Synthesis of substituted naphthalenes from α-substituted ketones and 1,2-bis(halomethyl)benzenes including a rearrangement aromatization of benzo[c]oxepine

Article abstract of DOI:10.1016/j.tet.2014.01.005

An efficient and practical method for the synthesis of cyano, sulfonyl and phosphoryl substituted naphthalene derivatives via the rearrangement aromatization of benzo[c]oxepine has been developed. The system holds the advantages of metal catalysts free, and mild reaction conditions.

Full text of DOI:10.1016/j.tet.2014.01.005

Tetrahedron 70 (2014) 1412e1417
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Synthesis of substituted naphthalenes from -substituted ketones
a
and 1,2-bis(halomethyl)benzenes including a rearrangement
aromatization of benzo[c]oxepine
*
Jungang Wang, Jiachen Xiang, Miao Wang, Jie Guan, Anxin Wu
Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
An efficient and practical method for the synthesis of cyano, sulfonyl and phosphoryl substituted
naphthalene derivatives via the rearrangement aromatization of benzo[c]oxepine has been developed.
The system holds the advantages of metal catalysts free, and mild reaction conditions.
Ó 2014 Elsevier Ltd. All rights reserved.
Received 13 November 2013
Received in revised form 24 December 2013
Accepted 3 January 2014
Available online 9 January 2014
Keywords:
Naphthalenes
Rearrangement
Benzo[c]oxepine
a
-Substituted ketones
1. Introduction
intermediate benzo[c]oxepine. However, the other carbonyl
group only functioned as an electron-withdrawing group. It was
Substituted naphthalenes are important building blocks in bi-
ologically active molecules,1 polycyclic aromatic electronic mate-
rials2 and chiral ligands in organic synthesis.3 The construction of
these privileged structural motifs contained two major strategies:
(i) the introduction of functional groups onto a naphthalene nu-
cleus and (ii) the assembly of naphthalene ring from benzene
precursor. Evidently, the annulation strategy is preferable since
high region selectivity (and yields) can be achieved from simple
and commercially available reagents.4 Much recent work has fo-
cused on efficient strategies for the construction of various
substituted naphthalenes.5 However, to the best of our knowledge,
there have been few reports of annulation strategies for the syn-
thesis of beta-site cyano,6 sulfonyl7 and phosphoryl8 substituted
naphthalene derivatives.
thus supposed that the conversion could be achieved through
other electron withdrawing groups, such as nitro, cyano, sulfo-
nyl, phosphoryl to obtain various
b-substituted naphthalenes.
Herein, the detailed research results from this conversion are
presented.
Scheme 1. Construction of naphthalenes via rearrangement aromatization of benzo[c]
oxepine intermediate.
In our recent reports,9 we proposed a novel rearrangement
aromatization of benzo[c]oxepine and established a simple, ef-
2. Results and discussion
ficient method for the preparation of
b-substituted naphtha-
lenes from 1,3-dicarbonyl compounds and 1,2-bis(halomethyl)
benzene compounds as substrates (Scheme 1). The proposed
reaction mechanism suggested that carbonyl was essential for
enolation during the conversion to form the important
To construct various substituted naphthalenes, an initial study
using a-cyanoacetophenone and 1,2-bis(bromomethyl)benzene as
reactants was performed with Cs2CO3 in DMSO at 80 ꢀC for 4 h,
which gave an 80% yield of the naphthalene-based product. Other
bases, such as K2CO3, KOH, Na2CO3, t-BuOK, Et3N and DBU were
seen to provide lower yields (Table 1, entries 2e7). Interestingly, the
conversion was also achieved in low yields using acids, such as
* Corresponding author. Tel./fax: þ86 027 6786 7773; e-mail address: chwuax@
mail.ccnu.edu.cn (A. Wu).
0040-4020/$ e see front matter Ó 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2014.01.005

J. Wang et al. / Tetrahedron 70 (2014) 1412e1417
1413
CH3COOH and Lewis acid ZnCl2 (Table 1, entries 9 and 10). More-
over, the desired product was obtained in DMF and EtOH in mod-
erate yields (Table 1, entries 11 and 12). Other solvents, such as THF,
CH3CN, CHCl3 and H2O were identified as unsuitable for the
transformation (Table 1, entries 13e16). The molar ratio and the
reaction temperature were then optimized to increase the product
yield but with no success (Table 1, entries 16e22). Ultimately, op-
timal conditions were identified as 1 equiv of 1,2-bis(bromomethyl)
benzene (1a), 1 equiv of a-cyanoacetophenone (2a) and 3 equiv of
Cs2CO3 in DMSO at 80 ꢀC (Table 1, entry 1).
