Bi(III)-catalyzed intermolecular reactions of (Z)-pent-2-en-4-yl acetates with ethynylarenes for the construction of multisubstituted fluorene skeletons through a cascade electrophilic addition/cycloisomerization sequence

Article abstract of DOI:10.1021/jo202607z

A Bi(III)-catalyzed method for the synthesis of highly conjugated aromatic multisubstituted fluorene with (Z)-pent-2-en-4-yl acetates and ethynylarenes via domino reaction is described. In this process, the reaction appears to be very general and suitable

Full text of DOI:10.1021/jo202607z

Note
pubs.acs.org/joc
Bi(III)-Catalyzed Intermolecular Reactions of (Z)-Pent-2-en-4-yl
Acetates with Ethynylarenes for the Construction of Multisubstituted
Fluorene Skeletons through a Cascade Electrophilic Addition/
Cycloisomerization Sequence
Xiang-Chuan Wang,† Ru-Long Yan,† Mei-Jin Zhong,† and Yong-Min Liang*,†,‡
†State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China
‡State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Science Lanzhou, Lanzhou
730000, P. R. of China
S
* Supporting Information
ABSTRACT: A Bi(III)-catalyzed method for the synthesis of highly conjugated aromatic multisubstituted fluorene with (Z)-
pent-2-en-4-yl acetates and ethynylarenes via domino reaction is described. In this process, the reaction appears to be very
general and suitable for a variety of multisubstituted fluorene.
olycyclic aromatic hydrocarbons (PAHs) have been of
great interest especially in materials science because of
acid. Herein, we report Bi(III)-catalyzed15 tandem isomer-
ization/Friedel−Crafts reaction to synthesize multisubstituted
fluorene via carbon−carbon bond formation.
P
their utility in organic electronics, such as light-emitting diodes,
field-effect transistors, and solar cells.1 In particular, fluorene
derivatives are notable structural motifs for the diverse PAH
derivatives having various applications as dyes or optical
brightening agents.2 In addition, while some types of fluorene-
bearing compounds exhibit interesting bioactivities,3 they are
also frequently utilized as effective ligands in organometallic
chemistry.4 Consequently, they have drawn considerable
interest for synthetic chemists. The classical method for the
synthesis of fluorenes includes addition of organometals to 9-
fluorenones;5 Friedel−Crafts ring closure of biarylmethanols,
which utilizes a large excess of strong Brønsted acids such as
HCl/HOAc1k6 or PPA at refluxing temperatures,7 or an equal
or excess amount of BF3·Et2O;8 Friedel−Crafts alkylation of
fluorenes;9 metal-catalyzed or -mediated reactions including
Pd-catalyzed rearrangement reactions;10 Pd-catalyzed annula-
tive reaction of dihalobenzenes with hindered Grignard
reagents;11 activation of C−F/C−H bonds of o-arylated
α,α,α-trifluorotoluene derivatives,12 etc. Although these meth-
ods are effective for the synthesis of fluorenes, they have certain
drawbacks, for example, a strong acid medium or a
stoichiometric amount of Lewis acid sometimes is required.
For these reasons, a direct and preparative method for
functionalized PAHs is considered to be highly urgent.
We started by treating (Z)-1,3,5-triphenylpent-2-en-4-ynyl
acetate 1a (0.3 mmol) and 1-ethynyl-4-methylbenzene 2a (2.0
equiv) with 5 mol % of Bi(OTf)3 in CH3NO2 (5 mL), and the
desired product 3aa was formed in 15% yield after 7 h. It is
worth mentioning that we confirmed the structure of 3la
unambiguously through an X-ray crystal analysis.16 Further
investigations demonstrated that the addition of certain ligands
dramatically changed the reaction progress and the 2,2′-
bipyridine was the best choice (entry 2) in all ligands we
examined, which would change the strength of the Lewis acid
and make the reaction proceed efficiently. Compared with
BiBr3, other Bi salts as catalysts were less effective (Table 1,
entries 8−10). In addition, other Lewis acids and Brønsted
acids as catalyst did not give better results (entries 11−15).
