Chlorinated N-Alkyl-3- and -5-(2-hydroxyphenyl)pyrazoles
807
3.95 [t, J ¼ 7.3 Hz, NCH2(CH2)8CH3], 5.14 (s, OCH2), 6.77
(s, H-4), 7.02 (d, J ¼ 1.9Hz, H-30), 7.03 (dd, J ¼ 7.0, 1.9 Hz,
H-50), 7.29–7.38 (m, OCH2C6H5 and H-600), 7.44 (dd, J ¼ 7.9,
1.6 Hz, H-500), 7.52 (d, J ¼ 1.6 Hz, H-300), 7.99 (d, J ¼ 7.0 Hz,
H-60) ppm; 13C NMR: ꢂ ¼ 14.1 (CH3), 22.6 [N(CH2)8CH2
CH3], 26.4, 29.0, 29.3, 29.4, 29.5, 30.3, and 31.8 [NCH2
(CH2)8CH2CH3], 49.8 [NCH2(CH2)8CH3], 70.7 (OCH2),
108.7 (C-4), 113.3 (C-30), 121.3 (C-50), 121.4 (C-10), 127.1
(C-500), 127.3 (C-2000,6000), 128.0 (C-4000), 128.5 (C-3000,5000),
128.9 (C-100), 129.4 (C-60), 129.8 (C-300), 132.7 (C-600), 133.7
(C-40), 135.1 (C-200), 135.5 (C-400), 136.4 (C-1000), 139.2 (C-5),
H-50), 7.24 (d, J ¼ 8.3 Hz, H-600), 7.30–7.37 (m, OCH2C6H5),
7.44 (dd, J ¼ 8.3, 1.9 Hz, H-500), 7.52 (d, J ¼ 1.9Hz, H-300),
7.99 (d, J ¼ 8.9 Hz, H-60) ppm; 13C NMR: ꢂ ¼ 14.1 (CH3),
22.7 [N(CH2)10CH2CH3], 26.5, 29.0, 29.3, 29.4, 29.5, 29.6,
30.3, and 31.9 [NCH2(CH2)9CH2CH3], 49.8 [NCH2(CH2)10
CH3], 70.7 (OCH2), 108.7 (C-4), 113.3 (C-30), 121.3 (C-50),
121.4 (C-1000)0, 127.1 (C-500), 127.3 (C-2000,6000), 128.0 (C-4000),
128.5 (C-3 ,5000), 128.9 (C-100), 129.4 (C-60), 129.8 (C-300),
132.7 (C-600), 133.7 (C-40), 135.1 (C-200), 135.5 (C-400),
136.4 (C-1000), 139.2 (C-5), 146.3 (C-3), 156.2 (C-20) ppm;
37
þ
þ
MS (EI): m=z (%) ¼ 602 (M ꢃ, 3ꢄ Cl, 5), 600 (M ꢃ,
35Clþ 2ꢄ
35Cl þ 37Cl, 71), 596
37
0
þ
þ
146.3 (C-3), 156.2 (C-2 ) ppm; MS (EI): m=z (%) ¼ 574 (M ꢃ,
Cl, 32), 598 (M ꢃ, 2ꢄ
37
37
35Cl þ 2ꢄ
35Cl þ
35Cl, 70), 562 (7), 519 (12), 507 (12), 485 (4),
þ
þ
þ
Cl, 3), 572 (M ꢃ, 2ꢄ
Cl, 20), 570 (M ꢃ, (M ꢃ, 3ꢄ
3ꢄ35Cl, 47), 534 (5), 491 (10), 463 (4), 443 (28), 428 (23),
407 (6), 393 (4), 365 (6), 351 (15), 337 (10), 273 (2), 261 (4),
210 (2), 176 (2), 91 (100), 65 (9).
442 (13), 428 (12), 407 (6), 393 (5), 365 (3), 353 (21), 352
(10), 351 (23), 338 (14), 322 (11), 275 (3), 243 (4), 212 (3),
176 (4), 138 (3), 105 (3), 91 (100), 69 (8).