Table 1
Optimization of the reaction conditionsa
Entry
Solvent
Base
(equiv)
Molar
ratio
Temp
(ꢀC)
Yieldb
(%)
1
2
3
4
5
6
7
8
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
Cs2CO3
K2CO3
KOH
Na2CO3
t-BuOK
Et3N
DBU
HCl
CH3COOH
ZnCl2
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:0.5
1:2
1:1
1:1
1:1
1:1
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
80
40
120
80
80
82
40
33
<5
<5
<5
<5
<5
12
26
72
52
<5
<5
<5
<5
78
82
23
82
78
<5
Scheme 2. Scope of
a-cyanoacetophenone compounds and 1,2-bis-(halomethyl)ben-
zene compounds.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
EtOH
THF
CH3CN
CHCl3
H2O
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
c
Cs2CO3
d
Cs2CO3
Fig. 1. X-ray crystal structure of compound 3aa.
The bold entries signifies the optimum condition.
a
Reaction conditions: 1a (0.2 mmol), 2a (0.2 mmol), solvent (2 mL). The reaction
Following our success in the construction of cyano-substituted
naphthalenes, the synthesis of other substituted naphthalene
was performed for 4 h.
b
Isolated yields.
Cs2CO3 (2.0 equiv).
Cs2CO3 (1.0 equiv).
c
compounds were next examined.
substituted ketones were selected to react with 1,4-dibromo-2,3-
bis(bromomethyl)benzene, and 1,2-bis(chloromethyl)-4,5-
a-Sulfonyl, phosphoryl, nitro
d
dimethyl benzene. To our delight, 1,4-dibromo-6-methyl-7-
(methylsulfonyl)naphthalene (Scheme 3, 3ch, 43%), 1,4-dibromo-6-
phenyl-7-(phenylsulfonyl)naphthalene (Scheme 3, 3ci, 68%) and
diethyl (5,8-dibromo-3-phenylnaphthalen-2-yl) phosphonate
(Scheme 3, 3cj, 26%) were successfully obtained in low to moderate
yields. Fortunately, the structures of 3ci and 3cj were confirmed by
With the optimized conditions in hand, the scope of the reaction
was then evaluated using a wide range of a-cyanoacetophenone and
1,2-bis(halomethyl) benzene compounds (Scheme 2). The desired
naphthalene products 3 were formed successfully in good to excellent
yields in all cases. Different benzyl halides, such as 1,2-
bis(chloromethyl)benzene, 1,2-bis(bromomethyl)benzene and 1,2-
bis(iodomethyl)benzene obtained the naphthalene-based product
3aa in 68%, 82% and 86% yields, respectively. Fortunately, the structure
of 3aa was confirmed by X-ray diffraction (Fig. 1). When different
substituents were attached to the aromatic rings of the 1,2-
X-ray diffraction10
.
bis(halomethyl)benzene and the a-cyanoacetophenone, the reaction
gave the corresponding naphthalene-based products in moderate to
good yields. In addition, the substrates containing sterically hindered
naphthyl ring and heterocycles (furan, thiophene) also delivered the
aromatic products in satisfactory yields (Scheme 2, 3be, 3ce, 3cf, 3cg,
62e76%). Much to our satisfaction, 2,3-bis(bromomethyl)quinoxaline
also took place smoothly to furnish substituted phenazines in mod-
erate yield (Scheme 2, 3fa, 3fe). Regretfully, 1,2-bis(bromomethyl)-4-
nitrobenzene, 2,20-bis(bromomethyl)-1,10-biphenyl and 3-(1-methyl-
1H-indol-3-yl)-3-oxopropanenitrile could not produce the desired
products (see Supplementary data).
Scheme 3. Scope of a-substituted ketones.
To gain some insight into the mechanism of the reaction, the
following experiments were performed (Scheme 4). First, 1,2-

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J. Wang et al. / Tetrahedron 70 (2014) 1412e1417
bis(bromomethyl)benzene (1a) was reacted with 3-oxo-3-
phenylpropanenitrile (2a) and Cs2CO3 in DMSO at 40 ꢀC. The re-
action was monitored by TLC and stopped after 30 min to obtained
2-benzoyl-2,3-dihydro-1H-indene-2-carbonitrile (5aa) and 3-
phenyl-1,5-dihydrobenzo[c]oxepine-4-carbonitrile (4aa) (Scheme
4a). When benzo[c]oxepine 4aa was treated with Cs2CO3 in
DMSO at 80 ꢀC, the aromatic product 3aa was obtained in good
yield after 30 min (96%, Scheme 4b). However, when the by-
product indene 5aa was treated under the same conditions, the
aromatic product 3aa was not observed in the experiment (Scheme
4c). Moreover, there was no indication that the seven-membered
ring 4aa and the five-membered ring 5aa interconverted under
the reaction conditions (Scheme 4d) (Fig. 2).
