 (C(1’)); 69.2 (CH2O); 73.5 (CH2O); 108.0
(C(2’’), C(6’’)); 124.9 (C(1’’)); 142.4 (C(4’’)); 152.8 (C(3’’), C(5’’)); 166.5 (COO). APCI-MS: 1007.8
([M þ H]þ), 961.8, 843.8 ([M þ H ꢀ BrC6H13]þ), 825.8, 783.5, 619.5, 575.5, 395.3, 351.3. HR-MS (APCI):
1005.7830 and 1007.7835 ([M þ H]þ, C61H113BrOþ5 ; calc. 1005.7844 and 1007.7841).
8. 3-Methoxy-6,7,10,11-tetrakis(octyloxy)triphenylen-2-ol. In analogy to [20b], anh. FeCl3 (13.4 g,
0.120 mol) was added portionwise to a soln. of 1,2-bis(octyloxy)benzene (10.0 g, 29.9 mmol) and guaiacol
(¼2-methoxyphenol; 7.42 g, 59.8 mmol) in anh. CH2Cl2 (80 ml) at 08, while N2 was passed through the
soln. The mixture was stirred at r.t. for 2 h, then poured in cold MeOH (100 ml), and the CH2Cl2 was
evaporated. The dark green precipitate was filtered off and separated by FC (SiO2, hexanes/AcOEt 40 :1,
20 :1, 10 :1, and 5 :1): 3,6,7,10,11-pentakis(octyloxy)triphenylen-2-ol (145 mg, 2%), 2,3,6,7,10,11-hexaki-
s(octyloxy)triphenylene (3.66 g, 36%), and the title product (774 mg, 10%). Rf 0.35 (hexanes/AcOEt
10 :1). M.p. 1098. FT-IR (ATR): 3535m, 2919s, 2850s, 2184w, 1974w, 1617m, 1514s, 1448s, 1427s, 1386m,

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1259s, 1166s, 1043.7s, 835s, 792s. H-NMR (300 MHz, CDCl3): 0.87 – 0.92 (m, 4 Me); 1.26 – 1.47 (m, 16
CH2); 1.51 – 1.61 (m, 4 CH2); 1.90 – 1.99 (m, 4 CH2); 4.13 (s, MeO); 4.18 – 4.25 (m, CH2OꢀC(6’’),
CH2OꢀC(7’’), CH2OꢀC(10’’), CH2OꢀC(11’’)); 5.86 (br. s, OH); 7.78 – 7.96 (m, 6 arom. H). 13C-NMR
(75 MHz, CDCl3): 14.1 (Me); 22.7, 26.17, 26.23, 29.4, 29.47, 29.51, 29.6, 30.9, 31.9 (CH2); 56.1 (MeO); 69.2,
69.7, 69.9 (CH2O); 103.5, 106.6, 107.4, 107.5, 107.6 (C(1’’), C(4’’), C(5’’), C(8’’), C(9’’), C(12’’)); 123.0,
123.3, 123.59, 123.61, 123.7, 124.1 (C(4’’a), C(4’’b), C(8’’a), C(8’’b), C(12’’a), C(12’’b)); 145.1 (C(2’’));
146.4 (C(3’’)); 148.8, 148.9, 149.1, 149.2 (C(6’’), C(7’’), C(10’’), C(11’’)). APCI-MS: 787.58 ([M þ H]þ),
675.5 ([M þ H ꢀ C8H18]þ), 658.5, 563.3, 451.2, 433.2, 339.1. Anal. calc. for C51H78O6 (787.16): C 77.82,
H 9.99; found: C 77.63, H 9.84.
9.1. 3,6,7,10,11-Pentakis(octyloxy)triphenylen-2-ol. In analogy to [20a], bis(octyloxy)benzene (10.0 g,
29.9 mmol) was added to a suspension of anh. FeCl3 (14.5 g, 90.0 mmol) and conc. H2SO4 (3 drops) in
anh. CH2Cl2 (80 ml) at 08, while N2 was passed through the soln. The mixture was stirred at r.t. for 1 h,
then cold MeOH was added, and the CH2Cl2 was evaporated. The precipitate was filtered off and
separated by FC (SiO2, hexanes/AcOEt 50 :1, and 40 :1): 2,3,6,7,10,11-hexakis(octyloxy)triphenylene
(5.56 g, 56%) and the title product (1.36 g, 15%). The spectroscopic data were in accordance with those in
[22].
