Suzuki-Miyaura reaction of chloroarenes using Pd(PPh3) 4 as catalyst

Article abstract of DOI:10.3184/030823410X12624523028293

The reactivity of a number of chloroarenes was investigated and chloro-nitroarenes were found to undergo facile arylation with Pd(PPh ₃)₄ / [Pd(PPh₃)₂Cl ₂/n.PPh₃] as catalyst. Furthermore, 4-chlorobenzaldehyde underwent arylation under the conditions, albeit with a higher catalyst loading.

Full text of DOI:10.3184/030823410X12624523028293

34 RESEARCH PAPER
JANUARY, 34–38
JOURNAL OF CHEMICAL RESEARCH 2010
Suzuki–Miyaura reaction of chloroarenes using Pd(PPh3)4 as catalyst
Thies Thiemann,a,c* Yasuko Tanaka,b Soleiman Hisaindeec and Maitha Kaabic
aInterdisciplinary Graduate School of Engineering Sciences and bInstitute of Materials Chemistry and Engineering, Kyushu University, 6–1,
Kasuga–koh–en, Kasuga–shi, Fukuoka 816–8580, Japan
cDepartment of Chemistry, Faculty of Science, United Arab Emirates University, PO Box 17551, Al Ain, United Arab Emirates
The reactivity of a number of chloroarenes was investigated and chloro–nitroarenes were found to undergo facile
arylation with Pd(PPh )4 / [Pd(PPh3)2Cl2/n.PPh3] as catalyst. Furthermore, 4–chlorobenzaldehyde underwent arylation
under the conditions, 3albeit with a higher catalyst loading.
Keywords: nitrochlorobenzenes, Suzuki–Miyaura cross–coupling, tetrakis(triphenylphosphino)palladium(0)
The Suzuki–Miyaura cross–coupling reaction of aryl– and
alkylboronic acids with bromo– and iodoarenes has become
a powerful tool in organic synthesis.1 For economic reasons,
the use of chloroarenes in this reaction has become of great
interest,2 and the development of new catalysts and reaction
protocols for such transformations has been found to be
important. Commencing in the late 1990s, a number of new
Pd–, Pt– and Ni–catalysts have been proposed1––11 with a
variety of exchangeable ligands. Furthermore, in the area of
ligandless catalysts for Suzuki–Miyaura reactions, a number
of highly reactive nanopalladium catalysts12 have been devel-
oped as effective catalysts for the coupling of chloroarenes.
It was also found that ligandless palladium catalysts could be
used with aryl tetrafluoroborates in coupling reactions with
aryl halides.13 Our interest in the application of the Suzuki–
Miyaura coupling to chloroarenes stems from our work on the
synthesis of arylated anthraquinones, where we were surprised
to find that chloroanthraquinones undergo C–C coupling
reactions with arylboronic acids under Pd(PPh3)4 catalysis
with great ease.14 We now report the effectiveness of Pd(PPh3)4
as a catalyst for the coupling of chloroarenes other than
chloroanthraquinones.
Thus, a number of electron donor and electron acceptor
substituted aryl chlorides were reacted with arylboronic acids
under Pd(PPh )4 catalysis. For comparison, the corresponding
aryl bromides3were reacted under the same conditions (biphasic
aq. Na2CO , DME, 65 °C). Generally, the Suzuki coupling
reaction of3 alkyl–, alkoxy–, and alkoxycarbonyl substituted
aryl chlorides such as 1–chloro–4–methylbenzene (1a) gave
poor results under Pd(PPh )4 catalysis, and a large difference in
reactivity between the chl3oroarenes and the bromoarenes was
observed.
Scheme 1
* Correspondent. E–mail: thies@uaeu.ac.ae

JOURNAL OF CHEMICAL RESEARCH 2010 35
Methyl 4p–propoxybiphenyl–4–carboxylate (3a);16 general pro-
cedure A: A solution of methyl 4–chlorobenzoate (1a, 170 mg,
1.0 mmol) or methyl 4–bromobenzoate (1b, 215 mg, 1.0 mmol),
4–propoxyphenylboronic acid (225 mg, 1.25 mmol) and Pd(PPh3)4
(45 mg, 4 × 10–5 mol) in a mixture of DME (15 mL) and aq. Na2CO3
(2.32 g Na2CO3 in 15 mL H2O, 9 mL) was kept at 70 °C for 18h under
an inert atmosphere. The cooled solution was then poured into water
(25 mL) and extracted with chloroform (3 × 15 mL). The combined
organic phase was dried over anhydrous MgSO4 and was concentrated
in vacuo. Column chromatography of the residue on silica gel (hexane/
CHCl3/ether 3:1:1) gave 3a (40 mg, [15%], 240 mg [89%], respec-
tively) as a colourless solid; m.p. 165 °C; (Found: M+, 270.1255.
