Synthesis of 1-Cyano-3-acylnaphthalenes via Formal [4+2] Benzannulation of 2-(2-Alkynylphenyl)acetonitriles and Alkynones

Article abstract of DOI:10.1021/acs.joc.9b00948

Effective transition-metal-free formal [4+2] benzannulation for the preparation of 1-cyano-3-acylnaphthalenes from 2-(2-alkynylphenyl)acetonitriles and alkynones through sequential C-C bond coupling has been developed. This protocol is characterized by mi

Full text of DOI:10.1021/acs.joc.9b00948

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Article
Synthesis of 1-Cyano-3-acylnaphthalenes via Formal [4+2] Ben-
zannulations of 2-(2-Alkynylphenyl)acetonitriles and Alkynones
Lu-Lu Chen, Jing-Wen Zhang, Wan-Wan Yang, Ji-Ya Fu, Jun-Yan Zhu, and Yan-Bo Wang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b00948 • Publication Date (Web): 29 May 2019
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Synthesis of 1-Cyano-3-acylnaphthalenes via Formal [4+2]
Benzannulations of 2-(2-Alkynylphenyl)acetonitriles and Alkynones
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Lu-Lu Chen, Jing-Wen Zhang, Wan-Wan Yang, Ji-Ya Fu, Jun-Yan Zhu and Yan-Bo Wang*
Institute of Functional Organic Molecular Engineering, Henan Engineering Laboratory of Flame-Retardant and Functional
Materials, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475004, China.
Supporting Information
ABSTRACT: An effective transition-metal-
free formal [4+2] benzannulations for the
preparation of 1-cyano-3-acylnaphthalenes
from 2-(2-alkynylphenyl)acetonitriles and
alkynones through a sequential C-C bond
coupling has been developed. This protocol is
characterized by mild conditions, excellent
functional
group
tolerance,
complete
regioselectivity and atom economy. The plausible mechanism, gram scale synthesis and further transformations of product
were studied.
INTRODUCTION
efficient base-catalyzed method for the synthesis of 1-cyano-3-
acylnaphthalene derivatives from 2-(2-alkynylphenyl)
acetonitriles and alkynones vis a sequential C-C bond coupling
with complete regioselectivity and atom economy under mild
conditions (Scheme 1e).
Polysubstituted naphthalenes have attracted much attention
owing to the fact that they are an important structural motif with
broad applications in optical and electronic materials.1
Furthermore, they are also critical skeletons exciting in many
biologically active compounds.2 Therefore, various methods for
the synthesis of the naphthalene skeleton using alkynes,3 arynes,
Scheme 1. Synthesis of Polysubstituted Naphthalene
Derivatives via Formal [4+2] Benzannulation Reaction
Involving Alkynes
4
6
olefins 5 or other reagents have been reported. Among the
reported methodologies, an efficient approach for the formal
[4+2] benzannulations using alkyne as a two-carbon unit to
synthesize the naphthalene derivatives is of significant interest.
7−10 For examples, a seminal work for benzannulation of alkynes
with 2-alkynylbenzaldehydes was reported by Asao and
Yamamoto.7a Subsequently, various catalytic systems suitable
for benzannulation of alkynes with 2-alkynylbenzaldehydes
were also reported (Scheme 1a).7b-7i Transition-metal-catalyzed
benzannulation of arene-containing vinylic iodides and triflates
or β‑enaminonitriles with alkynes was described, respectively
(Scheme 1b).8 Pallaium(0)-catalyzed annulation of 1-allyl-2-
bromobenzenes with alkynes has been demonstrated (Scheme
1c).9 Additionally, naphthalene derivatives could also be
synthesized by the condensation of phenylacetaldehydes with
alkynes using the Lewis acids or Brønsted-acid as catalysts
(Scheme 1d).10 Besides the above examples, other formal [4+2]
benzannulations using alkyne have been reported.11 However,
these catalytic systems usually need transition-metals, Lewis
acids or Brønsted-acid as catalysts and demand dehalogenation
or dehydration to run smoothly. To the best of our knowledge,
base-mediated [4+2] benzannulation involving alkynes for the
synthesis of polysubstituted naphthalenes has not been reported.
Due to the cyano and acyl substituents as important functional
groups, it is of critical interest to explore convenient and
efficient access to the construction of naphthalene ring with
diverse cyano and acyl groups. As a continuation of our interest
in the catalytic transition of alkyne,12 herein we firstly report an
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Initially, we choose 2-(2-(phenylethynyl)phenyl)acetonitrile 1a
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and alkynone 2a as model substrates and the experimental
results are summarized in Table 1. To our delight, when the
reaction of 2-(2-(phenylethynyl)phenyl)acetonitrile 1a and
alkynone 2a using 0.1 equiv. amount of K2CO3 as catalyst in
DMF under 40 ℃ was attempted, desired product 3aa was
obtained in 56% yield (Table 1, entry 1). The structure of 3aa
was unambiguously determined by X-ray crystallography (see
Supporting Information). Next, different inorganic bases were
screening and the experimental results revealed that LiOtBu was
superior, leading to a higher yield (entries 2−7). However, it
failed to deliver product 3aa by the usage of Et3N as catalyst
(Table 1, entry 8). When DBU was used as catalyst, the product
3aa was afforded in 54% yield. A decline in the yield of 3aa
appeared when the loading of LiOtBu was decreased from 0.1
to 0.05 equiv. (Table 1, entry 10). Further condition
optimization of reaction solvents was conducted. Solvent
including NMP or DMSO proved to be less effective (entries
11−12). However, other solvent such as CH3CN, 1,4-dioxane,
THF or CH2Cl2 afforded the product 3aa in trace or no yields
(Table 1, entries 13-16).
RESULTS AND DISCUSSION
Table 1. Optimization of Reaction Conditions a
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Entry
1
base
Solvent
DMF
Yield b (%)
K2CO3
Cs2CO3
KOtBu
NaOtBu
LiOtBu
NaOH
KOH
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76
65
72
88
76
74
-
2
DMF
3
DMF
4
DMF
5
DMF
6
DMF
7
DMF
Having identified the optimal conditions for this
benzannulations reaction, the scope of 2-(2-alkynylphenyl)
acetonitriles was then tested (Table 2). The electronic effect of
substituents at the 4-position of phenyl ring in the R1 group has
little influence on the reaction reactivity. Both electron-
donating (4-Me 1b, 4-OMe 1c, 4-tBu 1d) and electron-
withdrawing (4-Cl 1f, 4-F 1g, 4-CF3 1h) substituents could be
smoothly transformed into the corresponding products with
moderate to excellent yields. Substrate 1e with 3-Me group
could give good yield. Furthermore, 2-(2-(hex-1-yn-1-
yl)phenyl)acetonitrile 1i as substrate was also suitable to this
reaction, affording the product 3ia in 44% yield. The low yield
of the desired product 3ia may be affected by the conjugation
effect. In addition, substrate 1j with 5-F group was also
competent in this reaction. However, 1k with more electron-
donating substituent (4,5-dimethoxy group) may go against this
cyclization reaction to give the moderate yield.
8
Et3N
DMF
9
DBU
DMF
54
77
78
86
trace
-
10c
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16
LiOtBu
LiOtBu
LiOtBu
LiOtBu
LiOtBu
LiOtBu
LiOtBu
DMF
NMP
DMSO
CH3CN
1,4-dioxane
THF
-
CH2Cl2
-
a Reaction conditions: 1a (0.30 mmol), 2a (0.30 mmol), base
(0.03 mmol) and solvent (1.5 mL) at 40 oC for 1 h. b Isolated
yields. c1a (0.30 mmol), 2a (0.30 mmol) and base (0.015 mmol)
was used.
Table 2. Benzannulation Reaction of Various 2-(2-Alkynylphenyl)acetonitriles 1 with Alkynone 2aa
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aReaction conditions: 1 (0.30 mmol), 2a (0.30 mmol), LitOBu (0.03 mmol) and DMF (1.5 mL) at 40 oC for 1 h.
