P. E. Just et al. / Tetrahedron 58 ꢀ2002) 3467±3472
3471
3
18.0%); lmax ꢀCH CN)/nm 242 ꢀ1/dm mol cm 9300),
313 ꢀ12,800) and 340 ꢀ7200); dH ꢀCDCl ) 2.40 ꢀ12H, s,
3
21
21
S, 21.62. Found: C, 69.2; H, 6.3; N, 4.0; S, 18.7%; l
ꢀ
max
3
3 21
CH CN)/nm 241 ꢀ1/dm mol cm
21
9800) and 323
10,400); dH ꢀCDCl ) 2.42 ꢀ12H, s, CH ), 6.29 ꢀ4H,
3
ꢀ
CH ), 6.41 ꢀ4H, J3.5 Hz, 3-thienyl), 6.46 ꢀ4H, s, pyrrolyl),
3
3
3
J3.5 Hz, 3-thienyl), 6.45 ꢀ4H, s, pyrrolyl), 6.49 ꢀ4H,
6.51 ꢀ4H, J3.5 Hz, 4-thienyl), 7.16 ꢀ4H, J9.0 Hz,
phenyl), 7.24 ꢀ4H, J9.0 Hz, phenyl); m/z ꢀCI): 684
J3.5 Hz, 4-thienyl), 7.32 ꢀ4H, s, phenyl); m/z ꢀCI): 593
1
MH , 100), 574 ꢀ12.1) and 475 ꢀ7.5).
1
ꢀMH , 84.8), 566 ꢀ9.1), 391 ꢀ100) and 293 ꢀ43.2).
ꢀ
3
2
.3.3. Di{4-[2,5-diꢀ2-thienyl)-1H-1-pyrrolyl]phenyl}ether,
b. Yield 66% ꢀ829 mg); brown powder; mp 2508C; calcd
3.3.9. 1-Benzyl-2,5-diꢀ2-thienyl)-1H-pyrrole, 5b. Via
procedure B. Yield 47% ꢀ300 mg); pale brown powder;
mp 998C; calcd for C H NS : C, 71.03; H, 4.67; N, 4.36;
for C H N S O: C, 68.79; H, 3.82; N, 4.45; O, 2.55; S,
2
3
6
24
4
19 15
2
2
lmax ꢀCH CN)/nm 238 ꢀ1/dm mol cm 11,400) and
0.38. Found: C, 68.9; H, 4.1; N, 4.4; O, 2.7; S, 20.0%;
S, 19.94; Found: C, 70.5; H, 5.0; N, 4.2; S, 19.3%; l
max
3
3
21
21
21
21
ꢀCH CN)/nm 231 ꢀ1/dm mol cm
10,100) and 317
3
3
3
34 ꢀ11,300); dH ꢀCDCl ) 6.56 ꢀ4H, s, pyrrolyl), 6.65
3
ꢀ13,600); dH ꢀCDCl ) 5.39 ꢀ2H, s, CH ), 6.49 ꢀ2H, s, pyr-
3 2
ꢀ
4H, J3.6, 1.1 Hz, 3-thienyl), 6.87 ꢀ4H, J3.6, 5.1 Hz,
H 4-thienyl), 7.09 ꢀ4H, J1.1, 5.1 Hz, 5-thienyl), 7.12
4H, J8.7, 2.2 Hz, phenyl), 7.33 ꢀ4H, J8.7, 2.2 Hz,
phenyl).
rolyl), 6.81 ꢀ2H, J1.1, 3.6 Hz, 3-thienyl), 6.94 ꢀ2H, J3.6,
5.1 Hz, 4-thienyl), 6.97 ꢀ2H, m, phenyl), 7.21 ꢀ2H, J1.1,
5.1 Hz, 5-thienyl), 7.31 ꢀ3H, m, phenyl); m/z ꢀCI): 322
ꢀ
1
ꢀMH , 100).
