Grunder et al.
NMR (250 MHz, CDCl
3
, δ/ppm) 8.12 (2H, s), 7.74 (2H, s), 7.60
dry THF and 10 mL of diisopropylamine. The reaction mixture
was stirred for 24 h at 45 °C and was then poured into a mixture
3
3
(
2H, d, JHH ) 7.70 Hz), 7.51 (2H, d, JHH ) 7.70 Hz), 7.39 (2H,
3
3
t, JHH ) 7.70 Hz), 7.25 (2H, d, JHH ) 16.06 Hz), 7.00 (2H, d,
of 250 mL of hexane and 250 mL of aq 5% NH OH. The
4
3
13
J
HH ) 15.73 Hz), 1.36 (18H, s); C NMR (101 MHz, CDCl
3
,
precipitated solid was collected, dissolved in a minimum amount
δ/ppm) 141.2, 137.6, 137.4, 136.8, 136.4, 133.8, 132.2, 131.5,
of CH
The precipitate was collected and recrystallized from toluene/CH
Cl to give 1 as a yellow solid (246 mg, 0.39 mmol, 51%).
1,4-Bis(3-thioacetylstyryl)-2,5-bis(ethynyl)benzene (24) (1.0 equiv,
.167 mmol, 80 mg) was dissolved in a degassed mixture of 15
mL of dry THF and 2.5 mL of diisopropylamine. Then 4-pyridine-
halide (2.2 equiv, 0.368 mmol), Pd(PPH (10 mol %, 42 mg),
2 2
Cl , and dropped into 250 mL of rapidly stirring hexane.
+
1
5
4
29.3, 127.4, 100.7, 46.5, 31.4; MS (EI) 710 (15%, M ), 653 (11%),
98 (46%), 551 (12%), 469 (5%); EA calcd: C ) 50.71, H )
.54, found: C ) 50.24, H ) 4.46; mp 247-248 °C; IR (neat, ν,
2
-
2
-
1
cm ) 3055.0, 2958.6, 2858.3, 1809.1, 1566.1, 1454.2.
,4-Bis(4-thio-tert-butylstyryl)-2,5-diiodobenzene (20). 15 (190
mg, 0.98 mmol, 3.0 equiv) and the phosphonium salt (9) (340 mg,
.33 mmol, 1.0 equiv) were dissolved in 7 mL of CH Cl , then 6
0
1
3 4
)
0
2
2
and CuI (10 mol %, 7 mg) were added. The reaction mixture was
stirred for 24 h at 45 °C (X ) Br) or room temperature (X ) I),
respectively, and was then poured to a mixture of 100 mL of hexane
mL of 50% aq NaOH was added and the solution was stirred
vigorously for 69 h. The reaction mixture was then extracted with
water/toluene. The combined organic phases were dried over Na
SO
, filtrated, evaporated, and chromatographed (silica gel, 2 ×
2 cm, CH Cl ). The isomeric mixture was then refluxed in toluene
with catalytic amounts of iodine overnight. It was then extracted
with 10% aq NaHSO , washed with water, dried over Na SO
evaporated, and recrystallized from toluene to obtain 20 as a yellow
2
-
and 100 mL of aq 5% NH
dissolved in a minimum amount of CH
4
OH. The precipitated solid was collected,
4
1
2
2
2
Cl , and dropped into 200
2
mL of rapidly stirring hexane. The precipitate was collected and
3
2
4
,
recrystallized from toluene/CH Cl to give 1 as a yellow solid (X
2
2
1
) Br: <10%; X ) I: 52 mg, 50%). H NMR (250 MHz, CDCl ,
3
1
3
solid (170 mg, 0.24 mmol, 73%). TLC R
f
2
0.74 (CH Cl
2
); H NMR
δ/ppm) 8.67 (4H, d, J ) 6.06 Hz), 7.92 (2H, s), 7.64 (2H, s),
HH
(
250 MHz, CDCl , δ/ppm) 8.08 (2H, s), 7.53 (8H, m), 7.24 (2H,
3
3
3
7
.61 (2H, d, JHH ) 16.67 Hz), 7.58 (2H, d, JHH ) 8.08 Hz), 7.46
3
3
d, JHH ) 16.06 Hz), 6.98 (2H, d, JHH ) 16.06 Hz), 1.32 (18H, s);
3
3
(
4H, d, JHH ) 6.06 Hz), 7.45 (2H, t, JHH ) 8.08 Hz), 7.35 (2H,
13
C NMR (101 MHz, CDCl
3
, δ/ppm) 141.1, 138.2, 137.2, 136.8,
3
3
13
J
HH ) 7.58 Hz), 7.26 (2H, d, JHH ) 16.67 Hz), 2.47 (6H, s);
C
1
33.5, 132.1, 131.7, 127.3, 100.8, 46.8, 31.4; MS (EI) 710.0 (42.3%,
NMR (101 MHz, CDCl , δ/ppm) 194.4, 150.4, 138.5, 138.1, 134.3,
3
+
M ), 597.8 (100%); EA calcd: C ) 50.71, H ) 4.54, found: C )
1
33.1, 131.3, 131.0, 130.1, 129.8, 129.2, 128.2, 126.5, 125.9, 122.5,
-1
5
1
0.74, H ) 4.55; IR (neat, ν, cm ) 3018.9, 2954.7, 2858.3, 1892.5,
356.3; mp 232-233 °C.
