Notes
J . Org. Chem., Vol. 65, No. 25, 2000 8821
173.0-175.0 °C; 1H NMR δ 7.18 (dd, 1H, J ) 1.9, 8.4 Hz), 7.25-
7.36 (m, 3H), 7.42-7.51 (m, 4H), 7.59 (d, 1H, J ) 8.1 Hz), 7.74
(d, 1H, J ) 8.1 Hz), 7.87 (d, 2H, J ) 7.5 Hz), 8.82 (d, 1H, J )
7.7 Hz), 9.76 (br s, 1H); 13C NMR δ 67.0, 110.0, 119.4, 124.8,
127.4, 127.6, 128.3, 128.4, 129.5, 130.0, 131.2, 131.9, 132.6, 134.6,
136.2, 140.1, 145.0, 200.2. Anal. Calcd for C20H14Cl2N4S: C 58.12;
H 3.41; N 13.56. Found: C 58.38; H 3.26; N 13.75.
Eth yl 2-(2-fu r yl)-4-p h en yl-1H-p yr r ole-3-ca r boxyla te (6i):
65% pale brown oil; 1H NMR δ 1.04 (t, 3H, J ) 7.1 Hz), 4.14 (q,
2H, J ) 7.1 Hz), 6.42 (dd, 1H, J ) 2.1, 2.0 Hz), 6.62 (d, 1H, J )
2.7 Hz), 7.23-7.36 (m, 7H), 9.25 (s, 1H); 13C NMR δ 14.0, 60.1,
109.6, 109.7, 112.1, 117.8, 126.5, 127.8, 127.9, 128.0, 129.3, 135.6,
141.6, 146.1, 165.6. Anal. Calcd for C17H15NO3:N 4.98. Found:
N 5.32.
N-[1H-1,2,3-Ben zotr ia zol-1-yl(4-m eth ylp h en yl)m eth yl]-
4-ch lor oben zen eca r both ioa m id e (3c): yellowish microcrys-
tals; mp 152.0-154.0 °C; 1H NMR δ 2.37 (s, 3H), 7.19-7.48 (m,
7H), 7.55 (t, 1H, J ) 7.2 Hz), 7.73-7.83 (m, 3H), 8.03 (d, 1H, J
Eth yl 2-p h en yl-4-(tr iflu or om eth yl)-1H-p yr r ole-3-ca r box-
yla te (6j): red microcrystals; mp 120-121 °C, H NMR δ 1.15
(t, 3H, J ) 7.0 Hz), 4.08 (q, 2H, J ) 7.0 Hz), 6.96 (d, 1H, J ) 2.6
Hz), 7.33-7.42 (m, 5H), 9.17 (br s, 1H); 13C NMR δ 13.7, 60.4,
109.4, 119.8, 121.2, 124.7, 128.1, 128.8, 129.0, 131.1, 139.3, 157.7,
163.8, 186.4. Anal. Calcd for C14H12F3NO2: C 59.37, H 4.27, N
4.95. Found: C 59.25, H 4.34, N 4.94.
1
) 8.4 Hz), 8.64 (d, 1H, J ) 8.4 Hz), 9.25 (d, 1H, J ) 7.8 Hz); 13
C
NMR δ 21.1, 69.2, 109.8, 119.9, 124.5, 126.5, 128.1, 128.5, 128.7,
129.9, 132.4, 132.9, 138.2, 138.8, 139.8, 145.4, 198.5 Anal. Calcd
for C21H17ClN4S: C 64.20; H 4.36. Found: C 64.22; H 4.44.
Th e Syn th esis of Tr i- a n d Tetr a su bstitu ted P yr r oles 6
a n d 7. Gen er a l P r oced u r e. The t-BuOK (3.3 mmol) was added
to a solution of a N-(benzotriazol-1-ylmethyl)thioamide (2) (3
mmol) and iodomethane (3.3 mmol) in THF (50 mL) at 0 °C,
and the mixture was stirred for 2 h. After an appropriate Michael
acceptor (3.3 mmol) was added, the t-BuOK (9 mmol) was added
in two portions at 0 °C. The mixture was refluxed for 2 h, and
the solvent was removed on an evaporator. The solid residue
was dissolved in 50 mL of dichloromethane and washed with
5% NaHCO3 (100 mL × 3∼5) and dried over MgSO4. After
evaporation of the solvents, the residue was recrystallized from
dichloromethane-ethanol to give the expected product.
1,3-Dip h en yl-2-cya n o-1H-p yr r ole (6a ): gray plates, mp
255.0 °C; 1H NMR δ 7.06 (d, 1H, J ) 2.7 Hz), 7.25-7.30 (m,
1H), 7.35-7.50 (m, 5H), 7.66 (d, 2H, J ) 6.9 Hz), 7.83 (d, 2H, J
) 6.9 Hz), 11.94 (br s, 1H); 13C NMR δ 86.3, 116.2, 117.1, 125.0,
125.3, 125.7, 126.6, 127.2, 127.5, 127.7, 129.1, 132.1, 138.9. Anal.