3
.3.4. Di{4-[2,5-diꢀ5-methyl-2-thienyl)-1H-1-pyrrolyl]-
3.3.10. 1-Phenyl-2,5-diꢀ2-thienyl)-1H-pyrrole, 6b. Via
procedure B. Yield 65% ꢀ400 mg); brown±green powder;
mp 1808C; calcd for C H NS : C, 70.36; H, 4.23; N, 4.56;
phenyl}ether, 2c. Yield 24% ꢀ328 mg); brown powder;
mp 1828C; calcd for C H N S O: C, 70.17; H, 4.68; N,
4
0
32
2
4
18 13
2
4
2
1
6
.09; O, 2.34; S, 18.71. Found: C, 70.0; H, 5.0; N, 4.0; O,
S, 20.85. Found: C, 70.5; H, 4.2; N, 4.5; S, 20.9%); l
max
3
3 21
.6; S, 18.4%; lmax ꢀCH CN)/nm 241 ꢀ1/dm mol cm
21
21
21
ꢀCH CN)/nm 240 ꢀ1/dm mol cm
14,900) and 331
3
3
0,900) and 331 ꢀ11,000); d ꢀCDCl ) 2.38 ꢀ12H, s, CH ),
H
ꢀ22,400); dH ꢀCDCl ) 6.53ꢀ2H, J1.0, 3.6 Hz, 3-thienyl),
3
3
3
.39 ꢀ4H, J3.6 Hz, 3-thienyl), 6.46 ꢀ4H, s, pyrrolyl), 6.50
6.56 ꢀ2H, s, pyrrolyl), 6.82 ꢀ2H, J3.6, 5.1 Hz, 4-thienyl),
7.07 ꢀ2H, J1.0, 5.1 Hz, 5-thienyl), 7.33 ꢀ2H, m, J7.7,
2.0 Hz, phenyl), 7.44 ꢀ3H, m, phenyl); m/z ꢀCI): 308
ꢀ
4H, m, 4-thienyl), 7.11 ꢀ4H, J8.8 Hz, phenyl), 7.31 ꢀ4H,
1
J8.8 Hz, phenyl); m/z ꢀCI): 685 ꢀMH , 57.2), 567 ꢀ22.0),
1
3
10 ꢀ100) and 293 ꢀ65.9).
ꢀMH , 100).
3
.3.5. Di{4-[2,5-diꢀ2-thienyl)-1H-1-pyrrolyl]phenyl}sul-
de, 3b. Yield 22% ꢀ283mg); pink powder; mp 245 8C;
3.3.11. 1-ꢀ4-Nitrophenyl)-2,5-diꢀ2-thienyl)-1H-pyrrole,
7b. Via procedure B. Yield 61% ꢀ429 mg); pale orange
crystals; mp 2158C; calcd for C H N O S : C, 61.36; H,
®
calcd for C H N S : C, 67.08; H, 3.73; N, 4.35; S,
3
6
24
2
5
18 12
2
2 2
2
4.84. Found: C, 68.9; H, 4.9; N, 4.0; S, 22.3%; l
3.41; N, 7.95; O, 9.09; S, 18.18; Found: C, 61.3; H, 3.5; N,
8.0; O, 9.1; S, 18.3%; lmax ꢀCH CN)/nm 233
ꢀ1/dm mol cm 15,500) and 319 ꢀ15,000); d ꢀCDCl )
H 3
max
3 21
CH CN)/nm 251 ꢀ1/dm mol cm
21
ꢀ
15,800) and 326
14,400); dH ꢀCDCl ) 6.54 ꢀ4H, s, pyrrolyl), 6.60 ꢀ4H,
3
3
3
21
21
ꢀ
3
J3.6, 1.1 Hz, 3-thienyl), 6.84 ꢀ4H, J3.6, 5.1 Hz, 4-thi-
6.55 ꢀ2H, J1.1, 3.6 Hz, 3-thienyl), 6.56 ꢀ2H, s, pyrrolyl),
enyl), 7.08 ꢀ4H, J1.1, 5.1 Hz, 5-thienyl), 7.27 ꢀ4H, J8.6,
6.87 ꢀ2H, J3.6, 5.1 Hz, 4-thienyl), 7.15 ꢀ2H, J1.1,
2
.1 Hz, p henyl), 7.39 ꢀ4H, J8.6, 2.1 Hz, phenyl).
5.1 Hz, 5-thienyl), 7.41 ꢀ2H, J9.0, 2.1 Hz, phenyl), 8.23
1
ꢀ
2H, J9.0, 2.1 Hz, phenyl); m/z ꢀCI): 353 ꢀM , 100), 336
3
.3.6. Di{4-[2,5-diꢀ5-methyl-2-thienyl)-1H-1-pyrrolyl]-
ꢀ7.4) and 306 ꢀ4.2).
phenyl}sul®de, 3c. Yield 9% ꢀ126 mg); pale brown powder;
mp 1858C; calcd for C H N S : C, 68.57; H, 4.57; N, 4.00;
S, 22.86. Found: C, 68.6; H, 4.9; N, 3.9; S, 22.6%); l
3.3.12. 4-[2,5-Diꢀ2-thienyl)-1H-1-pyrrolyl]aniline, 8b.