+
93.7, 92.1, 30.8; MS (MALDI): 632 (M ); mp 227.7-228.7 °C
-
1
(melting followed by decomposition); IR (neat, ν, cm ) 3049.7,
1
,4-Bis(3-thioacetylstyryl)-2,5-diiodobenzene (21). 1,4-Bis(3-
thio-tert-butylstyryl)-2,5-diiodobenzene (19) (2.13 g, 3.00 mmol,
.0 equiv) was dissolved in a degassed mixture of 500 mL of dry
toluene and 100 mL of acetyl chloride, then 6 mL of a 1 M solution
of BBr in CH Cl (1.408 mol, 2.0 equiv) was added. The reaction
was stirred for 1 h at room temperature. Another 4.5 mL of the 1
M solution of BBr in CH Cl was added and then the mixture
3
008.3, 2201.1, 1699.2, 1588.3, 953.7; GPC (oligopore 6 µm,
toluene, UV/vis photodiode array detector) area 99.6%.
,4-Bis(4-thioacetylstyryl)-2,5-bis(ethynyl-4-pyridine)ben-
1
1
zene (2). 22 (155 mg, 0.227 mmol, 1.0 equiv) was dissolved in a
well-degassed mixture of 20 mL of dry THF and 2.5 mL of
diisopropylamine. 18 (58.6 mg, 0.568 mmol, 2.5 equiv), Pd(PPh )
3 4
3
2
2
3
2
2
was stirred for another hour at room temperature. While cooling
with an ice-bath, the reaction mixture was quenched with water.
The product precipitated as a yellow solid, which was filtrated off
and washed with water. The organic phase was washed with water,
(20 mg, 0.017mmol, 7.6 mol %), and CuI (8 mg, 0.042 mmol, 18.5
mol %) were added and the solution was stirred 7 h at room
temperature and 15 h at 50 °C. The reaction mixture was then
poured to a mixture of 50 mL of 5% aq NH
hexane. The precipitate was filtrated off, dissolved in CH
4
OH and 50 mL of
Cl , and
evaporated, and recrystallized from toluene to give more of product
2
2
1
2
1 (1.75 g, 2.56 mmol, 87%). TLC R
f
0.43 (CH
2
Cl
2
3
); H NMR
precipitated into 60 mL of rapidly stirring hexane. The insoluble
material was collected and recrystallized from toluene to give a
(250 MHz, CDCl
3
4
, δ/ppm) 8.06 (2H, s), 7.59 (2H, d, JHH ) 7.58
3
Hz), 7.58 (2H, d, JHH ) 1.52 Hz), 7.44 (2H, t, JHH ) 7.58 Hz),
1
yellow solid (75 mg, 0.119 mmol, 52%). H NMR (250 MHz,
3
3
7
(
.35 (2H, d, JHH ) 7.58 Hz), 7.19 (2H, d, JHH ) 15.66 Hz), 6.96
3
CDCl
3
, δ/ppm) 8.71 (4H, d, JHH ) 6.36 Hz), 7.97 (2H, s), 7.80
3
13
2H, d, JHH ) 16.17 Hz), 2.46 (6H, s); C NMR (101 MHz,
3
3
(
2H, d, JHH ) 16.40 Hz), 7.63 (4H, d, JHH ) 8.34 Hz), 7.48 (4H,
d, JHH ) 6.02 Hz), 7.47 (4H, d, JHH ) 8.03 Hz), 7.31 (2H, d,
HH ) 16.06 Hz), 2.48 (6H, s); C NMR (101 MHz, CDCl
δ/ppm) 194.3, 150.4, 138.4, 138.4, 138.1, 135.3, 131.3, 131.2,
29.9, 128.2, 127.9, 126.7, 125.8, 122.5, 93.6, 92.0, 30.7; MS
CDCl , δ/ppm) 194.2, 141.2, 138.1, 136.9, 134.6, 133.3, 131.9,
3
3
3
+
1
6
31.8, 130.0, 129.1, 128.2, 100.7, 30.7; MS (EI) 681 (84%, M ),
39 (34%), 597 (49%); EA calcd: C ) 45.76, H ) 2.95, found:
3
13
J
3
,
-
1
C ) 46.20, H ) 2.95; mp 214-215 °C; IR (neat, ν, cm ) 3051.1,
1
(
2
958.6, 1890.1, 1697.2, 1118.6.