C17H18O3 requires M+, 270.1256). δH (270 MHz, CDCl3) 1.06 (3H, t,
3J = 7.4 Hz, CH3), 1.83 (tt, 2H, 3J = 7.4 Hz, 3J = 6.5 Hz), 3.93 (3H, s,
CO2CH3), 3.97 (2H, t, 3J = 6.5 Hz, OCH2), 6.98 (2H, d, 3J = 8.9 Hz),
Results and discussion
Chloroaryl carbaldehydes such as 4–chlorobenzaldehyde (8b)
and 4,4p–chlorobiphenylcarbaldehyde (10) were found to
undergo Suzuki–cross coupling catalysed by Pd(PPh3)4. How-
ever, a relatively high catalyst loading was necessary for an
adequate reaction turnover to take place.
Nitroaryl chlorides were found to react well, especially with
electron donor substituted, very stable arylboronic acids such
as with alkoxyarylboronic acids. Nitroaryl halides are often
used as test substrates for testing the reactivity of new palladium
catalysts and it is interesting that they will in fact react easily
with most palladium catalysts, and thus they may not be a good
benchmark for the efficacy of a catalyst.
In conclusion, we have shown that certain aryl chlorides,
especially the electron poor nitroaryl halides undergo
Suzuki–Miyaura coupling with the commercially available tet
rakis(triphenylphosphine)palladium(0) [Pd(PPh3)4] and with
the combination of Pd(PPh3)2Cl2 and triphenylphosphine.
The ease with which these compounds undergo the reaction
should also indicate that they should not be used as substrates
to demonstrate the reactivity of catalysts in the Suzuki cross
coupling of aryl halides.
3
3
7.56 (2H, d, J = 8.9 Hz), 7.61 (2H, d, J = 8.6 Hz), 8.07 (2H, d,
3J = 8.6 Hz); δC (67.8 MHz, CDCl ) 10.5 (CH3), 22.6 (CH2), 50.05
(OCH ), 69.6 (OCH2), 114.9 (2C, C3H), 126.4 (2C, CH), 128.1 (Cquat),
128.3 3(2C, CH), 130.1 (2C, CH), 132.1 (Cquat), 145.3 (Cquat), 159.4
(Cquat), 167.1 (Cquat, CO); MS (EI, 70 eV) m/z (%) = 270 (M+) (61), 228
(100), 197 (83).
Methyl 4p–heptoxybiphenyl–4–carboxylate (3b);16 general proce-
dure A: Shiny flakes; m.p. 134 °C; (Found: M+, 326.1883. C21H26O3
3
requires M+, 326.1882). δH (270 MHz, CDCl3) 0.88 (3H, t, J = 7.0
Hz, CH3), 1.22–1.43 (8H, m), 1.76–1.86 (2H, m), 3.92 (3H, s,
CO2CH3), 3.95 (2H, t, 3J = 6.7 Hz, OCH2), 7.00 (2H, d, 3J = 8.9 Hz),
3
3
Experimental
7.58 (2H, d, J = 8.9 Hz), 7.62 (2H, d, J = 8.6 Hz), 8.08 (2H, d,
3J = 8.6 Hz); δC (67.8 MHz, CDCl ) 14.1 (CH3), 22.6 (CH ), 26.0
(CH ), 29.1 (CH ), 29.3 (CH ), 31.8 (3CH2), 52.1 (OCH3), 68.1 (2OCH2),
114.29 (2C, CH),2126.4 (2C, 2CH), 128.1 (C ), 128.3 (2C, CH), 130.1
(2C, CH), 132.1 (Cquat), 145.3 (Cquat), 159.q4ua(t Cquat), 167.1 (Cquat, CO);
MS (EI, 70 eV) m/z (%) = 326 (M+) (57), 228 (100), 197 (38). Calcd
for C21H26O3: C, 77.27; H, 8.03. Found: C, 77.13; H, 8.03%.
IR spectra were measured with JASCO IR–700, JASCO FTIR–6300
and Nippon Denshi JIR–AQ2OM machines. 1H and 13C NMR spectra
were recorded with a JEOL EX–270 spectrometer (1H at 270 MHz
and 13C at 67.8 MHz). The chemical shifts are relative to TMS (solvent
CDCl3, unless otherwise noted). Mass spectra were measured with
a JMS–01–SG–2 spectrometer [electron impact mode (EI), 70 eV or
fast atom bombardment (FAB)]. Column chromatography was carried
out on Wakogel C–300.