5-(2-Benzyloxy-4-chlorophenyl)-3-(2,4-dichlorophenyl)-1-
dodecylpyrazole (12b, C34H39N2OCl3)
5-(2-Benzyloxy-4-chlorophenyl)-3-(2,4-dichlorophenyl)-1-
decylpyrazole (12a, C32H35N2OCl3)
1H NMR: ꢂ ¼ 0.87 (t, J ¼ 6.8 Hz, CH3), 1.12–1.28 (m, N(CH2)2
(CH2)9CH3), 1.73 [quint, J ¼ 6.8 Hz, NCH2CH2(CH2)9CH3],
3.98 [t, J ¼ 7.4 Hz, NCH2(CH2)10CH3], 5.08 (s, OCH2), 6.77
(s, H-4), 7.07 (d, J ¼ 2.0 Hz, H-30), 7.05 (dd, J ¼ 7.8, 2.0 Hz,
H-50), 7.24–7.32 (m, OCH2C6H5 and H-500), 7.25 (d, J ¼
7.8 Hz, H-60), 7.45 (d, J ¼ 2.1 Hz, H-300), 7.84 (d, J ¼ 8.4 Hz,
H-600) ppm; 13C NMR: ꢂ ¼ 14.1 (CH3), 22.6 [N(CH2)10CH2
CH3], 26.4, 29.0, 29.3, 29.4, 29.5, 29.6, 30.3, and 31.9 [NCH2
(CH2)9CH2CH3], 50.1 [NCH2(CH2)10CH3], 70.6 (OCH2),
108.0 (C-4), 113.7 (C-30), 118.9 (C-10), 121.2 (C-50), 126.8
(C-2000,6000), 127.1 (C-500), 128.0 (C-4000), 128.6 (C-3000,5000),
129.9 (C-300), 131.16 (C-600), 131.22 (C-100), 132.4 (C-60),
132.6 (C-200), 133.4 (C-400), 135.8 and 135.9 (C-1000 and C-
1H NMR: ꢂ ¼ 0.87 (t, J ¼ 6.8 Hz, CH3), 1.12–1.28 [m,
N(CH2)2(CH2)7CH3], 1.73 [quint, J ¼ 6.6 Hz, NCH2CH2
(CH2)7CH3], 3.98 [t, J ¼ 7.3 Hz, NCH2(CH2)8CH3], 5.08 (s,
OCH2), 6.77 (s, H-4), 7.04 (d, J ¼ 1.9 Hz, H-30), 7.05 (dd,
J ¼ 8.2, 1.9 Hz, H-50), 7.24–7.34 (m, OCH2C6H5, H-500 and
H-60), 7.45 (d, J ¼ 2.1 Hz, H-300), 7.85 (d, J ¼ 8.2 Hz, H-600)
ppm; 13C NMR: ꢂ ¼ 14.1 (CH3), 22.6 [N(CH2)8CH2CH3],
26.4, 29.0, 29.2, 29.4, 29.5, 30.2, and 31.8 [NCH2(CH2)7
CH2CH3], 50.1 [NCH2(CH2)8CH3], 70.6 (OCH2), 108.0 (C-
4), 113.7 (C-30), 118.9 (C-10), 121.2 (C-50), 126.8 (C-2000,6000),
127.1 (C-500), 128.0 (C-4000), 128.6 (C-3000,5000), 129.9 (C-300),
131.16 (C-600), 131.22 (C-100), 132.4 (C-60), 132.6 (C-200),
133.4 (C-400), 135.8 and 135.9 (C-1000 and C-40), 139.3 (C-5),
40), 139.2 (C-5), 146.8 (C-3), 156.7 (C-20) ppm; MS (EI): m=z
0
þ
146.8 (C-3), 156.7 (C-2 ) ppm; MS (EI): m=z (%) ¼ 574 (M ꢃ,
37
35Clþ 2ꢄ37Cl, 32),
37
37
3ꢄ
35Cl þ 2ꢄ
þ
þ
þ
þ
(%) ¼ 602 (M ꢃ, 3ꢄ Cl, 5), 600 (M ꢃ,
Cl, 5), 572 (M ꢃ,
Cl, 31), 570 (M ꢃ,
37
35Cl þ
35Cl, 70), 562
2ꢄ35Clþ
35Cl, 65), 553 (2), 534
37
þ
þ
þ
598 (M ꢃ, 2ꢄ
Cl, 71), 596 (M ꢃ, 3ꢄ
Cl, 67), 568 (M ꢃ, 3ꢄ
(7), 555 (7), 519 (12), 507 (9), 485 (4), 443 (23), 428 (18),
407 (6), 393 (5), 365 (6), 351 (15), 337 (10), 322 (11), 317 (3),
275 (3), 261 (3), 243 (4), 210 (2), 174 (3), 138 (2), 91 (100),
69 (5).
