Synthesis of novel H-shaped chromophores

Article abstract of DOI:10.1016/j.tet.2012.02.014

A series of H-shaped chromophores with two parallel and non-conjugated D-π-A units have been synthesized, in which a 9,10-dihydroanthracene was employed as molecular backbone. The synthesis of these H-shaped chromophores 9a-11a was accomplished via an eight-step reaction, including double Claisen rearrangement, hydroboration-oxidation, Rieche formylation reaction, Knoevenagel condensation and Corey-Fuchs reaction, with a total yield about 12.5%. The corresponding mono-D-π-A unit compounds 9b-11b were also prepared in a similar procedure for the purpose of comparison. Crystal structures of three intermediates 5a, 7a and 8a were measured, which demonstrate that the two D-π-A units in a single H-shaped chromophore molecule are nearly arranged at the same direction. The studies of UV-vis spectra and the solvatochromic method indicate that the molecular second-order polarizabilities values (μβ) of H-shaped chromophores are remarkably increased compared with the corresponding mono-D-π-A unit reference compounds, without causing a large shift of the absorption band to longer wavelength.

Full text of DOI:10.1016/j.tet.2012.02.014

Tetrahedron 68 (2012) 2770e2777
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthesis of novel H-shaped chromophores
*
Jie-Ping Shi, De-Lin Wu, Yong Ding, Dong-Hua Wu, Hong-Wen Hu, Guo-Yuan Lu
Department of Chemistry, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, People’s Republic of China
a r t i c l e i n f o
a b s t r a c t
Article history:
A series of H-shaped chromophores with two parallel and non-conjugated D-p-A units have been
Received 12 October 2011
Received in revised form 21 January 2012
Accepted 7 February 2012
Available online 14 February 2012
synthesized, in which a 9,10-dihydroanthracene was employed as molecular backbone. The synthesis of
these H-shaped chromophores 9ae11a was accomplished via an eight-step reaction, including double
Claisen rearrangement, hydroborationeoxidation, Rieche formylation reaction, Knoevenagel condensa-
tion and CoreyeFuchs reaction, with a total yield about 12.5%. The corresponding mono-D-
compounds 9be11b were also prepared in a similar procedure for the purpose of comparison. Crystal
structures of three intermediates 5a, 7a and 8a were measured, which demonstrate that the two D- -A
p-A unit
Keywords:
Chromophores
D-p-A unit
H-shaped
9,10-Dihydroanthracene
Crystal structures
Synthesis
p
units in a single H-shaped chromophore molecule are nearly arranged at the same direction. The studies
of UVevis spectra and the solvatochromic method indicate that the molecular second-order polariz-
abilities values (mb) of H-shaped chromophores are remarkably increased compared with the corre-
sponding mono-D-
p
-A unit reference compounds, without causing a large shift of the absorption band to
longer wavelength.
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
second-order nonlinear optical chromophores with two non-
conjugated D-
lar hyperpolarizability (
-A unit reference compounds without red shift of the absorption
p
-A units, which exhibit much higher first molecu-
Organic and polymeric second-order nonlinear optical (NLO)
materials have attracted contemporary interest due to their large
first hyperpolarizabilities and potential possible applications in the
electrooptic devices.1 Generally, high performance electrooptic
elements, especially those for frequency doubling application, re-
quire both high nonlinearities and low optical loss (high trans-
parency). Traditional organic chromophores are organic molecules
that contain electron-donating and electron-accepting groups
b) values than the corresponding mono-D-
p
band. And we also synthesized some fluoro-containing aromatic
main-chain polyimides embedded with the H-shaped chromo-
phores, which exhibit the large macroscopic optical nonlinear
properties, good optical transparency and thermal properties.12 The
origin of the pronounced increase of the nonlinear second-order
optical response and good optical transparency of the H-shaped
chromophores have been explored with theoretical calculation by
connected via a conjugated
Generally, the first nonlinear hyperpolarizability
increases with increasing length of the conjugated
increasing strength of the donor and/or acceptor based on the two-
state model.2 Unfortunately, an increase in the
value is accom-
panied by a bathochromic shift due to a larger -conjugated length
p
system, i.e., so called D-
of a molecule
system and
p-A structure.
b
us.13,14 In comparison with the mono D-
p-A unit compound, the
p
H-shaped chromophore almost doubles the dipole moments and
hence increases the second-order polarizabilities, without a signif-
icant shift in the maximum absorption bands.13 It indicates that
this strategy may provide an opportunity for dealing with the
nonlinearity-transparency tradeoff in designing organic chromo-
phores with both high molecular second-order polarizability and
good transparency. In order to further investigate the structur-
eeproperty relationships of the H-shaped chromophores and im-
prove comprehensive properties of organic and polymeric second-
order nonlinear optical materials, we designed and synthesized
a series of novel H-shaped chromophores, which will be used in the
preparation for fluoro-containing polyimides embedded with
the H-shaped chromophores. Here we report the synthesis of
the H-shaped chromophores and their molecular second-order
polarizabilities determined by the solvatochromic method. The
synthesis of the polyimides and their macroscopic nonlinear optical
properties will be published elsewhere.
