Synthesis of triphenylene discotic liquid crystal dimers: Click chemistry as an efficient tool

Article abstract of DOI:10.1080/15421400903051093

Click chemistry between alkynes and azides high efficiently produces triazoles and would be a convenient tool for synthesis of discotic liquid crystal dimers, oligomers and polymers. In this report, triphenylenes containing terminal alkynes and azides were prepared, and the cycloaddition reaction (click chemistry) between them catalyzed by CuI-Et₃N in toluene produced discotic liquid crystal dimers in high yield and good selectivity. The dimers and intermediates have been fully characterized by ¹H NMR and high resolution MS. Polarized optical microscopy (POM) and differential scanning calorimetry (DSC) results show the dimers possess columnar mesophase in wide temperature range from very low temperature. The triazole moiety in the dimer can act as electron and hydrogen bond acceptor, and ionic forming part, rich chemical and physical properties can be expected from these new structure discotic dimers. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15421400903051093

Mol. Cryst. Liq. Cryst., Vol. 509, pp. 77=[819]–88=[830], 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 1542-1406 print=1563-5287 online
DOI: 10.1080/15421400903051093
Synthesis of Triphenylene Discotic Liquid Crystal
Dimers: Click Chemistry As an Efficient Tool
K. Q. Zhao1, Y. F. Bai1, P. Hu1, B. Q. Wang1,
and Y. Shimizu2
1College of Chemistry and Materials Science, Sichuan Normal
University, Chengdu, Sichuan, China
2Synthetic Nano-Function Materials Group, Nanotechnology
Research Institute, National Institute of Advanced Industrial Science
and Technology, Ikeda, Osaka, Japan
Click chemistry between alkynes and azides high efficiently produces triazoles and
would be a convenient tool for synthesis of discotic liquid crystal dimers, oligomers
and polymers. In this report, triphenylenes containing terminal alkynes and
azides were prepared, and the cycloaddition reaction (click chemistry) between
them catalyzed by CuI-Et3N in toluene produced discotic liquid crystal dimers
in high yield and good selectivity. The dimers and intermediates have been fully
characterized by 1H NMR and high resolution MS. Polarized optical microscopy
(POM) and differential scanning calorimetry (DSC) results show the dimers pos-
sess columnar mesophase in wide temperature range from very low temperature.
The triazole moiety in the dimer can act as electron and hydrogen bond acceptor,
and ionic forming part, rich chemical and physical properties can be expected from
these new structure discotic dimers.
Keywords: click chemistry; discotic liquid crystal; huisgen cycloadditon reaction; liquid
crystal dimer; triphenylene
1. INTRODUCTION
Discotic liquid crystals (DLC) such as triphenylene derivatives
have attracted much attention for their remarkable electro-optical
properties [1–4], and it offers potential applications as organic charge
Project supported by National Nature Science Foundation of China. (Project Nos.
50473062, 50673069, and 50811140156).
Address correspondence to K. Q. Zhao, College of Chemistry and Materials Science,
Sichuan Normal University, 5 Jing-An Road, Chengdu 610066, China. E-mail: kqzhao@
sicnu.edu.cn
77=[819]

78=[820]
K. Q. Zhao et al.
SCHEME 1 Synthesis of functional group containing triphenylenes.
transport materials in a variety of devices such as one-dimensional
conductors, photoconductors, field effect transistors, photovoltaic solar
cells, etc. [5–8]. So in the last decades lots of efforts have been made to
design, synthesis, and characterize various DLC.
It is well known that connecting two discotic mesogens (DLC
dimers) together via a flexible spacer or through a rigid spacer stabi-
lizes the columnar mesophase significantly [9], and triphenylene as
electron donor when doped with electron acceptor can form charge-
transfer (C-T) complex. C-T interaction also can stabilize the columnar
mesophase and increase the charge transport [10,11].
Huisgen 3 þ 2 cycloaddition reaction (‘‘click chemistry’’ CC), which
take place between terminal alkynes and high-energy azides under
thermal condition, get two isomer products, the 1,4- and 1,5-disubsti-
tuted 1,2,3-triazoles [12,13]. In 2001, Kolb, Finn, and Sharpless