To explore the potential applications of the b-substituted
naphthalene derivatives, the privileged structures were exploited
in transformations to access various frameworks with high degrees
of molecular complexity. Following the literature method,16 the
naphthalene rings we constructed would be converted to benzo-
fluorenones (Scheme 6), which were important basic core of bio-
active substances and widespread occurrence in many functional
molecules.17
Scheme 6. Synthesis of 11H-benzo[b]fluorenone from 3-phenyl-2-naphthonitrile
(3aa) and ethyl 3-phenyl-2-naphthoate.
3. Conclusion
In summary, an efficient method has been proposed for the
construction of
b-substituted cyano, sulfonyl and phosphoryl
naphthalenes from simple and commercially available reagents.
The success of this transformation was mainly attributed to the
rearrangement of benzo[c]oxepine. Further investigations into the
detailed mechanism and synthetic applications of this reaction are
currently underway in our laboratory.
4. Experimental
4.1. General
Scheme 4. The controlled experiments to prove the mechanism.
1,4-Dibromo-2,3-bis(bromomethyl)benzene,12 1,2-bis(chloro-
methyl)-4,5-dimethylbenzene,13 1,2-bis(bromomethyl)-4,5-dimet
hoxybenzene14 and 1,2-bis(iodomethyl)benzene15 were prepared
according to the literature procedures. Other substrates and re-
agents were commercially available and used without further
purification. TLC analysis was performed using pre-coated glass
plates. Column chromatography was performed using silica gel
(200e300 mesh). IR spectra were recorded on a PerkineElmer PE-
983 infrared spectrometer as KBr pellets with absorption in cmꢁ1
1H spectra were recorded in CDCl3 or DMSO on 400/600 MHz NMR
spectrometers and resonances ( ) are given in parts per million
relative to tetramethylsilane. Data are reported as follows:
chemical shift, multiplicity (s¼singlet, d¼doublet, t¼triplet,
m¼multiplet), coupling constants (Hertz) and integration. 13C
spectra were recorded in CDCl3 or DMSO on 100 MHz NMR
.
d
Fig. 2. X-ray crystal structure of compound 4aa.
On the basis of the aforementioned results described above and
in the literature,9,11 a plausible mechanism of this reaction is pro-
posed as illustrated in Scheme 5. First, the C-alkylation of com-
spectrometers and resonances (d) are given in ppm. HRMS were
pound
1 provided intermediate 6, which appeared in two
obtained on a Bruker 7-tesla FT-ICR MS equipped with an elec-
trospray source. MS was carried out on a Finnigan Trace MS
spectrometer (EI, 70 eV). The X-ray crystal structure de-
terminations of 3aa, 3ci, 3cj and 4aa were obtained on a Bruker
SMART APEX CCD system. Melting points were determined using
XT-4 apparatus and not corrected.
tautomeric forms: 6a and 6b. The subsequent O-alkylation of enolic
formed 6a and presented as the seven-membered ring 4. Mean-
while, the competing C-alkylation yielded the five-membered ring
5 as a by-product. Finally, rearrangement of 4 followed by aroma-
tization in the presence of Cs2CO3 afforded the desired
naphthalene-based product 3.
4.2. General procedure for synthesis of 3 (3aa as an example)
A mixture of 1,2-bis(bromomethyl)benzene (1.0 mmol), a-cya-
noacetophenone (1.0 mmol) and Cs2CO3 (3.0 mmol) in DMSO
(5 mL) was stirred at 80 ꢀC for 4 h till almost full conversion of the
substrates by TLC analysis. The resulting mixture was dropped into
100 mL 1 M HCl (aq) and extracted with EtOAc three times
(3ꢂ50 mL). The organic extract was dried with Na2SO4, filtered and
concentrated. The crude product was purified by column chroma-
tography on silica gel (eluent: petroleum ether/EtOAc¼50/1) to
afford the product 3aa as a white solid.
Scheme 5. The plausible mechanism of the present reaction.

J. Wang et al. / Tetrahedron 70 (2014) 1412e1417
1415
4.3. Characterization data
136.8, 136.2, 134.8, 133.8, 130.2, 130.0, 129.9, 127.8, 127.5, 127.3,
126.4, 119.4, 108.5, 20.5, 20.2, 19.9, 19.5. HRMS (ESI): m/z [MþH]þ
calcd for C21H19N: 286.1592; found: 286.1590.
