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4H, J ¼ 6.2 Hz), 3.11 (dd, 1H, J1 ¼ 19.0 Hz, J2 ¼ 5.2 Hz, pyrazole crystals, yield, 70%; mp 186–188 ꢁC; 1H NMR (500 MHz, CDCl3)
4-Ha), 3.65 (d, 1H, J ¼ 16 Hz), 3.97 (dd, 1H, J1 ¼ 12.0 Hz, J2 ¼ d (ppm): 0.91 (t, 6H, J ¼ 7.5 Hz), 1.47 (t, 4H, J ¼ 7.5 Hz), 2.70 (q,
19.0 Hz, pyrazole 4-Hb), 4.08 (d, 1H, J ¼ 16.0 Hz), 5.73 (dd, 1H, 4H, J ¼ 6.3 Hz), 3.25 (dd, 1H, J1 ¼ 19.2 Hz, J2 ¼ 5.5 Hz, pyrazole
J1 ¼ 12.0 Hz, J2 ¼ 5.2 Hz, pyrazole 5-H), 6.98–7.34 (m, 5H, ArH 4-Ha), 3.79 (d, 1H, J ¼ 16 Hz), 3.87 (dd, 1H, J1 ¼ 12.0 Hz, J2 ¼ 19.2
and chromen H), 8.08 (d, 1H, chromen 7-H), 8.27 (s, 1H, chro- Hz, pyrazole 4-Hb), 4.12 (d, 1H, J ¼ 16.0 Hz), 5.81 (dd, 1H, J1 ¼
men 5-H), 8.44 (s, 1H, chromen C4–H). ESI-MS: 555.37 12.0 Hz, J2 ¼ 5.2 Hz, pyrazole 5-H), 7.07–7.35 (m, 8H, ArH and
(C26H27BrN4O5, [M + H]+); anal. calcd for C26H27BrN4O5: C, chromen H), 8.47 (s, 1H, chromen C4–H). ESI-MS: 500.04
56.22; H, 4.90; N, 10.09%. Found: C, 56.54; H, 5.28; N, 10.01%. (C27H28F3N3O3, [M + H]+); anal. calcd for C27H28F3N3O3: C,
4g. 3-(1-(2-(Dipropylamino)acetyl)-5-p-tolyl-4,5-dihydro-1H- 64.92; H, 5.65; N, 8.41%. Found: C, 64.63; H,5.46; N, 8.75%.
pyrazol-3-yl)-6-nitro-2H-chromen-2-one, colorless crystals, yield,
4l. 3-(1-(2-(Dipropylamino)acetyl)-5-(4-(triuoromethyl)-
1
62%; mp 181–182 ꢁC; H NMR (500 MHz, CDCl3) d (ppm): 0.92 phenyl)-4,5-dihydro-1H-pyrazol-3-yl)-6-methyl-2H-chromen-2-
(t, 6H, J ¼ 7.5 Hz), 1.51 (t, 4H, J ¼ 7.5 Hz), 2.27 (s, 3H, 6-Me), 2.55 one, colorless crystals, yield, 60%; mp 178–179 ꢁC; 1H NMR (500
(q, 4H, J ¼ 6.2 Hz), 3.15 (dd, 1H, J1 ¼ 19.0 Hz, J2 ¼ 5.0 Hz, MHz, CDCl3) d (ppm): 0.91 (t, 6H, J ¼ 7.5 Hz), 1.62 (t, 4H, J ¼ 7.5
pyrazole 4-Ha), 3.69 (d, 1H, J ¼ 16 Hz), 3.92 (dd, 1H, J1 ¼ 12.0 Hz, Hz), 2.45 (s, 3H, 6-Me), 2.67 (q, 4H, J ¼ 6.2 Hz), 3.07 (dd, 1H, J1 ¼
J2 ¼ 19.0 Hz, pyrazole 4-Hb), 4.01 (d, 1H, J ¼ 16.0 Hz), 5.77 (dd, 19.0 Hz, J2 ¼ 5.2 Hz, pyrazole 4-Ha), 3.65 (d, 1H, J ¼ 16 Hz), 4.04
1H, J1 ¼ 12.0 Hz, J2 ¼ 5.0 Hz, pyrazole 5-H), 7.01–7.26 (m, 5H, (dd, 1H, J1 ¼ 12.0 Hz, J2 ¼ 19.0 Hz, pyrazole 4-Hb), 4.17 (d, 1H,
ArH and chromen H), 8.04 (d, 1H, chromen 7-H), 8.21 (s, 1H, J ¼ 16.0 Hz), 5.65 (dd, 1H, J1 ¼ 12.0 Hz, J2 ¼ 5.2 Hz, pyrazole 5-
chromen 5-H), 8.41 (s, 1H, chromen C4–H). ESI-MS: 489.78 H), 6.92–7.49 (m, 7H, ArH and chromen H), 8.61 (s, 1H, chro-
(C27H30N4O5, [M + H]+); anal. calcd for C27H30N4O5: C, 66.11; H, men C4–H). ESI-MS: 513.84 (C28H30F3N3O3, [M + H]+); anal.
