Paper
RSC Advances
1
4
3
2
21.26, 121.15, 116.31, 116.26, 74.23, 67.39, 56.59, 56.08, 50.03, might be favorable for the wide scopes of phase transfer
28,31–33
2.32, 40.63, 39.73, 39.42, 38.17, 36.92, 36.68, 36.19, 35.80, temperatures.
Thus, the 1,7-bay-substituted perylene
2.63, 31.82, 31.04, 29.71, 28.23, 28.02, 27.11, 24.72, 24.29, derivative 5 was chosen as building platform to construct the
3.83, 22.57, 20.98, 19.27, 18.65, 14.10, 11.79; MALDI-TOF-MS triads and pentads of perylene with multi-cholesterol units. The
+
calcd for m/z ¼ 1740.1, found: m/z ¼ 1740.8 (M ). HR-MS (ESI) synthetic routes were illustrated in Scheme 1. Firstly, by ester-
+
(C
114
H
150
N
2
O
12) [M] : calcd: 1740.1217. Found: 1740.1227.
ifying reaction with chlorinated carboxylic acid and subse-
quently etherifying reaction with excess p-benzenediol,
cholesterol was conveniently transferred to cholesterol deriva-
tives 3a and 3b with terminal phenolic hydroxyl group, which
easily react with halogen group on perylene. In this reaction,
two and four carbon atom chains for chlorinated carboxylic acid
were used to investigate the inuence of chain length on
mesomorphic and photophysical property. On the other hand,
Synthesis of compounds 10a and 10b
Under N atmosphere, the mixture of compound 8 (0.27 g, 0.3
2
mmol), compound 3a or 3b (1 mmol), anhydrous K
2
CO
3
(0.21 g,
ꢀ
1.5 mmol) was stirred in DMF (30 mL) at 105 C for 20 h. Then
the solution was treated by the similar synthetic procedure of
compound 9, and the products were puried by column chro-
matography (CH
the 1,7-dibrominated perylene bisanhydrides 5 was prepared by
2
Cl
2
/ethyl acetate (8/1, v/v)). The compounds
30
the previous literature.
By ammonolysis procedure of
10a and 10b were collected as red solids in the yields of 55% and
compound 5 with n-octylamine or 6-amino-1-hexanol, the cor-
responding perylene bisimides 6 and 7 with two halogen groups
were obtained in yields of 85% and 86%, respectively. Further-
more, compound 7 was reacted with chloroacetyl chloride to
afford perylene imides 8 containing four halogen groups in
yield of 75%. Due to the poor dissolubility, compounds 5 and 7
was not puried and used directly in next step. Compounds 6
and 8 were puried by column chromatography and some by-
products in the previous steps, such as the complicated
isomers in bromination reaction, were separated out. The pure
compounds 6 and 8 were obtained in ideal yields of 75% and
1
58%, respectively. Compound 10a: H NMR (400 MHz, CDCl )
3
d
ppm: 9.55 (d, J ¼ 8.0 Hz, 2H, ArH), 8.55 (d, J ¼ 8.0 Hz, 2H, ArH),
8
.23 (s, 2H, ArH), 7.09 (d, J ¼ 8.0 Hz, 4H, ArH), 6.98 (d, J ¼
.0 Hz, 4H, ArH), 6.80 (s, 8H, ArH), 5.39 (bs, 2H, C]CH), 5.34
8
(
(
bs, 2H, C]CH), 4.83 (bs, 4H, OCH), 4.63 (s, 4H, OCH
s, 4H, OCH CO), 4.50 (s, 4H, OCH CO), 4.06–4.19 (m, 8H, OCH
), 0.64–2.47 (m, 188H, CH, CH
100 MHz, CDCl ) dppm: 169.19, 168.45, 168.13, 162.94, 162.61,
2
CO), 4.55
2
2
2
1
3
and NCH
(
2
2 3
and CH ); C NMR
3
1
1
1
7
3
2
1
59.08, 155.74, 154.52, 152.61, 139.24, 133.50, 133.32, 131.98,
30.47, 130.15, 128.87, 124.86, 124.76, 123.13, 123.00, 122.15,
21.74, 121.05, 116.73, 116.07, 115.87, 115.78, 75.40, 75.03,
1.88, 66.28, 66.19, 65.27, 56.54, 56.05, 49.86, 42.43, 39.66,
9.43, 37.95, 36.88, 36.54, 36.27, 35.86, 31.85, 29.71, 28.24,
7.93, 27.73, 26.56, 25.52, 24.17, 23.85, 22.77, 22.50, 20.90,
9.41, 18.72, 11.97; MALDI-TOF-MS calcd for m/z ¼ 2812.7,
85%, respectively. Finally, by treating compound 3a(b) with
perylene imides 6 or 8 in K CO /DMF system, the triads 9a(b)
2
3
with two cholesterol units at the bay-position, and the pentads
0a(b) with four cholesterol units on both bay-position and
1
imides position were prepared in yields of 55–65% aer column
+
+
found: m/z ¼ 2812.3 (M ). HR-MS (ESI) (C
H
N O ) [M] :
1
80 238 2 24
chromatography, respectively.