Synthesis of Triphenylene Discotic Liquid Crystal Dimers
79/[821]
SCHEME 2 Synthesis of triphenylene dimers by click chemistry.
published a landmark review describing a new strategy for CC. They
have used Cu(I) salt as the catalyst, and just got the 1,5-disubstituted
1,2,3-triazoles selectively [14]. Since then the CC has been broadly
used in the areas of biological, materials, and medicinal chemistry
as for the high yield, many functional groups tolerance, and the simple
reaction condition and so on.
We have been focusing on the synthesis of triphenylene discotic
liquid crystals materials, and hope to enhance their charged carrier
mobility and electro-optical properties, and broaden the mesophase
range by simple syntheses way under mild condition. We believe that
new chemistry can synthesize new structure compounds and would
expect novel chemical and physical properties, and potential applica-
tions would be found. To our knowledge, there are few examples using
CC in liquid crystalline molecular designing and synthesis [15,16].
Here we design and synthesis triphenylene discotic dimers 7 and 8
(Schemes 1 and 2), in their structure heterocycle 1,2,3-triazole acts
as the linking bridge which formed by Huisgen 3 þ 2 cycloaddition
reaction.
2. RESULTS AND DISCUSSION
2.1. Synthesis and Characterization
2-Hydroxy-3,6,7,10,11-penta(hexyloxy)triphenylene, 1, was used as
the starting material, which has been synthesized and purified as

80/[822]
K. Q. Zhao et al.
described [17]. Etherification 1 with 3-bromo-1-propyne, 5-chloro-1-
pentyne, and ethyl 2-bromoacetate produced 6a, 6b and 4 respectively.
4 underwent ammonolysis in presence of mono-propargylamine
formed 5, which has a terminal alkynyl group. 3 was prepared in high
yield through nucleophilic substitution reaction of NaN3 with alkyl
bromide 2, which synthesized from etherification of 1 with 1,6-dibro-
mohexane or 1,3-dibromopropane. In the mono etherification reaction
of a,x-dibromoalkane, solvent is very important for its success. In
acetone, mono etherification is the main product. However, reaction
in DMF led to the byproduct of di-etherification. Finally, 3 clicked with
5, or 6 in toluene, and catalyzed by CuI-NEt3, produced successfully
the discotic dimer 7 and 8. The click chemistry took place in room
temperature in less than 12 hours. The dimer 7 and 8 were purified
1
by column chromatography and fully characterized by H NMR, and
high resolution Mass.
1
The Figure 1 shows the H NMR spectra of 8b and alkynes 6 in
chloroform-d. Figure 1A shows the alkyne proton resonance at d ¼
2.26, and the methylene proton resonance between amide and alkynes
around d ¼ 4.2. After click reaction, the alkyne proton resonance trans-
form to d ¼ 7.8, and the methylene proton resonance transform to
d ¼ 4.77. The differences have been shown in Figure 1B. Bertrand
[18], Stoddart [19], and others [20] have reported that the proton
resonance in 1,5-disubstituted 1,3,5-triazoles at d ¼ 7.8–8.6. Thus the
two 1H NMR spectra confirm that 8b is our desired molecular. All
the discotic dimers have been further characterized by high resolution
mass spectra, and the results support our conclusion.
FIGURE 1 1H NMR spectra of 5 and discotic dimer 8b.