b
p
and/or stronger donor and acceptor ability. Therefore, there is al-
ways a tradeoff between nonlinearity and transparency.3,4 To re-
solve this problem, much effects have been made, such as
employing special conjugated bridge5 or using different types of
conjugation bridge combinations,6 optimizing the combination of
different donors (D) and acceptors (A)7 and employing dual (mul-
tiple) charge-transfer chromophores like octupolar,8 V-shaped,9
Y-shaped,10 and X-shaped11 molecular. However, to relieve the
nonlinearity-transparency tradeoff of the chromophores is still one
of the major challenging topics. Recently, we developed H-shaped
* Corresponding author. E-mail address: lugyuan@nju.edu.cn (G.-Y. Lu).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2012.02.014

J.-P. Shi et al. / Tetrahedron 68 (2012) 2770e2777
2771
2. Results and discussion
out with allyl chloride in anhydrous acetone in the presence of
anhydrous potassium carbonate and NaI. 1,8-Dihydroxy-2,7-diallyl-
9,10-dihydroanthracene 4a as pale yellow solid was obtained by
a double Claisen rearrangement from 3a in yield of 71.2%. The
rearrangement reaction was cleaner when heated in N,N-dime-
thylaniline at 192e194 ꢀC under a nitrogen atmosphere.16 The op-
timum heating time was about 5 h after which polymeric
impurities started to form.17 The dimethylic etheration of 1,8-
dihydroxy-2,7-diallyl-9,10-dihydroanthracene 4a was carried by
general Williamson synthesis with methyl iodide, and then trans-
formed into the dialcohol 6a via hydroborationeoxidation with
BH3/THF and NaOH/H2O2 solution.5a The conversion of this dia-
lcohol 6a into dibromide 7a was then achieved in excellent yield
(95.2%) using tetrabromomethane and triphenylphosphine.18 After
an initial attempt to perform a Vilsmeier formylation on was failed,
we found that dialdehyde 8a could be constructed by the treatment
of dibromide 7a with dichloromethyl methyl ether and titanium
tetrachloride in dichloromethane in yield of about 60%.19 The sub-
sequent Knoevenagel condensation using this dialdehyde 8a and
nitromethane in the acetic acid solution with a catalytic amount of
ammonium acetate at 80e85 ꢀC for a few hours generated H-sha-
ped chromophore 9a.19b,20 To enhance yield, the Knoevenagel
condensation of the dialdehyde and malononitrile was performed
in the presence of a catalytic amount of triphenylphosphine under
nitrogen atmosphere to afford H-shaped chromophore 10a.21
According to the condition of CoreyeFuchs reaction, dialdehyde
8a was treated with carbon tetrabromide and triphenylphosphine
under nitrogen atmosphere at 0 ꢀC to afford geminated dibromo
alkene chromophore 11a.22
2.1. Design and synthesis of H-shaped chromophores
In order to investigate the structureeproperty relationships of
the chromophores and improve comprehensive properties, the
novel H-shaped second-order nonlinear optical chromophores were
designed. Compared with previous chromophores reported by us,12
the azo bonds are replaced by carbonecarbon double bonds to en-
hance thermal stability, and two aliphatic chains with three carbons
are introduced on two sides of phenyl rings of H-shaped chromo-
phore to improve molecular pliability. Our previous work12 has
demonstrated that the largerelectron-accepting groups (substituted
phenyl groups) result in non-coplanarity of p-conjugated unit in the
H-shaped chromophores due to steric effect so as to reduce the first
molecular hyperpolarizability, therefore nitro and cyano as electron-
accepting groups are directly connected with double bonds in the
present H-shaped chromophores. According to previous work,12 the
H-shaped chromophores as dibromide are excellent intermediate
for preparing fluoro-containing polyimides embedded with the
H-shaped chromophores, so bis(3-bromopropyl) dibromide are the
goal novel H-shaped chromophores.
The synthetic pathway towards H-shaped chromophores is
outlined in Scheme 1. Compounds 3ae11a are new compounds.
O
CH2 CHCH2Cl
Zn / NaOH
H2O
NaI, CH3COCH3
K2CO3, 45
°C
O
O
OH
O
OH
OH
OH
3a
2a
1a
For the purpose of comparison, mono D-p-A chromophores
were also prepared (Scheme 2). Compounds 7be11b are new
compounds.
CH3I
NaI, CH3COCH3
N ,N-dimethylaniline
192-194
°C
OH
OH
K2CO3, 45
°C
4a
(1) BH3 / THF
(2) 30% H2O2
HO
OH
CH2 CHCH2Cl
NaI, CH3COCH3
200-205
°C
200-205
°C
O
O
O
O
O
5a
6a
CHO
O
O
OH
K2CO3, 45
°C
CHO
O
1b
2b
3b
Br
Br
Br
Br
CBr4
TiCl4
(1) BH3 / THF
(2) NaOH/H2O2
CH3I
PPh3,DCM
R.T.
O
CH3OCH2Cl2
DCM, R.T.
O
NaI, CH3COCH3
K2CO3, 45
7a
8a
OH
OCH3
°C
NO2
CH
NO2
CH
4b
5b
CHO
O
CHO
CH
CH
CBr4 / PPh3
DCM, R.T.
Br
Br
HO
OH
6b
Br
Br
Br
Br
OCH3
CH3NO2
OCH3
7b
CHO
CH3COONH4/CH3COOH
80~85
O
O
O
9a
8a
°C
TiCl4
NC CN
C
NC
CN
Br
Br
C
CH3OCH2Cl2
DCM, R.T.
CHO
CHO
CH
CH
OCH3
NO2
8b
CH
CH
CH2(CN)2
Ph3P
CHO
Br
Br
Br
Br
O
O
O
O
CH3NO2
75~80
°C
10a
Br
Br
Br
Br
8a
Br
Br
CH3COONH4/CH3COOH
Br
Br
Br
OCH3
CHO
OCH3
8b
8b
9b
80~85
°C
C
C
CHO
CHO
CH
CH
NC CN
C
CH
CBr4
Ph3P
Br
Br
Br
Br
CH2(CN)2 , CH3COONH4
Br
O
O
O
O
0
°C
microwave
Br
Br
8a
11a
OCH3
CHO
10b
OCH3
Scheme 1. Synthesis of H-shaped chromophores.
Br
C
Br
CH
1,8-Dihydroxy-9,10-dihydroanthracene 2a was prepared by the
reduction of 1,8-dihydroxyl-9,10-anthraquinone 1a with zinc
powder in an aqueous solution of sodium hydroxide, which was
previously described by our group.15 The diallylation of 1,8-
dihydroxy-9,10-dihydroanthracene 2a was conveniently carried
CBr4
Ph3P
Br
Br
0
°C
Br
Br
OCH3
8b
11b
OCH3
Scheme 2. Synthesis of mono D-p-A chromophores.

2772
J.-P. Shi et al. / Tetrahedron 68 (2012) 2770e2777
2,6-Bis(3-hydroxypropyl)anisole 6b was documented in the
literature from starting compound 2,6-bis(bromomethyl)anisole
by a multistep reaction, which was a tedious procedure.23 There-
fore, the synthetic route similar to H-shaped chromophores was
adapted (Scheme 2). 2,6-Diallylphenol 4b was prepared by twice
the allylation-Claisen rearrangement according to literature pro-
cedure17 with some modification, and then which was sequencely
etherated with methyl iodide, hydroborationeoxidation, bromi-
nation and formylation to afford 3,5-bis(3-bromopropyl)-4-
methoxybenzaldehyde 8b. The chromophores 9b and 10b con-
taining mono D-p-A unit were obtained by the condensation of 8b
with nitromethane and malononitrile, respectively. Chromophore
11b was obtained by treating 8b with carbon tetrabromide and
triphenylphosphine.
2.2. Crystal structures of compounds 5a, 7a and 8a (CCDC
826597, CCDC 818704 and CCDC 818703)24
The crystal data and structures24 refinement for compounds
5a, 7a and 8a are summarized in Table 1. Their ORTEP views are
given in Fig. 1. The molecular packing diagrams of compounds 5a,
7a and 8a in crystal cell are shown in Supplementary data (Figs.
S69eS71).
It is found that the two non-conjugated D-p-A units (phenyl
units) in compounds 5a, 7a and 8a are nearly arranged in the
same direction due to fixing action of the two methylene bridges.
The crystal structure data also indicate that all atoms in each
D-p-A unit exist almost in a same plane. The planes of the two
non-conjugated phenyl units in compounds 5a, 7a and 8a make
a dihedral angle of 3.12ꢀ, 2.52ꢀ and 2.75ꢀ, respectively. Similarly,
the shortest distance (R) between two p-conjugated phenyl units
ꢀ
in 5a, 7a and 8a are 2.526, 2.534 and 2.536 A, respectively. Di
Bella et al.25 reported a theoretical analysis of the NLO response
for hypothetical p-NA (p-nitroaniline) dimmer based on a two-
level model. According to their estimation, the NLO response
Fig. 1. ORTEP views of compounds 5a, 7a and 8a.
