Direct Assembly of Polysubstituted Naphthalenes via a Tandem Reaction of Benzynes and α-Cyano-β-methylenones

Article abstract of DOI:10.1021/acs.joc.0c01975

A mild and transition-metal-free benzannulation reaction for the construction of the naphthalene skeleton has been described. Benzynes react with α-cyano-β-alkylenones through a tandem nucleophilic addition/cyclization/aromatization process to afford polysubstituted naphthalenes in 50-94% yields.

Full text of DOI:10.1021/acs.joc.0c01975

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Direct Assembly of Polysubstituted Naphthalenes via a Tandem
Reaction of Benzynes and α‑Cyano-β-methylenones
Qiang Wang,† Yi An,† Guangfen Du,* Zhi-Hua Cai, Bin Dai, and Lin He*
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ABSTRACT: A mild and transition-metal-free benzannulation
reaction for the construction of the naphthalene skeleton has been
described. Benzynes react with α-cyano-β-alkylenones through a
tandem nucleophilic addition/cyclization/aromatization process to
afford polysubstituted naphthalenes in 50−94% yields.
olysubstituted naphthalenes are privileged structural
motifs found in many natural products, biologically
Scheme 1. Transition-Metal-Free Synthesis of
Naphthalenes Involving Benzynes
P
active compounds, pharmaceuticals, and functional organic
materials.1 Due to their importance, tremendous efforts have
been exerted to develop efficient methods for the synthesis of
these ubiquitous frameworks.2 In the past decade, the
transition-metal-catalyzed Diels−Alder reaction,3 Dotz reac-
̈
tion,4 and other cyclizations5 have been extensively studied
for the construction of naphthalene scaffolds. On the other
hand, benzynes6 are highly reactive intermediates that have
been used widely in the synthesis of various carbocycles and
heterocycles.7 In particular, the annulation of benzynes
provides facile access to different polyaromatic hydro-
carbons.8 As one of the most convenient methods,
transition-metal-catalyzed [2+2+2] cycloaddition reactions9
of benzynes have been well established, which provide rapid
construction of polysubstituted naphthalenes. However, this
method often suffers from the use of expensive transition-
metal catalysts and the difficulty in controlling chemo- and
regioselectivity.
In 2007, Huang and Xue described a transition-metal-free
multicomponent reaction of benzynes, β-ketosulfones, and
activated alkenes, affording polysubstituted naphthols and
naphthalenes (Scheme 1a).10 In 2012, Biju and co-workers
reported an interesting Diels−Alder reaction of 1,2-
benzoquinones and benzynes to produce dioxobenzobicy-
clooctadienes, which can be further transformed to
naphthalenes via irradiation at 254 nm (Scheme 1b).11
Recently, Wu, Shu, and co-workers reported a formal
[2+2+2] cycloaddition of benzynes, ketones, and alkynoates,
which provided a novel method for the synthesis of
functionalized naphthalenes (Scheme 1c).12 Subsequently,
the same group further developed a tandem σ-bond
insertion/benzannulation reaction of benzynes to give two
classes of polysubstituted naphthalenes.13 Very recently,
Mukherjee and co-workers reported an impressive Diels−
Alder reaction of benzynes and glycal-derived dienes to
Received: August 15, 2020
https://dx.doi.org/10.1021/acs.joc.0c01975
© XXXX American Chemical Society
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construct meta-disubstituted naphthalenes with a chiral side
chain (Scheme 1d).14 Despite significant advances made in
this research field, the development of novel protocols for the
synthesis of polysubstituted naphthalene derivatives with
unprecedented C4 synthons is still highly significant.
With the optimized reaction conditions in hand, the
generality of the reaction was next examined, and the results
are summarized in Scheme 2. Both electron-withdrawing
substituents (R2 = 4-FC6H4, 4-ClC6H4, 4-BrC6H4) and
electron-donating substituents (R2 = 4-MeC6H4, 4-
MeOC6H4) substituted β-arylenones participated in the
benzannulation well, producing the corresponding naphtha-
lenes in high yields (Scheme 2, 3b−3f). The electronic
properties and position of the substituents on the β-aryl ring
have little influence on the reaction yield (Scheme 2, 3g−3l).
A bulky naphthyl-derived enone performed smoothly to give
the desired naphthalene 3m in 84% yield (Scheme 2, 3m). In
addition, β-heteroarylenone (R2 = 2-thienyl) 1n was proved
to be a successful candidate for the annulation, affording 3n
in 68% yield (Scheme 2, 3n). Interestingly, β-ethyl-β-phenyl-
substituted enone coupled with benzyne provided tetrasub-
stituted naphthalene 3o in a 61% yield (Scheme 2, 3o). The
bulky isopropyl-substituted enone 1p underwent the reaction
to afford 3p in a 60% yield (Scheme 2, 3p). However, when
β,β-dimethyl-substituted enone 1q was used to couple with
benzyne, it gave a complex reaction mixture, and no desired
product was obtained under the standard conditions (Scheme
2, 3q). This may be due to the instability of the dienolate
intermediate16e shown in Scheme 5. β-Arylenones containing
electron-deficient groups (R1 = 4-FC6H4, 4-MeO2C−C6H4)
or electron-rich groups (R1 = 4-MeC6H4, 4-MeOC6H4)
underwent the reaction to furnish the corresponding products
in high yields (Scheme 2, 3r−3u). Furthermore, heteroaryl-
substituted β-arylenones 1v and 1w (R1 = 2-furyl, 2-thienyl)
reacted with benzyne to afford 3v and 3w in 71% and 76%
yields, respectively (Scheme 2, 3v and 3w). Notably, alkyl-
substituted enone 1x was also suitable for the reaction, giving
3x in 50% yield (Scheme 2, 3x).
Other different types of enones and enoates were also
prepared and tested for the tandem reaction. As shown in
Scheme 3, when substrates 1y, 1z, and 1aa that have no
phenyl group at the β-position were used for the reaction,
these enones were consumed completely within 24 h.