4.3.1. 3-Phenyl-2-naphthonitrile (3aa). Yield 65% (X¼Cl), 82%
(X¼Br), 86% (X¼I); white solid; mp 161.0e162.2 ꢀC; IR (KBr): 3053,
2222, 1587, 1488, 1154, 891, 798, 751, 704, 474 cmꢁ1
;
1H NMR
4.3.8. 3-(3,4-Dichlorophenyl)-6,7-dimethyl-2-naphthonitrile
(3bd). Yield 74% (239.4 mg); pale yellow solid; mp 249.1e249.9 ꢀC;
IR (KBr): 3061, 2222, 1475, 1377, 1134, 1026, 902, 819, 477 cmꢁ1. 1H
(600 MHz, CDCl3)
d
(ppm) 8.32 (s, 1H), 7.90 (s, 1H), 7.88 (t, J¼7.2 Hz,
2H), 7.63 (t, J¼7.8 Hz, 3H), 7.58 (t, J¼7.8 Hz, 1H), 7.50 (t, J¼7.8 Hz,
2H), 7.45 (t, J¼7.8 Hz, 1H). 13C NMR (100 MHz, CDCl3)
d
139.6, 138.2,
NMR (600 MHz, CDCl3)
(s, 1H), 7.66 (s, 1H), 7.58 (d, J¼7.8 Hz, 1H), 7.49 (d, J¼7.8 Hz, 1H), 2.48
(s, 6H). 13C NMR (100 MHz, CDCl3)
140.3, 138.6, 138.3, 136.3, 135.1,
d 8.23 (s, 1H), 7.77 (s, 1H), 7.70 (s, 1H), 7.67
135.8, 134.7, 131.1, 129.3, 129.1, 128.9, 128.6, 128.4, 128.0, 127.9,
127.45, 118.8, 109.4. HRMS (ESI): m/z [MþH]þ calcd for C17H12N:
230.0967; found: 230.0964.
d
133.7, 132.9, 132.8, 130.9, 130.6, 128.4, 128.2, 127.7, 127.5, 118.7,
108.0, 20.4, 20.2. HRMS (ESI): m/z [MþNa]þ calcd for C19H13Cl2NNa:
348.0318; found: 348.0317.
4.3.2. 3-(4-Bromophenyl)-2-naphthonitrile
(3ab). Yield
54%
(167.8 mg); white solid; mp 204.2e205.2 ꢀC; IR (KBr): 2217, 1489,
1104, 1009, 907, 898, 835, 819, 750, 473 cmꢁ1. 1H NMR (400 MHz,
4.3.9. 60,70-Dimethyl-[1,20-binaphthalene]-30-carbonitrile
(3be).-
CDCl3)
d
8.37 (s, 1H), 7.94e7.87 (m, 3H), 7.70e7.61 (m, 4H), 7.52 (d,
Yield 62% (190.4 mg); pale yellow solid; mp 153.5e154.2 ꢀC; IR
J¼8.0 Hz, 2H). 13C NMR (100 MHz, CDCl3)
d
138.3, 137.1, 136.0, 134.7,
(KBr): 2972, 2217, 1588, 1491, 1447, 1376, 1025, 926, 896, 775,
131.9, 131.3, 130.6,129.6,129.0,128.1, 127.8, 123.0, 119.1, 109.1. HRMS
(APCI): m/z [MþH]þ calcd for C17H11BrN: 308.0070; found:
308.0069.
480 cmꢁ1. 1H NMR (600 MHz, CDCl3)
d
8.22 (s, 1H), 7.90 (t, J¼7.8 Hz,
2H), 7.76 (s, 1H), 7.65 (s, 1H), 7.58 (t, J¼9.0 Hz, 2H), 7.53 (t, J¼7.8 Hz,
1H), 7.49 (d, J¼7.2 Hz, 1H), 7.46 (d, J¼7.2 Hz, 1H), 7.39e7.36 (m, 1H),
2.43 (s, 3H), 2.42 (s, 3H). 13C NMR (100 MHz, CDCl3)
d 139.9, 137.8,
4.3.3. 3-(4-Bromophenyl)-2-naphthonitrile3-(3,4-dimethylphenyl)-
2-naphthonitrile (3ac). Yield 85% (218.4 mg); white solid; mp
177.8e179.3 ꢀC; IR (KBr): 3052, 2912, 2221, 1725, 1448, 1273, 1151,
137.3, 136.2, 134.1, 133.6, 133.3, 131.9, 130.3, 129.4, 128.8, 128.4, 127.8,
127.5, 127.4, 126.4, 125.9, 125.4, 125.1, 118.6, 110.3, 20.4, 20.2. HRMS
(ESI): m/z [MþH]þ calcd for C23H18N: 308.1434; found: 308.1434.
894, 827, 751, 477 cmꢁ1. 1H NMR (600 MHz, CDCl3)
d 8.34 (s, 1H),
7.91 (s, 2H), 7.91e7.89 (m, 3H), 7.65 (t, J¼7.8 Hz, 1H), 7.59 (t,
4.3.10. 5,8-Dibromo-3-phenyl-2-naphthonitrile (3ca). Yield 73%
(281.1 mg); white solid; mp 200.9e201.5 ꢀC; IR (KBr): 2922, 2224,
1444, 1133, 1002, 994, 911, 763, 696, 481 cmꢁ1. 1H NMR (600 MHz,
J¼7.2 Hz, 1H), 7.41 (s, 1H), 7.39 (d, J¼7.8 Hz, 1H), 7.28 (d, J¼7.8 Hz,
1H), 2.37 (s, 3H), 2.35 (s, 3H). 13C NMR (100 MHz, CDCl3)
d 139.7,
136.9,135.7, 130.9, 130.0, 129.8,129.1, 128.7, 127.9, 127.8, 127.1, 126.3,
118.9, 109.5, 19.7, 19.4. HRMS (ESI): m/z [MþH]þ calcd for C19H16N:
258.1278; found: 258.1277.