2.3. UVevis spectra and the molecular second-order
would have a sharp increase, when two D-p-A units of a hypo-
polarizabilities of chromophores
thetical p-NA dimer are arranged in the same direction and the
distance between them is shorter than 3.0 A. In the present case,
ꢀ
The maximum absorption wavelength (lmax) of 9ae11a and
9be11b in THF solution were summarized in Table 2. UVevis ab-
sorption spectra of 11a and 11b in THF are shown in Fig. 2. UVevis
absorption spectra of 8ae10a and 8be10b in THF solution are
shown in Supplementary data (Figs. S67 and S68). From Table 2 and
Fig. 2, the lmax of the H-shaped chromophores (9ae11a) have not
shown obvious red-shift compared with that of the corresponding
the two D-p-A units in a single molecule are nearly arranged in
the same direction and the limited distance in the 9,10-
ꢀ
dihydroanthracene moiety is about 2.53 A from the crystal
structure data of 5a, 7a and 8a. Therefore, it implies that the
novel H-typed chromophores will exhibit large second-order
NLO responses because the close contact between two
p-conju-
gated units in a molecule induces the strong dipoleedipole in-
mono D-
p-A unit chromophores (9be11b), because two D-p-A
teraction between two D-p-A units.
Table 1
Crystal data and structures refinement for compounds 5a, 7a and 8a
5a
7a
8a
Empirical formula
Molecular mass
C
22H24O2
C22H26Br2O2
482.25
C24H26Br2O4
538.27
320.41
Temperature [K]
293(2)
0.71073
293(2)
0.71073
293(2)
ꢀ
l
[A]
Crystal system space group
Monoclinic, P21/n
8.5980(17), 90.00
16.267(3), 101.15(3)
13.035(3), 90.00
0.30ꢁ0.20ꢁ0.20
1788.7(6)
Monoclinic, P2(1)/c
9.5538(15), 90.00
7.3896(12), 92.130(3)
28.663(4), 90.00
0.32ꢁ0.28ꢁ0.24
2022.2 (6)
Monoclinic, P2(1)/c
ꢀ ꢀ
a,
b,
c,
a
b
g
[A, ]
7.6246(11), 78.804(2)
9.7269(14), 82.453(2)
15.4112(2), 89.762(2)
0.30ꢁ0.26ꢁ0.24
1111.2(3)
ꢀ ꢀ
[A, ]
ꢀ ꢀ
[A, ]
Crystal size [mm]
3
ꢀ
Volume [A ]
Z
4
4
2
Calculated density [g/cm3]
1.190
0.074
1.584
4.02
1.609
3.676
m
[mmꢂ1
]
Final R indices [I>2
R indices (all data)
s
(I)]
R1¼0.0777, wR2¼0.1711
R1¼0.0829, wR2¼0.2045
R1¼0.0847, wR2¼0.2126
R1¼0.1476, wR2¼0.2023
R1¼0.1148, wR2¼0.2174
R1¼0.0989, wR2¼0.2203

J.-P. Shi et al. / Tetrahedron 68 (2012) 2770e2777
2773
Table 2
Crystal structures of three intermediates were measured, which
demonstrate that the two D- -A units in a single H-shaped chro-
lmax and second-order polarizabilities of the chromophores
p
mophore molecule are nearly arranged at the same direction. The
studies of UVevis spectra and the solvatochromic method indicate
that the molecular second-order polarizabilities of H-shaped
chromophores are remarkably increased compared with the cor-
responding mono-D-p-A unit reference compounds, without
causing a large shift of the absorption band to longer wavelength.
Chromophores
lmax
Red shift
(nm)b
mb
mb Enhancement
(nm)a
(10ꢂ48 esu)c
per D-p-A unit
9a
9b
10a
10b
11a
11b
331.5
331.0
332.0
332.0
269.5
269.0
0.5
0.0
0.5
4150.8
1137.0
1537.5
512.9
766.4
262.0
1.8
1.5
1.5
4. Experimental section
4.1. General
a
In THF (10ꢂ5 M, 25 ꢀC).
The red shift data of a compared with b.
Based on the solvatochromic method, p-nitroaniline (p-NA) as the reference.
b
c
Melting points were determined on a Yanaco micro melting point
apparatus (uncorrected). Elemental analyses (C, H, N) were per-
formed on a VARIO EL instrument. 1H NMR and 13C NMR were
1 0
269.5
11a
269.0
11b
recorded on Bruker AM 300 (Germany), and d was given in parts per
0.8
million (relative toTMS). Mass spectrawere recorded under EI mode
on a VG-Autospec mass spectrometer and ESI mode on an LCQ
electron spray mass spectrometer (Finnigan). UVevis spectra were
recorded on a lambda 25 PerkineElmer spectrophotometer. IR
spectra were recorded on a Brucker Vector 22 spectrophotometer, in
which samples were embedded in KBr thin films. Preparative col-
umn chromatography separations were performed on G60 silica gel,
while precoated silica gel plates (GF254) were used for analytical TLC.
All the solvents were purified by standard procedures. All other
chemicals were purchased from Sigma or Aldrich. Compound 1,8-
dihydroxy-9,10-dihydroanthracene was prepared according to pre-
vious procedure described by our group.15 The single crystals were
0.6
0.4
0.2
0.0
300
400
500
600
wavelength(nm)
measured by using a Bruker SMART CCD area detector diffractom-
Fig. 2. UVevis absorption spectra of 11a and 11b (10ꢂ5 M, 25 ꢀC) in THF.
ꢀ
eter with graphite monochromated Mo K
a
(l¼0.71073 A) radiation.
units in the H-shaped chromophores are non-conjugated. Fur-
thermore, the lmax (in THF) of H-shaped chromophores are all be-
low 335 nm. So, the novel H-shaped chromophores show good
optical transparency.
4.2. Synthesis of chromophores
4.2.1. 1,8-Diallyloxy-9,10-dihydroanthracene (3a). 1,8-Dihydroxy-
9,10-dihydroanthracene (4.24 g, 0.02 mol) and allyl chloride
(10 mL, 0.12 mol) were dissolved in anhydrous acetone (120 mL),
then anhydrous potassium carbonate (22.08 g, 0.16 mol) and NaI
(0.3 g) were added. The mixture was stirred at 45 ꢀC under an at-
mosphere of dry N2 for 48 h. Then the reaction mixture was cooled
and filtered. The filtrate was evaporated to dryness under vacuum.
