Synthesis of Schiff bases from substitute aromatic aldehydes and 2-(4-aminophenyl)acetonitrile catalysed by 3,5-difluoroarylboronic acid

Article abstract of DOI:10.3184/174751913X13647468553118

A simple efficient method for synthesis of Schiff bases in good yields from aromatic aldehydes and 2-(4-aminophenyl) acetonitrile catalysed by 3,5-difluoroarylboric acid at room temperature for 2 hours is reported.

Full text of DOI:10.3184/174751913X13647468553118

276 RESEARCH PAPER
MAY, 276–278
JOURNAL OF CHEMICAL RESEARCH 2013
Synthesis of Schiff bases from substitute aromatic aldehydes and
2-(4-aminophenyl)acetonitrile catalysed by 3,5-difluoroarylboronic acid
Zhiping Du, Tianhua Shen, Haibo Dang, Zhenfang Fu and Qingbao Song*
College of Chemical Engineering and Material Science, Zhejiang University ofTechnology, Hangzhou, 310032, P. R. China
A simple efficient method for synthesis of Schiff bases in good yields from aromatic aldehydes and 2-(4-amino-
phenyl)acetonitrile catalysed by 3,5-difluoroarylboric acid at room temperature for 2 hours is reported.
Keywords: Schiff bases, 3,5-difluoroaryllboronic acid, aromatic aldehydes, 2-(4-aminophenyl) acetonitrile
In recent years, the synthesis of Schiff base compounds
has attracted much interest among organic chemists. Schiff
bases have played a very important role in medical biology,1,2
functional materials,3 catalysis chemistry4 and coordination
chemistry5 in the few past decades, especially in asymmetric
catalytic reactions. Schiff bases are frequently used as ligands
in some organic synthesis reactions such as asymmetric
sulfoxidation,6 Suzuki-Miyaura7 and enantioselective Henry
reaction8 (Fig. 1). These reactions catalysed by chiral Schiff
bases provided high ee values. In the past, various catalysts
such as TiO2,9 MgSO4,10,11 NbCl5,12 Pt,13 ionic liquids,14 CaO,15
molecular sieves,16 clay,17 P2O5/SiO2,18 P2O5/Al2O3,19 dioxane/
AcOH20 and boric acid21 were successfully used to synthesise
Schiff bases. At the same time, some other reaction techniques
appeared, for instance, ultrasound irradiation22, microwave
irradiation23,24 and solvent-free reaction25. However, syntheses
of Schiff bases usually suffer from high reaction temperatures,
long reaction times and low yields. Therefore, improvement of
these reactions is required.
(entry 6). We found that ethanol was the most suitable solvent
by selecting solvents (entries 6 and 15–18). Finally, the effect
of reaction time was studied (entries 19–21) and the most
suitable reaction time was 2 hours (entry 6). On the basis
of these investigations, the preferred reaction conditions are
aromatic aldehydes: amine: 3,5-difluoroarylboric acid = 1: 1:
0.01 in ethanol (5 mL) at room temperature for 2 hours.
With the optimised conditions in hand, a variety of new
Schiff bases were synthesised in good yields, as shown
in Table 2. We found that aromatic aldehydes with electron-
withdrawing substituents gave higher yields than those with
electron-donating substituents.
In summary, we have developed a simple and efficient
method for the synthesis of Schiff bases from substituted
aromatic aldehydes and 2-(4-aminophenyl)acetonitrile
catalysed by 3,5-difluoroarylboric acid at room temperature.
This process may be useful in medical biology and asymmetric
chemistry.
To our knowledge, boronic acid, ferrocenic boronic acid or
substituted arylboronic acids have not been studied as catalysts
for the synthesis of Schiff bases. In this paper, we report our
research on substituted arylboronic acids as catalysts for the
synthesis of Schiff bases. We found that 3,5-difluoroarylboric
acid was an efficient catalyst for the synthesis of Schiff bases.
Under mild conditions, 18 new compounds were synthesised.