9.2. 3,6,7,10,11-Pentakis(dodecyloxy)triphenylen-2-ol. As described in 9.1, from bis(dodecyloxy)ben-
zene (12.0 g, 26.8 mmol): 2.95 g (28%) of the title product. Rf 0.72 (hexanes/AcOEt 10 :1). M.p. 848. FT-
IR (ATR): 3557w, 2917s, 2849s, 2368w, 2119w, 1975w, 1617m, 1515s, 1437s, 1259s, 1168s, 1044s, 835s, 721m.
1H-NMR (300 MHz, CDCl3): 0.86 – 0.90 (m, 5 Me); 1.21 – 1.46 (m, 40 CH2); 1.51 – 1.61 (m, 5 CH2); 1.88 –
1.98 (m, 5 CH2); 4.18 – 4.24 (m, 5 CH2O); 5.90 (br. s, OH); 7.76 – 7.96 (m, 6 arom. H). 13C-NMR (75 MHz,
CDCl3): 14.1 (Me); 22.7, 26.16, 26.20, 26.23, 29.37, 29.40, 29.5, 29.57, 29.64, 29.66, 29.70, 29.72, 29.8, 31.9
(CH2); 69.1, 69.6, 69.7, 69.9 (CH2O); 106.5, 107.2, 107.3, 107.4, 107.6 (C(1’’), C(4’’), C(5’’), C(8’’), C(9’’),
C(12’’)); 123.0, 123.2, 123.5, 123.59, 123.61, 123.7, 123.9 (C(4’’a), C(4’’b), C(8’’a), C(8’’b), C(12’’a),
C(12’’b)); 145.2, 145.8, 148.7, 148.9, 149.0, 149.1 (C(2’’), C(3’’), C(6’’), C(7’’), C(10’’), C(11’’)). APCI-MS:
1166.0 ([M þ H]þ), 997.8 ([M þ H ꢀ C12H26]þ), 829.6, 661.4, 643.4, 493.3, 475.3, 325.1. HR-APCI-MS:
1166.0088 ([M þ H]þ, C78H132O6þ ; calc. 1166.0097).
10.1. 2-[(6-Bromohexyl)oxy]-3-methoxy-6,7,10,11-tetrakis(octyloxy)triphenylene (14a). In analogy to
[21], a suspension of anh. K2CO3 (0.93 g, 6.70 mmol) and 3-methoxy-6,7,10,11-tetrakis(octyloxy)triphen-
ylen-2-ol (739 mg, 934 mmol) in butan-2-one (60 ml) was stirred at 958 for 30 min. Then, 1,6-
dibromohexane (2.12 g, 8.93 mmol) was added and the mixture stirred at 958 for another 16 h. The
mixture was filtered and the residue washed with CH2Cl2. The filtrate was concentrated and the residue
purified by FC (SiO2, hexanes/AcOEt 40 :1, 20 :1, 10 :1): 14a (790 mg, 89%). Rf 0.48 (hexanes/AcOEt
10 :1). M.p. 448. FT-IR (ATR): 3098w, 2920s, 2850s, 2366w, 2179w, 1974w, 1617m, 1517s, 1428s, 1258s,
1
1165s, 1048s, 836s, 723m. H-NMR (300 MHz, CDCl3): 0.87 – 0.92 (m, 4 Me); 1.28 – 1.47 (m, 16 CH2);
1.53 – 1.62 (m, 12 H, CH2, 2 HꢀC(3’), 2 HꢀC(4’)); 1.89 – 2.00 (m, 12 H, CH2, 2 HꢀC(2’), 2 HꢀC(5’));
3.44 (t, J ¼ 6.8, 2 HꢀC(6’)); 4.10 (s, MeO); 4.23 (m, 5 CH2O); 7.80 – 7.85 (m, 6 arom. H). 13C-NMR
(75 MHz, CDCl3): 14.1 (Me); 22.7, 25.4, 26.2, 28.0, 29.2, 29.4, 29.5, 31.9, 32.7 (CH2, C(2’), C(3’), C(4’),
C(5’)); 33.8 (C(6’)); 56.3 (MeO); 69.1 (C(1’)); 69.70, 69.74, 69.8 (CH2O); 105.0, 106.4, 107.3, 107.4 (C(1’’),
C(4’’), C(5’’), C(8’’), C(9’’), C(12’’)); 123.4, 123.45, 123.52, 123.7 (C(4’’a), C(4’’b), C(8’’a), C(8’’b),
C(12’’a), C(12’’b)); 148.3, 149.0, 149.1, 149.2 (C(2’’), C(3’’), C(6’’), C(7’’), C(10’’), C(11’’)). APCI-MS:
951.6 ([M þ H]þ), 839.5 ([M þ H ꢀ C8H18]þ), 787.6 ([M þ H ꢀ BrC6H13]þ), 727.3, 675.5, 597.2, 563.3,
451.2, 339.1. HR-APCI-MS: 949.5911 and 951.5907 ([M þ H]þ, C57H89BrO6þ ; calc. 949.5915 and
951.5910).
