3
8
H.G. Bonacorso et al. / Journal of Fluorine Chemistry 190 (2016) 31–40
1
H, H-8), 8.15 (s, 1H, H-3), 7.87–7.81 (m, 2H, H-7, H-5), 7.65 (ddd,
H-Ph), 7.31–7.27 (m, 2H, H-Ph), 4.07 (d, J = 19.3 Hz,1H, H-4), 3.72 (d,
1
2
3
=
8J = 8.2 Hz, = 7J = 7.0 Hz, = 1J = 1.1 Hz, 1H, H-6), 7.59–7.49 (m,
J = 19.3 Hz, 1H, H-4).
1
13
3
H, H-Ph); (Pyzl)
d
8.64 (s, 1H, OH), 7.45 (dd, = 8J = 8.8 Hz,
C NMR (100 MHz, DMSO-d
6
): (Qnzl)
d
165.30 (C O),163.40 (d,
¼
2
1
=
5J = 5.4 Hz, 2H, H-Ar), 7.14 (t, J = 8.9 Hz, 2H, H-Ar), 4.09 (d,
= 247J = 247.57 Hz, C-Ar), 154.58 (C-2), 147.42 (C-8a), 143.95 (C-4),
4
J = 19.2 Hz, 1H, H-4), 3.74 (d, J = 19.2 Hz, 1H, H-4).
134.51 (d, = 2J = 2.60 Hz, C-Ar), 130.33 (C-7), 129.59 (C-8), 129.51
13
3
C NMR (100 MHz, DMSO-d
a), 147.41 (C-8a), 143.54 (C-4), 137.95 (C-Ph), 129.94 (C-Ph), 129.57
C-7), 129.46 (C-8),128.63 (2C, C-Ph), 126.96 (3C, C-Ph, C-6), 124.27
6
): (Qnzl)
d
165.17 (C
¼O),155.45 (C-
(d, = 8J = 8.66 Hz, 2C, C-Ph), 127.28 (C-6), 124.46 (C-5), 122.59 (C-
2
2
(
(
4a), 115.78 (d, = 21J = 21.66 Hz, 2C, C-Ph), 115.52 (C-3); (Pyzl)
d
153.31 (C-3),130.82 (C-Ph),129.61 (C-Ph),128.71 (2C, C-Ph),126.46
1
1
2
C-5), 122.55 (C-4a); (Pyzl)
d
163.28 (d, = 249J = 249.50 Hz, C-Ar),
(2C, C-Ph), 123.24 (q, JCF = 285.72 Hz, CF
3
), 91.80 (d, JCF = 34.07 Hz,
3
1
52.14 (C-3), 128.68 (d, = 10J = 10.9 Hz, 2C, C-Ar), 126.14 (d,
C-5), 44.52 (C-4).
4
1
=
3J = 3.2 Hz, C-Ar), 123.05 (q,
J
CF = 285.66 Hz, CF
3
), 115.58 (d,
GC–MS (EI, 70 eV): m/z (%) 479 (M+, 33), 250 (100), 222 (82),101
(9), 75 (6).
Anal. Calcd. for C26
Found: C, 65.02; H, 3.66; H, 8.72.
2
2
J
CF = 22.16 Hz, 2C, C-Ar), 115.54 (C-3), 91.81 (q, = 34J = 34.25 Hz, C-
5), 44.46 (C-4).
17 4 3 2
H F N O (479.12): C, 65.14; H, 3.57; N, 8.76.
GC–MS (EI, 70 eV): m/z (%) 479 (M+, 27), 232 (100), 204 (80),101
(
9), 75 (7).
Anal. Calcd. for C26
H
17
F
4
N
3
O
2
(479.12): C, 65.14; H, 3.57; N, 8.76.
4.2.2.11.
(3-(4-Fluorophenyl)-5-hydroxy-5-(trifluoromethyl)-4,5-
Found: C, 64.34; H, 3.76; N, 8.70.
dihydro-1H-pyrazol-1-yl)(2-(4-fluorophenyl)quinolin-4-yl)
ꢀ
1
methanone (8cc). White solid, yield 71%, mp. 136–138 C. H NMR
1
2
4.2.2.8.