After successful catalytic transition of 2-(2-alkynylphenyl)
acetonitriles 1 into the 1-cyano-3-acylnaphthalenes 3, we next
investigated the generality of various alkynones 2 with 2-(2-
(phenylethynyl)phenyl)acetonitrile 1a. This catalytic system
exhibits broad substrate tolerance and various of 1-cyano-3-
acylnaphthalenes 3 were obtained in moderate to excellent
yields as depicted in Table 3. The R3 groups at the 3-positions
of alkynones were firstly studied. Using 3-aryl substituted
alkynones with different electron-rich (4-Me 2b, 4-OMe 2c, 4-
tBu 2d), electron-withdrawing (4-Cl 2f, 4-F 2g, 4-CO2Me 2h)
or heteroaromatic derivative (2i) as substrates, the
corresponding products could be smoothly generated. Substrate
2e with 3-Me on the phenyl ring was suitable to this reaction in
90% yield. Additionally, the substrate 2j bearing t-butyl-
substitution could also provide the product 3aj in 82% yield.
Different from the substrate 2j, alkynone 2k with n-butyl
substitution give the desired product 3ak in only 39% yield due
to the existence of unknown by-products. Furthermore, The R4
groups at the 1-positions of alkynones were next explored.
Similar to the R3 groups, common substituent containing alkyl
(2l-2n), ether (2o-2p), halo (2q-2r), or trifluoromethyl (2s)
group at para position of the phenyl ring, was all tolerated in
this reaction. Alkynone with naphthyl (2t) or heteroaromatic
(2u-2v) substrates were compatible with this reaction. Notably,
this protocol could also be extended to methyl substrate 2w,
leading to the product 3aw in 62% yield.
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Table 3. Benzannulation Reaction of 2-(2-Alkynylphenyl)acetonitrile 1a with Various Alkynones 2 a
aReaction conditions: 1a (0.30 mmol), 2 (0.30 mmol), LitOBu (0.03 mmol) and DMF (1.5 mL) at 40 oC for 1 h.
For the practicability and effectiveness of this new method to
be demonstrated, this reaction proceeded smoothly to give the
desired product 3aa in 80% isolated yield under the optimal
conditions, when we carried out a gram scale experiment
(Scheme 2). To further investigate application of this 1-cyano-
3-acylnaphthalenes for constructing functionalized compounds,
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the product 4 was given by the cyclization of 3aa in the yield under standard conditions (Scheme 4). On the basis of the
above results and previous literatures, 13 a plausible mechanism
was proposed and shown in Scheme 5. For the first step,
intermediate A could be produced by deprotonation of 2-(2-
alkynylphenyl)acetonitriles in the presence of LiOtBu. Then,
intermediate A added to triple bond of alkynones by
nucleophilic attack to obtain intermediate B. Subsequently, the
new intermediate C could be generated by intramolecular
cyclization. Usually, carbon anion could attack the triple bond
of terminal alkyne.14 However, this is rare example that carbon
anion directly adds to triple bond of internal alkyne without
electron-withdrawing group in absence of transition-metal or
1
2
3
4
5
6
7
8
presence of CF3SO3H (Scheme 3a), the structure of which was
characterized by X-ray crystallography (see Supporting
Information). 3aa was also reduced to deliver the product 5 in
the presence of HAl(iBu)2 (Scheme 3b).
Scheme 2. Gram-Scale Reaction for Synthesis of Product
3aa
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Lewis acids.14d Intermediate
C
was transmitted into
intermediate D by capturing hydrogen proton. Finally, the
products 3 were released by the aromatization.
CONCLUSION
Scheme 3. The Further Transformation of Product 3aa
In summary, we have demonstrated a convenient base-mediated
approach for the synthesis of 1-cyano-3-acylnaphthalenes from
2-(2-alkynylphenyl)acetonitriles and alkynones through a
sequential C-C bond coupling with complete regioselectiviy
and atom economy under mild conditions. This strategy
provides an efficient and transition-metal-free method and
various of the functional products were prepared in moderate to
excellent yields. This reaction mays undergo a rare process that
carbon anion directly attacks the triple bond of internal alkynes
without electron-withdrawing groups in the absence of
transition-metals and Lewis acids. What’s more, the suitability
for gram-scale reaction and facile further transformation of 1-
cyano-3-acylnaphthalenes enhance the utility of this new
method.
Scheme 4. Control Experiment
EXPERIMENTAL SECTION
General Information. Unless otherwise statement, all
manipulations were performed using standard Schlenk
techniques under a dry nitrogen atmosphere. NMR spectra were
recorded with tetramethylsilane as the internal standard. NMR
spectrawere recorded on a BrukerAvanceII400M type (1H
NMR, 400 MHz; 13C NMR, 100 MHz) spectrometer. High
resolution mass spectra (HRMS) were recorded on a Q-TOF
mass spectrometry (Micromass, Wythenshawe, UK) equipped
with Z-spray ionization source. Infrared spectra (IR) was
measured using a Nicolet NEXUS FT-IR spectrophotometer.
CH2Cl2, DMSO and DMF were distilled from calcium hydride
under N2 atmosphere. Acetonitrile was distilled from
phosphorus pentoxide under N2 atmosphere. Tetrahydrofuran
and 1,4-dioxane were distilled from sodium/benzophenone
under N2 atmosphere. The substrates 1 were synthesized from
Scheme 5. Plausible Mechanisms for the Synthesis of 1-
Cyano-3-acylnaphthalenes Naphthalenes.
2-(2-bromophenyl)acetonitriles and terminal alkynes according
15
the literatures.
The substrates 2 were prepared by the
Sonogashira coupling of acyl chlorides with terminal alkynes.
16
Representative
Experimental
Procedure
for
Benzannulations of 2-(2-Alkynylphenyl)acetonitriles and
Alkynones. A 10 mL oven-dried Schlenck tube was charged
with 2-(2-(phenylethynyl)phenyl)acetonitriles 1 (0.30 mmol),
alkynones 2 (0.30 mmol) and DMF (1.5 mL), then LiOtBu (2.4
To exclude a radical mechanism for this present method, we
conducted control experiment under the radical scavenger such
as TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl), and the
reaction could smoothly run to give the product 3aa in 61%
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mg, 0.03 mmol) was added into reaction solution. The tube was eluent: petroleum ether/ethyl acetate (50:1); mp 218.9–220.0
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8
1
sealed and the reaction mixture was stirred at 40 ℃ using oil
bath for 1 h. After completion of this reaction, the resulting
mixture was diluted with ethyl acetate (10 mL) and washed with
H2O (10 mL). The aqueous phase was extracted with ethyl
acetate (2 × 10 mL). The combined organic layers were then
washed with brine (10 mL) and dried over anhydrous Na2SO4,
filtered and concentrated in-vacuo. The crude reaction mixture
was purified by column chromatography on silica gel
(PE/EtOAc) to give products 3.
℃; H NMR (400 MHz, CDCl3) δ (ppm): 8.41 (d, J = 8.3 Hz,
1H), 8.19 (d, J = 8.5 Hz, 1H), 7.75 (t, J = 7.4 Hz, 1H), 7.67–
7.60 (m, 1H), 7.47–6.92 (m, 14H), 4.38 (q, J = 15.5 Hz, 2H),
1.21 (s, 9H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm): 197.4,
149.2, 143.6, 139.6, 138.5, 137.3, 136.3, 135.8, 133.4, 133.0,
131.3, 129.3, 128.7, 128.3, 128.2, 128.1, 126.4, 126.2, 125.4,
116.8, 110.0, 35.7, 34.3, 31.3; IR (KBr, cm-1): 3058, 2962,
2869, 2222, 1672, 1595, 1578, 1563, 1450; HRMS (ESI-TOF)
calcd for C35H30NO+ ([M+H]+): 480.2322, found: 480.2325.