10.2. 2-[(6-Bromohexyl)oxy]-3,6,7,10,11-pentakis(octyloxy)triphenylene (14b). As described for 14a,
from 3,6,7,10,11-pentakis(octyloxy)triphenylen-2-ol (988 mg, 1.12 mmol) and 1,6-dibromohexane (2.12 g,
8.93 mmol): 1.01 g (86%) of 14b. Rf 0.78 (hexanes/AcOEt 10 :1). M.p. 538. FT-IR (ATR): 2917s, 2849s,
1616m, 1517s, 1434s, 1258s, 1171s, 1029s, 855s, 603s. 1H-NMR (300 MHz, CDCl3): 0.88 – 0.92 (m, 5 Me);
1.26 – 1.47 (m, 20 CH2); 1.53 – 1.66 (m, 14 H, CH2, 2 HꢀC(3’), 2 HꢀC(4’)); 1.89 – 1.98 (m, 14 H, CH2,
2 HꢀC(2’), 2 HꢀC(5’)); 3.44 (t, J ¼ 6.8, 2 HꢀC(6’)); 4.20 – 4.25 (m, 6 CH2O); 7.84 (s, 6 arom. H).
13C-NMR (75 MHz, CDCl3): 14.1 (Me); 22.7, 25.4, 26.2, 28.0, 29.4, 29.5, 31.9, 32.8 (CH2, C(2’), C(3’),
C(4’), C(5’)); 33.7 (C(6’)); 69.5, 69.7, 69.76, 69.80 (CH2O, C(1’)); 107.3, 107.4 (C(1’’), C(4’’), C(5’’), C(8’’),
C(9’’), C(12’’)); 123.6, 123.68, 123.70, 123.8 (C(4’’a), C(4’’b), C(8’’a), C(8’’b), C(12’’a), C(12’’b)); 148.9,

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Helvetica Chimica Acta – Vol. 92 (2009)
149.01, 149.04, 149.1 (C(2’’), C(3’’), C(6’’), C(7’’), C(10’’), C(11’’)). APCI-MS: 1049.7 ([M þ H]þ), 937.6
([M þ H ꢀ C8H18]þ), 885.7 ([M þ H ꢀ BrC6H13]þ), 825.4, 773.6, 713.3, 661.4, 601.2, 549.3, 531.3, 489.1,
437.2, 325.1. HR-APCI-MS: 1047.7023 and 1049.7017 ([M þ H]þ, C63H103BrO6þ ; calc. 1047.7077 and
1049.7009).
10.3. 2-[(6-Bromohexyl)oxy]-3,6,7,10,11-pentakis(dodecyloxy)triphenylene (14c). As described for
14a, from 3,6,7,10,11-pentakis(dodecyloxy)triphenylen-2-ol (1.38 g, 1.19 mmol) and 1,6-dibromohexane
(2.12 g, 8.93 mmol): 1.38 g (87%) of 14c. Rf 0.74 (hexanes/AcOEt 10 :1). M.p. 498. FT-IR (ATR): 3102w,
2918s, 2849s, 2546w, 2369w, 2179w, 1976w, 1617m, 1516s, 1436s, 1387s, 1259s, 1172s, 1045s, 836m. 1H-NMR
(300 MHz, CDCl3): 0.86 – 0.90 (m, 5 Me); 1.23 – 1.47 (m, 40 CH2); 1.52 – 1.63 (m, 14 H, CH2, 2 HꢀC(3’),
2 HꢀC(4’)); 1.89 – 1.98 (m, 14 H, CH2, 2 HꢀC(2’), 2 HꢀC(5’)); 3.44 (t, J ¼ 6.8, 2 HꢀC(6’)); 4.22 (t, J ¼
6.6, 4 CH2O); 4.23 (t, J ¼ 6.4, CH2O); 7.83 (s, 6 arom. H). 13C-NMR (75 MHz, CDCl3): 14.1 (Me); 22.7,
25.4, 26.2, 28.0, 29.3, 29.4, 29.5, 29.6, 29.70, 29.72, 29.8, 32.0, 32.8 (CH2, C(2’), C(3’), C(4’), C(5’)); 33.7
(C(6’)); 69.5, 69.6, 69.72, 69.74 (OCH2, C(1’)); 107.2, 107.4 (C(1’’), C(4’’), C(5’’), C(8’’), C(9’’), C(12’’));
123.56, 123.57, 123.63, 123.65, 123.72 (C(4’’a), C(4’’b), C(8’’a), C(8’’b), C(12’’a), C(12’’b)); 148.8, 148.9,
148.97, 148.99, 149.00, 149.01 (C(2’’), C(3’’), C(6’’), C(7’’), C(10’’), C(11’’)). APCI-MS: 1330.0 ([M þ
H]þ), 1161.8 ([M þ H ꢀ C12H26]þ), 993.6, 825.4, 643.4, 475.3, 325.1. Anal. calc. for C84H143BrO6
(1328.93): C 75.92, H 10.85, N 6.01; found: C 76.12, H 10.72, N 5.93.