However, the reactions were very complex, and no desired
products were obtained. We attributed this result to a similar
reason as that of 3q (Scheme 2, 3q). Substrates 4a−4d did
not react with benzyne, and the starting materials were
recovered in high yields. We concluded that the acidity of the
methyl protons of these tested enones and enoates is weaker
than that of enone 1a. Therefore, they could be difficult to
generate the dienolate intermediate I shown in Scheme 5 and
trigger the following cyclization.
In line with our continued interest in benzyne chemistry,15
we hypothesized that α-cyano-β-methylenones, which have
been used successfully by Ye,16a−c Wang,16d and Shi16e as C4
synthon partners in the synthesis of polysubstituted benzenes,
may undergo benzannulation with benzynes to form
polysubstituted naphthalenes (Scheme 1e). Herein, we report
our development on the construction of polysubstituted
naphthalenes. As shown in Table 1, our study commenced by
a
Table 1. Optimization of Reaction Conditions
time
(h)
yield
b
entry
additives
solvent
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
THF
(%)
1
2
3
4
5
6
7
8
CsF (4.5 equiv)
24
24
24
24
24
24
24
24
24
24
48
48
48
24
24
37
39
40
47
81
55
65
51
62
48
17
21
18
94
95
KF/18-crown-6 (4.5 equiv)
TBAF (4.5 equiv)
TMAF (4.5 equiv)
TBAT (4.5 equiv)
TBAT (4.5 equiv)
TBAT (4.5 equiv)
TBAT (4.5 equiv)
TBAT (4.5 equiv)
TBAT (4.5 equiv)
TBAT (4.5 equiv)
TBAT (4.5 equiv)
TBAT (4.5 equiv)
TBAT (6.0 equiv)
TBAT (7.5 equiv)
DME
1,4-dioxane
CH2Cl2
ClCH2CH2Cl
toluene
DMF
DMSO
CH3CN
CH3CN
9
10
11
12
13
c
14
d
15
a
Standard conditions: 1a (0.10 mmol), 2a (0.15 mmol), 1.0 mL of
b
c
the solvent, room temperature. Isolated yield. 1a (0.10 mmol), 2a
(0.20 mmol), and TBAT (0.60 mmol). 1a (0.10 mmol), 2a (0.25
d
mmol), TBAT (0.75 mmol). TBAT: tetrabutylammonium difluoro-
triphenylsilicate.
selecting readily available α-cyano-β-methylenone 1a and
Kobayashi’s reagent17 2a as the model substrates for
optimization of the reaction conditions. With 4.5 equiv of
CsF as a fluoride source, the benzannulation smoothly
proceeded in acetonitrile at room temperature to afford the
desired polysubstituted naphthalene 3a in 37% yield (Table
1, entry 1). Encouraged by this success, several other fluoride
sources were subsequently investigated for the reaction. KF/
18-crown-6 gave the desired product in a 39% isolated yield
(Table 1, entry 2). TBAF and TMAF promoted the reaction
in moderate yield (Table 1, entries 3 and 4). Gratifyingly,
when tetrabutylammonium difluorotriphenylsilicate (TBAT)
was used as the fluoride source, the yield was dramatically
improved to 81% (Table 1, entry 5). A brief screening of the
reaction solvent showed that acetonitrile was optimal (Table
1, entries 6−13). Increasing the amount of benzyne precursor
to 2.0 equiv led to a higher reaction yield (Table 1, entry
14). However, a further increase of the benzyne precursor to
2.5 equiv did not give a significant change in the reaction
yield (Table 1, entry 15).
Substituted benzyne precursors were also tested for the
reaction. The symmetrical benzynes derived from precursors
2b, 2c, and 2d smoothly underwent the benzannulation with
enone 1a to afford the corresponding polysubstituted
naphthalenes in good yields (Scheme 4, 3y−3aa). Interest-
ingly, the polysubstituted anthracene 3ab was obtained in
56% yield when the symmetrical 2,3-naphthalyne 2e was
introduced to the reaction (Scheme 4, 3ab). Unsymmetrical
3-methoxybenzyne and 3-methylbenzyne derived from 2f and
2g performed smoothly in the reaction to give 3ac and 3ad
in 74% and 80% yields with excellent regioselectivity
(Scheme 4, 3ac and 3ad). Notably, the benzannulation
reaction can be conducted on a gram-scale, and a high yield
can be maintained (Scheme 4, 3ad).
B
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a
Scheme 2. Scope of α-Cyano-β-methylenones
a
General conditions: 1a (0.10 mmol), 2a (0.20 mmol), TBAT (0.60 mmol), CH3CN (1.0 mL), room temperature, 24 h. The yields reported are
isolated yields.
The products 3a and 3ad were crystallized from
tetrahydrofuran and n-hexane, and their structure was clearly
confirmed by single-crystal X-ray analysis.18
of intermediate II results in the formation of compound III.
Finally, the aromatization of III (via dehydration) leads to
the formation of the desired product.
Based on the pioneering work on the nucleophilic addition-
cyclization reactions of benzynes7,10 and the transformations
of α-cyano-β-methylenones,16 a plausible reaction mechanism
was proposed in Scheme 5. In the presence of basic fluoride,
α-cyano-β-methylenone undergoes deprotonation to generate
dienolate intermediate I. Subsequent cyclization of inter-
mediate I and benzyne lead to intermediate II. Protonation
In summary, we have demonstrated a benzannulation
reaction of benzynes and readily available α-cyano-β-
methylenones. The transition-metal-free and mild conditions,
simple procedure, and generally high yields provide a novel,
useful protocol for the synthesis of polysubstituted naph-
thalenes. Further studies of a broader substrate scope and the
C
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Scheme 3. Unsuccessful Substrates
Scheme 5. Proposed Mechanism
a
b
The reaction is very complex, indicated by TLC. The recovery yield
of the starting enones or enoates.
benzophenone prior to use. CH2Cl2, ClCH2CH2Cl, CH3CN, DMF,
and DMSO were distilled from calcium hydride prior to use.
Petroleum ether (PE), where used, has a boiling point range of 60−
90 °C.
synthetic applications of this method are ongoing in our
laboratory.