3-Benzoyl-4-(3-methylbenzyl)-2-phenyl-1-naphthonitrile (3ea):
yellow solid (108.9 mg, 83% yield); eluent: petroleum
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3-Benzoyl-4-benzyl-2-phenyl-1-naphthonitrile (3aa): white
solid (111.8 mg, 88% yield); eluent: petroleum ether/ethyl
acetate (50:1); mp 258.5–260.5 ℃; 1H NMR (400 MHz, CDCl3)
δ(ppm): 8.41 (d, J = 8.3 Hz, 1H), 8.14 (d, J = 8.5 Hz, 1H), 7.74
(t, J = 7.4 Hz, 1H), 7.61 (dd, J = 11.4, 4.0 Hz, 1H), 7.45–7.09
(m, 15H), 4.42 (q, J = 15.6 Hz, 2H); 13C{1H} NMR (100 MHz,
CDCl3) δ (ppm): 197.5, 143.7, 139.2, 139.1, 138.7, 137.3, 136.3,
133.6, 133.0, 131.3, 129.4, 128.8, 128.6, 128.5, 128.4, 128.3,
128.2, 126.5, 126.5, 126.2, 116.8, 110.2,36.4; IR (KBr, cm-1):
3436, 3080, 3061, 3027, 2929, 2222, 1669, 1594, 1579, 1498,
1449; HRMS (ESI-TOF) calcd for C31H22NO+ ([M+H]+):
424.1696, found: 424.1699.
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ether/ethyl acetate (50:1); mp 245.8–247.2 ℃; H NMR (400
MHz, CDCl3) δ (ppm): 8.41 (d, J = 8.3 Hz, 1H), 8.16 (d, J = 8.5
Hz, 1H), 7.74 (t, J = 7.6 Hz, 1H), 7.61 (t, J = 7.7 Hz, 1H), 7.48–
6.83 (m, 14H), 4.38 (q, J = 15.4 Hz, 2H), 2.19 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ (ppm): 197.5, 143.6, 139.4, 139.0,
138.7, 138.2, 137.3, 136.3, 133.6, 133.0, 131.4, 129.4, 129.4,
129.3, 128.8, 128.5, 128.3, 128.2, 127.3, 126.5, 126.3, 125.5,
116.9, 110.1, 36.3, 21.5; IR (KBr, cm-1): 3084, 3030, 2925,
2223, 1666, 1595, 1565, 1450; HRMS (ESI-TOF) calcd for
C32H24NO+ ([M+H]+): 438.1852, found: 438.1856.
4-(4-Chlorobenzyl)-3-benzoyl-2-phenyl-1-naphthonitrile
(3fa): white solid (129.1 mg, 94% yield); eluent: petroleum
ether/ethyl acetate (50:1); mp 189.1–190.3 ℃; 1H NMR (400
MHz, CDCl3) δ (ppm): 8.42 (d, J = 8.4 Hz, 1H), 8.08 (d, J = 8.5
Hz, 1H), 7.76 (t, J = 7.6 Hz, 1H), 7.63 (t, J = 7.7 Hz, 1H), 7.44–
7.05 (m, 14H), 4.37 (dd, J = 71.3, 15.7 Hz, 2H); 13C{1H} NMR
(100 MHz, CDCl3) δ (ppm): 197.4, 143.6, 138.7, 138.5, 137.5,
137.1, 136.1, 133.7, 133.0, 132.4, 131.1, 129.8, 129.5, 129.3,
128.9, 128.7, 128.5, 128.4, 128.2, 126.6, 125.9, 116.7, 110.4,
35.7; IR (KBr, cm-1): 3436, 3084, 3065, 3036, 2933, 2227, 1664,
1596, 1492, 1450; HRMS (ESI-TOF) calcd for C31H21ClNO+
([M+H]+): 458.1306, found: 458.1308.
3-Benzoyl-4-(4-methylbenzyl)-2-phenyl-1-naphthonitrile
(3ba): white solid (107.6 mg, 82% yield); eluent: petroleum
1
ether/ethyl acetate (50:1); mp 234.1–236.1 ℃; H NMR (400
MHz, CDCl3) δ (ppm): 8.40 (d, J = 8.3 Hz, 1H), 8.14 (d, J = 8.5
Hz, 1H), 7.73 (t, J = 7.6 Hz, 1H), 7.60 (t, J = 7.7 Hz, 1H), 7.48–
6.88 (m, 14H), 4.37 (dd, J = 66.3, 15.7 Hz, 2H), 2.23 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3) δ (ppm): 143.6, 139.5, 138.6,
137.3, 136.3, 136.0, 133.5, 133.0, 131.3, 129.3, 129.3, 129.23,
128.8, 128.3, 128.3, 128.3, 128.1, 126.4, 126.2, 116.8, 110.1,
36.0, 21.0; IR (KBr, cm-1): 3054, 2927, 2222 ，1669, 1595,
1579, 1448; HRMS (ESI-TOF) calcd for C32H24NO+ ([M+H]+):
438.1852, found: 438.1856.
4-(4-Fluorobenzyl)-3-benzoyl-2-phenyl-1-naphthonitrile
(3ga): white solid (98.0 mg, 74% yield); eluent: petroleum
4-(4-Methoxybenzyl)-3-benzoyl-2-phenyl-1-naphthonitrile
(3ca): white solid (125.2 mg, 92% yield); eluent: petroleum
1
ether/ethyl acetate (50:1); mp 246.9–247.2 ℃; H NMR (400
1
ether/ethyl acetate (20:1); mp 189.9–190.0 ℃; H NMR (400
MHz, CDCl3) δ (ppm): 8.42 (d, J = 8.3 Hz, 1H), 8.11 (d, J = 8.5
Hz, 1H), 7.76 (t, J = 7.6 Hz, 1H), 7.63 (t, J = 7.7 Hz, 1H), 7.50
– 7.02 (m, 12H), 6.86 (t, J = 8.6 Hz, 2H), 4.38 (dd, J = 70.7,
15.6 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm): 197.4,
161.5 (d, J C-F= 245.0 Hz), 143.6, 138.9, 138.6, 137.2, 136.1,
MHz, CDCl3) δ (ppm): 8.38 (d, J = 8.3 Hz, 1H), 8.13 (d, J = 8.5
Hz, 1H), 7.71 (dd, J = 11.3, 3.9 Hz, 1H), 7.62–7.55 (m, 1H),
7.46–6.62 (m, 14H), 4.32 (dd, J = 64.2, 15.6 Hz, 2H), 3.67 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm): 197.5, 158.2,
143.6, 139.6, 138.5, 137.3, 136.3, 133.5, 133.0, 131.2, 131.1,
129.4, 129.3, 128.8, 128.3, 128.3, 128.1, 126.4, 126.2, 116.8,
114.0, 110.0, 55.2, 35.5; IR (KBr, cm-1): 3064, 2997, 2834,
2223, 1676, 1608, 1581, 1509, 1448; HRMS (ESI-TOF) calcd
for C32H24NO2+ ([M+H]+): 454.1802, found: 454.1805.
134.6 (d, J C-F = 3.2 Hz), 133.7, 133.0, 131.1, 129.9 (d, J C-F
=
7.9 Hz), 129.4, 129.3, 128.8, 128.4, 128.3, 128.2, 126.5, 125.9,
116.7, 115.4 (d, J = 21.4 Hz), 110.3, 35.5; IR (KBr, cm-1): 3436,
3060, 2931, 2223, 1666, 1605, 1579, 1511, 1448, 1411; HRMS
(ESI-TOF) calcd for C31H21FNO+ ([M+H]+): 442.1602, found:
442.1606.
4-(4-Tert-butylbenzyl)-3-benzoyl-2-phenyl-1-
naphthonitrile (3da): white solid (118.0 mg, 82% yield);
4-(4-(Trifluoromethyl)benzyl)-3-benzoyl-2-phenyl-1-
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+
naphthonitrile (3ha): white solid (110.6 mg, 75% yield); eluent:
1433; HRMS (ESI-TOF) calcd for C33H26NO3 ([M+H]+):
1
2
3
4
5
6
7
8
1
484.1907, found: 484.1908.
petroleum ether/ethyl acetate (50:1); mp 210.9–202.4 ℃; H
3-Benzoyl-4-benzyl-2-p-tolyl-1-naphthonitrile (3ab): white
solid (105.0 mg, 80% yield); eluent: petroleum ether/ethyl
acetate (50:1); mp 234.8–236.7 ℃; 1H NMR (400 MHz, CDCl3)
δ (ppm): 8.39 (d, J = 8.3 Hz, 1H), 8.10 (d, J = 8.5 Hz, 1H), 7.72
(t, J = 7.6 Hz, 1H), 7.58 (t, J = 7.7 Hz, 1H), 7.44 (t, J = 7.4 Hz,
2H), 7.37 (t, J = 7.4 Hz, 1H), 7.31–6.76 (m, 11H), 4.38 (dd, J =
56.9, 15.7 Hz, 2H), 2.24 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ (ppm): 197.5, 143.8, 139.0, 139.0, 138.7, 138.7, 137.3,
133.6, 133.3, 133.0, 131.2, 129.4, 129.3, 128.9, 128.6, 128.4,
128.3, 128.2, 126.5, 126.4, 126.1, 116.9, 110.22, 36.4, 21.3; IR
(KBr, cm-1): 3063, 3029, 2921, 2221, 1671, 1594, 1497, 1448;
HRMS (ESI-TOF) calcd for C32H24NO+ ([M+H]+): 438.1852,
found: 438.1859.
