PdCl2(1-methylimidazole) 2-catalysed Suzuki-Miyaura and Mizoroki-Heck reactions performed in neat water

Article abstract of DOI:10.3184/174751913X13662179283121

PdCl₂(1-methylimidazole)2 was an effective catalyst in neat water for the Suzuki-Miyaura and Mizoroki-Heck reactions of aryl bromides and iodides with, respectively, arylboronic acids and acrylic acid. Under optimal conditions, the products, variously substituted biphenyls and monosubstituted trans-cinnamic acids, respectively, were formed in good to almost quantitative yields.

Full text of DOI:10.3184/174751913X13662179283121

294 RESEARCH PAPER
MAY, 294–297
JOURNAL OF CHEMICAL RESEARCH 2013
PdCl2(1-methylimidazole)2-catalysed Suzuki–Miyaura and Mizoroki–Heck
reactions performed in neat water
Yao Li, Xiao-Fang Lin, Meng-Yuan Liu, Lu-Lu Zhang, Ai-Ping Jin and Jian-Mei Lu*
College of Chemistry and Materials Engineering, Wenzhou University, Chashan UniversityTown, Wenzhou, Zhejiang Province 325035,
P. R. China
PdCl2(1-methylimidazole)2 was an effective catalyst in neat water for the Suzuki–Miyaura and Mizoroki–Heck reac-
tions of aryl bromides and iodides with, respectively, arylboronic acids and acrylic acid. Under optimal conditions,
the products, variously substituted biphenyls and monosubstituted trans-cinnamic acids, respectively, were formed
in good to almost quantitative yields.
Keywords: palladium complex, Suzuki–Miyaura coupling, Mizoroki–Heck coupling, water as solvent, green chemistry
As one of the 12 principles of green chemistry, the execution
of organic reactions in safe solvents has attracted much atten-
tion during the past 15 years.1,2 Of the green and safe solvents,
water is the least toxic and is non-flammable, cheap and easily
available. Consequently, chemists have shown great interest
in developing organic transformations performed in water.3
Because using water as the sole solvent can prevent pollution
of the environment, organic reactions performed in neat water
are of interest to both academia and industry.
When the temperature was lowered to 90 °C or 80 °C, 4a
was still obtained in almost quantitative yield, respectively
(Table 1, entries 11 and 12), but when the temperature was
lowered to 70 °C, 4a was obtained in somewhat lower yield
(Table 1, entry 13). So the optimal reaction conditions were
established as using 1.0 mol% Pd(II)–Im complex 1 as the
catalyst, NaOH as the base in neat water at 80 °C.
Next, we examined a variety of aryl bromides and iodides
2a–j with arylboronic acids 3b–g under these optimal reaction
conditions. The results are summarised in Table 2. We were
pleased to find that reactions afforded variously substituted
biphenyls 4b–l, n–o in excellent yields, whether substituents
were an electron-donating group such as methoxy or an elec-
tron-withdrawing group such as fluoro on the phenyl ring of 2
or of 3. 3-Bromopyridine 2f when reacted with 3d or 3e also
led to the corresponding 3-arylpyridines 4m and 4n in almost
quantitative yields, respectively (Table 2, entries 13 and 14).
Then, we investigated a Mizoroki–Heck coupling reaction
using Pd(II)–Im complex 1 as the catalyst in neat water.
For our initial investigation, we chose bromobenzene 2b
(1.0 mmol) and acrylic acid (1.2 mmol) as the model sub-
strates. After several trials and errors, we were pleased to find
Palladium catalysed Suzuki–Miyaura4,5 and Mizoroki–
Heck6,7 coupling reactions play important roles in the forma-
tion of carbon–carbon bonds. Traditionally, such reactions are
carried out in organic solvents with phosphine ligands being
used to facilitate the coupling reactions.8 However, most phos-
phine ligands are expensive, air- and/or moisture-sensitive, and
some of them require complicated synthetic routes. In order to
avoid the drawbacks associated with phosphine ligands, some
alternative non-phosphine catalytic systems such as transition
metal–diamine ligands catalyst,9–14 palladacycles15–17 and tran-
sition metal-N-heterocyclic carbene complexes,18–23 have been
developed. However, most such reactions were also performed
in organic solvents and some of the catalysts still required
lengthy reaction times or expensive starting materials.