Synthesis of Triphenylene Discotic Liquid Crystal Dimers
81/[823]
2.2. Mesomorphism
The liquid crystalline behaviors of the triphenylene derivatives and
discotic dimers were investigated by differential scanning calorimetry
(DSC), the results are summarized in Table 1, and the DSC traces of
intermediates and dimers are drawn in Figures 2 and 3. The textures
of the mesophases were observed and recorded by polarized optical
microscopy (POM) and typical photomicrographs are shown in Figure 4.
As showed in Table 1 and Figure 2, all triphenylene intermediates
exhibits mesophases. When heating the sample powder among two
plate untreated glasses to isotropic liquid, and slowly cooling, typical
fan shaped textures, the feature of hexagonal columnar mesophases,
were observed from the POM.
Figure 3 draws the DSC traces of triphenylene dimers, the click
chemistry products. Figure 3a is the first heating traces, and
Figure 3b is the second heating traces. There are two peaks for 7b,
8a, and 8b on the first heating traces. The first peak is the transition
of crystal phase to mesophase, and the second one, mesophase to iso-
tropic liquid. The crystallization can not be observed on the cooling
run until ꢀ50ꢁC. 7a showed different behavior from other dimmers,
that it appeared three peaks on the first heating trace. The second
peak is the transition between different mesophases, which can not
TABLE 1 Thermal and Thermodynamic Property of Triphenylene
Derivatives by DSC (10ꢁC minꢀ1) (Cr: Crystal; Colh: Hexagonal Columnar
Phase; I: Isotropic liquid)
Mesophases, transition temperature and enthalpy changes
Compd.
Heating=ꢁC (DH, kJ molꢀ1
)
Cooling=ꢁC (DH, kJ molꢀ1
)
2a
2b
3a
3b
4
Cr 56 (32.07) Colh 100 (4.79) I
Cr 60 (41.22) I
Cr 62 (37.20) Colh 92 (3.76) I
Cr 54 (40.33) I
Cr 48 (40.22) Colh 118 (7.65) I
Cr 67 (33.80) Colh 134 (5.01) I
Cr 66 (39.96) Colh 100 (4.48) I
Cr 52 (30.79) Colh 98 (4.97) I
Cr 48 (39.33) Col1 75 (2.44)
Col2 88 (12.31) I
I 98 (4.55) Colh 28 (32.12) Cr
I 51 (1.56) Colh 47 (38.22) Cr
I 92 (3.65) Colh 43 (33.60) Cr
I 49 (1.48) Colh 44 (38.69) Cr
I 118 (7.59) Colh 7 (29.98) Cr
I 133 (4.95) Colh 47 (33.03) Cr
I 100 (4.67) Colh 27 (30.44) Cr
I 97 (4.97) Colh 24 (25.56) Cr
I 86 (11.10) Col2 74 (2.60) Col1
5
6a
6b
7a
7b
8a
8b
Cr 18 (65.89) Colh 95 (60.21) I
Cr 71 (29.04) Colh 97 (9.54) I
Cr 81 (51.47) Colh 104 (10.47) I
I 67 (4.95) Colh
I 93 (9.42) Colh
I 103 (10.10) Colh
7 and 8 measured in the first heating and cooling run; others, the second heating and
cooling circle.

82/[824]
K. Q. Zhao et al.
FIGURE 2 DSC traces of the triphenylene intermediates.
been observed from POM textures. So we can say that all the discotic
triphenylene dimmers are room temperature liquid crystals after the
first heating to isotropic.
We have put lots of efforts on learning the effects of hydrogen
bonding among intermolecular amide functional groups on discotic
liquid crystalline properties [21–23]. 8a and 8b are amide containing
discotic dimers, the DSC data showed that they have higher clearing
points than 7a, 7b. This result may be caused by the intermolecular
hydrogen bonding of dimer 8.
Figure 4, the photomicrographs of 7 and 8, showed the same optical
textures of well-characterized discotic columnar mesophase [24]. The
detail information of molecular packing in the columnar organization
should be further studied with XRD. However, the dimers prepared by

Synthesis of Triphenylene Discotic Liquid Crystal Dimers
83/[825]
FIGURE 3 DSC traces of triphenylene discotic dimmers (A) first heating run;
(B) second heating run; heating and cooling rate 10ꢁC=min.
FIGURE 4 POM photographs of triphenylene dimers, obtained on slowly cool-
ing from the isotropic liquid, (A) 8b, 81ꢁC; (B) 8a, 89ꢁC; (C) 7a, 68ꢁC; (D) 7b, 69ꢁC.

84/[826]
K. Q. Zhao et al.
click chemistry have different thermotropic properties, such as wide
mesophase ranges and high viscosity, compared with triphenylene
dimers connected with alkyl chain [25].
The novel chemistry of click reaction produced new triphenylene
discotic dimers in chemical structure. New structure would result in
new physical properties. triphenylene is an electron-rich molecule
and it can form charge-transfer (C-T) complex with electron acceptor,
such as trinitrofluorenone (TNF), and stabilize the columnar assem-
bly. Although nitrogen-containing heteroaromatic rings such as pyri-
dine [26–28], pyrazine [29, 30], pyrimidine [31] and pyridazine [11]
and others such as 2,4,7-trinitrofluorenone (TNF) [32–35] and so on
[12,36] have been employed as electron acceptors, the heterocycle
1,2,3-triazole as an electron acceptor in the discotic dimer system
has not been reported. As the triphenylene moiety is electron-rich
and triazole moiety electron-poor, the C-T complex formed or not in
the columnar assembly should be further verified. Further more, tria-
zole moiety can be acted as hydrogen bond acceptor and forming ionic
liquid crystals after reacted with alkyl halide. The click chemistry
formed triazole discotic liquid crystalline dimers reported here would
expect rich chemical and physical properties.
3. CONCLUSION
Novel triphenylene discotic liquid crystalline dimers composed of two
triphenylene discogens and a triazole moiety have been prepared. The
click chemistry reaction catalyzed by CuI-NEt3 in toluene at room
temperature produced the discotic liquid crystal dimers in high yield
and good selectivity. The discotic dimers show mesophase in wide
mesophase range from very low temperature. This research work
has demonstrated that the click chemistry, combined with the easy
available of alkynes and azides, would be an efficient tool for synthesis
of novel liquid crystal dimers, oligomers and polymers.
4. EXPERIMENTAL
Instrumentation and Chemicals
1
1H NMR (600 MHz) spectra were recorded by Bruker-Avance-600, H
NMR (400 MHz) Varian UNITY INOVA-400, using CDCl3 as a solvent
and Me4Si as an internal standard. The high resolution Mass was
recorded on Varian 7.0 T FTICR-MS (ESI, or MALDI mode). Melting
points, phase transition temperatures and enthalpy changes were
measured using differential scanning calorimetry (DSC) on TA-DSC