Via procedure A. Yield 65%; grey powder; mp 1898C;
calcd for C H N S : C, 67.08; H, 4.35; N, 8.69; S,
4
0
32
2 5
max
3
21
21
ꢀ
ꢀ
CH CN)/nm 255 ꢀ1/dm mol cm
14,900) and 325
14,200); dH ꢀCDCl ) 2.53ꢀ12H, s, CH 3), 6.34 ꢀ4H,
3
18 14
2 2
19.87; Found: C, 67.7; H, 4.8; N, 8.3; S, 19.3%; dH
ꢀCDCl ) 3.87 ꢀ2H, NH ), 6.53ꢀ2H, s, pyrrolyl), 6.64 ꢀ2H,
3
J3.5 Hz, 3-thienyl), 6.45 ꢀ4H, s, pyrrolyl), 6.47 ꢀ4H,
3
2
J3.5 Hz, 4-thienyl), 7.26 ꢀ4H, J8.2 Hz, phenyl), 7.40
J3.65, 1.15 Hz, 3-thienyl), 6.84 ꢀ2H, J3.65, 5.10 Hz,
ꢀ
4H, J8.2 Hz, phenyl).
4-thienyl), 7.05 ꢀ2H, J1.15, 5.10 Hz, 5-thienyl), 6.72
ꢀ
2H, J6.58, 2.15 Hz, phenyl), 7.10 ꢀ2H, J6.58,
3.3.7. N,N-Di{4-[2,5-diꢀ2-thienyl)-1H-1-pyrrolyl]phenyl}-
amine, 4b. Yield 32% ꢀ401 mg); brown powder; mp 2578C;
2.15 Hz, phenyl).
calcd for C H N S : C, 68.90; H, 3.99; N, 6.70; S, 20.41;
3
3.3.13. N1-{4-[2,5-Diꢀ2-thienyl)-1H-1-pyrrolyl]phenyl}-
propanamide, 9b. Greenish grey powder, dH ꢀCDCl3)
1.28 ꢀ3H, J7.5 Hz, CH ), 2.44 ꢀ2H, J7.5 Hz, CH ),
6
25
3 4
Found: C, 70.6; H, 4.7; N, 6.1; S, 18.5%); l ꢀCH CN)/nm
max
3
3 21
37 ꢀ1/dm mol cm
21
2
ꢀ
9500), 312 ꢀ13,100) and 342
7000); dH ꢀCDCl ) 6.55 ꢀ4H, s, pyrrolyl), 6.68 ꢀ4H,
3
2
6.57 ꢀ2H, J3.65, 1.15 Hz, 3-thienyl), 6.53 ꢀ2H, s, pyrro-
lyl), 6.82 ꢀ2H, J3.65, 5.13 Hz, 4-thienyl), 7.05 ꢀ2H,
J1.15, 5.13Hz, 5-thienyl), 7.26 ꢀ2H, J8.7 Hz, phenyl),
7.60 ꢀ2H, J8.7 Hz, phenyl).
3
J3.6, 1.1 Hz, 3-thienyl), 6.86 ꢀ4H, J3.6, 5.1 Hz, 4-thi-
enyl), 7.08 ꢀ4H, J1.1, 5.1 Hz, 5-thienyl), 7.17 ꢀ4H, J9.0,
2
.5 Hz, phenyl), 7.33 ꢀ4H, J9.0, 2.5 Hz, phenyl).
3
.3.8.
N,N-Di{4-[2,5-diꢀ5-methyl-2-thienyl)-1H-1-pyr-
3.3.14. N1-{4-[2,5-Diꢀ2-thienyl)-1H-1-pyrrolyl]phenyl}a-
cetamide, 10b. Greenish grey powder, dH ꢀCDCl ) 2.23
rolyl]phenyl}amine, 4c. Yield 50% ꢀ683mg); brown
powder; mp 2028C; calcd for C H N S : C, 70.27; H,
3
ꢀ3H, CH ), 6.57 ꢀ2H, J3.65, 1.15 Hz, 3-thienyl), 6.53
4
0
33
3
4
3
4
.83; N, 6.15; S, 18.74; Found: C, 70.9; H, 5.2; N, 5.8; S,
ꢀ2H, s, pyrrolyl), 6.82 ꢀ2H, J3.65, 5.13 Hz, 4-thienyl),