Typical Procedure for the Tandem Reaction of Benzyne
and α-Cyano-β-methylenone. To a mixture of α-cyano-β-
methylenone 1a (0.10 mmol, 24.7 mg) and TBAT (0.60 mmol,
323.9 mg) in anhydrous acetonitrile (1.0 mL) was added 2-
(trimethylsilyl) aryl triflate 2a (0.20 mmol, 60.0 mg) under a
nitrogen atmosphere. The mixture was stirred at room temperature
until full consumption of the starting enone was indicated by TLC.
The reaction mixture was then diluted with ethyl acetate, filtered
through a short pad of silica gel, and concentrated. The crude
product was purified by flash column chromatography on silica gel
to afford the desired product 3a.
Scale-up Experiment. To a mixture of α-cyano-β-methylenone 1a
(3.92 mmol, 0.97g) and TBAT (23.52 mmol, 12.7 g) in anhydrous
acetonitrile (40.0 mL) was added 2-(trimethylsilyl) aryl triflate 2g
(7.84 mmol, 2.45g) under a nitrogen atmosphere. The mixture was
stirred at room temperature until full consumption of the starting
enone was indicated by TLC. The reaction mixture was then diluted
with ethyl acetate, filtered through a short pad of silica gel, washed
with ethyl acetate, and concentrated. The crude product was purified
EXPERIMENTAL SECTION
■
General Experimental Methods. Unless otherwise indicated,
all reactions were conducted under a nitrogen atmosphere in oven-
dried glassware. 1H NMR (400 MHz, CDCl3), 13C NMR (100
MHz, CDCl3), and 19F NMR (376 MHz) spectra are reported in
ppm (δ). High-resolution mass spectra (HRMS) were obtained on
an LTQ Orbitrap XL mass spectrometer equipped with an ESI
source from Thermo Scientific at Keeclound Biotech in Shanghai.
The X-ray diffraction study for products 3a and 3ad was carried out
on a Bruker D8 VENTURE photon II diffractometer with an Iμs 3.0
microfocus X-ray source using the APEX III program. Benzyne
precursors were obtained from commercial suppliers and used
without purification. Benzyne precursors 2b,19 2c,19α-cyano-β-
methylenones 1a−1x,16 1y-1z,201aa,21 4a,22 4b,23 4c,24 and 4d25
were prepared according to literature procedures. Anhydrous THF,
1,4-dioxane, toluene, and DME were distilled from sodium and
a
Scheme 4. Scope of Benzynes
a
General conditions: 1a (0.10 mmol), 2 (0.20 mmol), TBAT (0.60 mmol), CH3CN (1.0 mL), room temperature, 24 h. The yields reported are
b
c
1
isolated yields. The regioisomeric ratio (rr) was determined by H NMR analysis. 1a (3.92 mmol), 2g (7.84 mmol), TBAT (23.52 mmol),
CH3CN (40.0 mL), room temperature, 48 h.
D
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by flash column chromatography on silica gel (petroleum ether) to
give 3ad in 82% yield (1.02 g)
7.92 (s, 1H), 7.69−7.63 (m, 3H), 7.61−7.42 (m, 9H); 13C{1H}
NMR (100 MHz, CDCl3) δ (ppm) 148.2, 140.5, 138.4, 136.6,
134.6, 134.5, 131.0, 130.0, 129.8, 129.34, 129.29, 129.0, 128.8,
128.7, 128.6, 128.3, 127.7, 127.5, 127.4, 117.6, 109.7; HRMS (ESI)
m/z calcd for C23H15ClN+ [M + H]+ 340.0888, found 340.0886.
3-(3,5-Difluorophenyl)-1-phenyl-2-naphthonitrile (3h): white
solid (22.1 mg, 65% yield); mp 118.1−118.9 °C; Rf (silica,
petroleum ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1)
υ 3436, 3053, 2214, 1625, 1593, 1448, 1344, 1118, 989, 864, 757,
1,3-Diphenyl-2-naphthonitrile (3a): white solid (28.7 mg, 94%
yield); mp 144.3−144.8 °C; Rf (silica, petroleum ether/EtOAc/
methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3043, 2222, 1619, 1580,
1488, 1444, 1410, 1371, 1332, 1182, 1075, 1026, 895, 793, 696,
613, 516; 1H NMR (400 MHz, CDCl3) δ (ppm) 7.96−7.90 (m,
2H), 7.69−7.61 (m, 4H), 7.60−7.41 (m, 9H); 13C{1H} NMR (100
MHz, CDCl3) δ (ppm) 147.9, 139.9, 138.8, 136.9, 134.7, 130.8,
130.1, 129.3, 129.1, 128.9, 128.7, 128.63, 128.61, 128.5, 128.3,
127.39, 127.37, 118.0, 110.0; HRMS (ESI) m/z calcd for
C23H16N+[M + H]+ 306.1277, found 306.1278.
1
717; H NMR (400 MHz, CDCl3) δ (ppm) 7.96 (dd, J = 8.6, 1.3
Hz, 1H), 7.92 (s, 1H), 7.71−7.65 (m, 2H), 7.62−7.45 (m, 6H),
7.22−7.18 (m, 2H), 6.95−6.88 (m, 1H); 13C{1H} NMR (100 MHz,
CDCl3) δ (ppm) 162.9 (dd, J = 248.0, 13.0 Hz), 148.4, 141.8 (t, J =
9.6 Hz), 137.4 (t, J = 2.5 Hz), 136.5, 134.5, 131.2, 130.0, 129.5,
129.1, 128.8, 128.7, 128.4, 128.0, 127.5, 117.4, 112.5 (dd, J = 18.8,
7.3 Hz), 109.3, 103.9 (t, J = 25.0 Hz); 19F NMR (376 MHz,
CDCl3) δ (ppm) −108.96 (s, 2F); HRMS (ESI) m/z calcd for
C23H14F2N+ [M + H]+ 342.1089, found 342.1086.