Calcd for C17H12N2: C 83.58; H 4.95; N 11.47. Found: C 83.20;
H 4.96; N 11.49.
2,3-Dip h en yl-4-(p h en ylsu lfon yl)-1H-p yr r ole (6b): red mi-
crocrystals; mp 156.0-159.0 °C; 1H NMR δ 6.65 (d, 1H, J ) 2.5
Hz), 7.12 (q, 3H, J ) 8.2 Hz), 7.23-7.31 (m, 7H), 7.34-7.37 (m,
3H), 7.49-7.53 (m, 2H), 8.78 (br s, 1H); 13C NMR δ 118.0, 126.8,
127.1, 127.5, 127.9, 128.0, 128.9, 130.2, 130.5, 131.0, 131.8, 133.4,
137.0, 143.1. Anal. Calcd for C22H17NO2S: N 3.90. Found N 4.05.
Dim eth yl 2-(3-p yr id in yl)-1H-p yr r ole-3,4-d ica r boxyla te
(6c): white solid; mp 165-166 °C; 1H NMR δ 3.60 (s, 6H), 7.11-
7.21 (m, 2H), 7.69 (d, 1H, J ) 7.8 Hz), 8.33 (d, 1H, J ) 4.6 Hz),
8.55 (s, 1H), 11.61 (br s, 1H); 13C NMR δ 50.8, 51.5, 113.9, 115.6,
122.7, 124.7, 127.0, 130.4, 134.7, 147.9, 148.1, 163.6, 165.9. Anal.
Calcd for C13H12N2O4: C 60.00, H 4.65, N 10.76. Found: C 59.85,
H 4.79, N 10.72.
Eth yl 2-(4-m eth oxyp h en yl)-4-p h en yl-1H-p yr r ole-3-ca r -
1
boxyla te (6k ): white crystals; mp 136.0-138.0 °C, H NMR δ
0.99 (t, 3H, J ) 7.2 Hz), 3.82 (s, 3H), 4.06 (q, 2H, J ) 7.2 Hz),
6.71 (d, 1H, J ) 2.5 Hz), 6.93 (d, 2H, J ) 8.7 Hz), 7.25-7.47 (m,
7H), 8.47 (br s, 1H); 13C NMR δ 13.8, 55.3, 59.8, 110.5, 113.6,
116.8, 124.8, 126.3, 127.7, 129.0, 130.1, 135.5, 137.1, 159.5, 165.7.
Anal. Calcd for C20H19NO3: C74.75, H 5.96, N 4.36. Found: C
74.60, H 6.33, N 4.31.
1-[2,3-Dip h en yl-4-(p h en ylsu lfon yl)-1H-p yr r ol-1-yl]-1-eth -
1
a n on e (6l): white microcrystals; mp 136.0-138.0 °C, H NMR
δ 2.00 (s, 3H), 7.15-7.20 (m, 4H), 7.32-7.49 (m, 12H); 13C NMR
δ 25.3, 120.0, 126.5, 127.1, 127.6, 127.7, 128.0, 128.1, 129.5,
130.3, 130.5, 130.8, 132.1, 132.3, 136.6, 142.0, 168.8. Anal. Calcd
for C24H19NO3S: N 3.49. Found: N 3.55.
E t h yl 1-m et h yl-2,4-d ip h en yl-1H -p yr r ole-3-ca r b oxyla t e
(6m ): oil; 1H NMR δ 0.85 (t, 3H, J ) 7.1 Hz), 3.41 (s, 3H), 3.93
(q, 2H, J ) 8.0 Hz), 6.66 (s, 1H), 7.33-7.43 (m, 10H); 13C NMR
δ 13.5, 34.5, 59.2, 111.8, 121.5, 126.1, 126.2, 127.6, 127.8, 128.1,
129.0, 130.4, 132.0, 135.2, 138.9, 165.0. Anal. Calcd for C20H19
-
NO2: C 78.66, H 6.27, N 4.59. Found: C 78.54, H 6.63, N 4.45.
4-(2-F u r yl)-1-m et h yl-2-p h en yl-1H -p yr r ole-3-ca r b oxylic
a cid (6n ): brown oil; 1H NMR δ 3.34 (s, 3H), 6.38 (dd, 1H, J )
1.7, 3.2 Hz), 6.85 (d, 1H, J ) 3.3 Hz), 6.99 (s, 1H), 7.27-7.33
(m, 3H), 7.36-7.38 (m, 4H); 13C NMR δ 35.0 107.9, 109.3, 111.4,
116.6, 121.9, 128.2, 128.6, 130.6, 131.8, 140.6, 140.6, 149.0, 169.8;
HRMS calcd for C16H13NO3 (M): 267.0895, found 267.0907.