Other solvents such as CH3CN, CH2Cl2, and toluene were also
evaluated in the presence of BiBr3, and no superior result was
obtained (entries 16−18). The polar solvent of MeNO2 may
have good solubility with metal complexes. Thus, (Z)-pent-2-
en-4-yl acetates 1 (0.3 mmol), aryl acetylenes (0.6 mmol),
BiBr3 (10 mol %), 2,2′-bipyridine (20 mol %), and CH3NO2 (5
mL) at 80 °C were chosen as the standard conditions.
Encouraged by our initial results, we sought to examine the
scope and the generality of the method under the optimized
reaction conditions. The reactions of 1a with various aryl
acetylenes
In the context of our ongoing efforts to synthesis PAHs
derivatives,13 we found that (Z)-pent-2-en-4-yl acetates might
be perfect substrates in a domino process.14 We envision that
(Z)-1,3,5-triphenylpent-2-en-4-ynyl acetated derivatives could
realize an isomerization/Friedel−Crafts type reaction to afford
highly conjugated carbon-rich fluorene in the presence of Lewis
Received: December 19, 2011
Published: January 11, 2012
© 2012 American Chemical Society
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Note
a
Table 1. Optimization Conditions
entry
catalyst
solvent
ligand
time (h)
yield (%)
1
2
Bi(OTf)3
Bi(OTf)3
Bi(OTf)3
Bi(OTf)3
Bi(OTf)3
BiCl3
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3CN
CH2Cl2
none
7
9
15
61
51
42
39
72
78
65
32
2,2′-bipyridine
2,2′:6′,2″-terpyridine
TMEDA
3
12
18
13
10
9
4
5
1,10-phenanthroline
2,2′-bipyridine
2,2′-bipyridine
2,2′-bipyridine
2,2′-bipyridine
2,2′-bipyridine
2,2′-bipyridine
2,2′-bipyridine
2,2′-bipyridine
2,2′-bipyridine
2,2′-bipyridine
8
9
BiBr3
10
11
12
14
15
16
17
18
BiI3
9
FeCl3
6
CuBr2
10
6
BF3·Et2O
TsOH
BiBr3
trace
trace
48
11
12
14
14
BiBr3
trace
13
BiBr3
Toluene
a
Reactions were carried out at 80 °C using 1a (0.3 mmol), 2a (0.6 mmol), 10 mol % of catalyst, and 20 mol % of ligand.
a
Table 2. Test of Ethynylarene Scope
entry
R4
product
time (h)
yield (%)
1
2
3
4
5
6
7
4-CH3
H
3aa
3ab
3ac
3ad
3ae
3af
9
10
6
78
69
65
61
59
51
76
4-OCH3
2,4-diCH3
4-Ph
8
11
12
8
4-F
b
2g
3ag
a
b
General conditions: 1a (0.3 mmol) and 2 (0.6 mmol), BiBr3 (10 mol %), 2,2′-bipyridine(20 mol %), CH3NO2 (5 mL) at 80 °C. 2g = 2-
ethynylnaphthalene.
2a−g were investigated. The results are summarized in Table
2. The reactions of 1a with 2a−e resulted in 3aa-ae in good
yields (entries 2−5). When the ethynylarene with electron-
withdrawing substituent such as 2f was used, the yield
decreased in 51% (entry 6). Notably, the 2-ethynylnaphthalene
also showed good reaction activity and result in 76% (entry 7).