CDCl3)
d
8.77 (s, 1H), 8.35 (s, 1H), 7.79 (d, J¼7.8 Hz, 1H), 7.73 (d,
J¼7.8 Hz, 1H), 7.68 (d, J¼7.8 Hz, 2H), 7.56 (t, J¼7.2 Hz, 2H), 7.52 (t,
J¼7.2 Hz, 1H). 13C NMR (100 MHz, CDCl3)
d 142.1, 137.3, 135.8, 134.3,
133.3,131.5, 131.1, 129.2, 129.1, 128.9,122.5, 118.0,112.1. HRMS (APCI):
4.3.4. 3-(3,4-Dichlorophenyl)-2-naphthonitrile (3ad). Yield 71%
(210.9 mg); white grey solid; mp 198.3e199.2 ꢀC; IR (KBr): 3060,
m/z [MþH]þ calcd for C17H10Br2N: 358.9171; found: 358.9175.
2222, 1479, 1454, 1133, 1028, 892, 813, 742, 472 cmꢁ1
.
1H NMR
4.3.11. 5,8-Dibromo-3-(3,4-dimethylphenyl)-2-naphthonitrile
(3cc). Yield 88% (362.5 mg); white solid; mp 231.6e233.2 ꢀC; IR
(KBr): 2916, 2226, 1504, 1310, 1176, 990, 924, 888, 873, 817,
(400 MHz, CDCl3) d 8.35 (s, 1H), 7.92 (s, 1H), 7.90 (s, 2H), 7.70 (s, 2H),
7.64 (s, 1H), 7.58 (d, J¼7.8 Hz, 1H), 7.49 (d, J¼6.6 Hz, 1H). 13C NMR
(100 MHz, CDCl3)
d
138.1, 137.0, 136.1, 134.6, 132.9, 131.5, 130.8,
429 cmꢁ1. 1H NMR (600 MHz, CDCl3)
d 8.74 (s, 1H), 8.32 (s, 1H), 7.77
130.7, 129.8, 129.2, 128.3, 128.2, 128.1, 128.1, 118.4, 109.0. HRMS
(ESI): m/z [MþNa]þ calcd for C17H9Cl2NNa: 320.000576; found:
320.0004.
(d, J¼7.2 Hz, 1H), 7.71 (d, J¼7.8 Hz, 1H), 7.43e7.41 (m, 2H), 7.32 (d,
J¼7.2 Hz, 1H), 2.39 (s, 3H), 2.36 (s, 3H). 13C NMR (100 MHz, CDCl3)
d
142.3, 137.8, 137.2, 135.6, 134.9, 134.3, 133.2, 131.2, 131.0, 130.2,
128.9, 126.5, 122.4, 118.1, 112.2, 19.8, 19.6. HRMS (ESI): m/z [MþNa]þ
4.3.5. 6,7-Dimethyl-3-phenyl-2-naphthonitrile (3ba). Yield 72%
(185.1 mg); white solid; mp 138.3e139.9 ꢀC; IR (KBr): 2979, 2218,
1596, 1451, 917, 903, 763, 702, 478 cmꢁ1. 1H NMR (600 MHz, CDCl3)
calcd for C19H13Br2NNa: 435.93052; found: 435.93070.
4.3.12. 50,80-Dibromo-[1,20-binaphthalene]-30-carbonitrile
Yield 76% (330.7 mg); pale yellow solid; mp 159.4e162.2 ꢀC; IR
(KBr): 2922, 2225, 1578, 1266, 1088, 962, 906, 799, 772 cmꢁ1 1H
NMR (600 MHz, CDCl3)
(3ce).-
d
8.16 (s, 1H), 7.76 (s, 1H), 7.61e7.60 (m, 4H), 7.49 (t, J¼7.2 Hz, 2H),
7.43 (t, J¼7.2 Hz, 1H), 2.43 (s, 6H). 13C NMR (100 MHz, CDCl3)
.
d
139.8, 138.6, 138.5, 137.6, 134.8, 133.6, 130.0, 128.9, 128.5, 128.1,
d
8.83 (d, J¼2.3 Hz, 1H), 8.41 (t, J¼9.1 Hz,
127.9, 127.4, 127.2, 119.2, 108.2, 20.4, 20.1. HRMS (ESI): m/z [MþH]þ
1H), 8.01 (d, J¼7.9 Hz, 1H), 7.97 (d, J¼8.0 Hz, 1H), 7.81 (t, J¼7.8 Hz,
calcd for C19H16N: 258.1280; found: 258.1277.