1
calcd: 2813.7526. Found: 2813.7513. Compound 10b: H NMR
400 MHz, CDCl
1
13
All new compounds were characterized by H NMR,
C
(
8
6
3
) dppm: 9.64 (d, J ¼ 8.0 Hz, 2H, ArH), 8.61 (d, J ¼
.0 Hz, 2H, ArH), 8.29 (s, 2H, ArH), 7.11 (d, J ¼ 8.4 Hz, 4H, ArH),
.98 (d, J ¼ 8.4 Hz, 4H, ArH), 6.80 (s, 8H, ArH), 5.37 (bs, 4H, C]
CO and
), 3.94 (t, J ¼ 7.2 Hz, 4H,
NMR, MALDI-TOF-MS and HR-MS spectral analysis. Their mass
spectrometry spectra showed corresponding molecular ion
+
+
peaks for M or MNa . The deviations of HR-MS were less than
CH), 4.64 (bs, 4H, OCH), 4.12–4.19 (m, 8H, OCH
ArOCH ), 4.02–4.08 (m, 8H, OCH
NCH ), 0.62–2.59 (m, 204H, CH, CH
MHz, CDCl ) dppm: 169.19, 168.53, 168.23, 163.26, 162.85,
2
1
5
ppm. In the H NMR spectra, all protonic signals were well
2
2
assigned for the corresponding structures (see ESI†). Especially,
the protons of perylene core of compounds 9 and 10 showed two
symmetrical doublets and one singlet, suggesting the 1,7-bay-
1
3
2
2 3
and CH ); C NMR (100
3
1
1
1
6
3
2
1
¼
59.03, 155.93, 154.58, 152.68, 139.28, 133.60, 132.02, 130.50,
28.92, 124.86, 123.71, 123.13, 123.00, 122.15, 121.74, 121.05,
16.73, 116.10, 115.87, 115.78, 75.53, 75.03, 71.76, 66.33, 66.03,
5.20, 56.54, 56.02, 49.99, 42.43, 40.40, 39.71, 39.58, 38.00,
6.91, 35.80, 31.91, 31.85, 29.71, 28.38, 28.24, 28.03, 27.73,
7.66, 26.69, 25.57, 24.29, 23.85, 22.84, 22.50, 21.05, 19.33,
8.72, 11.87; MALDI-TOF-MS calcd for m/z ¼ 2926.0, found: m/z
13
positions of perylene skeleton. The signals of C NMR also
supported the 1,7-bay-substituents structures with two singlets
for C]O of imides. These data implied that the small quantities
of isomers or by-products (such as 1,6-dibrominated isomer in
preparing for compound 5) were removed completely by column
chromatography. All these characteristic data were in accor-
dance with the proposed structures of target compounds 9a, 9b,
+
+
2925.0 (M ). HR-MS (ESI) (C
H
N O ) [M] : calcd:
1
88 254 2 24
10a and 10b. Although compounds 5 and 7 showed the poor
2
925.8778. Found: 2925.8809.
dissolubility, the target perylene derivatives exhibited excellent
dissolubility in common organic solvents such as CH Cl ,
2
2
CHCl , toluene, THF and DMF.
3
Results and discussion
Synthesis and characterization
Mesomorphic properties
The previous reports had shown that the four bay-substituents
on perylene derivatives might destroy the p–p stacking of per- Compounds 9a, 9b, 10a and 10b were studied preliminarily by
ylene core and resulted in no liquid crystalline behaviors due to differential scanning calorimeter (DSC) to investigate their
31–33
the strong steric hindrance.
However, two bay-substituents phase transition behaviours. Compound 11 with two
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RSC Adv., 2017, 7, 4320–4328 | 4323