Therefore, much scope still remains for the development
of phosphine-free Suzuki–Miyaura and Mizoroki–Heck
reactions, especially with respect to the easy availability of
the catalytic systems, the stability and non-toxic nature of the
ligands and using green solvents. Recently, we found that
PdCl2(1-methylimidazole)2, which had been shown to be a
very effective catalyst for Suzuki–Miyaura reactions in (1:1)
isopropanol/water,24 was also a very effective catalyst for both
Suzuki–Miyaura and Mizoroki–Heck reactions performed in
neat water. In view of the appearance recently of several other
reports,25–33 we report here our results in detail.
Table
1 Optimisation for Pd(II)-Im complex 1 catalysed
reaction of 4-bromoanisole 2a with phenylboronic acid 3a
Results and discussion
Entrya
Base
Temp.
Yield/%b
In initial investigations, we examined the Suzuki–Miyaura
coupling reaction of the model substrate 4-bromoanisole (2a)
with phenylboronic acid (3a), using PdCl2–1-methylimidazole
complex [Pd(II)–Im] 1 (1.0 mol%) as the catalyst in neat water
under reflux to identify the best base. As can be seen from
Table 1, similar, very good results could be achieved when
NaOH, KOH, Na2CO3, K3PO4.3H2O, Na3PO4.12H2O and
Cs2CO3 are used, respectively (Table 1, entries 1–4, 7 and 8).
Other bases such as KHCO3, NaHCO3 and CH3COOK, all
gave the product 4a in lower yield within 12 h (Table 1, entries
5, 6 and 10). When HCOONa was used as the base, only 16%
yield of 4a was obtained (Table 1, entry 9). Owing to its lower
molecular mass and lower cost, NaOH was chosen as the base.
1
2
NaOH
KOH
Na2CO3
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
90 °C
99
99
96
95
81
79
99
97
16
57
99
99
89
3
4
K3PO4·3H2O
KHCO3
NaHCO3
Na3PO4·12H2O
Cs2CO3
HCOONa
CH3COOK
NaOH
5
6
7
8
9
10
11
12
13
NaOH
NaOH
80 °C
70 °C
a All reactions were carried out using 2a (1.0 mmol), 3a
(1.2 mmol), 1 (1.0 mol%), base (1.5 equiv.), H2O (2.0 mL) at the
listed temperature for 12 h.
b Isolated yields.
* Correspondent. E-mail: lujianmei1982@163.com

JOURNAL OF CHEMICAL RESEARCH 2013 295
Table
2
Pd(II)-Im complex
1
catalysed Suzuki–Miyaura
Table 3 Pd(II)-Im complex 1 catalysed Mizoroki–Heck coupling
of aryl halides 2 with acrylic acid under the optimal conditions
coupling of aryl halides 2 with arylboronic acids 3 under the
optimal conditions
Entrya
2 (R1/X)
3 (R2)
Yield/%b
Entrya
2 (R1/X)
Base
Yield/%b
1
2
2a (4-MeO/Br)
3b (4-F)
4b, 91
4c, 96
4d, 97
4e, 99
4f, 99
4a, 92
4g, 87
4h, 99
4i, 94
4j, 99
4k, 99
4l, 88
1
2
2b (H/Br)
KOtBu
LiOtBu
KOtBu
LiOtBu
KOtBu
LiOtBu
LiOtBu
LiOtBu
LiOtBu
LiOtBu
LiOtBu
5a, 88
5a, 92
5b, 83
5b, 33
5c, 88
5c, 32
5d, 90
5a, 97
5e, 92
5b, 97
5f, 93
2a
3c (2-Me)
3
2a
3d (3, 5-Me2)
2b
4
2a
2a
3e (3-Me)
3
2e (4-F/Br)
2e
2k (3-MeO/Br)
2k
2l (4-Ac/Br)
2g (H/I)
2i (4-MeO/I)
2j (4-F/I)
2m (4-CI/I)
5
3f (3-MeO)
4
6
2b (H/Br)
2b
3g (4-MeO)
5
7
3f
6
8
2b
3e
3e
3d
3e
3d
7
9
2c (2-Me/Br)
2d (4-Me/Br)
2d
8
10
11
12
9
10
11
2e (4-F/Br)
a All reactions were carried out using 2 (1.0 mmol), acrylic
acid (1.2 mmol), 1 (1.0 mol%), base (3.0 mmol), H2O (2.0 mL) at
100 °C for 12 h.