(8), 491 (13), 479 (10), 443 (11), 393 (4), 351 (14), 337
(11), 275 (2), 243 (3), 180 (2), 105 (2), 91 (100), 69 (4).
General Method for the Synthesis of 11b–11d and 12b–12d
3-(2-Benzyloxy-4-chlorophenyl)-5-(2,4-dichlorophenyl)-1-
dodecylpyrazole 11b–11d and 5-(2-benzyloxy-4-chlorophe-
nyl)-3-(2,4-dichlorophenyl)-1-dodecylpyrazole 12b–12d were
prepared by a procedure similar to that of 11a and 12a, except
the amount of dodecyl bromide (2.2molar equiv) and reaction
time (48 h). Two compounds have also been isolated in each
case, the 3-(2-benzyloxy-4-chlorophenyl)-5-(2,4-dichloro-
phenyl)-1-dodecylpyrazole 11b–11d and the 5-(2-benzyl-
oxy-4-chlorophenyl)-3-(2,4-dichlorophenyl)-1-dodecylpyrazole
12b–12d, both obtained as oils (11b, 56.4mg, 27%; 12b,
81.4mg, 39%; 11c, 15.6 mg, 8%; 12c, 143.0 mg, 73%; 11d,
22.5mg, 11%; 12d, 155.0 mg, 76%).
3-(2-Benzyloxy-4,6-dichlorophenyl)-5-(2,4-dichlorophenyl)-
1-decylpyrazole (11c, C32H34N2OCl4)
1H NMR: ꢂ ¼ 0.87 (t, J ¼ 6.9 Hz, CH3), 1.14–1.34 [m, N(CH2)2
(CH2)7CH3], 1.74 [quint, J ¼ 6.3 Hz, NCH2CH2(CH2)7CH3],
3.98 [t, J ¼ 7.2 Hz, NCH2(CH2)8CH3], 5.04 (s, OCH2), 6.33
(s, H-4), 6.93 (d, J ¼ 1.9 Hz, H-30), 7.15 (d, J ¼ 1.9 Hz, H-50),
7.28–7.31 (m, OCH2C6H5), 7.33–7.35 (m, H-500), 7.55 (d,
J ¼ 1.3Hz, H-300), 7.69 (m, H-600).
5-(2-Benzyloxy-4,6-dichlorophenyl)-3-(2,4-dichlorophenyl)-
1-decylpyrazole (12c, C32H34N2OCl4)
1H NMR: ꢂ ¼ 0.87 (t, J ¼ 6.8 Hz, CH3), 1.12–1.25 [m, N(CH2)2
(CH2)7CH3], 1.73 [quint, J ¼ 6.6 Hz, NCH2CH2(CH2)7CH3],
3.89 [t, J ¼ 7.2 Hz, NCH2(CH2)8CH3], 5.07 (s, OCH2), 6.77 (s,
H-4), 6.98 (d, J ¼ 1.8 Hz, H-50), 7.18 (d, J ¼ 1.8 Hz, H-30),
7.26–7.52 (m, OCH2C6H5), 7.30 (dd, J ¼ 8.2, 2.0 Hz, H-500),
7.46 (d, J ¼ 2.0 Hz, H-300), 7.86 (d, J ¼ 8.2Hz, H-600) ppm;
13C NMR: ꢂ ¼ 14.1 (CH3), 22.7 [N(CH2)8CH2CH3], 26.3,
3-(2-Benzyloxy-4-chlorophenyl)-5-(2,4-dichlorophenyl)-1-
dodecylpyrazole (11b, C34H39N2OCl3)
1H NMR: ꢂ ¼ 0.87 (t, J ¼ 6.7 Hz, CH3), 1.17–1.29 [m, N(CH2)2
(CH2)9CH3], 1.76 [quint, J ¼ 6.5 Hz, NCH2CH2(CH2)9CH3],
3.95 [t, J ¼ 7.4 Hz, NCH2(CH2)10CH3], 5.14 (s, OCH2), 6.77
(s, H-4), 7.02 (d, J ¼ 1.9Hz, H-30), 7.03 (dd, J ¼ 8.9, 1.9 Hz,