Experimental
1H NMR spectra and 13C NMR spectra were recorded on a Bruker
Avance III 500 MHz spectrometer, using CDCl3 as solvent (500 MHz
1
for H or 126 MHz for 13C, respectively). IR spectra (KBr) were
recorded on a NEXUS FI/IR spectrometer. Melting points were taken
on Büchi M-560. Mass spectra (MS) were carried out onVARIAN1200
and measured by the EI method. M+ values quoted for 35Cl and 79Br
where appropriate. The reaction mixture was monitored by TLC
on silica gel plates (60 F-254). Microanalyses were performed on
a LECO CHNS-932 Elemental Analyser. All boronic acids were
purchased from the Aladdin (Shanghai, China) chemical company.
Results and discussion
We optimised the reaction conditions in terms of catalysts,
loading of catalysts, solvents and reaction times. 4-Chloro-
benzaldehyde was selected as the model substrate. Ethanol
was initially used as the solvent. The results are summarised
in Table 1. Initially, we combined 4-chlorobenzaldehyde 1
(1.5 mmol) and 2-(4-aminophenyl)acetonitrile 2 (1.5 mmol)
together without catalyst and 52% yield (entry 1) was obtained.
When we used boric acid as the catalyst, the yield rose to 60%
(entry 2). Then we added phenylboronic acid (0.015 mmol)
as the catalyst to improve the reaction, and the desired 4a
was obtained in 79% yield (entry 3). Arylboronic acids
with electron-donating groups showed higher yields (entries
4 and 5). It is noteworthy that ideal yields were obtained
when the reaction was carried out using arylboronic acids with
electron-withdrawing groups (entries 6–8). To our surprise,
3,5-difluoroarylboric acid promoted the yield to 96% (entry 6).
The results above indicated that the electronic effect of
substituted arylboronic acid affected the yield of the present
reaction. At the same time, we examined naphthalen-1-
ylboronic acid (3h), 1,1′-ferrocenediboronic acid (3i) and
2-thienylboronic acid (3j) (entries 9–11), all of which were not
as efficient as 3,5-difluorophenylboronic acid (entry 6). The
effects of catalyst’s loading were tested (entries 12–14) and the
most appropriate loading of catalyst was found to be 1 mol %
Synthesis of Schiff bases (4a–r); general procedure
A mixture of 2-(4-aminophenyl)acetonitrile (1.5 mmol), an aldehyde
(1.5 mmol), 3,5-difluoroarylboric acid (0.015 mmol) and anhydrous
ethanol (5 mL) was stirred in a reaction flask for 2 hours. The reaction
mixture was monitored by TLC. After completion, the reaction mix-
ture was filtered, washed with ether, and recrystallised from anhydrous
ethanol. The structures and yield of the products are given in Table 2.
2-(4-(4-Chlorobenzylideneamino)phenyl)acetonitrile (4a): White
solid; IR (film) 2246, 1619 cm–1; 1H NMR (500 MHz, CDCl3) δ 8.43
(s, 1H), 7.86 (d, J = 8.3 Hz, 2H), 7.47 (d, J = 8.4 Hz, 2H), 7.37 (d,
J = 8.2 Hz, 2H), 7.23 (d, J = 8.3 Hz, 2H), 3.79 (s, 2H); 13C NMR
(126 MHz, CDCl3) δ 159.3, 151.6, 137.7, 134.5, 130.9, 130.0, 129.5,
129.1, 128.9, 128.8, 127.6, 121.6, 117.80, 115.4, 23.2; MS m/z 254
(M+). Anal. Calcd for C15H11ClN2: C, 70.73; H, 4.35; N, 11.00. Found:
C, 70.60; H, 4.19; N, 10.87%.
2-(4-(2-Nitrobenzylideneamino)phenyl)acetonitrile (4b): A yellow
solid; IR (film) 2249, 1610 cm–1; 1H NMR (500 MHz, CDCl3) δ 8.95
(s, 1H), 8.31 (dd, J = 7.8, 1.1 Hz, 1H), 8.07–8.12 (m, 1H), 7.77 (t,
* Correspondent. E-mail: qbsong@zjut.edu.cn
Fig. 1 Schiff bases in asymmetric catalytic reactions.