11.1. [1,1’-Biisoquinoline]-4,4’-diylbis(oxyhexane-6,1-diyl) Bis[(3,4,5-tris(alkyloxy)benzoates] 13d –
f. Bis-benzoates 13d – f were prepared as described below for 13b,g,h. For yields and m.p.s. of 13b,d –
h, see Table.
11.2. [1,1’-Biisoquinoline]-4,4’-diylbis(oxyhexane-6,1-diyl) Bis[(3,4,5-tris(octyloxy)benzoate] (13b).
In analogy to [19], a suspension of 4a · 2 HCl (185 mg, 275 mmol) and anh. K2CO3 (230 mg, 1.66 mmol) in
anh. DMF (10 ml) was stirred at 1008 for 1 h. After addition of 11b (185 mg, 275 mmol), the mixture was
stirred at 1008 for another 17 h. The mixture was hydrolyzed with H2O (10 ml) and extracted with CH2Cl2
(3 ꢁ 10 ml). The org. layer was washed with H2O and brine (10 ml each), dried (Na2SO4), and
concentrated. The residue was purified by FC (SiO2, hexanes/AcOEt 10 :1, 5 :1, and 2 :1): 13b (156 mg,
77%). Rf 0.53 (hexanes/AcOEt 2 :1). FT-IR (ATR): 3066w, 2951s, 2919s, 2825s, 2366w, 2169w, 1981w,
1707s, 1588s, 1579s, 1503s, 1468s, 1455s, 1428s, 1332s, 1296s, 1247s, 1218s, 1118s, 1097s, 985s, 858m, 780s,
764s. 1H-NMR (300 MHz, CDCl3): 0.86 – 0.90 (m, 6 Me); 1.26 – 1.38 (m, 24 CH2); 1.43 – 1.52 (m, 6 CH2);
1.57 – 1.67 (m, 4 H, 2 HꢀC(4’)); 1.69 – 1.92 (m, 20 H, CH2, 2 HꢀC(3’), 2 HꢀC(5’)); 1.97 – 2.08 (m, 4 H,
2 HꢀC(2’)); 4.02 (t, J ¼ 6.6, 4 H, CH2OꢀC(4’’)); 4.02 (t, J ¼ 6.5, 8 H, CH2OꢀC(3’’), CH2OꢀC(5’’)); 4.34
(t, J ¼ 6.3, 4 H, 2 HꢀC(1’)); 4.36 (t, J ¼ 6.8, 4 H, 2 HꢀC(6’)); 7.28 (s, 4 H, HꢀC(2’’), HꢀC(6’’)); 7.47 (ddd,
J ¼ 8.5, 6.9, 1.3, 2 H, HꢀC(7)); 7.68 (ddd, J ¼ 8.5, 6.9, 1.2, 2 H, HꢀC(6)); 7.74 (ddd, J ¼ 8.5, 1.2, 0.8, 2 H,
HꢀC(8)); 8.24 (br. s, 2 H, HꢀC(3)); 8.33 (ddd, J ¼ 8.5, 1.3, 0.8, 2 H, HꢀC(5)). 13C-NMR (75 MHz,
CDCl3): 14.1 (Me); 22.68, 22.70, 25.9, 26.0, 26.06, 26.10, 28.8, 29.29, 29.33, 29.4, 29.5, 30.3, 31.8, 31.9 (CH2,
C(2’), C(3’), C(4’), C(5’)); 65.0 (C(6’)); 68.7 (C(1’)); 69.2 (CH2O); 73.5 (CH2O); 108.1 (C(2’’), C(6’’));
121.3 (C(5)); 122.5 (C(3)); 125.0 (C(1’’)); 126.9 (C(8)); 127.7 (C(7)); 128.5 (C(8a)); 129.1 (C(4a)); 129.4
(C(6)); 142.4 (C(4’’)); 149.9 (C(4)); 150.4 (C(1)); 152.8 (C(3’’), C(5’’)); 166.5 (COO). ESI-MS: 1467.0
([M þ H]þ), 1353.9 ([M ꢀ C8H18]þ), 1253.8, 1141.7, 959.6, 877.6 ([M þ H ꢀ R]þ), 765.4, 665.3, 489.4,
377.3, 289.1. Anal. calc. for C92H140N2O12 (1466.10): C 75.37, H 9.62, N 1.91; found: C 75.12, H 9.52, N 1.88.