NMR (400 MHz, CDCl3) δ (ppm): 8.45 (d, J = 8.3 Hz, 1H), 8.07
(d, J = 8.5 Hz, 1H), 7.79 (t, J = 7.6 Hz, 1H), 7.66 (dd, J = 11.4,
4.1 Hz, 1H), 7.50–7.12 (m, 14H), 4.47 (dd, J = 70.2, 15.7 Hz,
2H); 13C{1H} NMR (75 MHz, CDCl3) δ (ppm): 197.5, 143.6,
143.1 (q, J
= 1.2 Hz), 138.9, 138.0, 137.0, 136.1, 133.8,
C-F
133.1, 131.0, 129.6, 129.3, 129.1, 128.9, 128.8, 128.7, 128.4,
128.3, 126.7, 125.7, 125.6 (q, J = 3.7 Hz), 124.2 (q, J
9
C-F
C-F
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
=270.3Hz), 116.7, 110.6, 36.1; IR (KBr, cm-1): 3059, 2929,
2226, 1667, 1596, 1565, 1449; HRMS (ESI-TOF) calcd for
C32H21F3NO+ ([M+H]+): 492.1570, found: 492.1572.
3-Benzoyl-4-pentyl-2-phenyl-1-naphthonitrile: (3ia): white
solid (53.3 mg, 44% yield); eluent: petroleum ether/ethyl
acetate (50:1); mp 172.5–173.9 ℃; 1H NMR (400 MHz, CDCl3)
δ (ppm): 7.92 (d, J = 7.4 Hz, 1H), 7.58–7.42 (m, 2H), 7.42–7.30
(m, 2H), 7.28–6.95 (m, 9H), 3.31 (d, J = 133.8 Hz, 2H), 2.33 (t,
J = 7.7 Hz, 2H), 1.64 (s, 2H), 1.32–1.14 (m, 2H), 0.90–0.75 (m,
3H); 13C{1H} NMR (75 MHz, CDCl3) δ (ppm): 195.4, 153.8,
152.9, 139.2, 138.3, 137.3, 133.9, 133.3, 133.1, 132.7, 130.5,
130.2, 129.4, 128.4, 128.4, 128.1, 128.0, 127.4, 127.1, 119.0,
114.1, 39.4, 35.8, 30.9, 22.8, 13.9; IR (KBr, cm-1): 2958, 2930,
2871, 2212, 1661, 1593, 1448; HRMS (ESI-TOF) calcd for
C29H26NO+ ([M+H]+): 404.2009, found: 404.2012.
3-Benzoyl-4-benzyl-2-(4-methoxyphenyl)-1-naphthonitrile
(3ac): yellow solid (129.3 mg, 95% yield); eluent: petroleum
1
ether/ethyl acetate (10:1); mp 219.2–221.2 ℃; H NMR (400
MHz, CDCl3) δ (ppm): 8.39 (d, J = 8.3 Hz, 1H), 8.12 (d, J = 8.5
Hz, 1H), 7.72 (t, J = 7.6 Hz, 1H), 7.58 (t, J = 7.5 Hz, 1H), 7.46
(d, J = 7.4 Hz, 2H), 7.37 (t, J = 7.4 Hz, 1H), 7.30–7.06 (m, 9H),
6.76 (s, 2H), 4.39 (dd, J = 58.1, 15.9 Hz, 2H), 3.70 (d, J = 17.4
Hz, 3H); 13C{1H} NMR (75 MHz, CDCl3) δ (ppm): 197.6,
159.8, 143.4, 139.0, 138.8, 137.2, 133.6, 133.0, 131.1, 129.3,
129.3, 128.6, 128.4, 128.4, 128.4, 128.2, 126.5, 126.3, 126.1,
117.0, 113.7, 110.2, 55.2, 36.4; IR (KBr, cm-1): 3060, 3030,
2969, 2939, 2222, 1670, 1608, 1594, 1569, 1516, 1497, 1449;
3-Benzoyl-4-benzyl-6-fluoro-2-phenyl-1-naphthonitrile
(3ja): white solid (117.9 mg, 89% yield); eluent: petroleum
1
ether/ethyl acetate (50:1); mp 227.8–229.6 ℃; H NMR (400
HRMS (ESI-TOF) calcd for C32H24NO2 ([M+H]+): 454.1802,
+
MHz, CDCl3) δ (ppm): 8.41 (dd, J = 9.1, 5.5 Hz, 1H), 7.73 (dd,
J = 10.5, 2.2 Hz, 1H), 7.57–7.47 (m, 1H), 7.44 (d, J = 7.5 Hz,
2H), 7.38 (t, J = 7.4 Hz, 2H), 7.24–7.11 (m, 10H), 4.34 (q, J =
15.7 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm): 197.1,
161.9 (d, J C-F= 250.5 Hz), 143.0 (d, J = 2.8 Hz), 139.6, 138.5
found: 454.1804.
3-Benzoyl-4-benzyl-2-(4-(tert-butyl)phenyl)-1-
naphthonitrile (3ad) : yellow solid (115.1 mg, 80% yield);
eluent: petroleum ether/ethyl acetate (50:1); mp 189.0–190.8 ℃;
1H NMR (400 MHz, CDCl3) δ (ppm): 8.41 (d, J = 8.2 Hz, 1H),
8.14 (d, J = 8.3 Hz, 1H), 7.74 (t, J = 7.2 Hz, 1H), 7.60 (t, J =
7.3 Hz, 1H),7.37–7.12 (m, 14H), 4.44 (dd, J = 55.2, 15.5 Hz,
2H), 1.21 (s, 9H); 13C{1H} NMR (75MHz, CDCl3) δ (ppm):
197.6, 159.8, 143.4, 139.0, 138.8, 137.2, 133.6, 133.0, 131.1,
129.3, 129.3, 128.6, 128.4, 128.4, 128.4, 128.12, 126.5, 126.3,
126.1, 117.0, 113.7, 110.2, 55.2, 36.4; IR (KBr, cm-1): 3062,
2956, 2869, 2219, 1667, 1598, 1581, 1496, 1451; HRMS (ESI-
TOF) calcd forC35H30NO+ ([M+H]+): 480.2322, found:
480.2325.
(d, J C-F = 5.6 Hz), 138.5, 137.1, 136.0, 133.7, 132.7 (d, J C-F
=
9.0 Hz), 129.9, 129.3, 129.2 (d, J = 9.2 Hz), 128.9, 128.8,
C-F
128.4, 128.4, 128.2, 126.7, 119.7 (d, J
= 25.4 Hz), 116.6,
C-F
110.3 (d, J C-F = 22.4 Hz), 110.2 (d, J C-F = 1.2Hz), 36.6; IR (KBr,
cm-1): 3085, 3061, 3028, 2924, 2225, 1669, 1594, 1579, 1503,
1409; HRMS (ESI-TOF) calcd for C31H21FNO+ ([M+H]+):
442.1602, found: 442.1604.