The residue was purified by column chromatography on silica gel
eluted with chloroform/petrol ether (v/v¼1:6) to give compound
3a (4.2 g, 14.4 mol), yield 71.9%, white solid, mp 113e114 ꢀC; 1H
Determination of the molecular second-order polarizabilities
(mb) of the chromophores was performed using the solvatochromic
method. The experimental procedure was similar to that in the lit-
erature.26 para-Nitroaniline (p-NA) was used as standard. The
second-order polarizabilities obtained by the solvatochromic
method compare well with those based on the electric field induced
second-harmonic generation (EFISH).26a,27 Therefore, the sol-
vatochromic method provides the chemist with a very useful and
simple method foranalyzingsecond-order polarizabilities of organic
molecules in chemistry laboratories.28e30 The molecular second-
order polarizabilities (mb) of the chromophores are summarized in
Table 2. It is seen from Table 2, the data of mb indicate that the mo-
lecular second-order polarizabilities of the H-shaped chromophores
9a,10a and 11a are 2.9e3.7 times that of the corresponding mono D-
NMR (CDCl3)
d
(ppm): 7.16 (t, 2H, J¼8.1 Hz, ArH), 6.89 (d, 2H,
J¼7.2 Hz, ArH), 6.75 (d, 2H, J¼8.1 Hz, ArH), 6.08e6.12 (m, 2H,
2ꢁCH]), 5.28e5.54 (m, 2H, 4ꢁ]CH2), 4.61 (d, 4H, J¼4.8 Hz,
2ꢁOeCH2e), 4.02 (s, 4H, 2ꢁAreCH2eAr); 13C NMR (CDCl3)
d
(ppm): 155.9,137.2,133.7,126.4,124.7,120.1,116.7,109.0 (CH]CH2
and aromatic C), 68.8 (OeCH2), 35.3 (CH2), 22.1 (CH2); MS (EI): m/
z¼292.2, calcd for C20H20O2 [Mþ]: 292.2. Anal. Calcd for C20H20O2:
C, 82.16; H, 6.89. Found: C, 82.29; H, 6.99%.
p
-Acompounds 9b,10b and 11b, respectively, i.e., the enhancements
of per D- -A unit from 1.5 to 1.8 are observed. Therefore, the H-
shaped chromophores exhibit much higher molecular second-order
polarizabilities than the corresponding mono-D- -A unit reference
p
p
4.2.2. 1,8-Dihydroxy-2,7-diallyl-9,10-dihydroanthracene
(4a).
compound without causing red-shift of the absorption band.
Compound 1,8-diallyloxy-9,10-dihydroanthracene 3a (2.92 g,
10 mmol) was dissolved in N,N-dimethylaniline (40 mL) and the
mixture was stirred at 192e194 ꢀC under dry N2 atmosphere for
5 h. The resulting reaction solution was cooled to room temper-
ature and then the pH was adjusted to 2e3 by adding 5 N
hydrochloric acid (90 mL). The resulting yellow suspension was
extracted with dichloromethane (2ꢁ50 mL), washed with satu-
rated solution of NaHCO3 (3ꢁ50 mL), brine (50 mL), dried over
anhydrous MgSO4, and the solvent was removed under reduced
pressure. The residue was purified by column chromatography on
silica gel eluted with chloroform/petrol ether (v/v¼3:1) to afford
4a (2.08 g, 7.12 mmol), yield 71.2%, pale yellow solid, mp
3. Conclusion
In summary, on the basis of the strategy in designing second-
order nonlinear optical chromophores with a combination of two
parallel and non-conjugated D-p-A units, novel H-shaped chro-
mophores were designed, in which the 9,10-dihydroanthracene
was employed as molecular backbone. The synthesis of a series of
H-shaped chromophores was achieved via an eight-step reaction
with a total yield about 12.5%. The corresponding mono-D-
compounds were also prepared for the purpose of comparison.
p-A unit

2774
J.-P. Shi et al. / Tetrahedron 68 (2012) 2770e2777
162e164 ꢀC; 1H NMR (D3CCOCD3)
d
(ppm): 7.34 (s, 2H, 2ꢁOH),
13.1 mmol), yield 95.2%, pale yellow solid, mp 70e71 ꢀC; 1H NMR
(D3CSOCD3)
6.93 (d, 2H, J¼7.8 Hz, ArH), 6.83 (d, 2H, J¼7.8 Hz, ArH), 5.98e6.06
(m, 2H, 2ꢁeCH]), 4.97e5.08 (m, 4H, 2ꢁ]CH2), 3.96 (s, 2H,
AreCH2eAr), 3.91 (s, 2H, AreCH2eAr), 3.43 (d, 4H, J¼6.3 Hz,
d
(ppm): 7.04 (d, 4H, J¼7.8 Hz, ArH), 7.00 (d, 2H, J¼7.8 Hz,
ArH), 3.92 (s, 2H, ArCH2Ar), 3.82 (s, 2H, ArCH2Ar), 3.75 (s, 6H,
2ꢁOeCH3), 3.52 (t, 4H, J¼6.3 Hz, 2ꢁeCH2eBr), 2.71 (t, 4H, J¼7.2 Hz,
2ꢁAreCH2e), 2.10e2.00 (m, 4H, 2ꢁeCH2e); 13C NMR (CDCl3)
2ꢁAreCH2eC]C). 13C NMR (D3CCOCD3)
d (ppm): 151.6, 137.2,
135.5, 127.3, 123.6, 122.9, 119.1, 114.6 (eCH]CH2 and aromatic C),
34.9 (CH2), 34.2 (CH2), 22.6 (CH2); MS (ESI): m/z¼291.3, calcd for
C20H20O2 [Mꢂ1]ꢂ: 291.2. Anal. Calcd for C20H20O2: C, 82.16; H,
6.89. Found: C, 82.34; H, 6.96%.
d (ppm): 155.9, 137.0, 131.1, 129.5, 128.0, 123.2 (aromatic C), 61.21
(OeCH3), 35.9 (CH2), 33.7 (CH2Br), 33.6 (CH2), 28.56 (CH2), 23.4
(CH2); MS (EI) m/z: 480.0[M]þ/482.0[Mþ2]þ/484.0[Mþ4]þ, calcd for
C22H26Br2O2: 480.0/482.0/484.0. Anal. Calcd for C22H26Br2O2: C,
54.79; H, 5.43. Found: C, 54.98; H, 5.50%.
4.2.3. 1,8-Dimethoxy-2,7-diallyl-9,10-dihydroanthracene (5a). 1,8-
Dihydroxy-2,7-diallyl-9,10-dihydroanthracene 4a (1.0 g, 3.42 mmol)
and CH3I (8 mL, 18.2 g, 128 mmol) were dissolved in anhydrous
acetone (50 mL), then anhydrous potassium carbonate (4.0 g,
29.0 mmol) and NaI (0.1 g) were added. The mixture was stirred at
45 ꢀC under dry N2 atmosphere for 48 h. The reaction mixture was
cooled to room temperature and filtered, and then filtrate was
evaporated to dryness under vacuum. The resulting residue was
purified by column chromatography on silica gel eluted with chlo-
roform/petrol ether (v/v¼1:3) to give 5a (0.986 g, 3.08 mol), yield
4.2.6. 1,8-Diformyl-3,6-bis(3-bromopropyl)-4,5-dimethoxy-9,10-
dihydroanthracene (8a). TiCl4 (18.0 mL, 0.163 mol) was dissolved in
anhydrous dichloromethane (25 mL) at about ꢂ10 ꢀC, and then the
solution of dichloromethyl methyl ether (8.7 mL, 0.1 mol) in an-
hydrous dichloromethane (12 mL) was added dropwise, followed
by a solution of 7a (4.82 g, 10 mmol) in dichloromethane (60 mL).