JOURNAL OF CHEMICAL RESEARCH 2013 277
Table 1 Optimisation for synthesis of Schiff basesa
Table 2 Synthesis of Schiff bases via 3,5-difluoroarylboric
acid cascade processa
Entry
R
Product
Yield/%b
M.p./°C
1
2
4-ClC6H4
2-NO2C6H4
3-NO2C6H4
2-CF3C6H4
4a
4b
4c
4d
4e
4f
4g
4h
4i
4j
4k
4l
4m
4n
4o
4p
4q
4r
95
90
91
87
85
90
92
84
83
75
80
79
81
71
78
68
82
80
106–108
115–117
116–117
70–71
109–111
98–100
76–78
102–104
88–90
96–98
108–110
122–124
127–129
125–127
104–106
130–132
205–207
107–109
3
4
5
4-BrC6H4
6
4-FC6H4
3-ClC6H4
2,4-Cl2C6H4
2-ClC6H4
3,4-(CH3O)2C6H4
2,5-(CH3O)2C6H4
4-CH3C6H4
7
8
9
10
11
12
13
14
15
16
17
18
3-OH-4-CH3C6H4
4-Pyridyl
3,5-(CH3O)2C6H4
2-Naphthyl
4-OHC6H4
Entry
Catalyst
Solvent
Time/h
Yield/%b
4-CH3OC6H4
1
2
None
3a
3b
3c
3d
3e
3f
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
MeOH
CH2Cl2
THF
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
3
4
52
60
79
77
75
96
90
84
65
61
83
78
95
95
89
30
21
10
72
95
93
a Reaction conditions: 3e (0.015 mmol),
(1.5 mmol), EtOH (5 mL), rt., 2 hours.
b Isolated yield.
2
(1.5 mmol), 5
3
4
5
6
7
(d, J = 8.3 Hz, 2H), 7.24–7.27 (m, 2H), 3.80 (s, 2H); 13C NMR (126
MHz, CDCl3) δ 157.0, 151.5, 133.9, 133.6, 132.1, 130.9, 129.1, 128.9,
128.5, 128.1, 125.8, 125.8, 121.7, 117.7, 115.5, 23.2; MS m/z 288
(M+). Anal. Calcd for C16H11F3N2: C, 66.66; H, 3.85; N, 9.720. Found:
C, 66.55; H, 3.72; N, 9.58%.
2-(4-(2-Bromobenzylideneamino)phenyl)acetonitrile (4e): White
solid; IR (film) 2247, 1619 cm–1; 1H NMR (500 MHz, CDCl3) δ 8.40
(s, 1H), 7.78 (d, J = 8.4 Hz, 2H), 7.63 (d, J = 8.4 Hz, 2H), 7.37 (d,
J = 8.2 Hz, 2H), 7.22 (d, J = 8.3 Hz, 2H), 3.78 (s, 2H); 13C NMR (126
MHz, CDCl3) δ 159.4, 151.5, 134.9, 132.4, 132.1, 130.9, 130.2, 128.9,
128.8, 127.6, 126.2, 121.5, 117.8, 115.4, 23.2; MS m/z 299 (M+).
Anal. Calcd for C15H11BrN2: C, 60.22; H, 3.71; N, 9.36. Found: C,
60.06; H, 3.64; N, 9.26%.
8
3g
3h
3i
9
10
11
12c
13d
14e
15
16
17
18
19
20
21
3j
3e
3e
3e
3e
3e
3e
3e
3e
3e
3e
Toluene
EtOH
EtOH
EtOH
2-(4-(2-Fluorobenzylideneamino)phenyl)acetonitrile (4f): White
solid; IR (film) 2244, 1598 cm–1; 1H NMR (500 MHz, CDCl3) δ 8.43
(s, 1H), 7.91 – 7.95 (m,2H), 7.37 (d, J = 8.2 Hz, 2H), 7.17–7.23
(m,4H), 3.79 (s, 2H); 13C NMR (126 MHz, CDCl3) δ 159.3, 151.74,
132.4, 132.4, 130.9, 130.9, 128.9, 128.8, 127.4, 121.5, 117.8, 116.1,
115.9, 115.4, 23.2; MS m/z 238 (M+). Anal. Calcd for C15H11FN2: C,
75.62; H, 4.65; N, 11.76. Found: C, 75.51; H, 4.54; N, 11.69%.