To study the scope of this formation of (Z)-pent-2-en-4-yl
acetates, various acetates bearing different aryl substituents
were examined using 2a as the electrophilic addition
component. It was found that the differently substituted (Z)-
pent-2-en-4-yl acetates 1a−g gave good yields. It should be
noted that the current condensation reaction of (Z)-pent-2-en-
4-yl acetates was dependent, to some degree, upon the
electronic properties of the aryl substituents R1−R3 in 1. For
example, as a R1 group when substrates bearing electron-
withdrawing aryl substituents (Table 3, entries 1−4) or weakly
electron-donating substituents (entries 5 and 6) were
employed, this reaction could proceed to give the expected
products in good yields. When either R2 or R3 in 1 was
electron-withdrawing (entries 7−11), the desired products were
afforded in good yields.
On the basis of the above experimental results, a possible
mechanism for the Bi(III)-catalyzed tandem reactions is
proposed (Scheme 1). Initially, BiBr3-promoted deacetoxyla-
tion of (Z)-pent-2-en-4-yl acetates 1 forms the allylic cation
center of 4. Subsequently, the intermediate 4 is followed by
electrophilic addition of ethynylarenes to give the propargylic
carbocation 5 and BiBr3 is released for the next catalytic cycle.
Then the propargylic carbocation 7 is generated from the
intermediate 5 through tandem intramolecular electrophilic
addition reaction. Finally, the intermediate 7 undergoes proton
elimination to give the intermediate 8 and the subsequent
aromatization reaction to afford product 3.17
In summary, we have developed a straightforward method for
the synthesis of multisubstituted fluorene with (Z)-pent-2-en-4-
yl acetates and ethynylarenes catalyzed by BiBr3 via domino
reaction, which involved intermolecular electrophilic addition
and cycloisomerization aromatization. Variation of substituted
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Note
a
Table 3. Bi(III)-Catalyzed Synthesis of Fluorene
entry
1
R1
R2
R3
product
time (h)
yield (%)
1
2
1b
1c
1d
1e
1f
4-F-Ph
4-Cl-Ph
4-Br-Ph
4-CN-Ph
4-CH3-Ph
2-naphthal
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
3ba
3ca
3da
3ea
3fa
3ga
3ha
3ia
9
8
72
71
73
82
61
62
70
69
78
76
73
3
8
4
8
5
11
8
6
1g
1h
1i
7
4-Cl-Ph
4-Cl-Ph
4-Br-Ph
H
12
11
9
8
Ph
4-Br-Ph
9
1j
Ph
4-CN-Ph
4-NO2-Ph
4-CN-Ph
3ja
10
11
1k
1l
Ph
H
3ka
3la
8
Ph
4-OCH3-Ph
9
a
General conditions: 1 (0.3 mmol), 2a (0.6 mmol), BiBr3 (10 mol %), 2,2′-bipyridine (20 mol %), CH3NO2 (5 mL) at 80 °C.
Scheme 1. Proposed Mechanism
5H), 7.27−7.19 (m, 8H), 6.97−6.95 (m, 3H), 6.67−6.52 (m, 2H),
5.30 (s, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 149.7, 144.9,
142.5, 141.2, 141.2, 140.6, 140.6, 140.4, 128.8, 128.6, 128.4, 128.1,
127.9, 127.7, 127.6, 127.4, 127.3, 127.3, 127.0, 126.0, 125.3, 119.9,
117.4, 53.8. IR (neat, cm−1): 3399, 2361, 1508, 1068, 696. Anal. Calcd
for C31H22: C, 94.38; H, 5.62. Found: C, 94.41; H, 5.58.
groups was proven possible and this reaction can proceed
smoothly in moderate to good yields.