After stirring for 1.0 h, the mixture was warmed to room temper-
ature and then stirred for 6.0 h. The reaction solution was poured
into concentrated hydrochloric acid (8 mL) and ice-water (100 g)
and stirred for 0.5 h. The organic layer was washed with 5% NaHCO3
solution (3ꢁ50 mL), brine (50 mL), and dried over anhydrous
MgSO4. The solvent was removed under reduced pressure. The
residue was purified by column chromatography on silica gel eluted
with chloroform/petrol ether (v/v¼2:1). The product was further
purified by recrystallization from diethyl ether/dichloromethane
(v/v¼20:1) to afford 8a (3.21 g, 5.97 mmol), yield 59.7%, pale yellow
90.0%, pale yellow solid, mp 85e87 ꢀC; 1H NMR (CDCl3)
d (ppm):
7.06 (d, 2H, J¼7.8 Hz, ArH), 7.03 (d, 2H, J¼7.8 Hz, ArH), 5.94e6.08 (m,
2H, 2ꢁeCH]), 5.06e5.12 (m, 4H, 2ꢁ]CH2), 4.04 (s, 2H, ArCH2Ar),
3.91 (s, 2H, ArCH2Ar), 3.84 (s, 6H, 2ꢁOeCH3), 3.46 (d, 4H, J¼6.6 Hz,
2ꢁAreCH2); 13C NMR (CDCl3)
d (ppm): 155.5, 137.6, 136.8, 130.4,
129.3, 128.0, 123.2, 115.6 (CH]CH2 and aromatic C), 61.22 (OeCH3),
35.87 (CH2), 33.94 (CH2), 23.26 (CH2); MS (EI): m/z¼320.0, calcd for
C22H24O2 [Mþ]: 320.2; IR (KBr): 1636 (CH]CH) cmꢂ1. Anal. Calcd for
C22H24O2: C, 82.46; H, 7.55. Found: C, 82.26; H, 7.51%.
needle crystals, mp 115e117 ꢀC; 1H NMR (CDCl3)
d (ppm): 10.30 (s,
2H, 2ꢁeCHO), 7.62 (s, 2H, ArH), 4.95 (s, 2H, ArCH2Ar), 4.06 (s, 2H,
ArCH2Ar), 3.91 (s, 6H, 2ꢁOeCH3), 3.43 (t, 4H, J¼6.3 Hz,
2ꢁeCH2eBr), 2.87 (t, 4H, J¼7.2 Hz, 2ꢁAreCH2e), 2.24e2.14 (m, 4H,
4.2.4. 1,8-Dimethoxy-2,7-bis(3-hydroxypropyl)-9,10-dihydroanthracene
(6a). BH3/THF (30 mL, 1 M in THF) was added dropwise to a stirred
solution of 5a (3.84 g, 12.0 mmol) in 150 mL of dry THF at ꢂ10 ꢀC
under nitrogen. The reaction mixture was stirred for 1.0 h while
warming to room temperature and then stirred for 2.5 h. NaOH so-
lution (65 mL, 1.0 M) was added dropwise over 15 min. Then 30%
H2O2 (19 mL) was added dropwise followed by 4.0 mL of water. The
mixture was stirred at room temperature for 1.0 h, and then was
heated for 2.0 h at 40 ꢀC. A saturated NaCl solution (50 mL) was
added. The aqueous layer was extracted with ethyl acetate
(3ꢁ40 mL)andcombinedorganic layers werewashed with saturated
NaCl solution (3ꢁ40 mL) and were dried over anhydrous MgSO4. The
solvent was removed under reduced pressure. The residue was pu-
rified by column chromatography on silica gel eluted with
dichloromethane/acetone (v/v¼4:1) to give 6a (2.93 g, 8.22 mmol),
yield 68.5%, pale yellow solid, mp 141e143 ꢀC; 1H NMR (CDCl3)
2ꢁeCH2e); 13C NMR (CDCl3)
d (ppm): 191.7 (CHO); 160.3, 138.4,
133.1,130.5,132.2, 129.4 (aromatic C), 61.3 (OeCH3), 33.3 (CH2), 33.1
(CH2), 28.4 (CH2), 26.1 (CH2), 23.11 (CH2); MS (ESI) m/z: 559.1
[MþNa]þ/561.1[Mþ2þNa]þ/563.0[Mþ4þNa]þ, calcd for NaC24H26
-
Br2O4: 559.0/561.0/563.0; IR (KBr): 1691 (C]O) cmꢂ1. Anal. Calcd
for C24H26Br2O4: C, 53.55; H, 4.87. Found: C, 53.73; H, 4.95%.
4.2.7. 1,8-Dinitroethylidene-3,6-bis(3-bromopropyl)-4,5-dimethoxy
-9,10-dihydroanthracene (9a). Compound 8a (1.08 g, 2.0 mmol) was
dissolved in nitromethane (5.13 mL, 96.0 mmol), ammonium acetate
(0.31 g, 4.0 mmol) and acetic acid (20 mL) were added. The mixture
was stirred for 8.0 h at 80e85 ꢀC under nitrogen. Aftercooling, water
(30 mL) was added. The aqueous layer was extracted with
dichloromethane (3ꢁ20 mL) and combined organic layers were
washed with a saturated NaCl solution (2ꢁ20 mL) and dried over
anhydrous MgSO4. The solvent was removed under reduced pres-
sure. The residue was purified by column chromatography on silica
gel eluted with dichloromethane/petrol ether (v/v¼3:2). The prod-
uct was further purified by recrystallization from diethyl ether/
dichloromethane (v/v¼20:1) to afford 9a (0.83 g, 1.33 mmol), yield
d
(ppm): 7.05 (d, 4H, J¼7.8 Hz, ArH), 7.02 (d, 2H, J¼7.8 Hz, ArH), 4.02
(s, 2H, ArCH2Ar), 3.89 (s, 2H, ArCH2Ar), 3.85 (s, 6H, 2ꢁOeCH3), 3.58 (t,
4H, J¼6.3 Hz, 2ꢁeCH2eOH), 2.76 (t, 4H, J¼7.2 Hz, 2ꢁAreCH2e), 2.43
(br, 2H, 2ꢁeOH),1.81e1.90 (m, 4H, 2ꢁeCH2e); 13C NMR (D3CSOCD3)
d
(ppm): 155.7, 136.7, 132.6, 129.4, 127.8, 123.2 (aromatic C), 61.0
(OeCH3), 61.2 (HOeCH2), 35.5 (CH2), 34.2 (CH2), 26.1 (CH2), 23.2
(CH2); MS (ESI) m/z: 379.3 [MþNa]þ, calcd for C22H28O4 [MþNa]þ:
379.2; HRMS (ESI) m/z: 379.1887 [MþNa]þ, calcd 379.1880; 357.2073
[MþH]þ, calcd 357.2060; IR (KBr): 3281 (br, eOH) cmꢂ1. Anal. Calcd
for C22H28O4: C, 74.13; H, 7.92. Found: C, 74.24; H, 8.00%.