1-Phenyl-3-o-tolyl-2-naphthonitrile (3i): white solid (24.2 mg,
76% yield); mp 119.8−120.6 °C; Rf (silica, petroleum ether/EtOAc/
methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3047, 2920, 2223,
1618, 1587, 1487, 1444, 1149, 1028, 900, 794, 757, 729, 700, 615;
1H NMR (400 MHz, CDCl3) δ (ppm) 7.92 (d, J = 8.2 Hz, 1H),
7.82 (s, 1H), 7.72−7.61 (m, 2H), 7.58−7.48 (m, 6H), 7.38−7.29
(m, 4H), 2.28 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm)
147.1, 140.0, 138.6, 136.7, 136.2, 134.6, 130.8, 130.3, 130.1, 129.9,
129.0, 128.84, 128.78, 128.7, 128.6, 128.2, 127.4, 127.3, 125.8,
117.5, 111.3, 20.1; HRMS (ESI) m/z calcd for C24H18N+ [M + H]+
320.1434, found 320.1432.
3-(4-Chlorophenyl)-1-phenyl-2-naphthonitrile (3b). white solid
(28.8 mg, 85% yield); mp 173.2−173.8 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3438,
3055, 2225, 1616, 1596, 1566, 1492, 1442, 1330, 1093, 1014, 900,
1
831, 754, 702, 613; H NMR (400 MHz, CDCl3) δ (ppm) 7.95−
7.89 (m, 2H), 7.67−7.53 (m, 7H), 7.53−7.46 (m, 5H); 13C{1H}
NMR (100 MHz, CDCl3) δ (ppm) 148.2, 138.6, 137.2, 136.7,
134.8, 134.6, 130.9, 130.6, 130.0, 129.3, 129.0, 128.9, 128.67,
128.65, 128.3, 127.6, 127.4, 117.8, 109.7; HRMS (ESI) m/z calcd
for C23H15ClN+ [M + H]+ 340.0888, found 340.0885.
3-(4-Fluorophenyl)-1-phenyl-2-naphthonitrile (3c): white solid
(28.1 mg, 87% yield); mp 146.9−147.6 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3060,
2227, 1600, 1508, 1487, 1442, 1228, 1161, 850, 835, 784, 700, 609;
1H NMR (400 MHz, CDCl3) δ (ppm) 7.96−7.91 (m, 1H), 7.90−
7.88 (m, 1H), 7.68−7.61 (m, 4H), 7.60−7.53 (m, 3H), 7.52−7.46
(m, 3H), 7.23−7.15 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ
(ppm) 163.0 (d, J = 246.0 Hz), 148.0, 138.8, 136.8, 134.8 (d, J =
4.0 Hz), 134.7, 131.0 (d, J = 8.0 Hz), 130.9, 130.0, 129.2, 128.9,
128.7, 128.3, 127.5, 127.4, 117.9, 115.7 (d, J = 21.7 Hz), 109.9; 19F
NMR (376 MHz, CDCl3) δ (ppm) −113.46; HRMS (ESI) m/z
calcd for C23H15FN+ [M + H]+ 324.1183, found 324.1182.
3-(2-Methoxyphenyl)-1-phenyl-2-naphthonitrile (3j): white solid
(24.8 mg, 74% yield); mp 190.3−190.8 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3448,
3057, 2923, 2837, 2229, 1600, 1587, 1490, 1465, 1249, 1110, 1022,
1
891, 763, 702; H NMR (400 MHz, CDCl3) δ (ppm) 7.92 (d, J =
8.2 Hz, 1H), 7.88 (s, 1H), 7.69−7.41 (m, 9H), 7.38 (dd, J = 7.5,
1.8 Hz, 1H), 7.10 (dd, J = 7.5, 1.0 Hz, 1H), 7.08−7.03 (m, 1H),
3.86 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm) 156.9,
146.6, 137.2, 136.9, 134.8, 131.2, 130.8, 130.24, 130.15, 129.1,
128.7, 128.6, 128.5, 128.2, 127.9, 127.3, 127.2, 120.8, 117.9, 112.0,
111.3, 55.6; HRMS (ESI) m/z calcd for C24H18NO+ [M + H]+
336.1383, found 336.1380.
3-(4-Bromophenyl)-1-phenyl-2-naphthonitrile (3d): white solid
(27.2 mg, 71% yield); mp 184.8−185.5 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3053,
2214, 1590, 1491, 1446, 1377, 1332, 1297, 1149, 1104, 1069, 1005,
1
990, 915, 831, 752, 702, 613, 524; H NMR (400 MHz, CDCl3) δ
(ppm) 7.91−7.81 (m, 2H), 7.63−7.55 (m, 4H), 7.52−7.39 (m,
8H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm) 148.2, 138.6,
137.6, 136.7, 134.6, 131.8, 130.94, 130.86, 130.0, 129.3, 129.0,
128.7, 128.6, 128.3, 127.6, 127.4, 123.0, 117.8, 109.6; HRMS (ESI)
m/z calcd for C23H15NBr+ [M + H]+ 384.0382, found 384.0380.
1-Phenyl-3-p-tolyl-2-naphthonitrile (3e): white solid (25.5 mg,
80% yield); mp 149.0−149.8 °C; Rf (silica, petroleum ether/EtOAc/
methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3049, 2219, 1616,
1512, 1485, 1440, 1373, 1330, 1186, 1026, 896, 815, 756, 702, 621,
1-Phenyl-3-m-tolyl-2-naphthonitrile (3k): white solid (23.9 mg,
75% yield); mp 109.7−110.5 °C; Rf (silica, petroleum ether/EtOAc/
methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3438, 3049, 2219,
1
1610, 1583, 1485, 1442, 1334, 1149, 892, 792, 754, 700; H NMR
(400 MHz, CDCl3) δ (ppm) 7.94 (d, J = 7.2 Hz, 2H), 7.69−7.62
(m, 2H), 7.61−7.54 (m, 3H), 7.52−7.46 (m, 5H), 7.44−7.38 (m,
1H), 7.28 (d, J = 7.8 Hz, 1H), 2.47 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ (ppm) 147.9, 140.1, 138.7, 138.2, 136.9, 134.7,
130.8, 130.1, 130.0, 129.2, 129.0, 128.8, 128.6, 128.5, 128.3, 127.4,
127.3, 126.4, 118.0, 110.1, 21.5; HRMS (ESI) m/z calcd for
C24H18N+ [M + H]+ 320.1434, found 320.1431.