Synthesis of Triphenylene Discotic Liquid Crystal Dimers
85/[827]
Q100 system, and heating and cooling scan rate of 10ꢁC minꢀ1. Transi-
tion enthalpies DH were changed into kJ molꢀ1. The texture of the
mesophases was observed using polarizing optical microscopy (POM)
XP-201, with a hot stage XP-201.
Commercial Chemicals and solvents were used without further pur-
ification if no special notification. 2-Hydroxy-3,6,7,10,11-pentakishex-
yloxytriphenylene was prepared according to reported method [17].
C18H6(OC6H13)5(OC6H12Br), 2b. 2-hydroxyl-3,6,7,10,11-pentakishe-
xyloxytriphenylene 1 (1.414 g, 1.9 mmol) and potassium carbonate
(1.04 g, 7.6 mmol) was added to acetone (20 mL). Then 1,6-dibromohex-
ane (1.113 g, 4.5 mmol) was added, and the solution was refluxed 12 h.
the mixture was poured into water and extracted with dichloro-
methane. The organic layer was dried with magnesium sulfate, and
the organic solvent was removed under vacuum. The crude compound
was purified by column chromatography with silica gel afforded 2b
white solid (1.3986 g, 81%, mp: 60ꢁC). 1H NMR (CDCl3, TMS, 400 MHz)
d: 7.83 (s, 6 H), 4.23 (t, J ¼ 6.4 Hz, 12 H), 3.45 (t, J ¼ 6.8 Hz, 2 H),
1.90–1.97 (m, 14 H), 1.56–1.60 (m, 14 H), 1.36–1.40 (m, 20 H), 0.93
(t, J ¼ 7.2 Hz, 15 H).
C18H6(OC6H13)5(OC3H6Br), 2a. 2a was synthesized as 2b (79%, Cr
1
56ꢁC Colh 100ꢁC Iso). H NMR (CDCl3, TMS, 400 MHz) d: 7.89 (s, 1
H), 7.84 (s, 5 H), 4.39 (t, J ¼ 5.6 Hz, 2 H), 4.23 (t, J ¼ 6.4 Hz, 10 H),
3.74 (t, J ¼ 6.4 Hz, 2 H), 2.44–2.50 (m, 2 H), 1.91–1.98 (m, 10 H),
1.54–1.60 (m, 10 H), 1.36–1.41 (m, 20 H), 0.93 (t, J ¼ 7.2 Hz, 15 H).
C18H6(OC6H13)5(OC6H12N3), 3b. A mixture of compound 2b (907 mg,
1 mmol) and NaN3 (845 mg, 13 mmol) in DMF was stirred at room
temperature for 12 h. After added 20 mL water, the reaction mixture
was extracted with dichloromethane. The organic layer was dried with
magnesium sulfate, and the organic solvent was removed under
vacuum. The residue recrystallization from ethanol afforded product
as white solid (824 mg, 95%, mp: 54ꢁC). 1H NMR (CDCl3, TMS,
400 MHz) d: 7.84 (s, 6 H), 4.24 (t, J ¼ 6.4 Hz, 12 H), 3.31 (t, J ¼ 6.8 Hz,
Hz, 2 H) 1.91–1.98 (m, 12 H), 1.50–1.72 (m, 16 H), 1.34–1.36 (m, 20H),
0.94 (t, J ¼ 6.8 Hz, 15 H).
C18H6(OC6H13)5(OC3H6N3), 3a. The synthetic procedure is the same
as 3b, except that the crude product was purified by column chroma-
tography with silica gel. (83%, Cr 62ꢁC Colh 92ꢁC Iso). 1H NMR
(CDCl3, TMS, 400 MHz) d: 7.87 (s, 1 H), 7.84 (s, 5 H), 4.33 (t, J ¼ 6 Hz,
Hz, 2 H), 4.23 (t, J ¼ 6.4 Hz, 10 H), 3.66 (t, J ¼ 6.8 Hz, 2 H), 2.20 (t,
J ¼ 6 Hz, 2 H), 1.90–1.98 (m, 10 H), 1.58–1.62 (m, 10 H), 1.36–1.46
(m, 20 H), 0.92–0.96 (m, 15 H).