66.4%, yellow crystals, mp 167e169 ꢀC; 1H NMR (CDCl3)
d (ppm):
8.44 (d, 2H, J¼13.5 Hz, 2ꢁ]CHeAr), 7.51 (d, 2H, J¼13.5 Hz, 2ꢁ]
CHeNO2), 7.36 (s, 2H, ArH), 4.16 (s, 2H, ArCH2Ar), 4.08 (s, 2H,
ArCH2Ar), 3.90 (s, 6H, 2ꢁOeCH3), 3.44 (t, 4H, J¼6.3 Hz, 2ꢁeCH2eBr),
2.85 (t, 4H, J¼7.2 Hz, 2ꢁAreCH2e), 2.24e2.14 (m, 4H, 2ꢁeCH2e);
13C NMR (D3CSOCD3)
d (ppm): 158.8,138.8, 132.6,129.5, 136.7, 136.1,
4.2.5. 1,8-Dimethoxy-2,7-bis(3-bromopropyl)-9,10-dihydroanthracene
(7a). The diol compound 6a (4.91 g, 13.8 mmol) was dissolved in
anhydrous dichloromethane (100 mL) along with CBr4 (11.1 g,
33.1 mmol). The mixture was then cooled to 0 ꢀC and a dichloro-
methane solution (60 mL) of Ph3P (9.09 g, 33.1 mmol) was added
dropwise. The mixture was stirred for 40 h at room temperature, and
the solvents were removed under reduced pressure. The residue was
purified by column chromatography on silica gel eluted with
dichloromethane/petrol ether (v/v¼1:2) to give 7a (6.33 g,
128.6,124.5 (CH]CHeNO2 and aromatic C), 61.3 (O-CH3), 35.2 (CH2),
33.3 (CH2), 28.6 (CH2), 28.1 (CH2), 23.3 (CH2); MS (EI) m/z: 622.0
[Mþ]/624.0[Mþ2]þ, calcd for C26H28Br2N2O6: 622.0/624.0; IR (KBr):
1630 (CH]CH) cmꢂ1. Anal. Calcd for C26H28Br2N2O6: C, 50.02; H,
4.52; N, 4.49. Found: C, 50.11; H, 4.56; N, 4.37%.
4.2.8. 1,8-Dicyanoethylidene-3,6-bis(3-bromopropyl)-4,5-
dimethoxy-9,10-dihydroanthracene (10a). The mixture of com-
pound 8a (1.08 g, 2.0 mmol), malononitrile (1.37 g, 20.8 mmol) and

J.-P. Shi et al. / Tetrahedron 68 (2012) 2770e2777
2775
Ph3P (0.22 g, 0.8 mmol) was stirred for 8.0 h at 75e80 ꢀC under
nitrogen. After cooling, water (20 mL) was added. The aqueous
layer was extracted with dichloromethane (3ꢁ20 mL) and com-
bined organic layers were washed with a saturated NaCl solution
(2ꢁ20 mL) and were dried over anhydrous MgSO4. The solvent was
removed under reduced pressure. The residue was purified by
column chromatography on silica gel eluted with dichloromethane/
petrol ether (v/v¼2:1). The product was further purified by re-
crystallization from diethyl ether/dichloromethane (v/v¼20:1) to
afford to give 10a (0.88 g, 1.39 mmol), yield 69.5%, pale yellow
diallylanisole 5b (4.0 g, 21.3 mmol) in 150 mL of dry THF at
ꢂ10 ꢀC under nitrogen. The reaction mixture was stirred for 1.0 h
while warming to room temperature and then stirred for 2.5 h.
NaOH solution (86 mL, 1.0 M) was added dropwise over 10 min.
Then 30% H2O2 (26 mL) was added dropwise followed by 6.0 mL of
water. The mixture was stirred at room temperature for 1.0 h, and
then was heated for 2.0 h at 40 ꢀC. A saturated NaCl solution
(85 mL) was added. The aqueous layer was extracted with THF
(3ꢁ30 mL) and combined organic layers were washed with a satu-
rated NaCl solution (2ꢁ30 mL) and were dried over anhydrous
MgSO4. The solvent was removed under reduced pressure. The
residue was purified by column chromatography on silica gel eluted
with ethyl acetate/petrol ether (v/v¼2:1) to give 6b (2.1 g,
9.38 mmol) as colourless and viscous liquid, yield 44.0%; 1H NMR
crystals, mp 210e212 ꢀC; 1H NMR (CDCl3)
d
(ppm): 8.30 (s, 2H, 2ꢁ]
CHeAr), 7.89 (s, 2H, ArH), 4.09 (s, 2H, ArCH2Ar), 3.98 (s, 2H,
ArCH2Ar), 3.93 (s, 6H, 2ꢁOeCH3), 3.47 (t, 4H, J¼6.3 Hz,
2ꢁeCH2eBr), 2.90 (t, 4H, J¼7.2 Hz, 2ꢁAreCH2e), 2.26e2.17 (m, 4H,
2ꢁeCH2e); 13C NMR (CDCl3)
d
(ppm): 160.6, 155.8, 135.8, 133.3,
(CDCl3) d (ppm): 7.03e7.06 (m, 3H, ArH), 3.77 (s, 3H, OCH3), 3.58 (t,
130.1, 129.2, 125.3, 114.4, 112.8 (CH], CN and aromatic C), 84.3
(C(CN)2), 61.4 (OeCH3), 33.1 (CH2), 32.8 (CH2), 29.0 (CH2),28.2
(CH2), 23.5 (CH2); MS (EI) m/z: 632.0[Mþ]/634.0[Mþ2]þ, calcd for
C30H26Br2N4O2: 632.0/634.0; IR (KBr): 2228 (CN), 1612 (CH]CH)
cmꢂ1. Anal. Calcd for C30H26Br2N4O2: C, 56.80; H, 4.13; N, 8.83.
Found: C, 56.97; H, 4.24; N, 8.76%.
4H, J¼6.3 Hz, 2ꢁCH2OH), 2.75 (t, 4H, J¼7.2 Hz, 2ꢁAreCH2),
1.82e1.90 (m, 4H, 2ꢁeCH2e); 13C NMR (CDCl3)
d (ppm): 156.6,
134.5, 128.3, 124.8 (aromatic C), 68.6 (CH2eOH), 61.7 (OCH3), 33.6
(eCH2), 25.7 (CH2).