3-Benzoyl-4-benzyl-6,7-dimethoxy-2-phenyl-1-
naphthonitrile (3ka): white solid (72.5 mg, 50% yield); eluent:
petroleum ether/ethyl acetate (5:1); mp 319.3–320.1℃; 1H
NMR (400 MHz, CDCl3) δ (ppm): 7.58 (s, 1H), 7.46 (d, J = 7.3
Hz, 2H), 7.41–7.06 (m, 14H), 4.32 (d, J = 11.8 Hz, 2H), 4.06
(s, 3H), 3.78 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm):
198.0, 152.2, 150.9, 141.5, 139.3, 137.6, 137.5, 137.0, 136.7,
133.5, 129.9, 129.4, 128.7, 128.6, 128.5, 128.3, 128.1, 127.1,
126.6, 117.4, 108.2, 105.1, 104.8, 56.4, 56.0, 37.1; IR (KBr, cm-
1): 3023, 2999, 2834, 2219, 1669, 1594, 1570, 1509, 1498, 1470,
3-Benzoyl-4-benzyl-2-m-tolyl-1-naphthonitrile
(3ae):
yellow solid (118.1 mg, 90% yield); eluent: petroleum
1
ether/ethyl acetate (50:1); mp 225.8–226.7 ℃; H NMR (400
MHz, CDCl3) δ (ppm): 8.40 (d, J = 8.3 Hz, 1H), 8.12 (d, J = 8.5
Hz, 1H), 7.73 (t, J = 7.6 Hz, 1H), 7.59 (t, J = 7.6 Hz, 1H), 7.44
(d, J = 7.5 Hz, 2H), 7.37 (t, J = 7.4 Hz, 1H), 7.31–6.83 (m, 11H).,
4.41 (dd, J = 58.4, 14.9 Hz, 2H), 2.20 (d, J = 86.3 Hz, 3H);
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13C{1H} NMR (100 MHz, CDCl3) δ (ppm): 197.5, 143.9, 139.1, 2H); 13C{1H} NMR (75 MHz, CDCl3) δ (ppm): 197.2, 139.2,
1
2
3
4
5
6
139.1, 138.7, 137.4, 136.2, 133.5, 133.0, 131.2, 129.5, 129.3,
128.6, 128.4, 128.3, 128.2, 128.0, 126.5, 126.4, 126.2, 116.8,
110.1, 36.4, 21.3; IR (KBr, cm-1): 3084, 3060, 3031, 2925, 2217,
1665, 1596, 1567, 1496, 1450; HRMS (ESI-TOF) calcd for
C32H24NO+ ([M+H]+): 438.1852, found: 438.1856.
139.1, 138.9, 137.0, 136.2, 135.8, 133.8, 133.0, 131.6, 131.2,
129.5, 129.5, 128.7, 128.6, 128.5, 128.4, 127.2, 126.6, 126.6,
126.2, 116.7, 111.4, 36.4; IR (KBr, cm-1): 3102, 3078, 3061,
3027, 2222, 1669, 1596, 1569, 1497; HRMS (ESI-TOF) calcd
for C29H20NOS+ ([M+H]+): 430.1260, found: 430.1263.
7
8
9
3-Benzoyl-4-benzyl-2-(4-chlorophenyl)-1-naphthonitrile
(3af): yellow solid (116.8 mg, 85% yield); eluent: petroleum
3-Benzoyl-4-benzyl-2-tert-butyl-1-naphthonitrile (3aj)
:
white solid (99.3 mg, 82% yield); eluent: petroleum ether/ethyl
acetate (50:1); mp 169.2–170.1; 1H NMR (300 MHz, CDCl3) δ
(ppm): 7.73 (d, J = 7.8 Hz, 1H), 7.57– 7.31 (m, 6H), 7.30 – 7.06
(m, 7H), 6.47 (d, J = 294.8 Hz, 2H), 1.46 (s, 9H); 13C{1H} NMR
(75 MHz, CDCl3) δ (ppm): 193.3, 162.7, 136.8, 134.8, 133.4,
133.1, 132.2, 132.1, 131.6, 129.2, 129.1, 128.8, 128.7, 128.6,
128.4, 128.0, 125.1, 123.8, 117.8, 111.8, 48.6, 37.8, 30.0; IR
(KBr, cm-1): 3368, 3063, 2997, 2958, 2909, 2216, 1688, 1639,
1596, 1481, 1448; HRMS (ESI-TOF) calcd for C29H26NO+
([M+H]+): 404.2009, found: 404.2012.
1
ether/ethyl acetate (50:1); mp 242.5–243.8 ℃; H NMR (300
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
MHz, CDCl3) δ (ppm): 8.40 (d, J = 8.3 Hz, 1H), 8.14 (d, J = 8.4
Hz, 1H), 7.76 (t, J = 7.6 Hz, 1H), 7.63 (t, J = 7.7 Hz, 1H), 7.52–
6.75 (m, 14H), 4.41 (q, J = 16.0 Hz, 2H); 13C{1H} NMR (75
MHz, CDCl3) δ (ppm): 197.3, 142.2, 139.4, 138.9, 138.4, 137.1,
135.1, 134.7, 133.9, 132.9, 131.3, 129.5, 129.3, 128.6, 128.6,
128.5, 128.4, 126.6, 126.4, 126.2, 116.6, 110.2, 36.4; IR (KBr,
cm-1): 3756, 2380, 2345, 2225, 1668, 1511, 1594, 1497, 1404;
HRMS (ESI-TOF) calcd for C31H21ClNO+ ([M+H]+): 458.1306,
found: 458.1309.
3-Benzoyl-4-benzyl-2-butyl-1-naphthonitrile (3ak) : white
solid (47.2 mg, 39% yield); eluent: petroleum ether/ethyl
acetate (100:1); mp 154–155.3 ℃; 1H NMR (300 MHz, CDCl3)
δ (ppm): 8.32 (d, J = 8.4 Hz, 1H), 8.01 (d, J = 8.5 Hz, 1H), 7.81–
7.64 (m, 3H), 7.63–7.48 (m, 2H), 7.41 (t, J = 7.7 Hz, 2H), 7.11
(ddd, J = 22.7, 14.5, 6.9 Hz, 5H), 4.29 (q, J = 16.1 Hz, 2H),
3.20–2.46 (m, 2H), 1.88– 1.46 (m, 2H), 1.33 (dq, J = 14.6, 7.3
Hz, 2H), 0.83 (t, J = 7.3 Hz, 3H); 13C{1H} NMR (75 MHz,
CDCl3) δ (ppm): 197.8, 144.4, 138.9, 138.5, 138.5, 137.0, 134.4,
133.2, 130.5, 129.6, 129.0, 128.9, 128.6, 128.3, 127.6, 126.5,
125.9, 116.9, 109.9, 36.5, 33.5, 33.5, 22.9, 13.6; IR (KBr, cm-
1): 3434, 3028, 2930, 2221, 1670, 1595, 1577, 1498, 1449;
HRMS (ESI-TOF) calcd for C29H26NO+ ([M+H]+): 404.2009,
found: 404.2012.
3-Benzoyl-4-benzyl-2-(4-fluorophenyl)-1-naphthonitrile
(3ag): yellow solid (102.0 mg, 77% yield); eluent: petroleum
1
ether/ethyl acetate (50:1); mp 228.6–229.5 ℃; H NMR (300
MHz, CDCl3) δ (ppm): 8.34 (d, J = 8.3 Hz, 1H), 8.08 (d, J = 8.5
Hz, 1H), 7.71 (t, J = 7.6 Hz, 1H), 7.57 (t, J = 7.6 Hz, 1H), 7.46–
7.00 (m, 14H), 4.35 (q, J = 15.7 Hz, 2H); 13C{1H} NMR (75
MHz, CDCl3) δ (ppm): 197.4, 162.8 (d, J = 249.2 Hz), 142.4,
139.3, 138.9, 138.6, 137.1, 133.8, 132.9, 132.2 (d, J = 3.5 Hz),
131.3, 129.4, 129.3, 128.6, 128.5, 128.4, 126.5, 126.4, 126.1,
116.7, 115.3 (d, J = 22.2 Hz), 110.3, 36.3; IR (KBr, cm-1): 3435,
2929, 2223, 1669, 1595, 1494, 1448, 1314; HRMS (ESI-TOF)
calcd for C31H21FNO+ ([M+H]+): 442.1602, found: 442.1604.
