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General Procedure
for the Synthesis of 2,3-Dibromo-5-arylthiophene 2
To
a mixture of 1 (0.159 g, 0.5 mmol), arylboronic
acid (0.55 mmol), Pd(PPh3)4 (5 mol%)
were added a mixture of 1,4-dioxane and toluene (1:1, 5 mL) and
an aq solution of K2CO3 (2 mL, 2 M) under
argon atmosphere. The reaction mixture was stirred at 100 ˚C
for 8 h and was subsequently allowed to cool to 20 ˚C.
The solution was poured into H2O and CH2Cl2 (25
mL each) and the organic and the aqueous layer were separated. The
latter was extracted with CH2Cl2 (3 × 25 mL),
dried (Na2SO4), filtered, and concentrated
in vacuo. The residue was purified by flash column chromatography (flash
silica gel, n-heptane).
Synthesis of 2,3-Dibromo-5-
p
-tolylthiophene
(2a)
Starting with 1 (0.320
g, 1.0 mmol) and 4-tolylboronic acid (0.149 g, 1.1 mmol), 2a was isolated (0.150 g, 47%)
as a colorless solid, mp 83-85 ˚C. ¹H
NMR (300 MHz, CDCl3): δ = 2.26
(s, 3 H, CH3), 6.94 (s, 1 H, Ar), 7.08 (d, ³
J = 8.0 Hz, 2
H, Ar), 7.26 (d, ³
J = 8.2
Hz, 2 H, Ar). ¹³C NMR (62 MHz, CDCl3): δ = 21.3
(CH3), 109.4, 114.5 (CBr), 125.0, 125.3, 128.7, 129.4,
129.8 (CH, Ar), 130.0, 138.6, 145.6 (C). IR (KBr): ν = 3091
(w), 3019 (w), 2918 (w), 2852 (w), 1498 (m), 1433 (w), 1118 (w),
997 (w), 821 (w), 801 (m), 550 (w) cm-¹.
GC-MS (EI, 70 eV): m/z (%) = 334 [M+, 8¹Br, 8¹Br], 332
(100) [M+, 8¹Br, 79Br],
331 (16) [M+], 330 (49) [M+, 79Br, 79Br],
172 (35), 171 (30), 86 (11). HRMS (EI, 70 eV): m/z calcd
for C11H8Br2S [M+, 8¹Br, 79Br]:
331.86875; found: 331.86882.
19 CCDC-749926 and 749927 contain all
crystallographic details of this publication and is available free
of charge at www.ccdc.cam.ac.uk/conts/retrieving.html
or can be ordered from the following address: Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB21EZ, UK; fax: +44
(1223)336033; or deposit@ccdc.cam.ac.uk.