1
522; H NMR (400 MHz, CDCl3) δ (ppm) 7.95−7.87 (m, 2H),
7.65−7.52 (m, 7H), 7.51−7.42 (m, 3H), 7.35−7.29 (m, 2H), 2.43
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm) 147.9, 140.0,
138.3, 136.9, 135.9, 134.7, 130.7, 130.0, 129.3, 129.1, 129.0, 128.8,
128.6, 128.5, 128.2, 127.3, 127.2, 118.1, 110.1, 21.3; HRMS (ESI)
m/z calcd for C24H18N+ [M + H]+ 320.1434, found 320.1433.
3-(4-Methoxyphenyl)-1-phenyl-2-naphthonitrile (3f): white solid
(27.1 mg, 81% yield); mp 128.3−129.1 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3047,
2839, 2221, 1610, 1571, 1514, 1465, 1286, 1245, 1180, 1028, 833,
3-(3-Methoxyphenyl)-1-phenyl-2-naphthonitrile (3l): white solid
(23.5 mg, 70% yield); mp 93.0−93.8 °C; Rf (silica, petroleum ether/
EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3051, 2964,
2831, 2221, 1579, 1490, 1452, 1433, 1282, 1255, 1224, 1155, 1053,
1
873, 773, 752, 700; H NMR (400 MHz, CDCl3) δ (ppm) 7.97−
7.90 (m, 2H), 7.67−7.62 (m, 2H), 7.60−7.52 (m, 3H), 7.52−7.45
(m, 3H), 7.45−7.38 (m, 1H), 7.24−7.23 (m, 1H), 7.21−7.19 (m,
1H), 7.02−6.98 (m, 1H), 3.88 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ (ppm) 159.6, 147.9, 140.1, 139.8, 136.9, 134.6, 130.9,
130.0, 129.7, 129.1, 128.8, 128.6, 128.3, 127.42, 127.37, 121.7,
117.9, 114.8, 114.3, 110.0, 55.4; HRMS (ESI) m/z calcd for
C24H18NO+ [M + H]+ 336.1383, found 336.1381.
1
756, 702, 613; H NMR (400 MHz, CDCl3) δ (ppm) 7.96−7.86
(m, 2H), 7.65−7.53 (m, 7H), 7.51−7.44 (m, 3H), 7.06−7.03 (m,
2H), 3.88 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm)
159.9, 147.9, 139.6, 136.9, 134.8, 131.1, 130.6, 130.5, 130.0, 129.0,
128.8, 128.6, 128.4, 128.2, 127.3, 127.2, 118.1, 114.1, 110.1, 55.4;
HRMS (ESI) m/z calcd for C24H18NO+ [M + H]+ 336.1383, found
336.1380.
3-(Naphthalen-2-yl)-1-phenyl-2-naphthonitrile (3m): white solid
(29.8 mg, 84% yield); mp 172.1−172.9 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3440,
3043, 2223, 1616, 1585, 1442, 1317, 1128, 889, 860, 815, 744, 702;
1H NMR (400 MHz, CDCl3) δ (ppm) 8.14 (s, 1H), 8.04 (s, 1H),
8.01−7.89 (m, 4H), 7.80 (d, J = 8.5 Hz, 1H), 7.71−7.63 (m, 2H),
3-(3-Chlorophenyl)-1-phenyl-2-naphthonitrile (3g): white solid
(28.8 mg, 85% yield); mp 132.0−132.7 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3055,
1
2218, 1595, 1562, 1477, 1446, 1332, 1080, 881, 786, 756, 709; H
NMR (400 MHz, CDCl3) δ (ppm) 7.95 (dd, J = 8.6, 1.2 Hz, 1H),
E
https://dx.doi.org/10.1021/acs.joc.0c01975
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
pubs.acs.org/joc
Note
7.62−7.48 (m, 8H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm)
148.1, 139.9, 136.9, 136.2, 134.7, 133.3, 133.1, 130.9, 130.1, 129.1,
129.0, 128.9, 128.7, 128.6, 128.4, 128.3, 127.8, 127.44, 127.41,
127.0, 126.6, 126.5, 118.0, 110.2; HRMS (ESI) m/z calcd for
C27H18N+ [M + H]+ 356.1434, found 356.1431.
129.4, 129.3, 129.1, 128.6, 128.5, 128.4, 128.3, 127.5, 127.3, 118.1,
110.0, 21.5; HRMS (ESI) m/z calcd for C24H18N+[M + H]+
320.1434, found 320.1431.
1-(4-Methoxyphenyl)-3-phenyl-2-naphthonitrile (3u): white
solid (26.8 mg, 80% yield); mp 161.5−162.3 °C; Rf (silica,
petroleum ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1)
υ 3062, 2933, 2223, 1610, 1575, 1514, 1492, 1382, 1249, 1031, 837,
773, 703; 1H NMR (400 MHz, CDCl3) δ (ppm) 7.95−7.90 (m,
2H), 7.74−7.60 (m, 4H), 7.56−7.40 (m, 6H), 7.13−7.07 (m, 2H),
3.92 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm) 160.0,
147.8, 140.0, 138.8, 134.7, 131.4, 131.1, 129.3, 129.0, 128.9, 128.6,
128.5, 128.4, 128.3, 127.4, 127.3, 118.2, 114.1, 110.2, 55.3; HRMS
(ESI) m/z calcd for C24H18NO+ [M + H]+ 336.1383, found
336.1381.
1-Phenyl-3-(thiophen-2-yl)-2-naphthonitrile (3n): white solid
(21.2 mg, 68% yield); mp 154.7−155.5 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3047,
2229, 1620, 1583, 1485, 1444, 1377, 1319, 1153, 1070, 954, 885,
1
854, 837, 756, 705; H NMR (400 MHz, CDCl3) δ (ppm) 8.05 (s,
1H), 7.93 (d, J = 8.2 Hz, 1H), 7.67−7.53 (m, 6H), 7.51−7.41 (m,
4H), 7.19 (dd, J = 5.1, 3.7 Hz, 1H); 13C{1H} NMR (100 MHz,
CDCl3) δ (ppm) 148.6, 139.8, 136.7, 134.6, 132.0, 130.9, 130.0,
129.3, 128.9, 128.69, 128.66, 128.3, 128.2, 127.9, 127.6, 127.4,
126.8, 118.0, 109.3; HRMS (ESI) m/z calcd for C21H14NS+ [M +
H]+ 312.0842, found 312.0841.