Phenylboronic acid (2d) (TCI), p–vinylphenylboronic acid (2f),
and 2–thienylboronic acid (2g) were acquired commercially. p–
Alkoxyphenylboronic acids 2a–2c, 2e, 2h, and 2i were prepared from
the corresponding p–alkoxy–bromobenzenes (a. n–BuLi, B(OR)3,
THF; b. HCl).15
4–Methoxy–4ppentoxybiphenyl (6a); general procedure A: Colour-
less solid; m.p. 131 °C; (Found: 270.1624. C18H22O2 requires M+,
270.1620). δH (270 MHz, CDCl3) 0.94 (3H, t, 3J = 7.0 Hz, CH3), 1.38–
1.44 (4H, m), 1.78–1.81 (2H, m), 3.84 (3H, s, OCH3), 3.98 (2H, t,
3
3
3J = 6.7 Hz, OCH2), 6.94 (2H, d, J = 8.9 Hz), 6.95 (2H, d, J = 8.9
3
3
Hz), 7.46 (2H, d, J = 8.9 Hz), 7.48 (2H, d, J = 8.9 Hz); δ (67.8
MHz, CDCl3) 14.0 (CH3), 22.5 (CH2), 28.2 (CH2), 29.0 (CH2C), 55.3
Scheme 2

36 JOURNAL OF CHEMICAL RESEARCH 2010
Scheme 3
(OCH3), 68.1 (OCH2), 114.1 (2C, CH), 114.7 (2C, CH), 127.7 (4C,
CH), 133.2 (Cquat), 133.6 (Cquat), 158.2 (Cquat), 158.6 (Cquat); MS (EI, 70
eV) m/z (%) = 270 (M+) (95), 200 (M+–C H ) (100), 185 (M+–CH3–
C H ). Calcd for C18H22O2: C, 79.96; H,58.1200. Found: C, 79.97; H,
8.5211%0 .
procedure A to give 9a (220 mg [92%], 127 mg [53%], respectively)
as a colourless solid; m.p. 94 °C; (Found: M+, 240.1149. C16H16O2
3
requires M+, 240.1150). δH (270 MHz, CDCl3) 1.06 (3H, t, J = 7.6
Hz, CH3), 1.83 (2H, tt, 3J = 7.6 Hz, 3J = 6.7 Hz), 3.98 (2H, t, 3J = 6.7
Hz, OCH2), 7.01 (2H, d, 3J = 8.9 Hz), 7.58 (2H, d, 3J = 8.9 Hz), 7.71
3
3
4–Methoxy–4p–heptoxybiphenyl (6b); general procedure A: Colour-
less solid; m.p. 123 °C; (Found: M+, 298.1931. C20H26O2 requires M+,
298.1933). δ (270 MHz, CDCl3) 0.88 (3H, t, 3J = 7.0 Hz, CH3), 1.21–
1.46 (8H, mH), 1.74–1.82 (2H, m), 3.83 (3H, s, OCH3), 3.98 (2H, t,
(2H, d, J = 8.4 Hz), 7.92 (2H, d, J = 8.4 Hz), 10.0 (1H, s, CHO);
δC (67.8 MHz, CDCl3) 10.5 (CH3), 22.6 (CH2), 69.6 (OCH2), 115.0
(2C, CH), 127.0 (2C, CH), 128.5 (2C, CH), 130.3 (2C, CH), 131.8
(Cquat), 134.6 (Cquat), 146.9 (Cquat), 159.7 (Cquat), 191.9 (CHO); MS (EI,
70 eV) m/z (%) 240 (M+) (61), 198 (100), 141 (26). Calcd for C16H16O2:
C, 79.97; H, 6.71. Found: C, 79.72; H, 6.71%.
3
3
3J = 6.7 Hz, OCH2), 6.94 (2H, d, J = 8.9 Hz), 6.95 (2H, d, J = 8.9
3
3
Hz), 7.46 (2H, d, J = 8.9 Hz), 7.48 (2H, d, J = 8.9 Hz); δ (67.8
MHz, CDCl3) 14.1 (CH3), 22.6 (CH2), 28.2 (CH ), 26.0 (CH2C), 29.1
(CH ), 29.3 (CH2), 55.3 (OCH3), 68.1 (OCH2), 1124.1 (2C, CH), 114.7
(2C,2 CH), 127.7 (4C, CH), 133.2 (Cquat), 133.5 (Cquat), 158.2 (Cquat),
158.6 (Cquat); MS (EI, 70 eV) m/z (%) = 298 (M+) (100), 200 (95), 185
(26). Calcd for C20H26O2: C, 80.50; H, 8.78. Found: C, 80.24; H,
8.76%.