2-(4-(3-Chlorobenzylideneamino)phenyl)acetonitrile (4g): White
solid; IR (film) 2247, 1623 cm–1; 1H NMR (500 MHz, CDCl3) δ 8.42
(s, 1H), 7.95 (s, 1H), 7.76 (d, J = 7.6 Hz, 1H), 7.46–7.50 (m, 1H), 7.43
(t, J = 7.8 Hz, 1H), 7.38 (d, J = 8.2 Hz, 2H), 7.23 (d, J = 8.3 Hz, 2H),
3.79 (s, 2H); 13C NMR (126 MHz, CDCl3) δ 159.2, 151.4, 137.7,
135.1, 131.5, 130.0, 128.9, 128.9, 128.4, 127.8, 127.2, 121.6, 117.8,
115.5, 23.2; MS m/z 254 (M+). Anal. Calcd for C15H11ClN2: C, 70.73;
H, 4.35; N, 11.00. Found: C, 70.62; H, 4.32; N, 10.88%.
2-(4-(2,4-Dichlorobenzylideneamino)phenyl)acetonitrile (4h): White
solid; IR (film) 2246, 1582 cm–1; 1H NMR (500 MHz, CDCl3) δ 8.85
(s, 1H), 8.21 (d, J = 8.3 Hz, 1H), 7.49 (d, J = 12.3 Hz, 1H), 7.39 (d,
J = 7.4 Hz, 3H), 7.24–7.29 (m, 2H), 3.80 (s, 2H); 13C NMR (126 MHz,
CDCl3) δ 156.2, 151.4, 137.9, 136.6, 131.6, 129.9, 129.8, 129.6,
128.9, 128.1, 127.8, 121.8, 117.7, 115.5, 23.3; MS m/z 288 (M+).
Anal. Calcd for C15H10Cl2N2: C, 62.31; H, 3.49; N, 9.69. Found: C,
62.15; H, 3.46; N, 9.62%.
a Reaction conditions: 1 (1.5 mmol), 2 (1.5 mmol), 3e (0.015
mmol), Solvent (5 mL), rt.
b Isolated yield.
c Reaction conditions: 1 (1.5 mmol), 2 (1.5 mmol), 3e (0.0075
mmol), Solvent (5 mL), rt.
d Reaction conditions: 1 (1.5 mmol), 2 (1.5 mmol), 3e (0.03
mmol), Solvent (5 mL), rt.
e Reaction conditions: 1 (1.5 mmol), 2 (1.5 mmol), 3e (0.075
mmol), Solvent (5 mL), rt.
J = 7.6 Hz, 1H), 7.62–7.69 (m, 1H), 7.40 (d, J = 8.3 Hz, 2H), 7.28–
7.32 (m, 2H), 3.81 (s, 2H); 13C NMR (126 MHz, CDCl3) δ 156.5,
151.0, 149.4, 133.6, 131.4, 130.9, 129.8, 129.6, 128.9, 128.4, 124.6,
121.9, 117.7, 115.5, 23.3; MS m/z 265 (M+). Anal. Calcd for
C15H11N3O2: C, 67.92; H, 4.18; N, 15.84. Found: C, 67.75; H, 4.04; N,
15.72%.
2-(4-(3-Nitrobenzylideneamino)phenyl)acetonitrile (4c): Yellow
solid; IR (film) 2246, 1625 cm–1; 1H NMR (500 MHz, CDCl3) δ 8.74–
8.77 (m, 1H), 8.55 (s, 1H), 8.33–8.35 (m, 1H), 8.26 (d, J = 7.7 Hz,
1H), 7.68 (t, J = 7.9 Hz, 1H), 7.40 (d, J = 8.3 Hz, 2H), 7.24–7.31 (m,
2H), 3.81 (s, 2H); 13C NMR (126 MHz, CDCl3) δ 157.8, 150.7, 148.7,
137.6, 134.2, 129.8, 128.9, 128.9, 128.3, 125.7, 123.4, 121.6, 117.7,
115.4, 23.2; MS m/z 265 (M+). Anal. Calcd for C15H11N3O2: C, 67.92;
H, 4.18; N, 15.84. Found: C, 67.84; H, 4.12; N, 15.79%.