3-(4-Chlorophenyl)-4-methyl-1-phenyl-2-naphthonitrile (3o):
white solid (21.6 mg, 61% yield); mp 198.1−198.8 °C; Rf (silica,
petroleum ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1)
υ3057, 2225, 1610, 1598, 1488, 1400, 1365, 1161, 1087, 1014, 1001,
842, 765, 700, 657, 624; 1H NMR (400 MHz, CDCl3) δ (ppm)
8.18−8.14 (m, 1H), 7.75−7.66 (m, 2H), 7.57−7.41 (m, 8H), 7.36−
7.29 (m, 2H), 2.53 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ
(ppm) 145.3, 137.5, 137.4, 136.9, 134.3, 134.2, 133.0, 131.14,
131.13, 130.1, 129.1, 128.83, 128.75, 128.6, 128.2, 127.1, 124.8,
117.8, 111.2, 16.8; HRMS (ESI) m/z calcd for C24H17ClN+ [M +
H]+ 354.1044, found 354.1046.
1-(Furan-2-yl)-3-phenyl-2-naphthonitrile (3v): white solid (21.0
mg, 71% yield); mp 145.3−150.1 °C; Rf (silica, petroleum ether/
EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3052, 2221,
1618, 1495, 1451, 1363, 1327, 1301, 1147, 1081, 1011, 901, 821,
1
760, 729, 694, 632; H NMR (400 MHz, CDCl3) δ (ppm) 8.05 (d,
J = 8.8 Hz, 1H), 7.92 (d, J = 11.2 Hz, 2H), 7.75 (dd, J = 1.8, 0.6
Hz, 1H), 7.69−7.62 (m, 3H), 7.62−7.56 (m, 1H), 7.55−7.44 (m,
3H), 6.95 (dd, J = 3.4, 0.6 Hz, 1H), 6.69 (dd, J = 3.4, 1.8 Hz, 1H);
13C{1H} NMR (100 MHz, CDCl3) δ (ppm) 148.6, 144.0, 140.3,
138.5, 136.0, 134.8, 130.6, 129.9, 129.3, 128.62, 128.55, 128.4,
127.9, 126.9, 117.9, 113.6, 111.6, 110.3; HRMS (ESI) m/z calcd for
C21H14NO+ [M + H]+ 296.1069, found 296.1068.
3-Phenyl-1-(thiophen-2-yl)-2-naphthonitrile (3w): white solid
(23.6 mg, 76% yield); mp 125.3−126.0 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3064,
2219, 1614, 1589, 1488, 1440, 1369, 1326, 1288, 1224, 1145, 1072,
902, 846, 767, 700, 624; 1H NMR (400 MHz, CDCl3) δ (ppm)
7.95 (s, 1H), 7.92 (d, J = 8.2 Hz, 1H), 7.88 (d, J = 8.5 Hz, 1H),
7.68−7.62 (M, 3H), 7.60 (dd, J = 5.1, 1.2 Hz, 1H), 7.57−7.43 (m,
4H), 7.31 (dd, J = 3.5, 1.1 Hz, 1H), 7.27−7.25 (m, 1H); 13C{1H}
NMR (100 MHz, CDCl3) δ (ppm) 140.3, 140.0, 138.5, 136.4,
134.5, 131.9, 129.9, 129.6, 129.27, 129.26, 128.7, 128.6, 128.2,
127.9, 127.8, 127.4, 127.1, 117.6, 111.9; HRMS (ESI) m/z calcd for
C21H14NS+ [M + H]+ 312.0842, found 312.0840.
1-Methyl-3-phenyl-2-naphthonitrile (3x): white solid (12.2 mg,
50% yield); mp 112.1−112.8 °C; Rf (silica, petroleum ether/EtOAc/
methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3058, 2219, 1625,
1586, 1494, 1445, 1410, 1379, 1326, 1181, 1072, 1028, 927, 883,
777, 764, 751, 698, 676, 615; 1H NMR (400 MHz, CDCl3) δ
(ppm) 8.11 (m, 1H), 7.91−7.84 (m, 1H), 7.77 (s, 1H), 7.68−7.58
(m, 4H), 7.54−7.40 (m, 3H), 3.03 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ (ppm) 142.8, 139.8, 139.0, 134.4, 130.7, 129.2,
128.94, 128.87, 128.6, 128.4, 127.5, 127.3, 124.9, 118.4, 110.2, 18.1;
HRMS (ESI) m/z calcd for C18H14N+ [M + H]+ 244.1121, found
244.1121.
4-Isopropyl-1,3-diphenyl-2-naphthonitrile (3p): white solid (42
mg, 60% yield); mp 214.2−214.7 °C; Rf (petroleum ether/EtOAc/
methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3059, 2221, 1484,
1441, 1332, 1365, 1332, 1241, 1152, 1091, 1071, 1025, 762, 699,
1
676; H NMR (400 MHz, CDCl3) δ (ppm) 8.30−8.24 (m, 1H),
7.65−7.57 (m, 1H), 7.55−7.47 (m, 6H), 7.43−7.38 (m, 3H), 7.32−
7.29 (m, 2H), 7.27−7.22 (m, 1H), 3.21−3.12 (m, 1H), 0.89 (d, J =
3.8 Hz, 3H), 0.87 (d, J = 3.8 Hz, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ (ppm) 147.6, 144.0, 141.9, 139.5, 139.1, 133.0, 130.6,
130.2, 129.7, 128.4, 128.14, 128.12, 127.9, 127.7, 127.5, 127.0,
125.1, 117.1, 112.1, 32.1, 23.0, 22.9; HRMS (ESI) m/z calcd for
C26H22N+ [M + H]+ 348.1752, found 348.1748.