86/[828]
K. Q. Zhao et al.
C18H6(OC6H13)5(OCH2COOC2H5),
4. BrCH2COOC2H5
(652 mg,
3.9 mmol), 2-hydroxyl-3,6,7,10,11-pentakishexyloxy-triphenylene
(858 mg, 1.3 mmol) were added to the suspension of potassium carbo-
nate and DMF. The mixture was refluxed 12 h, poured into the water
with ice, and extracted with dichloromethane. The organic layer was
dried with magnesium sulfate, and the organic solvent was removed
under vacuum. The residue recrystallization from ethanol afforded
1
the product as white solid (1.08 g, 89%, Cr 48ꢁC Colh 118ꢁC Iso). H
NMR (CDCl3, 600 MHz) d: 7.94 (s, 1 H), 7.83 (t, J ¼ 5.4 Hz, 4 H), 7.79
(s, 1 H), 4.87 (s, 2 H), 4.29–4.33 (q, 2 H), 4.20–4.23 (m, 10 H), 1.94–
1.99 (m, 10 H),1.56 ꢀ 1.60 (m, 10 H), 1.30–1.40 (m, 20 H), 1.29 (t,
J ¼ 3.78 Hz, 3 H), 0.93 (t, J ¼ 6.60 Hz, 15 H).
C18H6(OC6H13)5(OCH2CONHCH2CꢂCH), 5. A solution of 4 (166 mg,
0.2 mmol), and CHꢂCCH2NH2 (66 mg, 1.2 mmol) in THF (10 mL)
was refluxed 72 h. Then the mixture was poured into the water with
ice, and extracted with dichloromethane. The organic layer was dried
with magnesium sulfate, and the organic solvent was removed under
vacuum. The crude product was purified by column chromatography
with silica gel afforded product as white solid (167.8 mg, 77%, Cr
1
67ꢁC Colh 134ꢁC Iso). H NMR (CDCl3, TMS, 400MHz) d: 7.87 (s, 1 H),
7.83 (s, 4 H), 7.77 (s, 1 H), 7.43 (t, J ¼ 4.8 Hz, 1 H), 4.77 (s, 2 H),
4.19–4.28 (m, 12 H), 2.27 (t, J ¼ 2.4 Hz, 1 H) 1.92–1.98 (m, 10 H),
1.57–1.62 (m, 10 H), 1.40–1.46 (m, 20 H), 0.92–0.96 (m, 15 H).
C18H6(OC6H13)5(OC3H6CꢂCH),
6b. 2-hydroxyl-3,6,7,10,11-penta-
kishexyloxytriphenylene (201 mg, 0.27 mmol) and potassium carbonate
(147 mg, 1.08 mmol) was added to DMF (3 mL). Then the 5-chloropen-
tyne (1.113 g, 4.5 mmol) was added, and the solution was stirred over
12 h. After removing the solvent, the residue was washed with water
and extracted with dichloromethane. The organic layer was dried with
magnesium sulfate, and the organic solvent was removed under
vacuum. The crude compound was purified by column chromatography
with silica gel afforded the product as white solid (218.7 mg, 87%, Cr
1
52ꢁC Colh 98ꢁC Iso). H NMR (CDCl3, 600 MHz) d: 7.87 (s, 1 H), 7.84
(d, J ¼ 4.0 Hz, 5 H), 4.34 (t, J ¼ 6.1 Hz, 2 H), 4.23 (t, J ¼ 6.5 Hz, 10 H),
2.52–2.55 (m, 2 H), 2.13–2.17 (m, 2H), 2.00 (t, J ¼ 2.8 Hz, H),
1.91–1.96 (m, 10H), 1.57–1.60 (m, 10 H), 0.94 (t, J ¼ 7.1 Hz,15 H).
C18H6(OC6H13)5(OCH2CꢂCH), 6a. 6a was prepared as 6b (260.3 mg,
1
83%, Cr 66ꢁC Colh 100ꢁC Iso). H NMR (CDCl3, 600 MHz) d: 8.08 (s, 1
H), 7.84 (d, J ¼ 7.5 Hz, 5H), 4.96 (d, J ¼ 2.3 Hz, 2H), 4.22–4.26 (m,
10H), 2.56 (t, J ¼ 2.3 Hz, 1 H), 1.91–1.97 (m, 10H), 1.54–1.59 (m,
10H), 1.37–1.40 (m, 20H), 0.93 (t, J ¼ 7.0 Hz,15H).