13
2f
3d
4m, 99
b Isolated yields.
14
15
16
17
18
2f
3e
3d
3d
3d
3d
4n, 99
4o, 99
4j, 95
4d, 96
4l, 96
2g (H/I)
2h (4-Me/I)
2i (4-MeO/I)
2j (4-F/I)
Experimental
1H and 13C NMR spectra were recorded on a Bruker Avance AV-II
300 MHz or a Bruker Avance AV-III 500 MHz spectrometer in CDCl3
or in DMSO-d6 with tetramethylsilane (TMS) as an internal standard;
J-values are in Hz. Melting points are uncorrected. Commercially
obtained reagents were used without further purification. Flash column
chromatography was carried out using Huanghai 300–400 mesh silica
gel at increased pressure.
a All reactions were carried out using 2 (1.0 mmol), 3 (1.2 mmol),
1 (1.0 mol%), NaOH (1.5 equiv.), H2O (2.0 mL) at 80 °C for 12 h.
b Isolated yields.
Synthesis of Pd(II)–Im complex 1:24 PdCl2 (1.0 mmol), EtOH (5.0 mL)
and 1-methylimidazole (2.0 mmol) were successively added into a
reaction tube. The mixture was heated at 70 °C for 3 h. After cooling
to room temperature, the mixture was filtered and washed with EtOH,
then dried in vacuo to give a brown solid, which was used without any
further purification.
that when KOtBu or LiOtBu (3.0 equiv.) was used as the base,
the corresponding coupling product 5a can be obtained in 88%
or 92% yield, respectively (Table 3, entries 1 and 2). It is obvi-
ous that the bases KOtBu and LiOtBu will be hydrolysed to
KOH, LiOH and tBuOH under the reaction conditions. Further
studies showed that tBuOH was essential for the reactions with
KOH or LiOH as the base, respectively, which clearly illus-
trated the differences between the results using KOH or LiOH
and KOtBu or LiOtBu or as the base, respectively, which is also
accordant with our previous results (see ref. 31).
A series of aryl halides 2e, g, i–m were then subjected to the
optimal reaction conditions (Table 3). The results indicated
that the Pd(II)–Im complex 1 was also efficient for the
Mizoroki–Heck coupling reaction of aryl bromides and
iodides. All reactions afforded the desired coupling products,
monosubstituted trans-cinnamic acids 5 in good to high yields
when appropriate bases were used. For example, although
4-fluoro- (2e) and 3-methoxy-bromobenzen (2k) yielded the
corresponding coupling products 5b and 5c in only 33% and
32% yields, respectively when LiOtBu was used as the base
(Table 3, entries 4 and 6), when KOtBu was used as the base,
5b and 5c were obtained much more efficiently in 83% and
88% yields, respectively (Table 3, entries 3 and 5).