4p–Pentoxy–biphenyl–4–carbaldehyde (9b); general procedure B:
Colourless solid, m.p. 71 °C; (Found: M+, 268.1462. C18H20O2 requires
M+, 268.1463). δH (270 MHz, CDCl3) 0.95 (3H, t, 3J = 7.0 Hz, CH3),
1.43 (4H, m), 1.82 (2H, m), 4.01 (2H, t, 3J = 6.7 Hz, OCH2), 7.00 (2H,
3
3
3
d, J = 8.9 Hz), 7.58 (2H, d, J = 8.9 Hz), 7.71 (2H, d, J = 8.1 Hz),
7.92 (2H, d, 3J = 8.1 Hz), 10.0 (1H, s, CHO); δC (67.8 MHz, CDCl3)
14.0 (CH ), 22.4 (CH ), 28.2 (CH ), 28.9 (CH2), 68.1 (OCH2), 115.0
(2C, CH)3, 127.0 (2C,2 CH), 128.42(2C, CH), 130.3 (2C, CH), 131.8
(Cquat), 134.6 (Cquat), 146.9 (Cquat), 159.7 (Cquat), 191.9 (Cquat, CO); MS
(EI, 70 eV) m/z (%) 268 (M+), 198 (100). Calcd for C18H20O2: C,
80.56; H, 7.51. Found: C, 80.32; H, 7.47%.
4–Methyl–4p–pentoxybiphenyl (7);17 general procedure A: Colour-
less solid; m.p. 87 °C; (Found: M+, 254.1668. C18H22O requires M+,
254.1671). δH (270 MHz, CDCl ) 0.94 (3H, t, 3J = 7.0 Hz, CH3), 1.38–
1.44 (4H, m), 1.78–1.83 (2H,3m), 2.38 (3H, s, CH3), 3.99 (2H, t,
3
3
3J = 6.7 Hz, OCH2), 6.95 (2H, d, J = 8.9 Hz), 7.22 (2H, d, J = 7.8
3
3
Hz), 7.44 (2H, d, J = 7.8 Hz), 7.49 (2H, d, J = 8.9 Hz); δ (67.8
MHz, CDCl ) 14.0 (CH3), 21.0 (CH3), 22.5 (CH2), 28.2 (CHC), 29.0
(CH2), 68.1 3(OCH2), 114.7 (2C, CH), 126.5 (2C, CH), 1272.9 (2C,
CH), 129.4 (2C, CH), 133.5 (Cquat), 136.3 (Cquat), 138.0 (Cquat), 158.5
(Cquat); MS (EI, 70 eV) m/z (%) = 254 (M+) (50), 184 (100). Calcd for
C18H22O: C, 84.99; H, 8.72. Found: C, 84.77; H, 8.80%.
4p–Heptoxy–biphenyl–4–carbaldehyde (9c);18 general procedure B:
Colourless solid, m.p. 80 °C; (Found: M+, 296.1774. C20H24O2 requires
M+, 296.1776). δH (270 MHz, CDCl3) 0.88 (3H, t, 3J = 7.0 Hz, CH3),
3
1.19–1.43 (8H, m), 1.76–1.84 (2H, m), 3.96 (2H, t, J = 6.7 Hz,
OCH2), 7.00 (2H, d, 3J = 8.9 Hz), 7.60 (2H, d, 3J = 8.9 Hz), 7.71 (2H,
d, 3J = 8.1 Hz), 7.92 (2H, d, 3J = 8.1 Hz), 10.0 (1H, s, CHO); δ (67.8
MHz, CDCl ) 14.1 (CH3), 22.6 (CH2), 26.0 (CH2), 29.0 (CH2C), 29.2
(CH ), 31.8 3(CH ), 68.1 (OCH2), 115.0 (2C, CH), 127.0 (2C, CH),
128.24 (2C, CH),2130.3 (2C, CH), 131.7 (Cquat), 134.6 (Cquat), 146.8
(Cquat), 159.7 (Cquat), 191.9 (Cquat, CO); MS (EI, 70 eV) m/z (%) 296
(M+) (56), 198 (100). Calcd for C20H24O2: C, 81.04; H, 8.16. Found: C,
81.11; H, 8.17%.
4p–Propoxy–biphenyl–4–carbaldehyde (9a); general procedure B:
A solution of 4–bromobenzaldehyde (8a, 185 mg, 1.0 mmol) or 4–
chlorobenzaldehyde (8b, 140 mg, 1.0 mmol), 4–propoxyphenylbo-
ronic acid (2a, 225 mg, 1.25 mmol) and Pd(PPh3)4 (60 mg, 5.2 ×
10–5 mol) [or Pd(PPh3)2Cl2 (40 mg, 5.2. 10–5 mol) and triphenylphos-
phine (37 mg, 0.14 mmol)] was reacted and worked up according to

JOURNAL OF CHEMICAL RESEARCH 2010 37
4p–Propoxyterphenyl–4–carbaldehyde (11); general procedure B:
C H7NO2S: C, 58.52; H, 3.44; N, 6.82. Found: C, 58.53; H, 3.55, N,
6.1808%.