Synthesis of Triphenylene Discotic Liquid Crystal Dimers
87/[829]
C18H6(OC6H13)5[OC3H6CCHN3C6H12O]C18H6(OC6H13)5,
7b. 3b
(40.5 mg, 0.05 mmol) and 6b (43.45 mg, 0.05 mmol) were dissolved in
toluene (2 ml), then CuI (13 mg) and NEt3 (1.5 ml) were added. The
solution was stirred 12 h at room temperature. The toluene was
removed in vacuum, and the residue solid was purified by column
chromatography with silica gel afforded the product as white solid
(75.6 mg, 90%, Cr 18ꢁC Colh 94ꢁC Iso). 1H NMR (CDCl3, TMS,
400 MHz) d: 7.82 (t, J ¼ 4.8 Hz, 13 H), 4.16–4.41 (m, 26 H), 3.06–3.18
(m, 2 H), 2.32–2.41 (m, 2 H), 1.87–1.96 (m, 24 H), 1.53–1.79 (m, 24 H),
1.38–1.44 (m, 40 H), 0.89–0.95 (m, 30 H). Exact mass: calculated
(C105H157O12N3Naþ), 1675.1659; found, 1675.1665.
C18H6(OC6H13)5[OCH2CCHN3C6H12O]C18H6(OC6H13)5, 7a. 7a pre-
pared as 7b (93.5 mg, 81%, Cr 48ꢁC Col1 75ꢁC Col2 88ꢁC Iso). 1H
NMR (CDCl3, TMS, 600 MHz) d: 8.08 (s, 1 H), 7.81 (d, J ¼ 2.22 Hz,
12 H), 5.44–5.52 (m, 2 H), 4.40–4.43 (m, 2 H), 4.17–4.29 (m, 22 H),
1.88–1.95 (m, 24 H), 1.57–1.70 (m, 24 H), 1.32–1.48 (m, 40 H),
0.90–0.94 (m, 30 H). Exact mass: calculated (C107H162O12Nþ3 ),
1681.2153; found, 1681.2163.
C18H6(OC6H13)5[OCH2CONHCH2CCHN3C3H6O]C18H6(OC6H13)5, 8a. 8a
synthesized as 7b (84%, Cr 71ꢁC Colh 97ꢁC Iso). 1H NMR (CDCl3,
TMS, 600 MHz) d: 7.70–7.84 (m, 13 H), 7.43 (s, 1 H), 4.64–4.73 (m, 4
H), 4.13–4.26 (m, 24 H), 2.42–2.52 (m, 2 H), 1.91–1.93 (m, 20 H),
1.54–1.60 (m, 20 H), 1.38–1.40 (m, 40 H), 0.92–0.94 (m, 30 H). Exact
mass: calculated (C104H154O13N4Naþ), 1690.1404; found, 1690.1412.
C
18H6(OC6H13)5[OCH2CONHCH2CCHN3C6H12O]C18H6(OC6H13)5,
1
8b. 8b synthesized as 7b (75 mg, 88%, Cr 81ꢁC Colh 104ꢁC Iso). H
NMR (CDCl3, TMS, 600 MHz) d: 7.76 ꢀ 7.88 (m, 13 H), 7.52 (s, 1 H),
4.77 (s, 2 H), 4.68 ꢀ 4.71 (m, 2 H), 4.19 ꢀ 4.26 (m, 24 H), 1.74–1.87
(m, 28 H), 1.52 ꢀ 1.58 (m, 20 H), 1.34 ꢀ 1.43 (m, 40 H), 0.90 ꢀ 0.93
(m, 30 H). Exact mass: calculated, (C107H161O13Nþ4 ) 1710.2055; found,
1711.2091.
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