Pd(II)–Im complex 1 catalysed Suzuki–Miyaura coupling of aryl
halides 2 with arylboronic acids 3; general procedure
If aryl halide is a liquid: Under a N2 atmosphere, an arylboronic acid
3 (1.2 mmol), NaOH (1.5 equiv.), Pd(II)–Im complex 1 (1.0 mol%),
H2O (2.0 mL) and an aryl halide 2 (1.0 mmol) were successively
added into a Schlenk reaction tube. The mixture was stirred at 80 °C
for 12 h. After cooling to room temperature, the reaction mixture was
extracted with ethyl acetate and the organic layer dried over anhy-
drous Na2SO4. The solvent was evaporated in vacuo and the residue
purified by flash column chromatography on silica gel to give the pure
product 4.
If aryl halide is solid: Under a N2 atmosphere, an aryl halide 2
(1.0 mmol), an arylboronic acid 3 (1.2 mmol), NaOH (1.5 equiv),
Pd(II)–Im complex 1 (1.0 mol%) and H2O (2.0 mL) were successively
added into a Schlenk reaction tube. The mixture was stirred at 80 °C
for 12 h. After cooling to room temperature, the reaction mixture
was extracted with ethyl acetate and the organic layer dried over
anhydrous Na2SO4. The solvent was evaporated in vacuo and then
purified by flash column chromatography on silica gel to give the pure
product 4.
Conclusions
Pd(II)–Im complex 1 catalysed Mizoroki–Heck coupling of aryl
halides 2 with acrylic acid; general procedure
PdCl2(1-methylimidazole)2 complex 1 has been shown to be an
effective catalyst for the Suzuki–Miyaura and Mizoroki–Heck
reactions of aryl bromides and iodides performed in neat water,
potentially extending their use as industrial processes. Under
the optimal conditions, all reactions performed very well
to give the expected coupling products in good to almost
quantitative yields.
Under a N2 atmosphere, LiOtBu or KOtBu (3.0 mmol), H2O (2.0 mL)
and acrylic acid (1.2 mmol) were added into a Schlenk reaction tube
and the mixture was stirred at room temperature for 10 minutes. Then
an aryl halide 2 (1.0 mmol) and Pd(II)–Im complex 1 (1.0 mol%) were
added. The mixture was stirred at 100 °C for 12 h. After cooling to
room temperature, the reaction mixture was acidified by HCl (4 M) to
pH 1 and extracted with EtOAc. The organic layer was washed with

296 JOURNAL OF CHEMICAL RESEARCH 2013
brine and dried over anhydrous Na2SO4. The solvent was evaporated
in vacuo and the residue was purified by flash chromatography on
silica gel to afford the pure product 5.
J = 1.5, 5.0 Hz, 1H), 8.82 (d, J = 2.0 Hz, 1H); 13C NMR (75 MHz,
CDCl3) δ 21.3, 123.4, 125.0, 129.7, 134.4, 136.9, 137.7, 138.6, 148.2,
148.3 ppm.
3-(3-Methylphenyl)pyridine (4n):43 Colourless liquid; 1H NMR
(500 MHz, CDCl3) δ (ppm) 2.41 (s, 3H), 7.20 (d, J = 6.0 Hz, 1H),
7.31–7.37 (m, 4H), 7.84 (d, J = 8.0 Hz, 1H), 8.56 (d, J = 5.0 Hz, 1H),
8.83 (d, J = 2.5 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ 21.4, 123.4,
124.1, 127.8, 128.8, 128.9, 134.3, 136.7, 137.6, 138.6, 148.1 ppm.
3,5-Dimethylbiphenyl (4o):44 Pale yellow liquid; 1H NMR (500 MHz,
CDCl3) δ (ppm) 2.35 (s, 6H), 6.96 (s, 1H), 7.18 (s, 2H), 7.28 (t, J =
7.5 Hz, 1H), 7.38 (t, J = 7.5 Hz, 2H), 7.55 (d, J = 7.5 Hz, 2H); 13C
NMR (75 MHz, CDCl3) δ 21.4, 125.1, 127.0, 127.1, 128.6, 128.9,
138.2, 141.2, 141.4 ppm.