2-(4-(2-Chlorobenzylideneamino)phenyl)acetonitrile (4i): White
solid; IR (film) 2251, 1618 cm–1; 1H NMR (500 MHz, CDCl3) δ 8.92
(s, 1H), 8.25 (dd, J = 7.7, 1.4 Hz, 1H), 7.42–7.49 (m, 2H), 7.39 (dd,
J = 9.2, 3.3 Hz, 3H), 7.26 (d, J = 8.4 Hz, 2H), 3.80 (s, 2H); 13C NMR
(126 MHz, CDCl3) δ 157.5, 151.7, 136.2, 133.0, 132.4, 130.0, 128.9,
128.8, 128.6, 127.8, 127.2, 121.8, 117.8, 115.4, 23.2; MS m/z 254
2-(4-(2-(Trifluoromethyl)benzylideneamino)-phenyl)acetonitrile
1
(4d): White solid; IR (film) 2245, 1623 cm–1; H NMR (500 MHz,
CDCl3) δ 8.83 (d, J = 2.2 Hz, 1H), 8.46 (d, J = 7.8 Hz, 1H), 7.77 (d,
J = 7.8 Hz, 1H), 7.69 (t, J = 7.6 Hz, 1H), 7.60 (t, J = 7.6 Hz, 1H), 7.40

278 JOURNAL OF CHEMICAL RESEARCH 2013
(M+). Anal. Calcd for C15H11ClN2: C, 70.73; H, 4.35; N, 11.00. Found:
C, 70.68; H, 4.25; N, 10.90%.
MS m/z 236 (M+). Anal. Calcd for C15H12ON2: C, 76.25; H, 5.12; N,
11.86. Found: C, 76.09; H, 5.00; N, 11.70%.
2-(4-(4-Methoxybenzylideneamino)phenyl)acetonitrile (4r):Yellow
solid: IR (film) 2247, 1601 cm–1; 1H NMR (500 MHz, CDCl3) δ 8.38
(s, 1H), 7.86 (dd, J = 8.7, 4.4 Hz, 2H), 7.35 (d, J = 8.2 Hz, 2H), 7.21
(d, J = 8.3 Hz, 2H), 7.01 (d, J = 8.8 Hz, 2H), 3.90 (d, J = 6.7 Hz, 3H),
3.78 (s, 2H); 13C NMR (126 MHz, CDCl3) δ 162.5, 160.2, 152.2,
132.0, 130.7, 129.0, 128.9, 128.7, 126.9, 121.6, 117.9, 115.4, 114.3,
114.3, 55.4, 23.2; MS m/z 250 (M+). Anal. Calcd for C16H14ON2: C,
76.78; H, 5.64; N, 11.19. Found: C, 76.63; H, 5.47; N, 11.02%.
2-(4-(3,4-Dimethoxybenzylideneamino)phenyl)acetonitrile (4j):
White solid; IR (film) 2240, 1582 cm–1; 1H NMR (500 MHz, CDCl3)
δ 8.36 (s, 1H), 7.62 (d, J = 1.8 Hz, 1H), 7.36 (d, J = 8.3 Hz, 2H), 7.33
(dd, J = 8.2, 1.8 Hz, 1H), 7.18–7.25 (m, 2H), 6.96 (d, J = 8.2 Hz, 1H),
4.00 (s, 3H), 3.97 (s, 3H), 3.78 (s, 2H); 13C NMR (126 MHz, CDCl3)
δ 160.3, 152.3, 152.2, 149.6, 129.3, 128.9, 128.7, 126.9, 124.6, 121.6,
117.9, 115.4, 110.6, 109.1, 56.0, 56.0, 23.2; MS m/z 280 (M+). Anal.