4.2.12. 2,6-Bis(3-bromopropyl)anisole (7b). 2,6-Bis(3-hydroxypropyl)
anisole 6b (4.0 g, 17.9 mmol) was dissolved in anhydrous dichloro-
methane (100 mL) along with CBr4 (12.2 g, 36 mmol). The mixture
was then cooled to 0 ꢀC and a dichloromethane solution (60 mL) of
Ph3P (9.55 g, 36.0 mmol) was added dropwise. The mixture was
stirred for 24 h at room temperature, and the solvent was removed
under reduced pressure. The residue was purified by column chro-
matography on silica gel eluted with ethyl acetate/petrol ether
(v/v¼1:8) to give 7b (5.52 g, 15.8 mmol) as colourless liquid, yield
4.2.9. 1,8-Dibromoethylidene-3,6-bis(3-bromopropyl)-4,5-
dimethoxy-9,10-dihydroanthracene (11a). In a 100 mL three-necked
flask, CBr4 (1.21 g, 3.64 mmol) was dissolved in CH2Cl2 (6 mL) under
nitrogen atmosphere. The solution was cooled down by ice-water
bath. A solution of PPh3 (1.91 g, 7.28 mmol) dissolved in CH2Cl2
(5 mL) was added dropwise in 10 min to afford an orange solution.
Then the reaction mixture was stirred at 0 ꢀC for 20 min. After this,
the solution of 8a (0.49 g, 0.91 mmol) dissolved in CH2Cl2 (3 mL)
was added dropwise over 5 min. The reaction mixture was stirred
at 0 ꢀC for 2.5 h. Water (20 mL) was added to the reaction mixture.
The aqueous layer was separated and extracted with CH2Cl2
(2ꢁ15 mL). The organic layers were combined and dried over
MgSO4. After the solvent was removed under reduced pressure, the
crude product was purified by flash chromatography on silica gel
eluted with dichloromethane/petrol ether (v/v¼1:2) to afford 11a
(0.31 g, 0.36 mmol) as light yellow powder, yield 40.1%; 1H NMR
88.3%; 1H NMR (CDCl3)
d (ppm): 7.00e7.10 (m, 3H, ArH), 3.78 (s, 3H,
OCH3), 3.45 (t, 4H, J¼6.6 Hz, 2ꢁCH2Br), 2.81 (t, 4H, J¼7.2 Hz,
2ꢁAreCH2), 2.14e2.24 (m, 4H, 2ꢁeCH2e); 13C NMR (CDCl3)
d (ppm):
156.8, 134.0, 128.6, 124.3 (aromatic C), 61.3 (OCH3), 33.7 (CH2), 33.5
(CH2), 28.7 (CH2); MS (EI) m/z: 348.0[Mþ]/349.9[Mþ2]þ/352.0
[Mþ4]þ, calcd for C13H18Br2O: 348.0/350.0/352.0. Anal. Calcd for
C13H18Br2O: C, 44.60; H, 5.18. Found: C, 44.75; H, 5.27%.
4.2.13. 3,5-Bis(3-bromopropyl)-4-methoxybenzaldehyde (8b). TiCl4
(4.0 mL, 36.0 mmol) was dissolved in anhydrous dichloromethane
(20 mL) at about ꢂ10 ꢀC, and then the solution of methyl dichlor-
omethyl ether (1.0 mL, 12 mmol) in anhydrous dichloromethane
(5 mL) was added dropwise, followed by a solution of 7b (3.5 g,
10.0 mmol) in dichloromethane (20 mL). After stirring for 1.0 h, the
mixture was warmed to room temperature and then stirred for
3.0 h. The reaction solution was poured into concentrated hydro-
chloric acid (5 mL) and ice-water (100 g) and stirred for 0.5 h. The
organic layer was washed with 5% NaHCO3 solution (3ꢁ20 mL),
brine (20 mL), and dried over anhydrous MgSO4. The solvent was
removed under reduced pressure. The residue was purified by
column chromatography on silica gel eluted with ethyl acetate/
petrol ether (v/v¼2:1) to afford 8b (2.2 g, 5.82 mmol) as colourless
(CDCl3)
d
(ppm): 7.57 (s, 2H, 2ꢁ]CHeAr), 7.15 (s, 2H, ArH), 4.04 (s,
2H, ArCH2Ar), 3.87 (s, 6H, 2ꢁOeCH3), 3.69 (s, 2H, ArCH2Ar), 3.44 (t,
4H, J¼6.3 Hz, 2ꢁeCH2eBr), 2.83 (t, 4H, J¼7.2 Hz, 2ꢁAreCH2e),
2.23e2.14 (m, 4H, 2ꢁeCH2e); 13C NMR (CDCl3)
d (ppm): 155.7,
136.1, 133.9, 131.3, 130.1, 129.7, 128.4 (CH], and aromatic C), 92.9
(CBr2), 61.2 (OeCH3), 33.5 (CH2), 33.4 (CH2), 30.1 (CH2), 28.3 (CH2),
23.6 (CH2), MS (EI) m/z: 845.8[Mþ2]þ/847.8[Mþ4]þ/849.8[Mþ6]þ/
851.9[Mþ8]þ, calcd for C26H26Br6O2 845.7/847.7/849.7/851.7; IR
(KBr): 1605 (CH]CH) cmꢂ1. Anal. Calcd for C26H26Br6O2: C, 36.74;
H, 3.08. Found: C, 36.84; H, 3.18%.
4.2.10. 2,6-Diallylanisole
(5b). 2,6-Diallylphenol 4b (10.0 g,
57.0 mmol) and CH3I (4.4 mL, 12.2 g, 86.0 mmol) were dissolved in
anhydrous acetone (100 mL), then anhydrous potassium carbonate
(11.8 g, 86 mmol) and NaI (0.3 g) were added. The mixture stirred at
45 ꢀC under dry N2 atmosphere for 48 h. The reaction mixture was
cooled to room temperature and filtered, and then filtrate was
evaporated to dryness under vacuum. The resulting residue was
purified by column chromatography on silica gel eluted with ethyl
acetate/petrol ether (v/v¼1:30) to give 5b (7.6 g, 40.4 mmol) as pale
liquid, yield 58.2%; 1H NMR (CDCl3)
d (ppm): 9.88 (s, 1H, CHO), 7.60
(s, 2H, ArH), 3.81 (s, 3H, OCH3), 3.43 (t, 4H, J¼6.3 Hz, 2ꢁCH2Br), 2.84
(t, 4H, J¼7.2 Hz, 2ꢁAreCH2), 2.13e2.22 (m, 4H, 2ꢁeCH2e); 13C
NMR (CDCl3)
d (ppm): 191.4 (CHO), 162.2, 135.2, 132.6, 130.2 (aro-
matic C), 61.4 (OCH3), 33.3 (CH2), 33.0 (CH2), 28.6 (CH2); MS (EI)
m/z: 375.9[Mþ]/377.9[Mþ2]þ/380.0[Mþ4]þ, calcd for C14H18Br2O2:
376.0/378.0/380.0; IR (KBr): 1693 (C]O) cmꢂ1. Anal. Calcd for
C14H18Br2O2: C, 44.47; H, 4.80. Found: C, 44.59; H, 4.87%.