Bis-(1-methylimidazole)palladium(II) dichloride (1):24 Brown solid,
m.p. 163–165 °C; 1H NMR (300 MHz, CDCl3) δ (ppm) 3.69 (s, 6H),
6.77 (s, 2H), 7.40 (s, 2H), 7.98 (s, 2H).
4-Methoxybiphenyl (4a): White solid, m.p. 90–92 °C (lit.34 91–
1
93 °C); H NMR (500 MHz, CDCl3) δ (ppm) 3.82 (s, 3H), 6.96 (d,
J = 8.5 Hz, 2H), 7.29 (t, J = 7.5 Hz, 1H), 7.40 (t, J = 7.5 Hz, 2H), 7.52
(d, J = 8.5 Hz, 2H), 7.54 (d, J = 7.5 Hz, 2H); 13C NMR (75 MHz,
CDCl3) δ 55.3, 114.2, 126.6, 126.7, 128.1, 128.7, 133.8, 140.8, 159.1
ppm.
4-Fluoro-4′-methoxybiphenyl (4b): White solid, m.p. 92–93 °C
trans-Cinnamic acid (5a): White solid, m.p. 132–135 °C (lit.45 133–
1
(lit.34 92–96 °C); H NMR (300 MHz, CDCl3) δ (ppm) 3.85 (s, 3H),
1
134 °C); H NMR (300 MHz, CDCl3) δ (ppm) 6.46 (d, J = 16.2 Hz,
6.97 (d, J = 8.4 Hz, 2H), 7.10 (t, J = 8.7 Hz, 2H), 7.45–7.51 (m, 4H);
13C NMR (75 MHz, CDCl3) δ 55.3, 114.2, 115.5 (d, JC-F = 21.0 Hz),
128.0, 128.1 (d, JC-F = 8.3 Hz), 132.8, 136.9 (d, JC-F = 3.0 Hz), 159.1,
162.1 (d, JC-F = 243.8 Hz) ppm.
1H), 7.40–7.42 (m, 3H), 7.55–7.58 (m, 2H), 7.80 (d, J = 16.2 Hz, 1H);
13C NMR (125 MHz, CDCl3) δ 117.2, 128.4, 129.0, 130.7, 134.1,
147.1, 171.8 ppm.
2-Methyl-4′-methoxybiphenyl (4c):35 Colourless oil; 1H NMR
(300 MHz, CDCl3) δ (ppm) 2.26 (s, 3H), 3.79 (s, 3H), 6.92 (d, J =
8.7 Hz, 2H), 7.19–7.24 (m, 6H); 13C NMR (75 MHz, CDCl3) δ 20.5,
55.2, 113.5, 125.7, 126.9, 129.9, 130.2, 130.3, 134.3, 135.4, 141.5,
158.5 ppm.
trans-3-(4-Fluorophenyl)acrylic acid (5b): White solid, m.p. 204–
1
207 °C (lit.45 205–207 °C); H NMR (300 MHz, DMSO-d6) δ (ppm)
6.56 (d, J = 16.2 Hz, 1H), 7.29 (dd, J = 8.7, 18.3 Hz, 2H), 7.65 (d,
J = 16.2 Hz, 1H), 7.83 (dd, J = 5.7, 8.7 Hz, 2H), 12.5 (s, 1H); 13C
NMR (75 MHz, DMSO-d6) δ 115.9 (d, JC-F = 22.5 Hz), 119.0 (d,
JC-F = 2.5 Hz), 130.5 (d, JC-F = 8.75 Hz), 130.9 (d, JC-F = 3.75 Hz),
142.7, 163.1 (d, JC-F = 246.25 Hz), 167.4 ppm.
3,5-Dimethyl-4′-methoxybiphenyl (4d): White solid, m.p. 45–47 °C
1
(lit.36 46–47 °C); H NMR (300 MHz, CDCl3) δ (ppm) 2.35 (s, 3H),
trans-3-(3-Methoxyphenyl)acrylic acid (5c): White solid, m.p.