Colourless solid, m.p. 254 °C; (Found: M+, 316.1466. C22H20O2
3
requires M+, 316.1463). δH (270 MHz, CDCl3) 1.03 (3H, t, J = 7.6
2,4–Dinitrobiphenyl (14a); general procedure C: Pale yellow
solid; m.p. 110 °C; (Found: M+, 244.0480. C12H8O4N2 requires M+,
244.0484). ν (KBr/cm–1) 3100, 2920, 2850, 1605, 1540, 1470, 1360.
δH (270 MHmza,x CDCl3) 7.33–7.36 (2H, m), 7.47–7.52 (3H, m), 7.69
(1H, d, 3J = 8.4 Hz), 8.48 (1H, dd, 3J = 8.4 Hz, 4J = 2.4 Hz), 8.85 (1H,
d, 4J = 2.4 Hz); δ (67.8 MHz, CDCl3) 119.7 (CH), 126.5 (CH), 127.7
(2C, CH), 129.1C(2C, CH), 129.6 (CH), 130.7 (C ), 133.2 (CH),
135.2 (Cquat), 142.3 (Cquat), 146.8 (Cquat); MS (EI, 70 eqVua)t m/z (%) = 244
(M+) (45), 227 (38), 216 (100), 168 (36), 139 (81).
2,4–Dinitro–4p–heptoxybiphenyl (14b); general procedure C:
Colourless solid, m.p. 45 °C; νmax (KBr/cm–1) 3102, 2922, 2853, 1606,
1537, 1472, 1357, 1257, 1180, 836, 747; δH (270 MHz, CDCl3) 0.88
(3H, t, 3J = 5.8 Hz, CH3), 1.27–1.44 (8H, m), 1.76–1.84 (2H, m), 4.00
Hz, CH3), 1.81 (2H, tt, 3J = 7.6 Hz, 3J = 6.7 Hz), 3.96 (2H, t, 3J = 6.7
Hz, OCH2), 6.98 (2H, d, 3J = 8.9 Hz), 7.63 (2H, d, 3J = 8.9 Hz), 7.65
3
3
3
(2H, d, J = 8.1 Hz), 7.70 (2H, d, J = 8.4 Hz), 7.72 (2H, d, J = 8.4
Hz), 7.92 (2H, d, 3J = 8.1 Hz), 9.98 (1H, s, CHO); MS (EI, 70 eV) m/z
(%) = 316 (M+) (5.0).
4–Nitrobiphenyl (13a); general procedure C: A solution of p–
chloronitrobenzene (12a, 315 mg, 2.0 mmol), phenylboronic
acid (366 mg, 3.0 mmol) and Pd(PPh3)4 (32 mg, 2.8.10–5 mol) [or
Pd(PPh3)2Cl2 (20 mg, 2.8. 10–5 mol) and PPh (22 mg, 8.6.10–5 mol)] in
a biphasic mixture of DME (10 mL) and aq3. Na2CO3 (2.32 g Na2CO3
in 15 mL H2O, 6 mL) was kept at 70 °C for 10h. Work–up according
to procedure B gave 13a (330 mg, 83%) as a pale yellow solid, m.p.
114 °C; (Found: 199.0633. Calcd for C H9O2N: 199.0633). (KBr/
cm–1) ν 1592, 1508, 1420, 1336, 1183,112 106, 1027, 848, 836, 750,
728; δHma(x270 MHz, CDCl3) 7.42–7.54 (3H, m), 7.62–7.69 (2H, m),
3
3
(2H, t, J = 6.5 Hz, OCH2), 6.98 (2H, d, J = 8.6 Hz), 7.28 (2H, d,
3J = 8.6 Hz), 7.66 (1H, d, J = 8.4 Hz), 8.43 (1H, dd, J = 8.4 Hz,
3
3
4J = 2.2 Hz), 8.65 (1H, d, J = 2.2 Hz); δ (67.8 MHz, CDCl ) 14.1
4
(CH ), 22.6 (CH2), 26.0 (CH2), 29.0 (CH2C), 29.1 (CH2), 31.7 3(CH ),
68.23(OCH ), 115.1 (2C, CH), 119.7 (CH), 126.3 (CH), 126.8 (Cqua2t),
129.1 (2C, 2CH), 132.9 (CH), 141.9 (Cquat), 146.4 (Cquat), 149.0 (Cquat),
160.4 (Cquat); MS (EI, 70 eV) m/z (%) = 358 (M+) (64), 328 (16), 260
(100).