EXPERIMENTAL SECTION
General Procedure 1: Synthesis of (Z)-Pent-2-en-4-yl
Acetates. (Z)-Pent-2-en-4-yl acetates were prepared according to
the literature18
■
1
7-Methoxy-1,3,9-triphenyl-9H-fluorene (3ac). H NMR (400
MHz, CDCl3, ppm): δ 7.97 (s, 1H), 7.71−7.70 (m, 3H), 7.48−7.34
(m, 4H), 7.25−7.01 (m, 5H), 6.96−6.91 (m, 4H), 6.76−6.74 (m, 1H),
6.66−6.62 (m, 2H), 5.21 (s, 1H), 3.74 (s, 3H). 13C NMR (100 MHz,
CDCl3, ppm): δ 159.9, 151.0, 142.5, 140.4, 133.4, 129.6, 128.8, 128.8,
128.6, 128.1, 128.1, 127.9, 127.9, 127.8, 127.3, 126.8, 126.5, 126.0,
120.7, 116.6, 113.5, 113.3, 110.6, 55.4, 53.8. IR (neat, cm−1): 3369,
2361, 1384, 1066, 756. Anal. Calcd for C32H24O: C, 90.53; H, 5.70.
Found: C, 90.49; H, 5.74.
General Procedure for Synthesis of Multisubstituted
Fluorene. To a solution of (Z)-pent-2-en-4-yl acetates 1 (0.30
mmol) and ethynylarenes 2 (0.60 mmol) in CH3NO2 (5.0 mL) were
added 10 mmol % of BiBr3 and 20 mmol % of 2,2′-bipyridine at 80 °C.
When the reaction was considered complete as determined by TLC
analysis, the reaction mixture was quenched by addition of saturated
aqueous NH4Cl, diluted with ethyl ether (40 mL), washed with water,
and saturated brine, dried over Na2SO4, and evaporated under reduced
pressure. The residue was purified by chromatography on silica gel to
afford the corresponding 3.
5,7-Dimethyl-1,3,9-triphenyl-9H-fluorene (3ad). 1H NMR
(400 MHz, CDCl3, ppm): δ 8.26 (s, 1H), 7.76−7.74 (m, 2H),
7.51−7.40 (m, 4H), 7.22−7.07 (m, 6H), 6.97−6.92 (m, 4H), 6.61−
6.60 (m, 2H), 5.16 (s, 1H), 2.81 (s, 3H), 2.43 (s, 3H). 13C NMR (100
MHz, CDCl3, ppm): δ 147.6, 145.8, 143.8, 141.7, 141.3, 140.9, 140.9,
131.7, 129.3, 128.8, 128.6, 128.1, 127.8, 127.8, 127.4, 127.3, 126.8,
126.7, 125.7, 122.3, 121.1, 53.2, 20.3, 16.6. IR (neat, cm−1): 3062,
1708, 1592, 1076, 755. Anal. Calcd for C33H26: C, 93.80; H, 6.20.
Found: C, 93.71; H, 6.29.
7-Methyl-1,3,9-triphenyl-9H-fluorene (3aa). 1H NMR (400
MHz, CDCl3, ppm): δ 8.57 (s, 1H), 8.56−8.24 (m, 1H), 8.23−8.22
(m, 2H), 7.80−7.78 (m, 1H), 7.66−7.59 (m, 2H), 7.36−7.34 (m, 2H),
7.27−7.06 (m, 4H), 7.03−6.97 (m, 6H), 6.65−6.30 (m, 2H), 5.16 (s,
1H), 2.33 (s, 3H). 13C NMR (100 MHz, CDCl3, ppm): δ 149.2, 148.8,
146.1, 143.3, 142.8, 140.3, 139.8, 138.7, 138.6, 138.2, 137.1, 133.2,
133.1, 129.8, 129.7, 128.4, 128.1, 126.8, 126.3, 125.9, 122.2, 122.1,
119.9, 117.4, 53.7, 21.6. IR (neat, cm−1): 3398, 3057, 1601, 1026, 757.
Anal. Calcd for C32H24: C, 94.08; H, 5.92. Found: C, 94.12; H, 5.87.