1H), 7.78e7.77 (m, 1H), 7.62 (t, J¼6.0 Hz, 1H), 7.56e7.53 (m, 3H),
7.46 (d, J¼7.2 Hz, 1H). 13C NMR (100 MHz, CDCl3)
d 141.0, 134.9,
4.3.6. 3-(4-Bromophenyl)-6,7-dimethyl-2-naphthonitrile
(3bb). Yield 58% (195.7 mg); white solid; mp 151.1e152.2 ꢀC; IR
(KBr): 2970, 2215, 1633, 1485, 1450, 1070, 1006, 915, 828, 813,
134.1,133.6,133.4,131.6,131.6,131.4,130.6,129.6,128.6,127.9,126.9,
126.3, 125.2, 125.0, 122.6, 122.5, 117.4, 114.2. HRMS (APCI): m/z
[MþNa]þ calcd for C21H11Br2NNa: 457.9158; found: 457.9151.
481 cmꢁ1 1H NMR (400 MHz, CDCl3)
. d 8.16 (s, 1H), 7.72 (s, 1H),
7.60e7.58 (m, 4H), 7.44 (d, J¼8.0 Hz, 2H), 2.44 (s, 6H). 13C NMR
4.3.13. 5,8-Dibromo-3-(furan-2-yl)-2-naphthonitrile
72% (270.7 mg); white grey solid; mp 204.2e206.7 ꢀC; IR (KBr):
3446, 2227, 1662, 1495, 1030, 1002, 905, 736 cmꢁ1 1H NMR
(3cf). Yield
(100 MHz, CDCl3)
d 140.1, 137.9, 137.4, 134.9, 133.6, 131.7, 130.5,
130.2,127.9, 127.5, 127.3, 122.7, 119.0, 107.8, 20.4, 20.2. HRMS (APCI):
.
m/z [MþH]þ calcd for C19H15BrN: 336.0383; found: 336.0382.
(400 MHz, CDCl3)
d
8.65 (s, 2H), 7.74 (d, J¼8.0 Hz,1H), 7.66e7.64 (m,
2H), 7.47 (d, J¼5.4 Hz, 1H), 6.63e6.62 (m, 1H). 13C NMR (100 MHz,
4.3.7. 3-(3,4-Dimethylphenyl)-6,7-dimethyl-2-naphthonitrile
(3bc). Yield 76% (216.6 mg); white solid; mp 176.4e177.7 ꢀC; IR
(KBr): 2915, 2218, 1494, 1450, 1377, 1029, 905, 82, 724, 448 cmꢁ1. 1H
CDCl3) d 149.0, 144.0, 136.2, 134.2, 133.4, 131.2, 130.3, 129.4, 124.5,
122.5, 122.4, 118.3, 112.5, 111.4, 107.6. HRMS (APCI): m/z [MþH]þ
calcd for C15H8Br2NO: 375.8970; found: 375.8967.
NMR (600 MHz, CDCl3)
1H), 7.36 (d, J¼7.8 Hz,1H), 7.25 (d, J¼5.4 Hz,1H), 2.44 (s, 6H), 2.35 (s,
3H), 2.33 (s, 3H). 13C NMR (100 MHz, CDCl3)
139.7, 139.0, 137.4,
d 8.17 (s,1H), 7.75 (s,1H), 7.61 (s, 2H), 7.38 (s,
4.3.14. 5,8-Dibromo-3-(thiophen-2-yl)-2-naphthonitrile (3cg). Yield
74% (290.1 mg); pale yellow solid; mp 205.4e207.9 ꢀC; IR (KBr):
d

1416
J. Wang et al. / Tetrahedron 70 (2014) 1412e1417
3441, 2923, 2227,1652,1179, 961, 895, 698 cmꢁ1. 1H NMR (600 MHz,
CDCl3) 8.71 (s, 1H), 8.43 (s, 1H), 7.79e7.71 (m, 2H), 7.69 (d,
J¼7.8 Hz, 1H), 7.51 (s, 1H), 7.22 (s, 1H). 13C NMR (100 MHz, CDCl3)
2224,1590,1498,1394,1127, 906, 760, 555 cmꢁ1. 1H NMR (400 MHz,
CDCl3)
8.85 (s, 1H), 8.42 (s, 1H), 8.32 (t, J¼7.8 Hz, 1H), 8.28 (t,
J¼7.8 Hz, 1H), 8.04e7.95 (m, 4H), 7.66e7.63 (m, 3H), 7.58e7.54 (m,
1H), 7.49e7.45 (m, 1H). 13C NMR (100 MHz, CDCl3)
145.0, 144.5,
143.6, 141.8, 141.2, 137.4, 134.7, 133.6, 132.4, 132.2, 131.7, 131.4, 130.2,
129.8, 128.6, 127.9, 126.9, 126.4, 125.2, 125.0, 117.1, 116.5. HRMS
(ESI): m/z [MþH]þ calcd for C23H14N3: 332.1183; found: 332.1182.
d
d
d
138.5, 136.3, 134.2, 133.5, 131.5, 130.8, 128.5, 128.5, 128.3, 128.0,
d
122.4, 122.3, 118.1, 110.8. HRMS (APCI): m/z [MþH]þ calcd for
C
15H8Br2NS: 391.8739; found: 391.8739.