Calcd for C17H16O2N2: C, 72.84; H, 5.75; N, 9.99. Found: C, 72.77; H,
5.68; N, 9.89%.
2-(4-(2,5-Dimethoxybenzylideneamino)phenyl)acetonitrile (4k):
White solid; IR (film) 2244, 1594 cm–1; 1H NMR (500 MHz, CDCl3)
δ 8.89 (s, 1H), 7.70 (d, J = 2.9 Hz, 1H), 7.35 (d, J = 8.0 Hz, 2H), 7.24
(d, J = 8.2 Hz, 2H), 7.05 (dd, J = 9.0, 3.1 Hz, 1H), 6.94 (dd, J = 17.9,
9.1 Hz, 1H), 3.88 (s, 3H), 3.87 (s, 3H), 3.78 (s, 2H); 13C NMR (126
MHz, CDCl3) δ 156.9, 154.4, 153.9, 128.9, 128.7, 127.1, 123.5, 121.8,
120.3, 117.9, 115.5, 113.4, 112.9, 110.5, 56.3, 55.9, 23.2; MS m/z 280
(M+). Anal. Calcd for C17H16O2N2: C, 72.84; H, 5.75; N, 9.99. Found:
C, 72.78; H, 5.65; N, 9.90%.
2-(4-(4-Methylbenzylideneamino)phenyl)acetonitrile (4l): Yellow
solid: IR (film) 2245, 1617 cm–1; 1H NMR (500 MHz, CDCl3) δ 8.42
(s, 1H), 7.81 (d, J = 8.0 Hz, 2H), 7.36 (d, J = 8.2 Hz, 2H), 7.30 (d,
J = 7.9 Hz, 2H), 7.22 (d, J = 8.3 Hz, 2H), 3.79 (s, 2H), 2.44 (s, 3H);
13C NMR (126 MHz, CDCl3) δ 160.9, 152.2, 142.2, 133.5, 129.8,
129.7, 129.6, 128.9, 128.8, 127.1, 121.6, 119.3, 117.9, 115.5, 23.2,
21.6; MS m/z 234 (M+). Anal. Calcd for C16H14N2: C, 82.02; H, 6.02;
N, 11.96. Found: C, 81.95; H, 5.91; N, 11.82%.
Electronic Supplementary Information
Spectra of the products have been deposited in the ESI avail-
able through stl.publisher.ingentaconnect.com/content/stl/jcr/
supp-data.
This work was financially supported by the National Science
Foundation of Zhejiang Province (LY12B02016) and the State
Key Laboratory Breeding Base of Green Chemistry-Synthesis
Technology, Zhejiang University of Technology (P. R. China).
Received 10 December 2012; accepted 22 February 2013
Paper 1201670 doi: 10.3184/174751913X13647468553118
Published online: 15 May 2013
References
2-(4-(3-Hydroxy-4-methylbenzylideneamino)phenyl)acetonitrile
1
Y. Zhang, B. Zou, K. Wang, Y. Pan, H. Liang, X. Yi and H. Wang, Med.
1
(4m): Yellow solid: IR (film) 2270, 1587 cm–1; H NMR (500 MHz,
Chem. Res., 2012, 21, 1341.
CDCl3) δ 8.34 (s, 1H), 7.55 (d, J = 1.9 Hz, 1H), 7.39 (dd, J = 8.3,
1.9 Hz, 1H), 7.35 (d, J = 8.3 Hz, 2H), 7.21 (d, J = 8.3 Hz, 2H), 6.95
(d, J = 8.3 Hz, 1H), 5.73 (s, 1H), 3.98 (s, 3H), 3.78 (s, 2H); 13C NMR
(126 MHz, CDCl3) δ 160.3, 152.1, 149.6, 146.1, 129.9, 128.9, 128.7,
126.9, 122.5, 121.6, 117.9, 115.5, 113.9, 110.4, 56.1, 23.2; MS m/z
266 (M+). Anal. Calcd for C16H14O2N2: C, 72.17; H, 5.30; N, 10.52.