11.3. [1,1’-Biisoquinoline]-4,4’-diylbis(oxyhexane-6,1-diyl) Bis[(3,4,5-tris(tetradecyloxy)benzoate]
(13g). As described for 13b, from 4a · 2 HCl (185 mg, 275 mmol) and 11g (301 mg, 304 mmol): 163 mg
(60%) of 13g. Rf 0.53 (hexanes/AcOEt 2 :1). FT-IR (ATR): 2916s, 2849s, 1712s, 1579s, 1428s, 1335s,
1300s, 1212s, 1095s, 993m, 767s, 720s. 1H-NMR (300 MHz, CDCl3): 0.86 – 0.90 (m, 6 Me); 1.26 – 1.38 (m,
60 CH2); 1.43 – 1.52 (m, 6 CH2); 1.57 – 1.67 (m, 4 H, 2 HꢀC(4’)); 1.69 – 1.92 (m, 20 H, CH2, 2 HꢀC(3’),
2 HꢀC(5’)); 1.97 – 2.08 (m, 4 H, 2 HꢀC(2’)); 4.01 (t, J ¼ 6.6, 2 CH2O); 4.02 (t, J ¼ 6.5, 4 CH2O); 4.34 (t,
J ¼ 6.3, 4 H, 2 HꢀC(1’)); 4.35 (t, J ¼ 6.8, 4 H, 2 HꢀC(6’)); 7.28 (s, 4 H, HꢀC(2’’), HꢀC(6’’)); 7.47 (ddd,
J ¼ 8.5, 6.9, 1.3, 2 H, HꢀC(7)); 7.68 (ddd, J ¼ 8.5, 6.9, 1.2, 2 H, HꢀC(6)); 7.74 (ddd, J ¼ 8.5, 1.2, 0.8, 2 H,
HꢀC(8)); 8.24 (s, 2 H, HꢀC(3)); 8.33 (ddd, J ¼ 8.5, 1.3, 0.8, 2 H, HꢀC(5)). 13C-NMR (75 MHz, CDCl3):
14.1 (Me); 22.7, 25.9, 26.0, 26.1, 28.8, 29.3, 29.38, 29.43, 29.6, 29.67, 29.73, 30.4, 32.0 (CH2, C(2’), C(3’),
C(4’), C(5’)); 64.9 (C(6’)); 68.8 (C(1’)); 69.3 (CH2O); 73.5 (CH2O); 108.1 (C(2’’), C(6’’)); 121.4 (C(5));
122.4 (C(3)); 125.0 (C(1’’)); 126.9 (C(8)); 127.8 (C(7)); 128.5 (C(8a)); 129.2 (C(4a)); 129.5 (C(6)); 142.5
(C(4’’)); 150.0 (C(4)); 150.4 (C(1)); 152.9 (C(3’’), C(5’’)); 166.5 (COO). APCI-MS: 1971.6 ([M þ H]þ),

Helvetica Chimica Acta – Vol. 92 (2009)
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1775.4 ([M þ H ꢀ C14H30]þ), 1591.2, 1394.0, 1212.9, 1129.8 ([M þ 2 H ꢀ R]þ), 933.6, 741.7, 545.5, 349.2,