Methyl
4-(3-benzoyl-4-benzyl-1-cyanonaphthalen-2-
4-Benzyl-3-(4-methylbenzoyl)-2-phenyl-1-naphthonitrile
yl)benzoate (3ah): yellow solid (115.6 mg, 80% yield); eluent:
petroleum ether/ethyl acetate (10:1); mp 203.5–204.8; 1H NMR
(300 MHz, CDCl3) δ (ppm): 8.33 (d, J = 8.3 Hz, 1H), 8.08 (d, J
= 8.5 Hz, 1H), 8.00–7.65 (m, 3H), 7.56 (t, J = 7.7 Hz, 1H), 7.42–
6.96 (m, 12H), 4.34 (q, J = 15.7 Hz, 2H), 3.80 (s, 3H); 13C{1H}
NMR (75 MHz, CDCl3) δ (ppm): 197.1, 166.5, 142.4, 140.8,
139.4, 138.8, 138.1, 137.0, 133.9, 132.8, 131.4, 130.3, 129.5,
129.3, 128.6, 128.6, 128.5, 128.4, 126.6, 126.5, 126.2, 116.5,
110.1, 52.3, 36.4; IR (KBr, cm-1): 3400, 2344, 2224, 1725, 1665,
14978, 1449, 1433, 1404; HRMS (ESI-TOF) calcd for
C33H24NO3+ ([M+H]+): 482.1751, found: 482.1755.
(3al): white solid (99.8 mg, 76% yield); eluent: petroleum
1
ether/ethyl acetate (50:1); mp 189.1–191.1 ℃; H NMR (400
MHz, CDCl3) δ (ppm): 8.39 (d, J = 8.4 Hz, 1H), 8.09 (d, J = 8.5
Hz, 1H), 7.71 (t, J = 7.6 Hz, 1H), 7.57 (t, J = 7.7 Hz, 1H), 7.37–
7.09 (m, 12H), 6.98 (d, J = 7.9 Hz, 1H), 4.37 (dd, J = 56.0, 16.0
Hz, 2H), 2.27 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ
(ppm): 196.9, 144.7, 143.7, 139.1, 138.9, 138.9, 136.4, 134.9,
133.0, 131.3, 129.6, 129.2, 129.1, 128.8, 128.6, 128.4, 128.2,
128.2, 126.4, 126.4, 126.2, 116.8, 110.2, 36.5, 21.8; IR (KBr,
cm-1): 3062, 3028, 2223, 1665, 1602, 1496, 1446, 1415; HRMS
(ESI-TOF) calcd for C32H24NO+ ([M+H]+): 438.1852, found:
438.1856.
3-Benzoyl-4-benzyl-2-(thiophen-2-yl)-1-naphthonitrile (3ai):
yellow solid (100.5 mg, 78% yield); eluent: petroleum
4-Benzyl-3-(4-ethylbenzoyl)-2-phenyl-1-naphthonitrile
1
ether/ethyl acetate (50:1); mp 219.1–220.1 ℃; H NMR (400
(3am): yellow solid (103.0 mg, 76% yield); eluent: petroleum
MHz, CDCl3) δ (ppm): 8.39 (d, J = 8.4 Hz, 1H), 8.09 (d, J = 8.5
Hz, 1H), 7.73 (t, J = 7.6 Hz, 1H), 7.63–7.36 (m, 4H), 7.30–6.98
(m, 9H), 6.88 (t, J = 4.2 Hz, 1H), 4.38 (dd, J = 51.7, 16.0 Hz,
1
ether/ethyl acetate (50:1); mp 201.5–202.3 ℃; H NMR (300
MHz, CDCl3) δ (ppm): 8.41 (d, J = 8.4 Hz, 1H), 8.12 (d, J = 8.4
Hz, 1H), 7.74 (t, J = 7.6 Hz, 1H), 7.60 (t, J = 7.6 Hz, 1H), 7.47–
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7.32 (m, 3H), 7.17 (dt, J = 12.3, 9.9 Hz, 11H), 4.41 (q, J = 16.0
Hz, 2H), 2.55 (q, J = 7.5 Hz, 2H), 1.14 (t, J = 7.5 Hz, 3H);
13C{1H} NMR (75 MHz, CDCl3) δ (ppm): 197.6, 144.8, 143.8,
139.1, 138.8, 137.3, 133.5, 133.0, 131.1, 129.3, 128.6, 128.4,
128.3, 128.2, 127.7, 126.5, 126.4, 126.1, 117.0, 110.1, 36.3,
28.6, 15.2; IR (KBr, cm-1): 3031, 2969, 2923, 2853, 2220, 1670,
1595, 1567, 1514, 1497, 1450, 1408; HRMS (ESI-TOF) calcd
for C33H26NO+ ([M+H]+): 452.2009, found: 452.2011.
ether/ethyl acetate (50:1); mp 199.7–202.3 ℃; H NMR (400
MHz, CDCl3) δ (ppm): 8.44 (d, J = 8.3 Hz, 1H), 8.18 (d, J = 8.5
Hz, 1H), 7.79 (t, J = 7.6 Hz, 1H), 7.66 (t, J = 7.7 Hz, 1H), 7.35–
7.27 (m, 5H), 7.26–7.03 (m, 9H), 4.53–4.32 (m, 2H); 13C{1H}
NMR (100 MHz, CDCl3) δ (ppm): 196.3, 143.3, 139.6, 138.7,
137.9, 136.0, 134.5, 133.3, 133.1, 131.2, 129.6, 129.6, 129.0,
129.0, 128.6, 128.5, 128.4, 128.3, 127.3, 126.6, 126.5, 126.2,
116.7, 110.2, 36.1; IR (KBr, cm-1): 3433, 3065, 2928, 2345,
2225, 1668, 1597, 1511, 1449, 1408, 1315; HRMS (ESI-TOF)
calcd for C31H21ClNO+ ([M+H]+): 458.1306, found: 458.1304.
4-Benzyl-3-(4-bromobenzoyl)-2-phenyl-1-naphthonitrile
(3ar) : white solid (102.5 mg, 68% yield); eluent: petroleum
1
2
3
4
5
6
7
8
9
4-Benzyl-3-(4-tert-butylbenzoyl)-2-phenyl-1-naphthonitrile
(3an): yellow solid (126.6 mg, 88% yield); eluent: petroleum
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
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ether/ethyl acetate (50:1); mp 211.6–212.5 ℃; H NMR (400
MHz, CDCl3) δ (ppm): 7 8.39 (d, J = 8.3 Hz, 1H), 8.11 (d, J =
8.5 Hz, 1H), 7.72 (t, J = 7.6 Hz, 1H), 7.58 (t, J = 7.7 Hz, 1H),
7.44–6.93 (m, 14H), 4.38 (q, J = 15.7 Hz, 2H), 1.22 (s, 9H);
13C{1H} NMR (100 MHz, CDCl3) δ (ppm): 197.0, 157.5, 143.8,
139.1, 138.9, 136.4, 134.8, 132.9, 131.3, 129.4, 129.2, 128.7,
128.6, 128.4, 128.2, 128.1, 126.4, 126.1, 125.3, 116.8, 110.2,
36.5, 35.2, 31.0; IR (KBr, cm-1):3316, 3085, 3060, 2968, 2873,
2224, 1665, 1601, 1567, 1454, 1446; HRMS (ESI-TOF) calcd
for C35H30NO+ ([M+H]+): 480.2322, found: 480.2325.
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ether/ethyl acetate (50:1); mp 191.2–193 ℃; H NMR (400
MHz, CDCl3) δ (ppm): 8.40 (d, J = 8.3 Hz, 1H), 8.14 (d, J = 8.5
Hz, 1H), 7.75 (t, J = 7.6 Hz, 1H), 7.62 (t, J = 7.6 Hz, 1H), 7.38–
6.99 (m, 14H), 4.40 (q, J = 14.8 Hz, 2H); 13C{1H} NMR (75
MHz, CDCl3) δ (ppm): 196.5, 143.4, 139.4, 138.8, 138.0, 136.0,
136.0, 133.1, 131.7, 131.2, 130.7, 129.5, 129.0, 128.9, 128.7,
128.5, 128.4, 128.3, 126.6, 126.45, 126.1, 116.7, 110.2, 36.2;
IR (KBr, cm-1): 3065, 3039, 2927, 2222, 1673, 1583, 1584,
1568, 1496, 1446, 1409; HRMS (ESI-TOF) calcd for
C31H21BrNO+ ([M+H]+): 502.0801, found: 502.0805.