Found: C, 72.08; H, 5.22; N, 10.40%.
2
N. Zhang, Y.-h. Fan, Z. Zhang, J. Zuo, P.-f. Zhang, Q. Wang, S.-b. Liu and
C.-j. Bi, Inorg. Chem. Commun., 2012, 22, 68.
M. Ruf, W.S. Durfee and C.G. Pierpont, Chem. Commun., 2004, 1022.
V.J. Mayani, S.H.R. Abdi, R.I. Kureshy, N.-u. Kahn, H. Das and
H.C. Bajaj, J. Org. Chem., 2010, 75, 6191.
3
4
5
6
7
8
9
P. Seth, L.K. Das, M.G.B. Drew and A. Ghosh, Eur. J. Inorg. Chem., 2012,
2232.
Y.-C. Jeong, Y. D. Huang, S. Choi and K.-H. Ahn, Tetrahedron Asymmetry,
2005, 16, 3497.
T. Mahamo, M.M. Mogorosi, J.R. Moss, S.F. Mapolie, J.C. Slootweg,
K. Lammertsma and G.S. Smith, J. Organomet. Chem., 2012, 703, 34.
M. Çolak, T. Aral, H. Hoşgören and N. Demirel, Tetrahedron Asymmetry,
2007, 18, 1129.
2-(4-(Pyridine-4-ylmethyleneamino)phenyl)acetonitrile (4n):
A
yellow solid: IR (film) 2248, 1595 cm–1; 1H NMR (500 MHz, CDCl3)
δ 8.78 (d, J = 5.8 Hz, 2H), 8.46 (s, 1H), 7.76 (d, J = 5.9 Hz, 2H), 7.39
(d, J = 8.3 Hz, 2H), 7.26 (d, J = 8.3 Hz, 2H), 3.80 (s, 2H); 13C NMR
(126 MHz, CDCl3) δ 158.6, 151.2, 150.8, 150.5, 150.5, 142.5, 128.9,
128.5, 122.4, 121.6, 121.6, 117.7, 115.4, 23.2; MS m/z 221 (M+).
Anal. Calcd for C14H11N3: C, 75.98; H, 5.01; N, 18.99. Found: C,
75.88; H, 4.94; N, 18.89%.
M. Hosseini-Sarvari, Chinese Chem. Lett., 2011, 22, 547-550.
10 D. Blanco-Ania, P.H.H. Hermkens, L.A.J.M. Sliedregt, H.W. Scheeren and
F.P.J.T. Rutjes, Tetrahedron, 2009, 65, 5393.
11 A.K. Chakraborti, S. Bhagat and S. Rudrawar, Tetrahedron Lett., 2004, 45,
7641.
12 L.C. da Silva-Filho, V. Lacerda Jr, M.G. Constantina and G.V.J. da Silva,
Synthesis, 2008, 2527.
13 L. Hu, X. Cao, D. Ge, H. Hong, Z. Guo, L. Chen, X. Sun, J. Tang, J. Zheng,
J. Lu and H. Gu, Chem. A Eur. J., 2011, 17, 14283.
14 M.C. Law, T.W. Cheung, K.-Y. Wong and T.H. Chan, J. Org. Chem, 2007,
72, 923.
2-(4-(3,5-Dimethoxybenzylideneamino)phenyl)acetonitrile (4o):
Yellow solid: IR (film) 2244, 1594 cm–1; 1H NMR (500 MHz, CDCl3)
δ 8.89 (s, 1H), 7.69 (d, J = 3.2 Hz, 1H), 7.35 (d, J = 8.3 Hz, 2H), 7.24
(d, J = 8.3 Hz, 2H), 7.05 (dd, J = 9.0, 3.2 Hz, 1H), 6.92 (d, J = 9.0 Hz,
1H), 3.88 (s, 3H), 3.87 (s, 3H), 3.78 (s, 2H); 13C NMR (126 MHz,
CDCl3) δ 156.9, 154.4, 153.9, 128.9, 128.7, 127.1, 123.5, 121.8,
120.4, 117.9, 115.4, 113.4, 112.9, 110.5, 56.3, 55.9, 23.2; MS m/z 280
(M+). Anal. Calcd for C17H16O2N2: C, 72.84; H, 5.75; N, 9.99. Found:
C, 72.76; H, 5.64; N, 9.87%.