1-(4-Fluorophenyl)-3-phenyl-2-naphthonitrile (3r): white solid
(27.5 mg, 85% yield); mp 178.8−179.6 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3057,
1
2223, 1606, 1514, 1490, 1218, 1161, 896, 844, 763, 752, 698; H
NMR (400 MHz, CDCl3):δ (ppm) 7.97−7.92 (m, 2H), 7.70−7.59
(m, 4H), 7.56−7.43 (m, 6H), 7.30−7.26 (m, 2H); 13C{1H} NMR
(100 MHz, CDCl3) δ (ppm) 163.1 (d, J = 248.4 Hz), 146.8, 139.9,
138.6, 134.7, 132.7 (d, J = 3.5 Hz), 131.9 (d, J = 8.3 Hz), 130.9,
129.23, 129.18, 128.9, 128.6, 128.5, 128.4, 127.6, 127.1, 117.9, 115.9
(d, J = 21.7 Hz), 110.2; 19F NMR (376 MHz, CDCl3) δ (ppm)
−112.54; HRMS (ESI) m/z calcd for C23H15NF+ [M + H]+
324.1183, found 324.1181.
6,7-Difluoro-1,3-diphenyl-2-naphthonitrile (3y): white solid
(26.6 mg, 78% yield); mp 175.1−175.8 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3070,
2216, 1724, 1598, 1580, 1515, 1493, 1458, 1441, 1388, 1306, 1275,
1253, 1201, 1311, 1075, 1035, 905, 870, 822, 761, 739, 700, 613,
Methyl 4-(2-Cyano-3-phenylnaphthalen-1-yl)benzoate (3s):
white solid (29.0 mg, 80% yield); mp 183.4−184.3 °C; Rf (silica,
petroleum ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1)
υ 3429, 3060, 2948, 2221, 1716, 1614, 1492, 1434, 1278, 1107, 867,
763, 707; 1H NMR (400 MHz, CDCl3) δ (ppm) 8.28−8.24 (m,
2H), 7.96 (d, J = 9.1 Hz, 2H), 7.70−7.62 (m, 3H), 7.62−7.44 (m,
7H), 3.99 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm)
166.7, 146.7, 141.6, 139.9, 138.5, 134.7, 130.6, 130.4, 130.3, 130.0,
129.3, 129.24, 129.16, 128.7, 128.6, 128.4, 127.7, 126.9, 117.7,
1
569, 508; H NMR (400 MHz, CDCl3):δ (ppm) 7.86 (s, 1H), 7.67
(dd, J = 10.4, 7.8 Hz, 1H), 7.65−7.62 (m, 2H), 7.61−7.56 (m, 3H),
7.55−7.44 (m, 5H), 7.39 (dd, J = 11.7, 8.0 Hz, 1H); 13C{1H} NMR
(100 MHz, CDCl3):δ (ppm) 151.9 (dd, J = 255.0, 16.0 Hz), 150.7
(dd, J = 251.5, 15.4 Hz), 147.2 (dd, J = 5.7, 2.1 Hz), 140.7 (d, J =
2.2 Hz), 138.2, 136.2, 132.0 (dd, J = 7.9, 1.0 Hz), 129.8, 129.3,
129.2, 128.9, 128.74, 128.71, 128.1 (d, J = 6.8 Hz), 127.8 (dd, J =
4.9, 1.8 Hz), 117.4, 114.1 (d, J = 17.0 Hz), 113.9 (d, J = 18.5 Hz),
110.6 (d, J = 2.7 Hz); 19F NMR (376 MHz, CDCl3) δ −131.66 (d,
J = 20.8 Hz), −133.10 (d, J = 20.8 Hz); HRMS (ESI) m/z calcd for
C23H14F2N+ [M + H]+ 342.1089, found 342.1090.
6,7-Dimethyl-1,3-diphenyl-2-naphthonitrile (3z): white solid
(25.0 mg, 75%, yield); mp 173.4−174.2 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3440,
3060, 2916, 2219, 1623, 1591, 1494, 1450, 1375, 1024, 902, 761,
698, 613; 1H NMR (400 MHz, CDCl3) δ (ppm) 7.80 (s, 1H),
+
109.8, 52.3; HRMS (ESI) m/z calcd for C25H18NO2 [M + H]+
364.1332, found 364.1333.
3-Phenyl-1-p-tolyl-2-naphthonitrile (3t): white solid (24.9 mg,
78% yield); mp 119.3−120.2 °C; Rf (silica, petroleum ether/EtOAc/
methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3025, 2221, 1613,
1584, 1513, 1489, 1446, 1375, 1332, 1294, 1184, 1151, 1113, 1070,
1023, 899, 832, 790, 699, 652; 1H NMR (400 MHz, CDCl3) δ
(ppm) 7.93 (d, J = 9.2 Hz, 2H), 7.71−7.58 (m, 4H), 7.54−7.45 (m,
4H), 7.38 (s, 4H), 2.48 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3)
δ (ppm) 148.1, 139.9, 138.8, 138.7, 134.7, 133.9, 131.0, 129.9,
F
https://dx.doi.org/10.1021/acs.joc.0c01975
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
pubs.acs.org/joc
Note
7.69−7.63 (m, 3H), 7.61−7.40 (m, 8H), 7.36 (s, 1H), 2.46 (s, 3H),
2.33 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm) 147.0,
139.5, 139.13, 139.06, 137.6, 137.2, 133.7, 130.0, 129.6, 129.3,
128.7, 128.6, 128.5, 128.2, 127.8, 127.7, 126.6, 118.3, 108.9, 20.4,
20.3; HRMS (ESI) m/z calcd for C25H20N+ [M + H]+ 334.1590,
found 334.1590.