116–118 °C (lit.46 116–119 °C); 1H NMR (300 MHz, CDCl3) δ (ppm)
3.84 (s, 3H), 6.44 (d, J = 16.2 Hz, 1H), 6.97 (dd, J = 2.7, 7.8 Hz, 1H),
7.08 (s, 1H), 7.15 (d, J = 7.8 Hz, 1H), 7.32 (dd, J1 = J2 = 7.8 Hz, 1H),
7.76 (d, J = 16.2 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ 55.3, 113.1,
116.7, 117.5, 121.1, 130.0, 135.4, 147.0, 159.9, 172.1 ppm.
2.36 (s, 3H), 3.81 (s, 3H), 6.91–6.96 (m, 3H), 7.16 (s, 2H), 7.49 (d,
J = 8.7 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ 21.4, 55.3, 114.1,
124.7, 128.1, 128.3, 134.0, 138.2, 140.8, 159.0 ppm.
3-Methyl-4′-methoxybiphenyl (4e): Pale yellow solid, m.p. 49–
51 °C (lit.37 50 °C); 1H NMR (300 MHz, CDCl3) δ (ppm) 2.41 (s, 3H),
3.84 (s, 3H), 6.96 (dd, J = 2.1, 6.6 Hz, 2H), 7.12 (d, J = 7.8 Hz, 1H),
7.30–7.36 (m, 3H), 7.52 (dd, J = 2.1, 6.6 Hz, 2H); 13C NMR (125
MHz, CDCl3) δ 21.5, 55.3, 114.1, 123.8, 127.4, 127.5, 128.1, 128.6,
133.9, 138.3, 140.8, 159.1 ppm.
trans-3-(4-Acetylphenyl)acrylic acid (5d): White solid, m.p. 225–
1
226 °C (lit.45 224–226 °C); H NMR (300 MHz, DMSO-d6) δ (ppm)
2.59 (s, 3H), 6.66 (d, J = 15.9 Hz, 1H), 7.64 (d, J = 15.9 Hz, 1H), 7.83
(d, J = 8.4 Hz, 2H), 7.96 (d, J = 8.4 Hz, 2H), 12.60 (br, 1H); 13C NMR
(75 MHz, DMSO-d6) δ 26.8, 121.8, 128.4, 128.7, 137.6, 138.6, 142.6,
167.3, 197.4 ppm.
3,4′-Dimethoxybiphenyl (4f): White solid, m.p. 59–60 °C (lit.37
56–58 °C); 1H NMR (300 MHz, CDCl3) δ (ppm) 3.81 (s, 3H), 3.82 (s,
3H), 6.84 (dd, J = 2.4, 8.1 Hz, 1H), 6.95 (dd, J = 2.1, 6.6 Hz, 2H), 7.08
(t, J = 2.4 Hz, 1H), 7.12 (dd, J = 0.9, 7.8 Hz, 1H), 7.31 (t, J = 7.8 Hz,
1H), 7.51 (dd, J = 2.1, 6.6 Hz, 2H); 13C NMR (75 MHz, CDCl3)
δ 55.19, 55.25, 112.0, 112.5, 114.1, 119.2, 128.1, 129.7, 133.5, 142.3,
159.2, 159.9 ppm.
trans-3-(4-Methoxyphenyl)acrylic acid (5e): White solid, m.p.
172–174 °C (lit.45 175–176 °C); 1H NMR (300 MHz, CDCl3) δ (ppm)
3.85 (s, 3H), 6.32 (d, J = 15.9 Hz, 1H), 6.92 (d, J = 8.7 Hz, 2H), 7.51
(d, J = 8.7 Hz, 2H), 7.74 (d, J = 15.9 Hz, 1H); 13C NMR (125 MHz,
CDCl3) δ 55.4, 114.4, 114.6, 126.8, 130.1, 146.7, 161.8, 172.1 ppm.
trans-3-(4-Chlorophenyl)acrylic acid (5f): White solid, m.p. 248–
250 °C (lit.47 249–250.3 °C); 1H NMR (300 MHz, DMSO-d6) δ (ppm)
6.55 (d, J = 16.2 Hz, 1H), 7.47 (d, J = 8.4 Hz, 2H), 7.58 (d, J =
16.2 Hz, 1H), 7.73 (d, J = 8.4 Hz, 2H), 12.4 (s, 1H); 13C NMR
(125 MHz, DMSO-d6) δ 120.0, 128.9, 129.9, 133.2, 134.8, 142.6,
167.3 ppm.