4-Benzyl-3-(4-methoxybenzoyl)-2-phenyl-1-naphthonitrile
(3ao): yellow solid (130.6 mg, 96% yield); eluent: petroleum
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ether/ethyl acetate (20:1); mp 181.2–183 ℃; H NMR (300
4-Benzyl-2-phenyl-3-(4-(trifluoromethyl)benzoyl)-1-
MHz, CDCl3) δ (ppm): 8.37 (d, J = 8.3 Hz, 1H), 8.08 (d, J = 8.5
Hz, 1H), 7.70 (t, J = 7.6 Hz, 1H), 7.57 (t, J = 7.6 Hz, 1H), 7.48–
7.04 (m, 12H), 6.68 (t, J = 16.9 Hz, 2H), 4.36 (q, J = 16.0 Hz,
2H), 3.74 (s, 3H); 13C{1H} NMR (75 MHz, CDCl3) δ (ppm):
195.7, 163.9, 143.7, 139.2, 138.9, 138.9, 136.4, 132.9, 131.9,
131.3, 130.4, 129.2, 128.8, 128.6, 128.4, 128.3, 128.2, 126.5,
126.4, 126.1, 116.9, 113.7, 110.1, 55.5, 36.5; IR (KBr, cm-
1):3066, 3028, 2970, 2367, 2218, 1660, 1591, 1507, 1496, 1445;
naphthonitrile (3as): yellow solid (112.1 mg, 76% yield);
eluent: petroleum ether/ethyl acetate (50:1); mp 183.8–184.2 ℃;
1H NMR (400 MHz, CDCl3) δ (ppm): 8.43 (d, J = 8.3 Hz, 1H),
8.20 (d, J = 8.5 Hz, 1H), 7.79 (t, J = 7.6 Hz, 1H), 7.66 (t, J =
7.6 Hz, 1H), 7.56–6.98 (m, 14H), 4.44 (s, 2H); 13C{1H} NMR
(100 MHz, CDCl3) δ (ppm): 196.7, 143.3, 139.9, 139.7, 138.6,
137.8, 135.9, 134.4 (q, JC-F= 32.6 Hz), 133.1, 131.3, 129.7,
129.3, 129.0, 128.6, 128.5, 128.4, 128.3, 126.6, 126.5, 126.1,
125.2 (q, J C-F = 3.7 Hz), 123.4 (q, J C-F = 271.1Hz), 116.5, 110.3,
35.9; IR (KBr, cm-1): 3064, 3028, 2946, 2874, 2225, 1673,
1581, 1566, 1495, 1446, 1415; HRMS (ESI-TOF) calcd for
C32H21F3NO+ ([M+H]+): 492.1570, found: 492.1572.
HRMS (ESI-TOF) calcd for C32H24NO2 ([M+H]+): 454.1802,
+
found: 454.1806.
3-(Benzo[d][1,3]dioxole-5-carbonyl)-4-benzyl-2-phenyl-1-
naphthonitrile (3ap): white solid (79.9 mg, 57% yield); eluent:
1
petroleum ether/ethyl acetate (10:1); mp 200.0–201.6 ℃; H
3-(1-Naphthoyl)-4-benzyl-2-phenyl-1-naphthonitrile (3at):
NMR (300 MHz, CDCl3) δ (ppm): 8.40 (d, J = 8.3 Hz, 1H), 8.11
(d, J = 8.5 Hz, 1H), 7.74 (t, J = 7.6 Hz, 1H), 7.60 (t, J = 7.7 Hz,
1H), 7.35–7.07 (m, 10H), 7.04 (s, 1H), 6.97 (d, J = 8.2 Hz, 1H),
6.56 (d, J = 8.1 Hz, 1H), 5.94 (d, J = 3.5 Hz, 2H), 4.39 (q, J =
16.1 Hz, 2H); 13C{1H} NMR (75 MHz, CDCl3) δ (ppm): 195.2,
152.3, 148.1, 143.6, 139.1, 138.9, 138.7, 136.3, 132.9, 132.2,
131.2, 129.3, 128.8, 128.6, 128.4, 128.3, 128.2, 127.1, 126.5,
126.4, 126.1, 116.8, 110.1, 108.2, 107.7, 102.0, 36.4; IR (KBr,
cm-1): 3433, 3027, 2907, 2221, 1653, 1600, 1567, 1485, 1442,
yellow solid (90.9 mg, 64% yield); eluent: petroleum
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ether/ethyl acetate (10:1); mp 203.6–204.7 ℃; H NMR (400
MHz, CDCl3) δ (ppm): 8.74 (d, J = 8.0 Hz, 1H), 8.41 (d, J = 8.2
Hz, 1H), 8.18 (d, J = 8.3 Hz, 1H), 7.91–6.78 (m, 18H), 4.56 (s,
2H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm): 199.0, 144.1,
140.2, 139.5, 139.3, 136.4, 134.4, 134.2, 133.7, 133.0, 132.3,
131.4, 130.3, 129.9, 129.4, 128.6, 128.5, 128.4, 128.3, 128.2,
128.1, 126.6, 126.5, 126.4, 126.4, 126.0, 123.8, 116.8, 110.3,
36.3; IR (KBr, cm-1): 3084, 3063, 2222, 1659, 1621, 1592, 1508,
1494, 1454; HRMS (ESI-TOF) calcd for C35H24NO+ ([M+H]+):
474.1852, found: 474.1856.
1358 ; HRMS (ESI-TOF) calcd for C32H22NO3 ([M+H]+):
+
468.1594, found: 468.1598.
4-(4-Chlorobenzyl)-3-benzoyl-2-phenyl-1-naphthonitrile
(3aq): yellow solid (104.4 mg, 76% yield); eluent: petroleum
4-Benzyl-3-(4-methylbenzoyl)-2-phenyl-1-naphthonitrile
(3au): yellow solid (96.6 mg, 75% yield); eluent: petroleum
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7.4 Hz, 1H), 7.85–7.76 (m, 1H), 7.73–7.58 (m, 2H), 7.57–7.51
ether/ethyl acetate (10:1); mp 219.3–220.9 ℃; H NMR (400
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7
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(m, 2H), 7.48 (d, J = 7.4 Hz, 1H), 7.39 (t, J = 7.3 Hz, 1H), 7.31
(t, J = 7.1 Hz, 1H), 7.11–7.00 (m, 3H), 6.77 (dd, J = 6.4, 2.9 Hz,
2H), 4.49 (d, J = 17.3 Hz, 1H), 3.74 (d, J = 17.2 Hz, 1H); 13C{1H}
NMR (75 MHz, CDCl3) δ (ppm): 151.3, 147.3, 142.4, 141.5,
139.6, 138.8, 138.0, 137.8, 133.4, 130.3, 128.9, 128.4, 127.9,
127.7, 127.0, 126.8, 126.8, 126.7, 126.5, 126.1, 125.6, 124.2,
123.8, 117.7, 98.5, 59.5, 32.6; IR (KBr, cm-1): 3644, 3057, 2857,
2214, 1596, 1513, 1476, 1443, 1417; HRMS (ESI-TOF) calcd
for C31H20N+ ([M+H]+): 406.1590, found: 406.1588.
MHz, CDCl3) δ (ppm): 8.38 (d, J = 8.1 Hz, 1H), 8.11 (d, J = 8.3
Hz, 1H), 7.82–6.97 (m, 14H), 6.81 (s, 1H), 4.46 (q, J = 16.1 Hz,
2H); 13C{1H} NMR (100 MHz, CDCl3) δ (ppm): 189.1, 144.8,
143.5, 139.2, 139.1, 138.6, 136.3, 135.6, 135.1, 133.1, 131.2,
129.5, 128.9, 128.6, 128.4, 128.3, 128.2, 128.0, 126.5, 126.4,
126.2, 116.8, 110.2, 36.5; IR (KBr, cm-1): 3059, 3027, 2220,
1651, 1602, 1567, 1496, 1410; HRMS (ESI-TOF) calcd for
C29H20NOS+ ([M+H]+): 430.1260, found: 430.1263.
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4-Benzyl-3-(furan-2-carbonyl)-2-phenyl-1-naphthonitrile
(3av): yellow solid (91.8 mg, 74% yield); eluent: petroleum
General Procedure for Product 5: To a solution of 3aa (0.30
mmol) in PhCH3 (3 mL) at 0 °C under N2 was added iBu2AlH
(0.6 mL, 1.5 M in toluene) dropwise. The mixture was stirred
at 0 °C for 5 min and then warmed to 25 °C for 2 h. After
completion of this reaction, the reaction mixture was quenched
with brine. Then, the mixture was diluted with EtOAc (10 mL)
and washed with brine (10 mL). The aqueous phase was
extracted with EtOAc (3×10 mL). The combined organic layers
were dried over anhydrous Na2SO4, filtered and concentrated
in-vacuo. The crude reaction mixture was purified by column
chromatography on silica gel (petroleum ether/EtOAc) to give
product 5.
