Diphenyl chloro(4-chlorophenyl)methylphosphonate 2 ( X=Cl)
Yield 56% mp 91 °C; d [(CD ) SO] 5.17 (1H, d, CH, J 14),
1.32 (6H, t, CH ), 3.75 (4H, q, CH ), 5.50 (1H, s, CH), 7.60
3
2
(2H, d, aromatic H), 8.15 (2H, d, aromatic H). The acetal (3 g,
12 mmol) was hydrolysed with 0.5 sulfuric acid (50 cm3) at
110°C for 40 min, and the reaction was extracted with CH Cl
H
3 2
HP
6.90–7.50 (14H, m, aromatic H) (Found: C, 57.94; H, 3.67.
C H O PCl requires C, 58.04; H, 3.85%).
2
2
to give 3-(4-nitrophenyl)prop-2-ynal in 54% yield, mp 95 °C;
d (CDCl ) 7.78 (2H, d, aromatic H), 8.30 (2H, d, aromatic
19 15
3
2
H
3
Diphenyl bromo(4-bromophenyl)methylphosphonate 2 ( X=Br)
Yield 29%, mp 107 °C; d [(CD ) SO] 5.17 (1H, d, CH, J
HP
H), 9.50 (1H, s, CH); n (KBr)/cm−1 2260m (COC), 1620s
max
(CNO) (Found: C, 61.50; H, 3.05; N, 7.87. C H NO requires
9
5
3
H
3 2
C, 61.71; H, 2.88; N, 8.00%).
14), 6.50–7.30 (10H, m, aromatic H), 7.48 (4H, s) (Found: C,
51.84; H, 3.40. C H O PClBr requires C, 52.14; H, 3.45%).
19 15
3
1-(4-Ethynylphenyl)-2-(4-nitrophenyl )acetylene 9 ( X=NO )
2
1-(4-Methoxyphenyl )-2-(4-nitrophenyl )acetylene 3
Compound 2 (X=NO ) (2.01 g, 4.9 mmol) and 4-ethynylben-
2
( X=NO , Y=MeO)
zaldehyde 8 (0.65 g, 4.9 mmol) were treated with ButOK
2
(1.20 g, 10.7 mmol) in THF (30 cm3) for 3 h at room tempera-
ture. After evaporation of the solvent, the residue was extracted
with CH Cl , and the solution dried over MgSO . The solvent
Compound 2 (X=NO ) (1.25 g, 3.07 mmol) and 4-methoxy-
2
benzaldehyde (0.60 g, 4.0 mmol) in THF (30 cm3) were treated
with ButOK (1.0 g, 8.9 mmol) for 3 h at room temperature.
After evaporation of the solvent, water (20 cm3) was added to
the residue, the aqueous mixture was extracted with CH Cl ,
2
2
4
was removed and the residue recrystallized from ethanol to
give the product in 44% yield, mp 211 °C; d (CDCl ) 3.23
H
3
2
2
(1H, s, CH), 7.52 (2H, d, aromatic H), 7.70 (2H, d, aromatic
and the organic fractions were dried over MgSO . The solvent
4
H), 8.13 (2H, d, aromatic H), 8.28 (2H, d, aromatic H);
was removed in vacuo and the residue was recrystallized
n
(KBr)/cm−1 3240m (C–H), 2200m (COC), 1500s and
from ethanol to give the product in 58% yield, mp 115 °C;
d (CDCl ) 3.90 (3H, s, CH ), 7.09–8.24 (8H, m, aromatic H);
max
1335s (NO ) (Found: C, 77.62; H, 3.60; N, 5.58. C H NO
2
16
9
2
H
max
3
3
requires C, 77.72; H, 3.67; N, 5.67%).
n
(KBr)/cm−1 2210m (COC), 1510s and 1335s (NO )
2
(Found: C, 71.06; H, 4.39; N, 5.50. C H NO requires C,
15 11
3
1-(4-Cyanophenyl)-2-(4-ethynylphenyl)acetylene 9 ( X=CN)
71.14; H, 4.38; N, 5.53%).
Mp 207 °C; d (CDCl ) 3.10 (1H, s, CH), 7.38 (4H, m, aromatic
H
3
1-(4-Cyanophenyl )-2-(4-pentyloxyphenyl)acetylene 3
H), 7.52 (4H, m, aromatic H); n (KBr)/cm−1 3225m (C–H),
max
( X=CN, Y=C H O)
2220m (CON), 2200 (COC) (Found: C, 89.63; H, 3.80; N,
5
11
6.05. C H N requires C, 89.84; H, 3.99; N, 6.16%).
Yield 34%, mp 83 °C; d (CDCl ) 0.63–2.65, (8H, m, CH ),
17
9
H
3
2
3.65 (3H, t, CH ), 6.54–7.25 (8H, m, aromatic H);
3
6,6-Bis[2-(4-nitrophenyl)ethynyl]-1,4-dithiafulvene 5
n
(KBr)/cm−1 2940s, 2910s and 2840s (C–H), 2210m (CON),
max
2200m (COC) (Found: C, 82.64; H, 6.63; N, 4.57. C H NO
Compound 2 (X=NO ) (1.61 g, 4 mmol) and 6,6-diformyl-1,4-
20 19
2
requires C, 83.01; H, 6.62; N, 4.84%).
dithiafulvene (0.30 g, 1.7 mmol) were treated with ButOK
(1.0 g, 9.2 mmol) in THF (50 cm2) for 4 h at room temperature.