,4-Bis(4-thioacetylstyryl)-2,5-diiodobenzene (22). 20 (356 mg,
.521 mmol, 1.0 equiv) was dissolved in a degassed mixture of 85
(1 M in
, 3.6 mL, 3.6 mmol, 6.9 equiv) was added portionwise during
.5 h at room temperature. The reaction mixture was quenched with
+
-1
MALDI) 633.6 (100%,M ); IR (neat, ν, cm ) 3046.4, 2217.5,
1
1
699.2, 1588.3; mp 192.2-199.5 °C dec; GPC (oligopore 6 µm,
0
toluene, UV/vis photodiode array detector) area 100%.
mL of dry toluene and 15 mL of concentrated AcCl. BBr
CH Cl
3
2
2
2
Acknowledgment. M.T.G. thanks the “Ministerio de Edu-
caci o´ n y Ciencia” for financial support. This work was supported
by the Swiss National Center of Competence in Research
water at 0 °C. A precipitate was formed, which was filtered off
and recrystallized from toluene to give 15 as a yellow solid (283
1
mg, 0.41 mmol, 80%). TLC R
CDCl
f
0.48 (CH
2
Cl
2
); H NMR (250 MHz,
“
Nanoscale Science” (NCCR), the Swiss National Science
3
3
, δ/ppm) 8.08 (2H, s), 7.59 (4H, d, JHH ) 8.37 Hz), 7.43
3
3
Foundation (SNF), and the European Science Foundation
EUROCORES program on Self-Organized Nanostructures
(
4H, d, JHH ) 8.37 Hz), 7.24 (2H, d, JHH ) 16.06 Hz), 6.97 (2H,
3
+
d, JHH ) 16.16.40 Hz), 2.45 (6H, s); MS (EI) 681.8 (76%, M ),
(SONS).
6
39.8 (56%), 597.8 (100%); EA calcd: C ) 45.76, H ) 2.95,
-
1
found: C ) 45.81, H ) 2.97; mp 253-255 °C; IR (neat, ν, cm
)
2920.0, 2854.5, 1905.5, 1689.5, 1122.5.
Supporting Information Available: NMR spectra of compound
1
,4-Bis(3-thioacetylstyryl)-2,5-bis(ethynyl-4-pyridine)ben-
zene (1). 4-(Ethynyl)pyridine (18) (2.2 equiv, 1.65 mmol, 170 mg),
,4-bis(3-thioacetylstyryl)-2,5-diiodobenzene (21) (1.0 equiv, 0.76
mmol, 520 mg), Pd(PPh (10 mol %, 87 mg), and CuI (10 mol
, 14 mg) were dissolved in a well-degassed mixture of 90 mL of
1
-4, 6, 7, 9, 14, 15, and 17-28, GPC spectra of compounds 1-4,
and the synthesis of 3, 4, 6, 7, 14, 15, 17, 18, and 24-28. This
materialisavailablefreeofchargeviatheInternetathttp://pubs.acs.org.
1
3 4
)
%
JO7013998
8344 J. Org. Chem., Vol. 72, No. 22, 2007