289.1. Anal. calc. for C128H212N2O12 (1971.06): C 78.00, H 10.84, N 1.42; found: C 78.03, H 10.74, N 1.40.
11.4. [1,1’-Biisoquinoline]-4,4’-diylbis(oxyhexane-6,1-diyl) Bis[(3,4,5-tris(hexadecyloxy)benzoate]
(13h). As described for 13b, from 4a · 2 HCl (185 mg, 275 mmol) and 11h (613 mg, 609 mmol): 216 mg
(36%) of 13h. Rf 0.64 (hexanes/AcOEt 2 :1). FT-IR (ATR): 2916s, 2848s, 2185w, 1973w, 1709s, 1579m,
1
1467s, 1429s, 1330s, 1302s, 1219s, 1116s, 1099s, 991m 866m, 767s, 720m. H-NMR (300 MHz, CDCl3):
0.86 – 0.90 (m, 6 Me); 1.26 – 1.38 (m, 72 CH2); 1.43 – 1.52 (m, 6 CH2); 1.57 – 1.67 (m, 4 H, 2 HꢀC(4’));
1.69 – 1.92 (m, 20 H, CH2, 2 HꢀC(3’), 2 HꢀC(5’)); 1.97 – 2.08 (m, 4 H, 2 HꢀC(2’)); 4.02 (t, J ¼ 6.6,
2 CH2OꢀC(4’’)); 4.02 (t, J ¼ 6.5, 8 H, CH2OꢀC(3’’), CH2OꢀC(5’’)); 4.34 (t, J ¼ 6.3, 4 H, 2 HꢀC(1’));
4.36 (t, J ¼ 6.8, 4 H, 2 HꢀC(6’)); 7.28 (s, 4 H, HꢀC(2’’), HꢀC(6’’)); 7.47 (ddd, J ¼ 8.5, 6.9, 1.3, 2 H,
HꢀC(7)); 7.68 (ddd, J ¼ 8.5, 6.9, 1.2, 2 H, HꢀC(6)); 7.74 (ddd, J ¼ 8.5, 1.2, 0.8, 2 H, HꢀC(8)); 8.24 (s, 2 H,
HꢀC(3)); 8.33 (ddd, J ¼ 8.5, 1.3, 0.8, 2 H, HꢀC(5)). 13C-NMR (75 MHz, CDCl3): 14.1 (Me); 22.7, 25.9,
26.0, 26.09, 26.12, 28.8, 29.2, 29.36, 29.38, 29.44, 29.6, 29.67, 29.68, 29.73, 29.8, 30.4, 31.9 (CH2, C(2’), C(3’),
C(4’), C(5’)); 64.9 (C(6’)); 69.0 (C(1’)); 69.3 (CH2O); 73.5 (CH2O); 108.1 (C(2’’), C(6’’)); 121.6 (C(5));
122.4 (C(3)); 125.0 (C(1’’)); 127.0 (C(8)); 128.2 (C(7)); 128.4 (C(4a), C(8a)); 129.4 (C(6)); 142.5 (C(4’’));
149.8 (C(4)); 150.3 (C(1)); 152.9 (C(3’’), C(5’’)); 166.5 (COO). APCI-MS: 2139.8 ([M þ H]þ), 1915.5
([M þ H ꢀ C16H34]þ), 1703.3 , 1237.0, 1213.9, 989.7, 825.8, 601.5, 379.3. Anal. calc. for C140H236N2O12
(2139.38): C 78.60, H 11.12, N 1.31; found: C 78.40, H 11.00, N 1.27.
11.5. 4,4’-Bis{{6-{[3-methoxy-6,7,10,11-tetrakis(octyloxy)triphenylen-2-yl]oxy}hexyl}oxy}-1,1’-biiso-
quinoline (15a). As described for 13b, from 4a · 2 HCl (100 mg, 207 mmol), 14a (579 mg, 609 mmol),
and K2CO3 (612 mg, 4.43 mmol) with stirring for 45 h and purification by FC (SiO2, hexanes/AcOEt
20 :1, 10 :1, 5 :1, 4 :1, 3 :1, 2 :1, 1:1, and 2 :3): 387 mg (69%) of 15a. Rf 0.60 (hexanes/AcOEt 1:1). FT-IR
(ATR): 3069w, 2921s, 2852s, 2367w, 2186w, 1970w, 1616m, 1507s, 1427s, 1258s, 1162s, 1042s, 835s, 767m.
1H-NMR (300 MHz, CDCl3): 0.87 – 0.92 (m, 8 Me); 1.28 – 1.47 (m, 32 CH2); 1.53 – 1.63 (m, 8 CH2); 1.75 –