3
3
7.74 (2H, d, J = 8.9 Hz), 8.31 (2H, d, J = 8.9 Hz); δC (67.8 MHz,
CDCl ) 124.1 (2C, CH), 127.4 (2C, CH), 127.8 (2C, CH), 128.9 (CH),
129.13(2C, CH), 138.7 (Cquat), 147.0 (Cquat), 147.6 (Cquat); MS (EI, 70
eV) m/z (%) = 199 (M+) (100), 169 (29), 152 (63).
4–Nitro–4p–pentoxybiphenyl (13b);19general procedure C: Colour-
less solid; m.p. 63 °C (Found: M+, 285.1366. C17H19O3N requires M+,
285.1365). νmax (KBr/cm–1) 3105, 2920, 2855, 1610, 1539, 1470, 1355,
1255, 1180, 835, 750; δH (270 MHz, CDCl3) 0.95 (3H, t, 3J = 6.5 Hz),
1.39–1.49 (4H, m), 1.79–1.85 (2H, m), 4.01 (2H, t, 3J = 6.7 Hz), 7.00
2,4–Dinitro–4p–nonyloxybiphenyl (14c); general procedure C: Pale
yellow solid; m.p. 39 °C; (Found: M+, 386.1844. C21H26O5N2 requires
M+, 386.1842). νmax (KBr/cm–1) 3099, 2920, 1606, 1539, 1471, 1358,
1255, 1185, 840, 749; δH (270 MHz, CDCl3) 0.88 (3H, t, 3J = 5.8 Hz,
3
3
3
3
CH3), 1.30–1.47 (12H, m), 1.78–1.84 (2H, m), 4.00 (2H, t, J = 6.5
(2H, d, J = 8.9 Hz), 7.57 (2H, d, J = 8.9 Hz), 7.69 (2H, d, J = 8.9
Hz), 8.27 (2H, d, 3J = 8.9 Hz); δ (67.8 MHz, CDCl3) 14.0 (CH ), 22.4
(CH ), 28.2 (CH2), 28.9 (CH2),C68.2 (OCH ), 115.1 (2C, CH)3, 124.1
(2C,2CH), 127.0 (2C, CH), 128.5 (2C, CH), 2130.7 (Cquat), 146.4 (Cquat),
147.2 (Cquat), 160.0 (Cquat); MS (EI, 70 eV) m/z (%) = 285 (M+), 215
(M+–C5H10) (100).
Hz, OCH2), 6.98 (2H, d, 3J = 8.6 Hz), 7.28 (2H, d, 3J = 8.6 Hz), 7.66
(1H, d, 3J = 8.6 Hz), 8.43 (1H, dd, 3J = 8.6 Hz, 4J = 2.2 Hz), 8.65 (1H,
4
d, J = 2.2 Hz); δ (67.8 MHz, CDCl3) 14.1 (CH ), 22.7 (CH ), 26.0
(CH ), 29.1 (CH2C), 29.3 (CH2), 29.4 (CH2), 29.53(CH2), 31.92(CH ),
68.22(OCH ), 115.2 (2C, CH), 119.8 (CH), 126.4 (CH), 126.8 (Cqua2t),
129.1 (2C, 2CH), 132.9 (CH), 141.9 (Cquat), 146.3 (Cquat), 148.9 (Cquat),
160.4 (Cquat); MS (EI, 70 eV) m/z (%) = 386 (M+) (68), 356 (19), 260
(100).
4–Nitro–4p–heptoxybiphenyl (13c); general procedure C: Pale
yellow oil; (Found: M+, 313.1677. C19H23O3N requires M+, 313.1678).
νmax (KBr/cm–1) 3100, 2920, 2850, 1605, 1535, 1470, 1360, 1260,
1180, 840, 750; δH (270 MHz, CDCl3) 0.90 (3H, t, 3J = 6.5 Hz), 1.27–
1.46 (8H, m), 1.79–1.82 (2H, m), 4.02 (2H, t, 3J = 6.7 Hz), 7.00 (2H,
2,4–Dinitro–4p–octadecanyloxybiphenyl (14d); general procedure
C:At 80 °C for 15h. Final work–up consisted of flash chromatography
on silica gel (ethyl acetate/PE 80–100); yellow solid; m.p. 75 °C;
(Found: M+, 512.3254. C30H44O5N2 requires M+, 512.3250). IR (KBr/
cm–1) 3101, 2916, 2851, 1604, 1575, 1521, 1471; δH (CDCl3, 200
MHz) 0.80–2.00 (32H, m), 4.03 (2H, t, J 5.8 Hz), 7.01 (2H, m, J 8.0
Hz), 7.29 (2H, m, J = 8.0 Hz), 7.68 (1H, J = 8.2 Hz, 1H), 8.45 (1H, d,
J = 8.6 Hz), 8.67 (1H, m); δ (CDCl3, 50 MHz) 14.4, 22.9, 26.2, 29.3–
29.9 (overlapping peaks), C32.1, 68.2, 115.0, 119.6, 126.1, 126.6,
128.9, 132.7, 141.6, 146.1, 148.7, 160.1; MS (FAB, 3–nitrobenzyl
alcohol) m/z (%) = 512 (M+) (13).