(5-Hydroxy-3-(thiophen-2-yl)-5-(trifluoromethyl)-4,5-
(400 MHz, DMSO): (Qnzl)
d 8.40 (dd, = 8J = 8.8 Hz, = 5J = 5.6 Hz,
dihydro-1H-pyrazol-1-yl)(2-phenylquinolin-4-yl)methanone
2H, H-Ar), 8.18–8.16 (m, 2H, H-8, H-3), 7.86–7.81 (m, 2H, H-7, H-5),
ꢀ
1
1
2
3
(
8bd). White solid, yield 70%, mp. 189–191 C. H NMR (400 MHz,
DMSO-d ): (Qnzl) 8.31 (d, J = 8.15 Hz, 2H, H-Ph), 8.19 (d, J = 8.5 Hz,
H, H-8), 8.12 (s, 1H, H-3), 7.88 (d, J = 8.3 Hz, 1H, H-5), 7.83 (t,
J = 7.7 Hz, 1H, H-7), 7.64 (t, J = 7.6 Hz, 1H, H-6), 7.59–7.49 (m, 3H, H-
Ph); (Pyzl) 8.59 (s, 1H, OH), 7.59–7.49 (m, 2H, H-Thienyl), 7.07 (t,
7.64 (ddd, = 8J = 8.3 Hz, = 7J = 7.0 Hz, = 1J = 1.2 Hz, 1H, H-6), 7.37
(t, J = 8.9 Hz, 2H, H-Ar); (Pyzl) 8.65 (s, 1H, OH), 7.45 (dd,
= 8J = 8.8 Hz, = 5J = 5.4 Hz, 2H, H-Ar), 7.14 (t, J = 8.9 Hz, 2H, H-Ar),
4.08 (d, J = 19.3 Hz, 1H, H-4), 3.74 (d, J = 19.3 Hz, 1H, H-4).
6
d
d
1
2
1
1
3
d
C NMR (100 MHz, DMSO-d
6
): (Qnzl)
d
165.29 (C
¼
O),163.43 (d,
1
J = 4.3 Hz, 1H, H-Thienyl), 4.08 (d, J = 19.0 Hz, 1H, H-4), 3.75 (d,
J = 19.0 Hz, 1H, H-4).
= 249J = 249.34 Hz, C-Ar), 154.56 (C-2), 147.42 (C-8a), 143.90 (C-4),
4
134.49 (d, = 2J = 2.85 Hz, C-Ar), 130.27 (C-7), 129.58 (C-8), 129.48
1
3
3
C NMR (100 MHz, DMSO-d
C-2), 147.52 (C-8a), 143.27 (C-4), 138.04 (C-Ph), 130.15 (C-Ph),
29.75 (C-7), 129.57 (C-8), 128.81 (2C, C-Ph), 127.14 (C-6), 127.10
2C, C-Ph), 124.48 (C-5), 122.71 (C-4a), 116.03 (C-3); (Pyzl) 148.95
C-3), 132.48 (C-Thienyl), 131.12 (C-Thienyl), 130.10 (C-Thienyl),
6
): (Qnzl)
d
164.90 (C
¼
O), 155.48
(d, = 8J = 8.60 Hz, 2C, C-Ar), 127.24 (C-6), 124.44 (C-5), 122.58 (C-
2
(
1
(
(
4a), 115.73 (d, = 21J = 21.55 Hz, 2C, C-Ar), 115.48 (C-3); (Pyzl)
163.38 (d, = 247J = 247.58 Hz, C-Ar), 152.42 (C-3), 128.91 (d,
d
1
3
4
d
= 8J = 8.83 Hz, 2C, C-Ar), 126.24 (d, = 2J = 2.93 Hz, C-Ar), 123.21
1
2
3
(q, JCF = 285.62 Hz, CF ), 115.81 (d, JCF = 22.12 Hz, 2C, C-Ar), 91.90
1
2
1
27.88 (C-Thienyl), 123.12 (q,
CF = 34.23 Hz, C-5), 45.01 (C-4).