1.80 (m, 8 H, 2 HꢀC(3’), 2 HꢀC(4’)); 1.90 – 1.99 (m, 8 CH2); 2.04 – 2.13 (m, 8 H, 2 HꢀC(2’), 2
HꢀC(5’)); 4.10 (s, 2 MeO); 4.23 (t, J ¼ 6.6, 4 H, CH2OꢀC(6’’)); 4.24 (t, J ¼ 6.6, 12 H, CH2OꢀC(7’’),
CH2OꢀC(10’’), CH2OꢀC(11’’)); 4.32 (t, J ¼ 6.4, 4 H, 2 HꢀC(6’)); 4.37 (t, J ¼ 6.3, 4 H, 2 HꢀC(1’)); 7.46
(ddd, J ¼ 8.5, 6.9, 1.2, 2 H, HꢀC(7)); 7.66 (ddd, J ¼ 8.5, 6.9, 1.2, 2 H, HꢀC(6)); 7.73 (ddd, J ¼ 8.5, 1.2, 0.8,
2 H, HꢀC(8)); 7.81 – 7.86 (m, 12 H, HꢀC(1’’), HꢀC(4’’), HꢀC(5’’), HꢀC(8’’), HꢀC(9’’), HꢀC(12’’));
8.26 (s, 2 H, HꢀC(3)); 8.34 (ddd, J ¼ 8.5, 1.2, 0.8, 2 H, HꢀC(5)). 13C-NMR (75 MHz, CDCl3): 14.1 (Me);
22.7, 26.08, 26.13, 26.2, 29.4, 29.5, 31.9 (CH2, C(2’), C(3’), C(4’), C(5’)); 56.3 (MeO); 68.7 (C(1’)); 69.2
(C(6’)); 69.7, 69.8 (CH2O); 105.0, 106.4, 107.3, 107.5 (C(1’’), C(4’’), C(5’’), C(8’’), C(9’’), C(12’’)); 121.4
(C(5)); 122.4 (C(3)); 123.4, 123.46, 123.54, 123.65, 123.68 (C(4’’a), C(4’’b), C(8’’a), C(8’’b), C(12’’a),
C(12’’b)); 126.9 (C(8)); 127.8 (C(7)); 128.5 (C(8a)); 129.1 (C(4a)); 129.5 (C(6)); 148.4, 148.99, 149.01,
149.03, 149.1, 149.2 (C(2’’), C(3’’), C(6’’), C(7’’), C(10’’), C(11’’)); 150.1 (C(4)); 150.4 (C(1)). APCI-MS:
2027.4 ([M þ H]þ), 1902.2, 1838.2, 1201.8, 1014.7. Anal. calc. for C132H188N2O14 (2026.91): C 78.22, H 9.35,
N 1.38; found: C 78.27, H 9.30, N 1.37.
11.6. 4,4’-Bis{{6-{[3,6,7,10,11-pentakis(octyloxy)triphenylen-2-yl]oxy}hexyl}oxy}-1,1’-biisoquinoline
(15b). As described for 13b, from 4a · 2 HCl (100 mg, 207 mmol), 14b (639 mg, 609 mmol), and K2CO3
(612 mg, 4.43 mmol) with stirring for 45 h and purification by FC (SiO2, hexanes/AcOEt 20 :1, 10 :1, 5 :1,
and 4 :1): 193 mg (31%) of 15b. Rf 0.47 (hexanes/AcOEt 4 :1). FT-IR (ATR): 2882s, 1682m, 1558s, 1485s,
1407s, 1350s, 1188m, 1086s, 929s, 743s, 679s. 1H-NMR (300 MHz, CDCl3): 0.85 – 0.92 (m, 10 Me); 1.27 –
1.47 (m, 40 CH2); 1.53 – 1.63 (m, 10 CH2); 1.75 – 1.80 (m, 8 H, 2 HꢀC(3’), 2 HꢀC(4’)); 1.90 – 1.99 (m,
10 CH2); 2.03 – 2.11 (m, 8 H, 2 HꢀC(2’), 2 HꢀC(5’)); 4.23 (t, J ¼ 6.6, 16 H, CH2OꢀC(6’’), CH2OꢀC(7’’),
CH2OꢀC(10’’), CH2OꢀC(11’’)); 4.24 (t, J ¼ 6.5, 4 H, CH2OꢀC(3’’)); 4.30 (t, J ¼ 6.4, 4 H, 2 HꢀC(6’));
4.37 (t, J ¼ 6.3, 4 H, 2 HꢀC(1’)); 7.46 (ddd, J ¼ 8.5, 6.9, 1.2, 2 H, HꢀC(7)); 7.65 (ddd, J ¼ 8.5, 6.9, 1.2, 2 H,
HꢀC(6)); 7.74 (ddd, J ¼ 8.5, 1.2, 0.8, 2 H, HꢀC(8)); 7.83 – 7.87 (m, 12 H, HꢀC(1’’), HꢀC(4’’), HꢀC(5’’),
HꢀC(8’’), HꢀC(9’’), HꢀC(12’’)); 8.25 (s, 2 H, HꢀC(3)); 8.34 (ddd, J ¼ 8.5, 1.2, 0.8, 2 H, HꢀC(5)).