4–Docosanyloxy–2,p4p–dinitrobiphenyl (14e); general procedure C:
Analogous to the preparation of 14d: yellow solid; m.p. 82 °C; (Found:
M+, 568.3871. C34H52O5N2 requires M+, 568.3876). IR (KBr/cm–1)
3101, 2950, 2850, 1604, 1575, 1525, 1471; δ (CDCl3, 200 MHz)
0.85–0.91 (6H, m), 1.15–1.57 (38H, m), 1.72–1.H88 (2H, m), 3.98 (2H,
t, J = 6.6 Hz), 6.96 (2H, m, J = 8.6, 2.0 Hz), 7.25 (2H, m, J = 8.6, 2.0
Hz), 7.63 (1H, m, J = 8.6, 1.4 Hz), 8.68 (1H, m, J = 8.2, 2.4 Hz, 1H),
8.62 (1H, m, J = 2.4Hz); δ (CDCl3, 50 MHz) 14.3, 22.9, 26.2, 29.3–
29.9 (overlapping peaks),C 32.1, 68.2, 115.0, 119.6, 126.1, 126.6,
128.9, 132.7, 141.7, 146.0, 148.7, 160.1; MS (FAB, 3–
nitrobenzyl alcohol) m/z (%) = 568 (M+) (8.8), 481 (6.2), 437 (12),
393 (20), 349 (25), 305 (26).
3
3
3
d, J = 8.9 Hz), 7.57 (2H, d, J = 8.9 Hz), 7.69 (2H, d, J = 8.9 Hz),
3
8.27 (2H, d, J = 8.9 Hz); δ (67.8 MHz, CDCl ) 14.1 (CH ), 22.6
(CH ), 26.0 (CH ), 28.2 (CHC), 29.0 (CH ), 31.8 (3CH2), 68.2 (3OCH2),
115.21 (2C, CH),2 124.1 (2C,2CH), 127.02(2C, CH), 128.5 (2C, CH),
130.7 (Cquat), 146.4 (Cquat), 147.2 (Cquat), 160.0 (Cquat); MS (EI, 70 eV)
m/z (%) = 313 (M+) (43), 283 (12), 215 (100), 185 (22).
4–Nitro–4p–nonyloxybiphenyl (13d); general procedure C: Pale
yellow solid; m.p. 60 °C; (Found: M+, 341.1987. C21H27O3N requires
M+, 341.1991). νmax (KBr/cm–1) 3100, 2920, 2850, 1610, 1540, 1470,
1357, 1255, 1180, 836, 747; δH (270 MHz, CDCl3) 0.89 (3H, t, 3J = 7.0
Hz), 1.28–1.48 (12H, m), 1.76–1.84 (2H, m), 4.01 (2H, t, 3J = 6.7 Hz),
7.00 (2H, d, 3J = 8.9 Hz), 7.57 (2H, d, 3J = 8.9 Hz), 7.68 (2H,
d, 3J = 8.9 Hz), 8.27 (2H, d, 3J = 8.9 Hz); δC (67.8 MHz, CDCl3) 14.1
(CH ), 22.7 (CH2), 26.0 (CH2), 29.2 (CH2), 29.3 (CH2), 29.4 (CH2),
29.53 (CH ), 31.9 (CH2), 68.2 (OCH2), 115.1 (2C, CH), 124.1 (2C,
CH), 1272.0 (2C, CH), 128.5 (2C, CH), 130.8 (Cquat), 146.4 (Cquat),
147.3 (Cquat), 160.0 (Cquat); MS (EI, 70 eV) m/z (%) = 341 (M+) (68),
215 (100). Calcd for C H27NO3: C, 73.87; H, 7.97; N, 4.10. Found:
C, 73.89; H, 7.95, N, 4.2019%.
4–Nitro–4p–vinylbiphenyl (13e); general procedure C: Colourless
solid, m.p. 123 °C; (Found: 225.0789. C14H11O N requires M+,
225.0790). (KBr/cm–1) νmax 1629, 1512, 1341, 11062, 1031, 930, 855;
δH (270 MHz, CDCl3) 5.35 (1H, d, J = 10.8 Hz), 5.85 (1H, d, J = 17.5
Hz), 6.77 (1H, dd, J = 17.5 Hz, J = 10.8 Hz), 7.54 (2H, d, 3J = 8.1 Hz),
The research was supported partially by the Global Centre of
Excellence on New Carbon Resources, Kyushu University,
Japan.