1
ether/ethyl acetate (10:1); mp 193.5–194.6 ℃; H NMR (400
MHz, CDCl3) δ (ppm): 8.41 (d, J = 8.4 Hz, 1H), 8.14 (d, J = 8.6
Hz, 1H), 7.75 (t, J = 7.6 Hz, 1H), 7.61 (t, J = 7.7 Hz, 1H), 7.35
(t, J = 13.5 Hz, 6H), 7.20–7.08 (m, 5H), 6.75 (d, J = 3.0 Hz,
1H), 6.34–6.26 (m, 1H), 4.50 (q, J = 16.2 Hz, 2H); 13C{1H}
NMR (75 MHz, CDCl3) δ (ppm): 184.5, 152.9, 147.3, 143.7,
139.6, 139.0, 137.6, 136.2, 133.0, 131.2, 130.3, 129.5, 128.9,
128.5, 128.3, 128.3, 126.4, 126.4, 126.2, 120.0, 116.8, 112.6,
110.0, 36.0; IR (KBr, cm-1): 3126, 3062, 3028, 2219, 1662,
1601, 1559, 1497, 1459, 1414; HRMS (ESI-TOF) calcd for
C29H20NO2+ ([M+H]+): 414.1489, found: 414.1492.
4-Benzyl-3-(hydroxy(phenyl)methyl)-2-phenyl-1-
3-Acetyl-4-benzyl-2-phenyl-1-naphthonitrile (3aw): yellow
solid (67.2 mg, 62% yield); eluent: petroleum ether/ethyl
acetate (100:1); mp 162.4–163 ℃; 1H NMR (300 MHz, CDCl3)
δ (ppm): 8.38 (d, J = 8.3 Hz, 1H), 8.12 (d, J = 8.5 Hz, 1H), 7.74
(t, J = 7.6 Hz, 1H), 7.64–7.58 (m, 1H), 7.50 (s, 5H), 7.30–7.07
(m, 5H), 4.50 (s, 2H), 1.77 (s, 3H); 13C{1H} NMR (75 MHz,
CDCl3) δ (ppm): 205.6, 141.9, 141.4, 139.1, 137.5, 136.4, 132.7,
131.3, 130.1, 129.4, 129.4, 128.9, 128.8, 128.4, 128.4, 126.6,
126.4, 126.1, 116.8, 110.0, 35.3, 32.4; IR (KBr, cm-1): 3381,
3027, 2218, 1701,1600, 1566, 1450,1407; HRMS (ESI-TOF)
calcd for C26H20NO+ ([M+H]+): 362.1539, found: 362.1542.
General Procedure for Product 4. A 10 mL oven-dried
Schlenck tube was successively charged with 0.30 mmol 3aa,
1.5 mL DCE and 0.3 mmol CF3SO3H. The tube was sealed and
the reaction mixture was stirred at 80 °C for 12 h. After
completion of this reaction, the mixture was diluted with
dichloromethane (10 mL) and washed with brine (10 mL). The
aqueous phase was extracted with dichloromethane (3 × 10 mL).
The combined organic layers were dried over anhydrous
Na2SO4, filtered and concentrated in-vacuo. The crude reaction
mixture was purified by column chromatography on silica gel
(petroleum ether/EtOAc) to give product 4.
naphthaldehyde (5): white solid (104.1 mg, 81% yield); eluent:
1
petroleum ether/ethyl acetate (20:1); mp 185.5–187.3 ℃; H
NMR (400 MHz, CDCl3) δ (ppm): 9.98 (s, 1H), 9.23 (d, J = 8.6
Hz, 1H), 7.99 (d, J = 8.6 Hz, 1H), 7.73–7.58 (m, 1H), 7.47 (t, J
= 7.4 Hz, 1H), 7.43–7.35 (m, 4H), 7.30 (d, J = 6.8 Hz, 1H),
7.24–7.07 (m, 8H), 6.92 (d, J = 7.1 Hz, 2H), 6.11 (d, J = 5.9 Hz,
1H), 4.58 (dd, J = 39.1, 16.9 Hz, 2H), 2.36 (d, J = 6.2 Hz, 1H);
13C{1H} NMR (100 MHz, CDCl3) δ (ppm): 195.2, 147.7, 143.6,
142.9, 140.4, 138.7, 137.3, 133.6, 130.1, 130.1, 130.1, 129.6,
129.0, 128.5, 128.4, 128.4, 128.3, 128.2, 128.1, 127.1, 126.7,
126.0, 125.8, 125.6, 125.4, 71.7, 36.0; IR (KBr, cm-1): 3457,
3081, 3027, 2872, 2782, 1681, 1601, 1555, 1494, 1450, 1401;
+
HRMS (ESI-TOF) calcd for C31H25O2 ([M+H]+): 429.1849,
found: 429.1848.
ASSOCIATED CONTENT
Supporting Information
X-ray crystallographic file in CIF format for the structure
1
determination of products 3aa and 4; Copies of H NMR and
13C NMR spectra for all new compounds. This material is
available free of charge via the Internet at http://pubs.acs.org.
14b-Phenyl-5,14b-dihydroindeno[1,2,3-gh]tetraphene-10-
carbonitrile (4): white solid (104.6 mg, 86% yield); eluent:
AUTHOR INFORMATION
Corresponding Author
1
petroleum ether/ethyl acetate (100:1); mp 285.1–286.7 ℃; H
NMR (300 MHz, CDCl3) δ (ppm): 8.67 (dd, J = 5.6, 3.1 Hz,
1H), 8.49–8.31 (m, 1H), 8.18 (d, J = 7.6 Hz, 1H), 8.03 (d, J =
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Benzenes and Polycyclic Aromatic and Benzene-Fused
Email: wangyanbokf@henu.edu.cn
ORCID: 0000-0002-5676-1437
Notes
Heteroaromatic Compounds. Org. Lett. 2014, 16, 3792−3795. (b)
Chang, M.-Y.; Cheng, Y.-C. Synthesis of 1-Aryltetralins and 1-
Arylnaphthalenes via (4+ 2) Annulation of β-Ketosulfones with Styryl
Bromides. Org. Lett. 2016, 18, 1682−1685. (c) Chan, C.-K.; Chen, Y.-
H.; Tsai, Y.-L.; Chang, M.-Y. Synthesis of Substituted 1,6-
Diarylnaphthalenes via a Tandem Claisen Rearrangement and Ene
Reaction Protocol. J. Org. Chem. 2017, 82, 3317−3326.
(6) For selected references, see: (a) Shao, L.-X.; Zhang, Y.-P.; Qi,
M.-H.; Shi, M. Lewis Acid Catalyzed Rearrangement of
Vinylcyclopropenes for the Construction of Naphthalene and Indene
Skeletons. Org. Lett. 2007, 9, 117−120. (b) Glass, A. C.; Morris, B. B.;
Zakharov, L. N.; Liu, S.-Y. Synthesis of Substituted Naphthalenes via
A Catalytic Ring-Expansion Rearrangement. Org. Lett. 2008, 10,
4855−4857. (c) Boeck, F.; Kribber, T.; Xiao, L.; Hintermann, L. Mixed
Phosphane η5-CpRuCl(PR3)2 Complexes as Ambifunctional Catalysts
for Anti-Markovnikov Hydration of Terminal Alkynes. J. Am. Chem.
Soc. 2011, 133, 8138−8141. (d) Wang, J.-G.; Wang, M.; Xiang, J.-C.;
Zhu, Y.-P.; Xue, W.-J.; Wu, A.-X. Direct Synthesis of Substituted
Naphthalenes from 1,3-Dicarbonyl Compounds and 1,2-
1
2
3
4
5
6
7
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The authors declare no competing financial interest.
ACKNOWLEDGMENT
9
This work was financially supported by the National Natural
Science Foundation of China (No. U1504205), the Key
Research Project of Education Department of Henan Province
(No. 17A150002) and Henan University (yqpy20170009).
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