AUTHOR INFORMATION
■
Corresponding Authors
Guangfen Du − Key Laboratory for Green Processing of
Chemical Engineering of Xinjiang Bingtuan, School of
Chemistry and Chemical Engineering, Shihezi University,
Xinjiang Uygur Autonomous Region 832000, China;
Email: duguangfen@shzu.du.cn
Lin He − Key Laboratory for Green Processing of Chemical
Engineering of Xinjiang Bingtuan, School of Chemistry and
Chemical Engineering, Shihezi University, Xinjiang Uygur
Autonomous Region 832000, China; orcid.org/0000-
0003-1767-9980; Email: helin@shzu.edu.cn
6,7-Dimethoxy-1,3-diphenyl-2-naphthonitrile (3aa): white solid
(21.9 mg, 60%, yield); mp 176.9−177.4 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3019,
2221, 1617, 1571, 1506, 1460, 1428, 1248, 1225, 1142, 1073, 1031,
1
1013, 888, 851, 824, 768, 745, 704; H NMR (400 MHz, CDCl3) δ
(ppm) 7.77 (s, 1H), 7.67−7.62 (m, 2H), 7.60−7.46 (m, 7H), 7.46−
7.40 (m, 1H), 7.19 (s, 1H), 6.88 (s, 1H), 4.04 (s, 3H), 3.76 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm) 151.9, 150.4,
145.7, 139.1, 139.0, 137.4, 131.4, 129.9, 129.2, 128.8, 128.7, 128.5,
128.2, 127.0, 126.7, 118.4, 107.9, 106.4, 105.5, 56.1, 55.8; HRMS
Authors
+
(ESI) m/z calcd for C25H20NO2 [M + H]+ 366.1489, found
Qiang Wang − Key Laboratory for Green Processing of
Chemical Engineering of Xinjiang Bingtuan, School of
Chemistry and Chemical Engineering, Shihezi University,
Xinjiang Uygur Autonomous Region 832000, China
Yi An − Key Laboratory for Green Processing of Chemical
Engineering of Xinjiang Bingtuan, School of Chemistry and
Chemical Engineering, Shihezi University, Xinjiang Uygur
Autonomous Region 832000, China
Zhi-Hua Cai − Key Laboratory for Green Processing of
Chemical Engineering of Xinjiang Bingtuan, School of
Chemistry and Chemical Engineering, Shihezi University,
Xinjiang Uygur Autonomous Region 832000, China;
orcid.org/0000-0002-4861-7056
366.1489.
1,3-Diphenylanthracene-2-carbonitrile (3ab): yellow solid (19.9
mg, 56% yield); mp 174.5−175.2 °C; Rf (silica, petroleum ether/
EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3049, 2219,
1602, 1495, 1442, 1362, 1282, 1074, 1025, 998, 909, 772, 745, 697,
1
603; H NMR (400 MHz, CDCl3):δ (ppm) 8.49 (s, 1H), 8.21 (s,
1H), 8.07 (s, 1H), 8.02 (d, J = 8.4 Hz, 1H), 7.87 (d, J = 8.4 Hz,
1H), 7.74−7.67 (m, 2H), 7.66−7.41 (m, 10H); 13C{1H} NMR (100
MHz, CDCl3) δ (ppm) 149.3, 138.8, 137.9, 137.1, 133.3, 132.3,
131.7, 130.1, 129.3, 129.03, 129.00, 128.78, 128.77, 128.6, 128.4,
127.9, 127.5, 127.4, 126.9, 126.3, 118.1, 109.7; HRMS (ESI) m/z
calcd for C27H18N+ [M + H]+ 356.1434, found 356.1432.
8-Methoxy-1,3-diphenyl-2-naphthonitrile (3ac): white solid
(24.8 mg, 74% yield); mp 182.9−183.6 °C; Rf (silica, petroleum
ether/EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3001,
2218, 1614, 1558, 1496, 1454, 1369, 1348, 1292, 1259, 1109, 777,
744, 702; 1H NMR (400 MHz, CDCl3) δ (ppm) 7.86 (s, 1H),
7.67−7.61 (m, 2H), 7.59−7.39 (m, 8H), 7.37−7.32 (m, 2H), 6.81
(dd, J = 7.5, 1.2 Hz, 1H), 3.43 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ (ppm) 157.1, 146.7, 141.6, 140.1, 138.6, 136.5, 129.8,
129.2, 128.7, 128.5, 128.4, 128.3, 127.4, 127.3, 122.5, 121.0, 117.8,
111.4, 107.3, 55.5; HRMS (ESI) m/z calcd for C24H18NO+ [M +
H]+ 336.1383, found 336.1382.
8-Methyl-1,3-diphenyl-2-naphthonitrile (3ad): white solid (25.5
mg, 80% yield); mp 138.1−138.8 °C; Rf (silica, petroleum ether/
EtOAc/methanol, 100:1:1) = 0.3; IR (KBr, cm−1) υ 3062, 2223,
1591, 1479, 1446, 1380, 1325, 1311, 1178, 1074, 1028, 889, 811,
769, 759, 742, 700, 646, 586, 540, 514; 1H NMR (400 MHz,
CDCl3) δ (ppm) 8.07 (s, 1H), 7.72−7.64 (m, 2H), 7.60−7.41 (m,
10H), 7.37 (dd, J = 8.5, 7.0 Hz, 1H), 2.75 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3) δ (ppm) 148.3, 139.7, 139.2, 137.3, 134.8,
133.9, 131.1, 130.0, 129.8, 129.4, 128.8, 128.61, 128.56, 128.4,
127.0, 125.8, 125.1, 118.0, 109.8, 19.7; HRMS (ESI) m/z calcd for
C24H18N+ [M + H]+ 320.1434, found 320.1433.
Bin Dai − Key Laboratory for Green Processing of Chemical
Engineering of Xinjiang Bingtuan, School of Chemistry and
Chemical Engineering, Shihezi University, Xinjiang Uygur
Autonomous Region 832000, China; orcid.org/0000-
0001-9254-6606
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.joc.0c01975
Author Contributions
†Q.W. and Y.A. contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (21462034), the Excellent Young
Teachers Plan of Bingtuan (2017CB001 and CZ027203),
and the International Cooperation Project of Shihezi
University (GJHZ201801). We also thank Ms. K. Yeung of
the University of Bristol for proofreading this paper.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.joc.0c01975.
■
sı
REFERENCES
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1H, 13C, and 19F NMR spectra for all products and the
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