3
3
7.61 (2H, d, J = 8.1 Hz), 7.75 (2H, d, J = 8.6 Hz), 8.30 (2H, d,
3J = 8.6 Hz); δC (67.8 MHz, CDCl3) 115.1, 124.1 (2C,), 126.9 (2C),
127.5 (4C), 135.9 (Cquat), 137.9 (Cquat), 138.2 (Cquat), 147.1 (Cquat); MS
(EI, 70 eV) m/z (%) 225 (M+) (100), 195 (18), 178 (39), 152 (21).
Calcd for C H NO2: C, 74.65; H, 4.92; N, 6.22. Found: C, 74.59; H,
5.00, N, 6.2194%1.1
Received 21 November 2009; accepted 11 December 2009
Paper 090882 doi: 10.3184/030823410X12624523028293
Published online: 22 January 2010
1–Nitro–4–(thien–2–yl)benzene (13f); general procedure C: Solid;
m.p. 197 °C; (Found: M+, 205.0198. C10H7O2NS requires M+,
205.0198). δH (270 MHz, CDCl ) 7.16 (1H, dd, J = 5.1 Hz, J = 3.8
Hz), 7.44 (1H, dd, J = 5.1 Hz, J 3= 1.1 Hz), 7.48 (1H, dd, J = 3.8 Hz,
J = 1.1 Hz), 7.74 (2H, d, J = 8.9 Hz), 8.24 (2H, d, J = 8.9 Hz); δC
(67.8 MHz, CDCl ) 124.4 (2C, CH), 125.7 (CH), 126.0 (2C, CH),
127.7 (CH), 128.7 3(CH), 140.5 (Cquat), 141.6 (Cquat), 146.5 (Cquat); MS
(EI, 70 eV) m/z (%) = 205 (M+) (100), 175 (39), 115 (58). Calcd for
References
1
2
3
A.F. Littke and G.C. Fu, Angew. Chem. Int. Ed. Engl., 1998, 37, 3387.
G.C. Fu, Pure Appl. Chem., 2002, 74, 33.
J.P. Wolfe, R.A. Singer, B.H. Yang, and S.L. Buchwald, J. Am. Chem. Soc.,
1999, 121, 9550.
3
3
4
J.P. Wolfe and S.L. Buchwald, Angew. Chem. Int. Ed. Engl., 1999, 38,
2413.

38 JOURNAL OF CHEMICAL RESEARCH 2010
5
6
7
C.A. Parrish and S. Buchwald, J. Org. Chem., 2001, 66, 3280.
C. Zhang and M.L. Trudell, Tetrahedron Lett., 2000, 41, 595.
C. Zhang, J. Huang, M.L. Trudell and S.P. Nolan, J. Org. Chem., 1999, 64,
3804.
M.G. Andreu, A. Zapf and M. Beller, Chem. Commun., 2000, 2475.
G.Y. Li, Angew. Chem. Int. Ed. Engl., 2001, 40, 1513.
13 G. Lu, R. Franzen, Q. Zhang andY. Xu, Tetrahedron |Lett. 2005, 46, 4253.
14 T. Thiemann, Y. Tanaka, J. Iniesta, H.T. Varghese and C.Y. Panicker,
J. Chem. Res., 2009, 732.
15 K. Fuchibe and T. Akiyama, J. Am. Chem. Soc., 2006, 128, 1434.
16 V.V. Brilev, D.A. Vasilevskii, V.A. Tarasevich, Yu. V. Matveenko and A.A.
Erdman, Russ. J. Gen. Chem., 1999, 69, 122.
8
9
10 L. Botella and C. Najera, Angew. Chem. Int. Ed. Engl., 2002, 41, 179.
11 J. Zhang, L. Zhao, M. Song, T.C.W. Mak andY. Wu, J. Organomet. Chem.,
2006, 691, 1301.
12 B.M. Choudary, S. Madhi, N.S. Chowdari, M.L. Kantam and B. Sreedhar,
J. Am. Chem. Soc., 2002, 124, 14127.
17 V.V. Brilev, V.E. Agabekov, V.A. Tarasevich, D.A. Vasilevskii and K.M.
Makovetskii, Vest. Nat. Akad. Nauk Belarus., Ser. Khim. Nauk, 2000, 62.
18 V. Vashchenko, L. Kutulya and A. Krivoshey, Synthesis, 2007, 2125.
19 G.W. Gray, K.J. Harrison, J.A. Nash, J. Constant, D.S. Hulme, J. Kirton
and E.P. Raynes, Liq. Cryst. Ord. Fluids, 1973, 2, 617.

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.