GC–MS (EI, 70 eV): m/z (%) 467 (M+, 28), 232 (100), 204 (80),101
J
CF = 285.34 Hz, CF
3
), 91.80 (q,
(q, JCF = 34.06 Hz, C-5), 44.58 (C-4).
2
J
GC–MS (EI, 70 eV): m/z (%) 497 (M+, 24), 250 (100), 222 (83),101
(11), 75 (Anal. Calcd. for C26
16 5 3 2
H F N O (497.12): C, 62.78; H, 3.24; N,
(
8), 75 (8).
8.45. Found: C, 62.84; H, 3.61; N, 8.22.
16 3 3 2
Anal. Calcd. for C24H F N O S (467.09): C, 61.67; H, 3.45; N,
8
.99. Found: C, 61.81; H, 3.45; N, 8.88.
4.2.2.12. (2-(4-Fluorophenyl)quinolin-4-yl)(5-hydroxy-3-(thiophen-
-yl)-5-(trifluoromethyl)-4,5-dihydro-1H-pyrazol-1-yl)methanone
2
ꢀ
1
4.2.2.9. (2-(4-Fluorophenyl)quinolin-4-yl)(5-hydroxy-3-methyl-5-
(8cd). White solid, yield 60%, mp. 165–167 C. H NMR (400 MHz,
DMSO-d ): (Qnzl) 8.38 (dd, J = 8.8 Hz, 5.5 Hz, 2H, H-Ar), 8.17–8.15
(m, 2H, H-8, H-3), 7.86–7.80 (m, 2H, H-7, H-5), 7.64 (t, J = 8.1 Hz, 1H,
(trifluoromethyl)-4,5-dihydro-1H-pyrazol-1-yl)methanone
6
d
ꢀ
1
(
8ca). White solid, yield 65%, mp. 163–165 C. H NMR (400 MHz,
): (Qnzl) 8.37–8.34 (m, 2H, H-Ph), 8.13 (d, J = 8.3 Hz, 1H,
H-8), 8.03 (s, 1H, H-3), 7.84–7.78 (m, 2H, H-7, H-5), 7.64 (ddd,
DMSO-d
6
d
H-6), 7.38 (t, J = 8.8 Hz, 2H, H-Ar); (Pyzl)
d
8.74 (s, 1H, OH), 7.56 (dd,
1
2
2
1
= 5J = 5.0 Hz, = 0J = 0.8 Hz, 1H, H-Thienyl), 7.50 (dd, = 3J = 3.6 Hz,
1
2
3
1
2
J = 8.2 Hz, J = 6.9 Hz, J = 1.1 Hz, 1H, H-6), 7.37 (t, J = 8.9 Hz, 2H, H-
= 0J = 0.8 Hz, 1H, H-Thienyl), 7.07 (dd, = 5J = 5.0 Hz, = 3J = 3.7 Hz,
Ph); (Pyzl)
d
8.37–8.34 (m, 1H, OH), 3.58 (d, J = 19.4 Hz, 1H, H-4),
).
164.94 (C
1H, H-Thienyl), 4.09 (d, J = 19.0 Hz, 1H, H-4), 3.74 (d, J = 19.0 Hz, 1H,
3
.22 (d, J = 19.4 Hz, 1H, H-4), 1.80 (s, 3H, CH
3
H-4).