1,3,9-Triphenyl-9H-fluorene (3ab). 1H NMR (400 MHz,
CDCl3, ppm): δ 8.06 (s, 1H), 7.76−7.74 (m, 2H), 7.50−7.40 (m,
1,3,7,9-Tetraphenyl-9H-fluorene (3ae). 1H NMR (400 MHz,
CDCl3, ppm):δ 8.04 (s, 1H), 7.95−7.88 (m, 1H), 7.75−7.73 (m, 2H),
7.60−7.36 (m, 9H), 7.25−7.18 (m, 5H), 6.95−6.92 (m, 3H), 6.68−
6.66 (m, 2H), 5.29 (s, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ
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Note
149.2, 145.0, 141.2, 141.2, 140.6, 140.2, 139.7, 129.0, 128.8, 128.8,
128.7, 128.6, 128.2, 127.9, 127.7, 127.4, 127.3, 127.3, 127.1, 127.1,
126.6, 126.0, 125.3, 124.0, 119.9, 117.5, 53.9. IR (neat, cm−1): 3396,
2361, 1384, 1076, 695. Anal. Calcd for C37H26: C, 94.43; H, 5.57.
Found: C, 94.51; H, 5.50.
7.24 (m, 6H), 7.12−7.05 (m, 3H), 6.89−6.85 (m, 3H), 6.60−6.58 (m,
2H), 5.60 (s, 1H), 2.41(s, 3H). 13C NMR (100 MHz, CDCl3, ppm): δ
146.7, 142.5, 141.0, 138.6, 137.9, 136.6, 133.6, 130.2, 129.5, 128.9,
128.8, 128.8, 128.7, 128.6, 128.4, 128.3, 128.0, 127.8, 127.4, 127.3,
127.1, 126.9, 126.4, 125.8, 125.2, 124.2, 118.5, 117.1, 53.2, 21.2. IR
(neat, cm−1): 3396, 2924, 1425, 1066, 670. Anal. Calcd for C36H26: C,
94.29; H, 5.71. Found: C, 94.31; H, 5.66.
3,9-Bis(4-chlorophenyl)-7-methyl-1-phenyl-9H-fluorene
(3ha). 1H NMR (400 MHz, CDCl3, ppm): δ 7.91 (s, 1H), 7.63−7.61
(m, 2H), 7.44−7.04 (m, 11H), 6.91−6.87 (m, 2H), 6.56−6.51 (m,
2H), 5.18 (s, 1H), 2.32 (s, 3H). 13C NMR (100 MHz, CDCl3, ppm): δ
149.3, 144.8, 142.8, 141.3, 141.1, 140.7, 139.3, 139.2, 137.8, 137.6,
132.8, 129.9, 128.9, 128.6, 128.3, 128.2, 128.1, 128.0, 127.2, 127.3,
127.0, 126.2, 125.9, 119.8, 117.5, 53.7, 21.6. IR (neat, cm−1): 3399,
2921, 1384, 1024, 757. Anal. Calcd for C32H22Cl2: C, 80.50; H, 4.64.
Found: C, 80.49; H, 4.68.
7-Fluoro-1,3,9-triphenyl-9H-fluorene (3af). 1H NMR (400
MHz, CDCl3, ppm): δ 8.02 (s, 1H), 7.71−7.70 (m, 2H), 7.50−7.37
(m, 5H), 7.25−7.22 (m, 3H), 7.11−7.08 (m, 2H), 6.98−6.65 (m, 5H),
6.64−6.63 (m, 2H), 5.20 (s, 1H). 13C NMR (100 MHz, CDCl3, ppm):
δ 149.1, 144.9, 142.6, 141.3, 141.1, 140.5, 140.3, 139.6, 130.2, 130.1,
128.8, 128.5, 128.1, 128.0, 127.9, 127.7, 127.6, 127.4, 127.3, 126.1,
125.3, 120.0, 117.6, 114.8, 53.8. IR (neat, cm−1): 3398, 2362, 1488,
1089, 696. Anal. Calcd for C31H21F: C, 90.26; H, 5.13. Found: C,
90.31; H, 5.08.