4.3.15. 1,4-Dibromo-6-methyl-7-(methylsulfonyl)naphthalene
(3ch). Yield 43% 162.5 mg; white solid; mp 192.3e193.0 ꢀC; IR
(KBr): 3465, 2929, 1579, 1457, 1305, 1293, 1169, 1134, 1029, 765,
4.3.22. 3-Phenyl-1,5-dihydrobenzo[c]oxepine-4-carbonitrile
(4aa). Yield 82% (202.9 mg); pale yellow solid; mp 125.3e126.7 ꢀC;
IR (KBr): 3030, 2888, 2194, 1607, 1592, 1301, 1268, 1254, 1128, 960,
486 cmꢁ1. 1H NMR (600 MHz, CDCl3)
d 9.02 (s, 1H), 8.20 (s, 1H), 7.77
(d, J¼8.0 Hz, 1H), 7.69 (d, J¼8.0 Hz, 1H), 3.19 (s, 3H), 2.92 (s, 3H). 13
C
784, 769, 755 cmꢁ1. 1H NMR (600 MHz, CDCl3)
d
7.58 (d, J¼8.4 Hz,
1H), 7.40e7.35 (m, 4H), 7.33e7.31 (m, 1H), 7.28 (d, J¼7.2 Hz, 1H),
5.39 (s, 2H), 3.93 (s, 2H). 13C NMR (100 MHz, CDCl3)
168.2, 138.9,
NMR (100 MHz, CDCl3)
d 139.2, 134.8, 134.7, 133.1, 131.4, 130.9,
130.6, 123.6, 121.2, 109.7, 43.7, 20.5. HRMS (APCI): m/z [MþH]þ
d
calcd for C12H11 Br2O2S: 376.8847; found: 376.8841.
135.0, 134.4, 130.3, 129.5, 128.6, 128.4, 128.2, 127.9, 127.6, 121.7, 83.9,
71.7, 34.2. HRMS (ESI): m/z [MþH]þ calcd for C17H14NO: 248.10670;
found: 248.1070.
4.3.16. 1,4-Dibromo-6-phenyl-7-(phenylsulfonyl)naphthalene
(3ci). Brown solid (yield 68%); mp 233.1.3e237.6 ꢀC; IR (KBr): 3448,
2982, 1723, 1389, 1236, 1052, 1021, 959, 766, 538 cmꢁ1
.
1H NMR
4.3.23. 2-Benzoyl-2,3-dihydro-1H-indene-2-carbonitrile
(5aa). Yield 12% (29.7 mg); white grey solid; mp 99.2e101.2 ꢀC; IR
(KBr): 2232, 1680, 1448, 1240, 753, 724 cmꢁ1. 1H NMR (400 MHz,
(600 MHz, CDCl3)
J¼7.2Hz,1H), 7.36(t, J¼7.2 Hz, 1H), 7.26e7.19 (m, 6H), 7.04 (d,J¼7.8 Hz,
2H). 13C NMR (100 MHz, CDCl3)
140.1,139.9,137.0,132.8,132.1,131.6,
d 9.41 (s,1H), 8.05 (s,1H), 7.81e7.77 (m, 2H), 7.42 (t,
d
CDCl3)
d
8.18 (d, J¼7.8 Hz, 1H), 7.66 (t, J¼7.2 Hz, 1H), 7.56e7.53 (m,
131.3, 130.5, 130.3, 128.5, 128.0, 127.4, 123.9, 122.0, 114.5. HRMS (ESI):
2H), 7.24 (s, 4H), 3.94 (d, J¼16.2 Hz, 2H), 3.75 (t, J¼16.2 Hz, 2H). 13
C
m/z [MþH]þ calcd for C22H15Br2O2S: 500.9154; found: 500.9154.
NMR (100 MHz, CDCl3) d 190.8, 137.9, 134.0, 132.8, 129.5, 128.7,
127.5, 124.3, 122.2, 49.7, 42.9. HRMS (ESI): m/z [MþH]þ calcd for
4.3.17. Diethyl (5,8-dibromo-3-phenylnaphthalen-2-yl)phosphonate
C17H14NO: 248.1070; found: 248.1070.