13
13C NMR (100 MHz, DMSO-d
C NMR (100 MHz, DMSO-d
6
): (Qnzl)
d
¼O),163.38 (d,
6
): (Qnzl)
d
164.99 (C
¼
O),163.45 (d,
1
1
=
247J = 247.50 Hz, C-Ar), 154.66 (C-2), 147.46 (C-8a), 144.29 (C-4),
= 247J = 247.66 Hz, C-Ar), 154.56 (C-2), 147.52 (C-8a), 143.57 (C-4),
4
4
1
34.55 (d, = 2J = 2.79 Hz, C-Ar), 130.31 (C-7), 129.56 (C-8), 129.52
134.58 (d,
= 2J = 2.89 Hz, C-Ar), 129.63 (C-8), 129.54 (d,
= 8J = 8.69 Hz, 2C, C-Ar), 127.34 (C-6), 124.59 (C-5), 122.70 (C-
4a),115.93 (C-3); (Pyzl) 149.17 (C-3),132.54 (C-Thienyl),131.38 (C-
3
3
(
d, = 8J = 8.47 Hz, 2C, C-Ar), 127.26 (C-6), 124.40 (C-5), 122.53 (C-
2
4a), 115.75 (d, = 21J = 21.51 Hz, 2C, C-Ar), 115.15 (C-3); (Pyzl)
d
d
1
2
1
55.80 (C-3), 123.31 (d, JCF = 285.92 Hz, CF
Hz, C-5), 48.00 (C-4), 15.03 (CH ).
GC–MS (EI, 70 eV): m/z (%) 417 (M+, 27), 250 (93), 222 (100), 101
3
), 90.95 (q, JCF = 34.23
Thienyl), 130.35 (2C, C-7, C-Thienyl), 128.05 (C-Thienyl), 123.24 (q,
1
2
2
3
J
3
CF = 285.73 Hz, CF ), 115.85 (d, JCF = 21.56 Hz, 2C, C-2c), 91.89 (q,
JCF = 34.0 Hz, C-5), 45.09 (C-4).
(
13), 75 (12).
GC–MS (EI, 70 eV): m/z (%) 485 (M+, 26), 250 (100), 222 (86),101
Anal. Calcd. for C21
Found: C, 60.89; H, 3.94; N, 9.66.
H
15
F
4
N
3
O
2
(417.11): C, 60.42; H, 3.62; N,10.07.
(10), 75 (8).
Anal. Calcd. for C24
.66. Found: C, 59.35; H, 3.53; N, 8.35.
15 4 3 2
H F N O S (485.08): C, 59.38; H, 3.11; N,
8
4.2.2.10. (2-(4-Fluorophenyl)quinolin-4-yl)(5-hydroxy-3-phenyl-5-
(
trifluoromethyl)-4,5-dihydro-1H-pyrazol-1-yl)methanone
4.2.2.13. (5-Hydroxy-3-methyl-5-(trifluoromethyl)-4,5-dihydro-1H-
ꢀ
1
(8cb). White solid, yield67%, mp. 156–158 C. H NMR (400 MHz,
pyrazol-1-yl)(2-(thiophen-2-yl)quinolin-4-yl)methanone
1
2
ꢀ
1
DMSO-d
6
): (Qnzl)
d
8.39 (dd, = 9J = 9.0 Hz, = 5J = 5.5 Hz, 2H, H-Ar),
(8da). White solid, yield 71%, mp. 100–102 C. H NMR (400 MHz,
1
2
8
.18–8.15 (m, 2H, H-8, H-3), 7.85–7.81 (m, 2H, H-7, H-5), 7.63 (ddd,
DMSO-d
6
): (Qnzl) d 8.08 (dd, = 3J = 3.8 Hz, = 1J = 1.1 Hz, 1H, H-
1
2
3
1
=
8J = 8.0 Hz, = 6J = 6.9 Hz, = 1J = 1.2 Hz, 1H, H-6), 7.40–7.35 (m,
Thienyl), 8.04–8.02 (m, 2H, H-8, H-3), 7.79 (ddd, = 8J = 8.4 Hz,
= 6J = 6.7 Hz, = 1J = 1.4 Hz, 1H, H-7), 7.75 (dd, = 5J = 5.0 Hz,
2
3
1
2
H, H-Ar, H-13c, H-13d); (Pyzl)
d
8.64 (s, 1H, OH), 7.40–7.35 (m, 3H,