7,8,10-Triphenyl-7H-benzo[c]fluorene (3ag). 1H NMR (400
MHz, CDCl3, ppm): δ 8.06−8.03 (m, 2H), 7.95−7.85 (m, 2H), 7.74−
7.68 (m, 3H), 7.47−7.45 (m, 2H), 7.37−7.15 (m, 10H), 6.91−6.85
(m, 2H), 6.59−6.57 (m, 2H), 5.60 (s, 1H). 13C NMR (100 MHz,
CDCl3, ppm): δ 146.6, 144.4, 142.6, 141.2, 141.0, 140.8, 140.4, 140.1,
138.6, 133.7, 128.9, 128.9, 128.8, 128.7, 128.3, 128.0, 127.9, 127.3,
127.3, 127.0, 126.4, 125.8, 125.3, 124.2, 118.5, 117.3, 53.2. IR (neat,
cm−1): 3405, 2921, 1383, 1075, 697. Anal. Calcd for C35H24: C, 94.56;
H, 5.44. Found: C, 94.51; H,5.49.
3,9-Bis(4-bromophenyl)-7-methyl-1-phenyl-9H-fluorene
1
(3ia). H NMR (400 MHz, CDCl3, ppm): δ 7.94 (s, 1H), 7.91−7.84
(m, 1H), 7.57 (s, 2H), 7.35−6.97 (m, 12H), 6.50−6.45 (m, 2H), 5.16
(s, 1H), 2.32 (s, 3H). 13C NMR (100 MHz, CDCl3, ppm): δ 148.78,
144.7, 140.7, 140.3, 140.1, 139.8, 137.9, 137.6, 131.1, 130.9, 130.2,
129.8, 129.7, 129.6, 128.9, 128.7, 128.5, 128.3, 128.0, 127.8, 127.1,
127.1, 126.8, 125.8, 119.8, 116.9, 53.0, 21.7. IR (neat, cm−1): 3398,
2920, 1384, 1021, 757. Anal. Calcd for C32H22Br2: C, 67.87; H, 3.92.
Found: C, 67.79; H, 3.88.
1-(4-Fluorophenyl)-7-methyl-3,9-diphenyl-9H-fluorene
1
(3ba). H NMR (400 MHz, CDCl3, ppm): δ8.02 (s, 1H), 7.80−7.73
4-(7-Methyl-1,9-diphenyl-9H-fluoren-3-yl)benzonitrile (3ga).
1H NMR (400 MHz, CDCl3, ppm): δ 7.94 (s, 1H), 7.63−7.58 (m,
4H), 7.46−7.37 (m, 1H), 7.28−7.27 (m, 2H), 7.21−7.02 (m, 5H),
6.95−6.92 (m, 4H), 6.63−6.60 (m, 2H), 5.20 (s, 1H), 2.30 (s, 3H).
13C NMR (100 MHz, CDCl3, ppm): δ 149.3, 146.2, 145.7, 143.0,
140.9, 140.4, 140.1, 138.9, 138.0, 137.3, 132.5, 131.6, 129.6, 129.3,
128.4, 128.1, 127.9, 127.8, 127.0, 126.0, 125.9, 119.7, 118.9, 117.0,
110.8, 53.7, 21.6. IR (neat, cm−1): 3398, 2923, 1601, 1026, 697. Anal.
Calcd for C33H23N: C, 91.42; H, 5.35; N: 3.23 Found: C, 91.36; H,
5.41; N, 3.19.
7-Methyl-3-(4-nitrophenyl)-1,9-diphenyl-9H-fluorene (3ka).