yellow liquid, yield 70.9%; 1H NMR (CDCl3)
d (ppm): 7.66e7.68 (m,
3H, ArH), 5.89e6.03 (m, 2H, 2ꢁCH]), 5.08e5.18 (m, 4H, 2ꢁ]CH2),
3.81 (s, 3H, OCH3), 3.45 (d, 4H, J¼6.3 Hz, AreCH2); 13C NMR
4.2.14. 4-Nitroethylidene-2,6-bis(3-bromopropyl)anisole
(9b). Compound 8b (1.5 g, 4.0 mmol) was dissolved in nitrometh-
ane (10 mL), ammonium acetate (0.15 g, 2.0 mmol) and acetic acid
(10 mL) were added. The mixture was stirred for 5.0 h at 80e85 ꢀC
under nitrogen. After cooling, water (20 mL) was added. The
aqueous layer was extracted with dichloromethane (3ꢁ20 mL) and
(CD3COCD3)
d (ppm): 156.4, 137.6, 133.0, 128.4, 124.0, 115.1 (eCH]
CH2 and aromatic C), 60.7 (OCH3), 33.8 (AreCH2).
4.2.11. 2,6-Bis(3-hydroxypropyl)anisole (6b). BH3/THF (40 mL, 1 M
in THF) was added dropwise to
a stirred solution of 2,6-

2776
J.-P. Shi et al. / Tetrahedron 68 (2012) 2770e2777
the combined organic layers were washed with a saturated NaCl
solution (2ꢁ20 mL) and dried over anhydrous MgSO4. The solvent
was removed under reduced pressure. The residue was purified by
column chromatography on silica gel eluted with ethyl acetate/
petrol ether (v/v¼1:10) to afford 9b (0.87 g, 2.07 mmol) as viscous
dichloromethane/ethanol (v/v¼2:1), dichloromethane/n-hexane
(v/v¼1:30) and dichloromethane/ether (v/v¼1:20), respectively.
The single crystals 5, 7 and 8 were, respectively, mounted on a glass
fibre and data were collected by using a Bruker SMART CCD area
detector diffractometer with graphite monochromated Mo K
a
liquid, yield 51.8%; 1H NMR (CDCl3)
d
(ppm): 7.92 (d, 1H, J¼13.8 Hz,
(l¼0.71073 A) radiation. Cell parameters were determined and
ꢀ
AreCH]), 7.53 (d, 1H, J¼13.8 Hz, AreC]CH), 7.29 (s, 2H, ArH), 3.81
(s, 3H, OCH3), 3.44 (t, 4H, J¼6.6 Hz, 2ꢁCH2Br), 2.81 (t, 4H, J¼7.5 Hz,
2ꢁAreCH2), 2.13e2.22 (m, 4H, 2ꢁeCH2e); 13C NMR (CDCl3)
refined using the SMART software.31 Empirical absorption correc-
tions were calculated and applied by SADABS program.32 The
structures were solved by direct methods and all non-hydrogen
atoms were refined anisotropically on F2 by full-matrix least
squares using SHELXTL (Version 6.10).
d
(ppm): 160.4, 138.7, 136.4, 135.5, 129.8, 126.1 (ArCH]CH and ar-
omatic C), 61.5 (OCH3), 33.3 (CH2), 33.1 (CH2), 28.7 (CH2); MS (EI) m/
z: 419.0[Mþ]/421.0[Mþ2]þ/423.0[Mþ4]þ, calcd for C15H19Br2NO3:
419.0/421.0/423.0; IR (KBr): 1633 (CH]CH) cmꢂ1. Anal. Calcd for
C15H19Br2NO3: C, 42.78; H, 4.55; N, 3.33. Found: C, 42.91; H, 4.51; N,
3.32%.
Acknowledgements
This work was supported by the National Science Foundation
(20872061, 20774039) and National Basic Research (2007CB925103)
of P.R. China.
4.2.15. 4-Cyanoethylidene-2,6-bis(3-bromopropyl)anisole (10b). The
mixture of compound 8b (1.89 g, 5.0 mmol), malononitrile (0.33 g,
5.0 mmol) and ammonium acetate (0.38 g, 5.0 mmol) was ground
in a mortar at room temperature. Then the mixture was heated in
a 600 W microwave oven for 60 s. The reaction mixture was dis-
solved in dichloromethane (25 mL) and washed with water
(20 mL). The organic layer was separated and dried over anhydrous
MgSO4. The solvent was removed under reduced pressure. The
residue was purified by column chromatography on silica gel eluted
with ethyl acetate/dichloromethane (v/v¼1:8) to afford 10b (1.1 g,
Supplementary data
The contents of Supplementary data include the following: (A)
1H NMR, 13C NMR and MS spectra of compounds 3ae11a, IR spectra
of 5ae11a; (B) 1H NMR, 13C NMR spectra of compounds 1be11b, MS
and IR spectra of compounds 7be11b; (C) UVevis absorption
spectra of 8ae10a and 8be10b; (D) The molecular packing dia-
grams of compounds 5a, 7a and 8a in crystal cell. Supplementary
data associated with this article can be found in the online version,
at doi:10.1016/j.tet.2012.02.014. These data include MOL files and
InChIKeys of the most important compounds described in this
article.
2.58 mmol) as viscous liquid, yield 51.6%; 1H NMR (CDCl3)
d (ppm):
7.70 (s, 1H, CH]), 7.66 (s, 2H, ArH), 3.85 (s, 3H, OCH3), 3.44 (t, 4H,
J¼6.3 Hz, 2ꢁCH2Br), 2.85 (t, 4H, J¼7.2 Hz, 2ꢁAreCH2), 2.16e2.21
(m, 4H, 2ꢁCH2); 13C NMR (CDCl3)
d (ppm): 162.5, 159.2, 136.0, 131.5,
127.2, 114.0, 113.0 (CN, ArCH] and aromatic C), 81.2 (C(CN)2), 61.6
(OCH3), 33.1 (CH2), 32.8 (ArCH2), 28.6 (CH2); MS (EI) m/z: 424.0
[Mþ]/426.0[Mþ2]þ/428.0[Mþ4]þ, calcd for C17H18Br2N2O: 424.0/
426.0/428.0; IR (KBr): 2227 (CN), 1588 (CH]CH) cmꢂ1. Anal. Calcd
for C17H18Br2N2O: C, 47.91; H, 4.26; N, 6.57. Found: C, 48.07; H, 4.34;
N, 6.43%.
References and notes
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