2-(4-(Naphthalen-2-ylmethyleneamino)phenyl)acetonitrile (4p):
White solid: IR (film) 2245, 1618 cm–1; 1H NMR (500 MHz, CDCl3)
δ 8.62 (s, 1H), 8.23 (s, 1H), 8.16–8.19 (m, 1H), 7.95 (t, J = 7.4 Hz,
2H), 7.91 (d, J = 7.6 Hz, 1H), 7.54–7.62 (m, 2H), 7.39 (d, J = 8.2 Hz,
2H), 7.29 (d, J = 8.3 Hz, 2H), 3.80 (s, 2H); 13C NMR (126 MHz,
CDCl3) δ 160.9, 152.0, 135.2, 133.7, 133.1, 131.5, 129.1, 128.9,
128.8, 128.7, 128.0, 127.7, 127.4, 126.7, 123.9, 121.6, 117.9, 115.5,
23.2; MS m/z 270 (M+). Anal. Calcd for C19H14N2: C, 84.42; H, 5.22;
N, 10.36. Found: C, 84.30; H, 5.11; N, 10.22%.
15 M. Gopalakrishnan, P. Sureshkumar, V. Kanagarajan and J. Thanusu, Res.
Chem. Intermed., 2007, 33, 541.
16 C.K.Z. Andrade, S.C.S. Takada, L.M. Alves, J.P. Rodrigues, P.A.Z. Suarez,
R.F. Brandao and V.C.D. Soares, Synlett, 2004, 2135.
17 R.S. Varma, R. Dahiya and S. Kumar, Tetrahedron Lett., 1997, 38, 2039.
18 H. Naeimi, H. Sharghi, F. Salimi and K. Rabiei, Heteroatom Chemistry,
2008, 19, 43.
19 H. Naeimi, F. Salimi and K. Rabiei, J. Mol. Catal. A: Chem., 2006, 260,
100.
20 P.A. Kerneghan, S.D. Halperin, D.L. Bryce and K.E. Maly, Canad. J.
Chem., 2011, 89, 577.
21 B.T. Cho and S.K. Kang, Tetrahedron, 2005, 61, 5725.
22 K.P. Guzen, A.S. Guarezemini, A.T.G. Órfão, R. Cella, C.M.P. Pereira and
H.A. Stefani, Tetrahedron Lett., 2007, 48, 1845.
2-(4-(4-Hydroxybenzylideneamino)phenyl)acetonitrile (4q): Yellow
solid: IR (film) 2252, 1579 cm–1; 1H NMR (500 MHz, CDCl3) δ 8.37
(s, 1H), 7.83 (d, J = 8.5 Hz, 2H), 7.35 (d, J = 8.2 Hz, 2H), 7.21 (d,
J = 8.2 Hz, 2H), 6.94 (d, J = 8.5 Hz, 2H), 5.15 (s, 1H), 3.78 (s, 2H);
13C NMR (126 MHz, d-DMSO) δ 160.7, 160.2, 151.3, 132.0, 130.7,
128.9, 128.6, 128.0, 127.4, 121.3, 119.3, 115.8, 115.6, 114.1, 21.9;
23 M. Gopalakrishnan, P. Sureshkumar, V. Kanagarajan, J. Thanusu and
R. Govindaraju, J. Chem. Res., 2005, 5, 299.
24 R.S. Varma and R. Dahiya, Synlett, 1997, 1245.
25 P.C. Andrews, A.C. Peatt and C.L. Raston, Tetrahedron Lett., 2004, 45,
243.

Copyright of Journal of Chemical Research is the property of Science Reviews 2000 Ltd. and
its content may not be copied or emailed to multiple sites or posted to a listserv without the
copyright holder's express written permission. However, users may print, download, or email
articles for individual use.