After evaporation of the solvent, the residue was extracted
with CH Cl and the solution dried over MgSO . The solvent
1-(4-Chlorophenyl )-2-(4-dimethylaminophenyl )acetylene 3
( X=Cl, Y=NMe )
2
2
4
2
was removed and residue recrystallized from ethanol to give
Yield 32%, mp 150 °C; d (CDCl ) 2.03 (6H, d, CH ) 6.55–7.43
the product in 15% yield, mp 115 °C; d (CDCl ) 7.15–8.25
H
3
3
H
3
(8H, m, aromatic H); n (KBr)/cm−1 2890s, 2850s and 2800s
(8H, m, aromatic H); n (KBr)/cm−1 2200m (COC), 1510s
max
max
(C–H), 2200m (COC) (Found: C, 75.10; H, 5.37; N, 5.17.
and 1330s (NO ) (Found: C, 58.52; H, 2.85; N, 6.52.
2
C H NCl requires C, 75.14; H, 5.52; N, 5.48%).
C H N O S requires C, 58.81; H, 2.96; N, 6.86%).
16 14
20 12
2 4 2
1-(4-Bromophenyl )-2-(4-methoxyphenyl)acetylene 3
1-(4-Methoxyphenylethynyl)-4-(4-nitrophenylethynyl)benzene
13
( X=Br, Y=MeO)
Yield 26%, mp 155 °C; d (CDCl ) 3.86 (3H, s, CH ) 6.36–7.50
Compound 2 (X=NO ) (2.01 g, 5.01 mmol) and compound
H
3
3
2
(8H, m, aromatic H); n (KBr)/cm−1 2970m, 2930m and
10 (1.0 g, 4.81 mmol) were treated with ButOK (1.2 g,
max
2840m (C–H), 2200m (COC) (Found: C, 62.48; H, 3.77.
10.7 mmol) in THF (30 cm3) for 3 h at room temperature.
After evaporation of the solvent the residue was stirred with
1 hydrochloric acid (50 cm3) for 30 min, then the reaction
was extracted with CH Cl , and the organic fractions dried
C H OBr requires C, 62.74; H, 3.86%).
15 11
3-(4-Nitrophenyl )prop-2-ynal 6 (Y=NO )
2
2
2
over MgSO . The solvent was removed under reduced pressure,
4-Bromonitrobenzene (50 g, 247 mmol) and 2-methylbut-3-yn-
2-ol (25 g, 297 mmol) were refluxed for 2 h in triethylamine
(500 cm3). The solvent was evaporated under reduced pressure
and the residue was recrystallized from benzene to give 4-(4-
nitrophenyl)-2-methylbut-3-yn-2-ol in 79% yield, mp 102 °C;
d (CDCl ) 1.62 (6H, s, CH ), 2.17 (1H, s, OH), 7.50 (2H, d,
4
and the residue recrystallized from ethanol to give 1-(4-
formylphenyl)-2-(4-nitrophenyl)acetylene 12 (X=NO ) in
2
60% yield. Compound 12 (X=NO ) (0.15 g, 1 mmol) and
2
compound 2 (X=MeO) (0.39 g, 1 mmol) were similarly treated
with ButOK (0.23 g, 2.02 mmol) to give the final product in
20% yield, mp 193 °C; d (CDCl ) 6.75–7.50 (8H, m, aromatic
H
3
3
aromatic H), 8.13 (2H, d, aromatic H). The alcohol (15 g,
73 mmol) and ButOK (2 g, 17.8 mmol) were refluxed for 50 min
in ButOH (50 cm3), the solvent was evaporated under reduced
pressure and the residue was recrystallized from ethanol
to give 1-ethynyl-4-nitrobenzene in 67% yield, which can
also be prepared from 1-bromo-4-nitrobenzene and tri-
methylsilylacetylene.6a Thus, 1-ethynyl-4-nitrobenzene (1.48 g,
10.0 mmol) and triethyl orthoformate (30 cm3) were heated in
the presence of zinc iodide (0.14 g, 0.4 mmol) at 140 °C for 2 h
to remove ethanol by distillation. The residue was distilled
under reduced pressure to give 3-(4-nitrophenyl)prop-2-ynal
diethyl acetal (bp 150 °C at 1 torr) in 60% yield; d (CDCl )
H
3
H), 7.55 (2H, d, aromatic H), 8.10 (2H, d, aromatic H);
n
(KBr)/cm−1 2200m (COC), 1505s and 1335s (NO )
max
2
(Found: C, 78.05; H, 4.18; N, 3.85. C H NO requires C,
23 15
3
78.17; H, 4.28; N, 3.96%).
1-(4-Methoxyphenyl)-4-(4-nitrophenyl )buta-1,3-diyne 7
(X=MeO, Y=NO )
2
3-(4-Nitrophenyl)prop-2-ynal (0.175 g, 1 mmol) and com-
pound 2 (X=MeO) (0.388 g, 1 mmol) were treated with ButOK
(0.25 g, 2.2 mmol) in THF (30 cm3) for 4 h at room tempera-
ture. After evaporation of the solvent, the residue was dissolved
H
3
432
J. Mater. Chem., 1997, 7(3), 429–433