1
3-Methoxybiphenyl (4g):38 Colourless liquid; H NMR (300 MHz,
CDCl3) δ (ppm) 3.82 (s, 3H), 6.86–6.89 (m, 1H), 7.11–7.18 (m, 2H),
7.30–7.38 (m, 2H), 7.41–7.43 (m, 2H), 7.57 (d, J = 8.4 Hz, 2H); 13
C
NMR (75 MHz, CDCl3) δ 55.2, 112.6, 112.8, 119.6, 127.1, 127.4,
128.7, 129.7, 141.0, 142.7, 159.9 ppm.
3-Methylbiphenyl (4h):39 Colorless liquid; 1H NMR (500 MHz,
CDCl3) δ (ppm) 2.38 (s, 3H), 7.13 (d, J = 7.5 Hz, 1H), 7.29 (t, J =
7.5 Hz, 2H), 7.37 (d, J = 7.5 Hz, 2H), 7.40 (d, J = 7.5 Hz, 2H), 7.56
(d, J = 7.5 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ 21.5, 124.3, 127.1,
127.2, 127.965, 127.974, 128.6, 128.7, 138.3, 141.2, 141.4 ppm.
2,3′-Dimethylbiphenyl (4i):40 Colourless liquid; 1H NMR (500 MHz,
CDCl3) δ (ppm) 2.26 (s, 3H), 2.39 (s, 3H), 7.11–7.15 (m, 3H), 7.21–
7.30 (m, 5H); 13C NMR (125 MHz, CDCl3) δ 20.4, 21.4, 125.7, 126.2,
127.1, 127.4, 127.9, 129.7, 129.9, 130.2, 135.2, 137.5, 141.9, 142.1
ppm.
Financial support from the National Natural Science Founda-
tion of China (No. 21002072) is greatly appreciated. Yao
Li thanks Science and Technology Department of Zhejiang
Province (Xinmiao Programme) for financial support (No.
2011R424016). Meng-Yuan Liu and Lu-Lu Zhang thank the
University Students’ innovative undertaking training program
for financial support.
3,5,4′-Trimethylbiphenyl (4j):41 Colourless liquid; 1H NMR (500 MHz,
CDCl3) δ (ppm) 2.336 (s, 3H), 2.343 (s, 3H), 2.35 (s, 3H), 6.93 (s,
1H), 7.17 (s, 2H), 7.18 (d, J = 7.5 Hz, 2H), 7.44 (d, J = 7.5 Hz, 2H);
13C NMR (75 MHz, CDCl3) δ 21.1, 21.4, 124.9, 127.0, 128.6, 129.3,
136.8, 138.2, 138.6, 141.2 ppm.
Received 24 January 2013; accepted 22 February 2013
Paper 1301746 doi: 10.3184/174751913X13662179283121
Published online: 15 May 2013
1
3,4′-Dimethylbiphenyl (4k):42 Colourless liquid; H NMR (500 MHz,
CDCl3) δ (ppm) 2.37 (s, 3H), 2.39 (s, 3H), 7.12 (d, J = 7.5 Hz, 1H),
7.22 (d, J = 7.5 Hz, 2H), 7.29 (t, J = 7.5 Hz, 1H), 7.37 (d, J = 7.0 Hz,
2H), 7.47 (d, J = 7.0 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ 21.1, 21.5,
124.1, 127.0, 127.7, 127.8, 128.6, 129.4, 136.9, 138.2, 138.5, 141.1
ppm.
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