13C-NMR (75 MHz, CDCl3): 14.1 (Me); 22.7, 26.1, 26.2, 29.4, 29.5, 31.9 (CH2, C(2’), C(3’), C(4’), C(5’));
68.8 (C(1’)); 69.6 (C(6’)); 69.6, 69.7, 69.8 (OCH2); 107.2, 107.3, 107.35, 107.42 (C(1’’), C(4’’), C(5’’), C(8’’),
C(9’’), C(12’’)); 121.4 (C(5)); 122.4 (C(3)); 123.60, 123.64, 123.7 (C(4’’a), C(4’’b), C(8’’a), C(8’’b),
C(12’’a), C(12’’b)); 126.9 (C(8)); 127.8 (C(7)); 128.5 (C(8a)); 129.1 (C(4a)); 129.5 (C(6)); 148.9, 149.0
(C(2’’), C(3’’), C(6’’), C(7’’), C(10’’), C(11’’)); 150.0 (C(4)); 150.4 (C(1)). APCI-MS: 2223.6 ([M þ H]þ),

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Helvetica Chimica Acta – Vol. 92 (2009)
1971.5, 1338.9, 1299.9, 1186.9, 1160.9, 1112.8, 1070.8, 1026.8, 985.8, 967.8, 873.7, 855.7. Anal. calc. for
C146H216N2O14 (2223.28): C 78.87, H 9.79, N 1.26; found: C 78.73, H 9.65, N 1.22.
11.7. 4,4’-Bis{{6-{[3,6,7,10,11-pentakis(dodecyloxy)triphenylen-2-yl]oxy}hexyl}oxy}-1,1’-biisoquino-
line (15c). As described for 13b, from 4a · 2 HCl (100 mg, 207 mmol), 14c (809 mg, 609 mmol), and
K2CO3 (612 mg, 4.43 mmol) with stirring for 45 h and purification by FC (SiO2, hexanes/AcOEt 20 :1,
10 :1, 8 :1, 5 :1, and 2 :1): 105 mg (14%) of 15c. Rf 0.56 (hexanes/AcOEt 4 :1). FT-IR (ATR): 3077w,
2918s, 2849s, 2559w, 2368w, 2119w, 1969w, 1617m, 1517s, 1436s, 1387s, 1259s, 1172s, 1044m, 836s, 721m.
1H-NMR (300 MHz, CDCl3): 0.83 – 0.90 (m, 10 Me); 1.22 – 1.47 (m, 80 CH2); 1.52 – 1.62 (m, 10 CH2);
1.75 – 1.80 (m, 8 H, 2 HꢀC(3’), 2 HꢀC(4’)); 1.90 – 1.99 (m, 10 CH2); 2.03 – 2.13 (m, 8 H, 2 HꢀC(2’),
2 HꢀC(5’)); 4.23 (t, J ¼ 6.6, 16 H, CH2OꢀC(6’’), CH2OꢀC(7’’), CH2OꢀC(10’’), CH2OꢀC(11’’)); 4.24 (t,
J ¼ 6.5, 4 H, CH2OꢀC(3’’)); 4.30 (t, J ¼ 6.4, 4 H, 2 HꢀC(6’)); 4.37 (t, J ¼ 6.3, 4 H, 2 HꢀC(1’)); 7.46 (ddd,
J ¼ 8.5, 6.9, 1.2, 2 H, HꢀC(6) or HꢀC(7)); 7.65 (ddd, J ¼ 8.5, 6.9, 1.2, 2 H, HꢀC(6) or HꢀC(7)); 7.74
(ddd, J ¼ 8.5, 1.2, 0.8, 2 H, HꢀC(5) or HꢀC(8)); 7.83 – 7.87 (m, 12 H, HꢀC(1’’), HꢀC(4’’), HꢀC(5’’),
HꢀC(8’’), HꢀC(9’’), HꢀC(12’’)); 8.25 (s, 2 H, HꢀC(3)); 8.34 (ddd, J ¼ 8.5, 1.2, 0.8, 2 H, HꢀC(5) or
HꢀC(8)). 13C-NMR (75 MHz, CDCl3): 14.1 (Me); 22.7, 26.16, 26.23, 29.4, 29.5, 29.6, 29.70, 29.73, 29.8,
31.9 (CH2, C(2’), C(3’), C(4’), C(5’)); 68.8 (C(1’)); 69.6 (C(6’)); 69.7 (CH2O); 107.2, 107.4 (C(1’’), C(4’’),
C(5’’), C(8’’), C(9’’), C(12’’)); 121.4 (C(5)); 122.4 (C(3)); 123.6, 123.7 (C(4’’a), C(4’’b), C(8’’a), C(8’’b),
C(12’’a), C(12’’b)); 126.9 (C(8)); 127.8 (C(7)); 128.5 (C(8a)); 129.1 (C(4a)); 129.5 (C(6)); 148.9, 149.0
(C(2’’), C(3’’), C(6’’), C(7’’), C(10’’), C(11’’)); 150.0 (C(4)); 150.4 (C(1)). APCI-MS: 2785.3 ([M þ H]þ),
2658.0, 2596.1, 2475.9, 2223.6, 2122.0, 1992.5, 1648.2. HR-APCI-MS: 2785.2624 ([M þ H]þ,
C
186H296N2Oþ14 ; calc. 2785.2652).
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Received March 12, 2009