1H NMR (400 MHz, CDCl3, ppm): δ 8.29 (s, 2H), 8.05−8.01 (m,
1H), 7.98−7.83 (m, 2H), 7.40−7.02 (m, 9H), 6.97−6.91 (m, 3H),
6.64−6.60 (m, 2H), 5.22 (s, 1H), 2.32 (s, 3H). 13C NMR (100 MHz,
CDCl3, ppm): δ 149.3, 147.7, 146.5, 143.1, 141.0, 140.3, 140.1, 138.6,
138.1, 137.2, 129.6, 128.6, 128.5, 128.3, 128.1, 128.0, 128.0, 127.9,
127.9, 127.1, 126.0, 124.1, 119.8, 117.2, 53.7, 21.7. IR (neat, cm−1):
3396, 2361, 1384, 1075, 698. Anal. Calcd for C32H23NO2: C, 84.74; H,
5.11; N, 3.09. Found: C, 84.66; H, 5.18; N, 3.11.
(m, 3H), 7.54−7.21 (m, 8H), 7.11−7.01 (m, 5H), 6.71−6.69 (m, 2H),
5.20 (s, 1H), 2.36 (s, 3H). 13C NMR (100 MHz, CDCl3, ppm): δ
149.3, 144.8, 142.7, 141.2, 140.8, 139.5, 137.7, 130.8, 128.9, 128.8,
128.2, 128.0, 127.4, 127.3, 127.1, 126.1, 125.9, 119.7, 117.3, 114.8,
53.7, 21.3. IR (neat, cm−1): 3408, 2923, 1452, 1026, 697 Anal. Calcd
for C32H23F: C, 90.11; H, 5.44. Found: C, 90.17; H,5.38.
1-(4-Chlorophenyl)-7-methyl-3,9-diphenyl-9H-fluorene
(3ca). 1H NMR (400 MHz, CDCl3, ppm): δ 8.04 (s, 1H), 7.81−7.74
(m, 3H), 7.52−7.48 (m, 2H), 7.42−7.22 (m, 6H), 7.14−6.89 (m, 5H),
6.69−6.68 (m, 2H), 5.18 (s, 1H), 2.35 (s, 3H). 13C NMR (100 MHz,
CDCl3, ppm): δ 149.3, 144.8, 142.8, 141.2, 141.1, 140.7, 139.3, 139.2,
137.5, 137.6, 132.8, 129.9, 128.6, 128.3, 128.2, 128.1, 128.0, 127.5,
127.3, 127.0, 126.2, 125.9, 119.8, 117.5, 53.7, 21.6. IR (neat, cm−1):
3408, 2920, 1512, 813, 701. Anal. Calcd for: C32H23Cl: C, 86.76; H,
5.23. Found: C, 86.69; H,5.28.
1-(4-Bromophenyl)-7-methyl-3,9-diphenyl-9H-fluorene
(3da). 1H NMR (400 MHz, CDCl3, ppm): δ 7.98 (s, 1H), 7.75−7.68
(m, 3H), 7.47−7.44 (m, 2H), 7.37−7.17 (m, 5H), 7.07−6.97 (m, 6H),
6.65−6.63 (m, 2H), 5.13 (s, 1H), 2.30 (s, 3H). 13C NMR (100 MHz,
CDCl3, ppm): δ 149.2, 144.7, 142.8, 141.2, 141.1, 140.7, 139.6, 139.2,
137.8, 137.6, 130.9, 130.2, 128.8, 128.2, 128.1, 128.0, 127.4, 127.3,
126.8, 126.2, 125.9, 121.0, 119.7, 117.4, 53.6, 21.6. IR (neat, cm−1):
3437, 2361, 1634, 1068, 695. Anal. Calcd for: C32H23Br: C, 78.85; H,
4.76. Found: C, 78.79; H, 4.85.
4-(9-(4-Methoxyphenyl)-7-methyl-1-phenyl-9H-fluoren-3-
1
yl)benzonitrile (3la). H NMR (400 MHz, CDCl3, ppm): δ 7.97 (s,
1H), 7.84−7.75 (m, 5H), 7.40−7.36 (m, 1H), 7.26−7.15 (m, 5H),
7.06−7.05 (m, 2H), 6.51−6.48 (m, 4H), 5.20 (s, 1H), 3.68 (s, 3H),
2.35 (s, 3H). 13C NMR (100 MHz, CDCl3, ppm): δ 157.8, 149.6,
146.5, 145.8, 142.9, 140.9, 140.3, 138.9, 138.0, 137.2, 132.6, 129.0,
128.6, 128.5, 128.4, 128.2, 128.0, 127.8, 127.1, 125.9, 119.7, 117.0,
113.4, 110.9, 55.1, 52.9, 21.6. IR (neat, cm−1): 3405, 2923, 1450, 1072,
758, 698. Anal. Calcd for C34H25NO: C, 88.09; H, 5.44; N, 3.02.