(3cj). Yellow solid (yield 26%); mp 121.7e124.4 ꢀC; IR (KBr): 3446,
2924, 1289, 1149, 735, 640, 562, 549 cmꢁ1
.
1H NMR (600 MHz,
4.3.24. 11H-Benzo[b]fluoren-11-one (7aa).16 Yellow solid; (yield
72%); mp 151.2e152.1 ꢀC (lit.17a 152 ꢀC); IR (KBr): 2963, 2926, 1708,
CDCl3)
d
8.97 (d, J¼16.2 Hz, 1H), 8.17 (s, 1H), 7.74 (d, J¼7.8 Hz, 1H),
7.70 (d, J¼7.2 Hz, 1H), 7.55 (d, J¼5.4 Hz, 2H), 7.46e7.45 (m, 3H),
1632, 1602, 1262, 1102, 1021 cmꢁ1. 1H NMR (600 MHz, CDCl3)
d 8.18
4.00e3.98 (m, 2H), 3.94e3.92 (m, 2H), 1.19 (t, J¼6.6 Hz, 6H). 13C
(s, 1H), 7.90 (d, J¼7.8 Hz, 1H), 7.88 (s, 1H), 7.84 (d, J¼7.8 Hz, 1H), 7.76
(d, J¼7.8 Hz, 1H), 7.73 (d, J¼7.2 Hz, 1H), 7.55 (t, J¼7.8 Hz, 2H). 7.48 (t,
J¼7.2 Hz, 1H), 7.36 (t, J¼7.2 Hz, 1H). 13C NMR (100 MHz, CDCl3)
NMR (100 MHz, CDCl3)
d 143.0, 140.4, 135.4, 134.1, 132.5, 130.8,
130.1, 129.7, 127.8, 127.6, 123.3, 122.1, 62.3, 16.1. HRMS (APCI): m/z
[MþH]þ calcd for C20H20Br2O3P: 496.9509; found: 496.9511.
d
193.1, 144.8, 138.3, 136.8, 136.1, 135.0, 133.5, 130.8, 129.1, 129.0,
128.7. 126.9, 125.6, 124.4, 120.9, 119.0, 109.7. HRMS (ESI): m/z
4.3.18. 6,7-Dimethoxy-3-phenyl-2-naphthonitrile (3da). Yield 85%
(246.3 mg); white solid; mp 132.4e133.9 ꢀC; IR (KBr): 3001, 2829,
2224, 1624, 1499, 1478, 1435, 1276, 1240, 1210, 1161, 1141, 1010, 905,
[MþH]þ calcd for C17H11O: 231.0804; found: 231.0804.
Acknowledgements
773, 703, 476 cmꢁ1. 1H NMR (400 MHz, CDCl3)
d
8.16 (s, 1H), 7.77 (s,
1H), 7.63 (d, J¼6.8 Hz, 1H), 7.52e7.48 (m, 2H), 7.45 (d, J¼6.4 Hz, 1H),
7.15 (s, 2H), 4.04 (s, 6H). 13C NMR (100 MHz, CDCl3)
152.0, 150.5,
We thank the National Natural Science Foundation of China
(Grants 21032001 and 21272085). We also thank Dr. Xianggao
Meng for his help with X-ray diffraction analysis and Dr. Chuanqi
Zhou, Hebei University, for analytical support.
d
138.4, 138.2, 133.5, 131.2, 128.8, 128.4, 128.0, 127.2, 127.1, 119.3,
106.9, 106.0, 105.8, 55.9. HRMS (ESI): m/z [MþNa]þ calcd for
C
19H15NNaO2: 312.0996; found: 312.0995.
Supplementary data
4.3.19. 3-(3,4-Dimethylphenyl)-6,7-dimethyl-5,8-dinitro-2-
naphthonitrile (3ec). Yield 73% (273.7 mg); pale yellow solid; mp
222.7e224.0 ꢀC; IR (KBr): 2921, 2227, 1626, 1603, 1529, 1484, 1365,
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.tet.2014.01.005.
853, 822 cmꢁ1. 1H NMR (600 MHz, CDCl3)
d
8.13 (s, 1H), 7.70 (s, 1H),
7.34 (d, J¼5.7 Hz, 2H), 7.34e7.33 (m, 2H), 7.29 (d, J¼7.8 Hz, 1H), 2.48
(s, 6H), 2.36 (s, 3H), 2.35 (s, 3H). 13C NMR (100 MHz, CDCl3)
148.6,
References and notes
d
148.2, 143.7, 138.5, 137.5, 133.9, 131.2, 130.2, 129.9, 129.2, 129.0,
126.3, 124.6, 121.3, 117.2, 113.6, 19.8, 19.6, 15.8, 15.6. HRMS (ESI): m/z
[MþH]þ calcd for C21H18N3O4: 376.1293; found: 376.1292.
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