Eth yl 2-(2-fu r yl)-4-p h en yl-1-N-m eth yl-p yr r ole-3-ca r box-
yla te (6o): 85% colorless oil; 1H NMR δ 1.00 (t, 3H, J ) 7.2
Hz), 3.51 (s, 3H), 4.05 (q, 2H, J ) 7.2 Hz), 6.47 (dd, 1H, J ) 1.5,
3.6 Hz), 6.63 (s, 1H), 6.64 (d, 1H, J ) 3.6 Hz), 7.22-7.25 (m,
1H), 7.28-7.33 (m, 2H), 7.37-7.40 (m, 2H), 7.50 (d, 1H, J ) 1.8
Hz); 13C NMR δ_13.9, 35.3, 59.8, 110.9, 112.1, 114.1, 122.9, 126.2,
126.4, 127.5, 127.8, 128.5, 128.9, 135.0, 142.7, 144.4, 164.9. Anal.
Calcd for C18H17NO3: C 73.20, H 5.80, N 4.74. Found: C 73.28,
H 5.96, N 4.73.
2-P h en yl-3-(4-m et h ylb en zoyl)-3-(2-t h ien yl)-1H -p yr r ole
(6d ): yellow prisms; mp 199.0-200.0 °C; 1H NMR δ 2.26 (s, 3H),
6.79-6.84 (m, 3H), 6.99-7.03 (m, 3H), 7.08-7.11 (m, 3H), 7.17-
7.21 (m, 2 H), 7.70 (d, 2H, J ) 7.2 Hz), 9.25 (br s, 1H); 13C NMR
δ 21.6, 117.5, 118.9, 119.7, 123.1, 124.5, 127.2, 127.3, 128.5,
128.7, 130.2, 131.4, 134.2, 135.9, 136.6, 143.5, 195.4. Anal. Calcd
for C22H17NOS: N 4.08. Found: N 4.02.
Eth yl 1-m eth yl-2-p h en yl-4-(tr iflu or om eth yl)-1H-p yr r ole-
3-ca r boxyla te (6p ): pale yellow needles; mp 51-52 °C; 1H
NMR δ 1.05 (t, 3H, J ) 7.2 Hz), 3.39 (s, 3H), 4.07 (q, 2H, J )
7.1 Hz), 7.03 (s, 1H), 7.27-7.31 (m, 2H), 7.40-7.44 (m, 3H); 13
C
NMR δ 13.7, 35.0, 59.9, 114.1 (C, J C-F ) 36.7 Hz), 123.2 (C, J C-F
Eth yl 2,4-d ip h en yl-1H-p yr r ole-3-ca r boxyla te (6e): oil; 1H
NMR δ 0.92 (t, 3H, J ) 7.1 Hz), 3.95 (q, 2H, J ) 7.1 Hz), 6.48
(d, 1H, J ) 1.5 Hz), 7.30-7.40 (m, 10H), 8.94 (s, 1H); 13C NMR
δ 13.6, 59.9, 110.4, 117.5, 126.2, 127.2, 127.7, 127.8, 127.9, 128.6,
128.8, 132.2, 135.3, 136.8, 166.1. Anal. Calcd for C19H17NO2: C
78.33, H 5.88, N 4.81. Found: C 77.97, H 6.06, N 4.90.
4-(2-F u r yl)-2-p h en yl-1H-p yr r ole-3-ca r boxylic a cid (6h ):
) 264 Hz), 123.6 (CH, J C-F ) 6.3 Hz), 128.2, 128.4 (C, J C-F
)
11.4 Hz), 129.0, 130.5, 130.9, 140.7, 163.0. Anal. Calcd for
C15H14F3NO2: N 4.71. Found: N 5.01.
5-(2,4-Dich lor op h en yl)-2,4-d ip h en yl-1H-p yr r ole-3-ca r bo-
n itr ile (7b): white microcrystalls; mp 193.0-196.0 °C; 1H NMR
δ 7.07-7.15 (m, 2H), 7.32 (br s, 5H), 7.43-7.53 (m, 4H), 7.78 (d,
2H, J ) 7.3 Hz), 8.96 (br s, 1H); 13C NMR δ 91.7, 117.2, 125.6,
126.2, 127.7, 127.8, 128.3, 128.5, 128.9, 129.2, 129.4, 129.5, 129.6,
1
oil; H NMR δ 6.41 (dd, 1H, J ) 1.9, 3.4 Hz), 6.85 (d, 1H, J )
3.2 Hz), 7.09 (d, 1H, J ) 2.6 Hz), 7.33-7.37 (m, 4H), 7.41-7.49
(m, 3H), 9.02 (br s, 1H); 13C NMR δ 107.7, 111.2, 117.7, 118.0,
128.1, 128.4, 129.1, 132.1, 139.3, 140.6, 148.7, 170.2, 171.4, 177.4;
HRMS calcd for C15H11NO3 (M): 253.0739, found: 253.0737.
130.5, 132.3, 133.7, 134.1, 135.3, 139.7. Anal. Calcd for C23H14
Cl2N2: N 7.20. Found: N 7.15.
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J O001160W