Found: C, 88.03; H,5.41; N, 3.09.
4-(7-Methyl-3,9-diphenyl-9H-fluoren-1-yl)benzonitrile (3ea).
1H NMR (400 MHz, CDCl3, ppm): δ 8.06 (s, 1H), 7.81−7.73 (m,
3H), 7.54−7.36 (m, 5H), 7.28−7.25 (m, 3H), 7.06−6.99 (m, 5H),
6.67−6.65 (m, 2H), 5.17 (s, 1H), 2.36 (s, 3H). 13C NMR (100 MHz,
CDCl3, ppm): 149.0, 145.5, 144.5, 141.5, 140.3, 138.5, 138.0, 137.3,
131.6, 129.3, 128.9, 128.8, 128.4, 128.1, 128.1, 127.6, 127.3, 126.5,
126.3, 125.8, 119.8, 118.0, 110.7, 53.6, 21.6. IR (neat, cm−1): 3398,
2360, 1382, 1067, 695. Anal. Calcd for C33H23N: C, 91.42; H, 5.35; N,
3.23. Found: C, 91.35; H,5.42; N, 3.18.
ASSOCIATED CONTENT
■
S
* Supporting Information
1H NMR and 13C NMR spectra of all products and X-ray data
of 3la (CIF). This material is available free of charge via the
Internet at http://pubs.acs.org.
7-Methyl-3,9-diphenyl-1-p-toyl-9H-fluorene (3fa). 1H NMR
(400 MHz, CDCl3, ppm): δ 7.96 (s, 1H), 7.78−7.70 (m, 2H), 7.48−
7.44 (m, 2H), 7.37−7.25 (m, 2H), 7.24−7.17 (m, 3H), 7.05−6.94 (m,
7H), 6.67−6.65 (m, 2H), 5.21 (s, 1H), 2.31 (s, 6H). 13C NMR (100
MHz, CDCl3, ppm): δ 149.4, 144.8, 142.6, 141.3, 141.0, 140.5, 137.8,
137.8, 137.5, 136.4, 129.5, 128.7, 128.6, 128.4, 128.4, 128.2, 127.8,
127.3, 127.3, 125.9, 125.9, 119.6, 116.9, 53.7, 21.6, 21.1. IR (neat,
cm−1): 3400, 2923, 1450, 1071,758, 695. Anal. Calcd for C33H26: C,
93.80; H, 6.20. Found: C, 93.75; H, 6.24.
AUTHOR INFORMATION
Corresponding Author
*E-mail: liangym@lzu.edu.cn.
■
ACKNOWLEDGMENTS
We thank the National Basic Research Program of China (973
Program) 2010CB8- 33203 for financial support. We thank the
■
7-Methyl-1-(naphthalen-2-yl)-3,9-diphenyl-9H-fluorene
1
(3ga). H NMR (400 MHz, CDCl3, ppm): δ 8.05−8.03 (m, 2H),
7.94−7.85 (m, 2H), 7.70−7.68 (m, 2H), 7.48−7.45 (m, 2H), 7.36−
2067
dx.doi.org/10.1021/jo202607z | J. Org. Chem. 2012, 77, 2064−2068

The Journal of Organic Chemistry
Note
National Basic Research Program of China (973 Program)
(No. 2010CB8-33203) for financial support. We also acknowl-
edge support by the “111” Project.
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