6.16; N, 11.42%. Found: C, 65.85; H, 6.00; N, 11.73%.
calcd for C28H30F3N3O3: C, 65.49; H, 5.89; N, 8.18%. Found: C,
4h. 3-(1-(2-(Dipropylamino)acetyl)-5-(2-(triuoromethyl)- 65.66; H, 6.00; N, 8.45%.
phenyl)-4,5-dihydro-1H-pyrazol-3-yl)-6-methyl-2H-chromen-2-
one, colorless crystals, yield, 62%; mp 181–182 ꢁC; 1H NMR (500
MHz, CDCl3) d (ppm): 0.98 (t, 6H, J ¼ 7.5 Hz), 1.55 (t, 4H, J ¼ 7.5
General synthetic procedure process for compound 10a–e
Hz), 2.42 (s, 3H, 6-Me), 2.63 (q, 4H, J ¼ 6.2 Hz), 3.11 (dd, 1H, J1 ¼ To a chloroform (20 mL) solution of 3-(1-(2-bromoacetyl)-3-
19.0 Hz, J2 ¼ 5.2 Hz, pyrazole 4-Ha), 3.73 (d, 1H, J ¼ 16 Hz), 3.99 phenyl-4,5-dihydro-1H-pyrazol-5-yl)-4-chloro-2H-chromen-2-one
(dd, 1H, J1 ¼ 12.0 Hz, J2 ¼ 19.0 Hz, pyrazole 4-Hb), 4.12 (d, 1H, 9 (10 mmol) was added dipropylamine (12 mmol), DMAP
J ¼ 16.0 Hz), 5.66 (dd, 1H, J1 ¼ 12.0 Hz, J2 ¼ 5.2 Hz, pyrazole 5- (12 mmol) and catalytic KI, the reaction mixture was allowed to
H), 6.87–7.49 (m, 7H, ArH and chromen H), 8.45 (s, 1H, chro- stand at 40–50 ꢁC for 5 h. The mixture was cooled, washed with
men C4–H). ESI-MS: 513.21 (C28H30F3N3O3, [M + H]+); anal. water. The product was collected by ltration and the crude
calcd for C28H30F3N3O3: C, 65.49; H, 5.89; N, 8.18%. Found: C, residue was puried by chromatography on SiO2 (dichloro-
65.25; H, 6.14; N, 8.03%.
methane–methanol, v:v¼ 68 : 1) to give title compounds 10a–e
4i. 3-(1-(2-(Dipropylamino)acetyl)-5-(4-uorophenyl)-4,5- (Scheme 2) as colorless solids.
dihydro-1H-pyrazol-3-yl)-6-methyl-2H-chromen-2-one, colorless
10a. 4-Chloro-3-(1-(2-(dipropylamino)acetyl)-3-(4-(triuoro-
crystals, yield, 71%; mp 185–186 ꢁC; 1H NMR (500 MHz, CDCl3) methyl)phenyl)-4,5-dihydro-1H-pyrazol-5-yl)-2H-chromen-2-one,
d (ppm): 0.91 (t, 6H, J ¼ 7.5 Hz), 1.48 (t, 4H, J ¼ 7.5 Hz), 2.48 (s, colorless crystals, yield, 65%; mp 195–197 ꢁC; 1H NMR (500
3H, 6-Me), 2.74 (q, 4H, J ¼ 6.2 Hz), 3.15 (dd, 1H, J1 ¼ 19.0 Hz, MHz, CDCl3) d (ppm): 0.91 (t, 6H, J ¼ 7.5 Hz), 1.46 (t, 4H, J ¼ 7.5
J2 ¼ 5.0 Hz, pyrazole 4-Ha), 3.77 (d, 1H, J ¼ 16 Hz), 3.91 (dd, 1H, Hz), 2.65 (q, 4H, J ¼ 6.3 Hz), 3.14 (dd, 1H, J1 ¼ 19.0 Hz, J2 ¼ 5.0
J1 ¼ 12.0 Hz, J2 ¼ 19.0 Hz, pyrazole 4-Hb), 4.16 (d, 1H, J ¼ 16.0 Hz, pyrazole 4-Ha), 3.56 (d, 1H, J ¼ 16 Hz), 3.71 (dd, 1H, J1 ¼ 12.0
Hz), 5.78 (dd, 1H, J1 ¼ 12.0 Hz, J2 ¼ 5.0 Hz, pyrazole 5-H), 6.95– Hz, J2 ¼ 19.0 Hz, pyrazole 4-Hb), 3.87 (d, 1H, J ¼ 16.0 Hz), 5.70
7.18 (m, 7H, ArH and chromen H), 8.43 (s, 1H, chromen C4–H). (dd, 1H, J1 ¼ 12.0 Hz, J2 ¼ 5.0 Hz, pyrazole 5-H), 6.97–7.72 (m,
ESI-MS: 463.01 (C27H30FN3O3, [M + H]+); anal. calcd for 8H, ArH and chromen H). Anal. calcd for C27H27ClF3N3O3: C,
C
27H30FN3O3: C, 69.96; H, 6.52; N, 9.06%. Found: C, 70.13; H, 60.73; H, 5.10; N, 7.87%. Found: C, 61.00; H, 4.83; N, 8.14%.
6.65; N, 8.89%.
10b. 4-Chloro-3-(1-(2-(dipropylamino)acetyl)-3-p-tolyl-4,5-
4j. 3-(5-(4-Bromophenyl)-1-(2-(dipropylamino)acetyl)-4,5-dihy- dihydro-1H-pyrazol-5-yl)-2H-chromen-2-one, colorless crystals,
dro-1H-pyrazol-3-yl)-6-methyl-2H-chromen-2-one, colorless crys- yield, 61%; mp 190–191 ꢁC; 1H NMR (500 MHz, CDCl3) d (ppm):
1
tals, yield, 62%; mp 175–177 ꢁC; H NMR (500 MHz, CDCl3) d 0.89 (t, 6H, J ¼ 7.5 Hz), 1.55 (t, 4H, J ¼ 7.5 Hz), 2.29 (s, 3H, –CH3),
(ppm): 0.98 (t, 6H, J ¼ 7.5 Hz), 1.44 (t, 4H, J ¼ 7.5 Hz), 2.39 (s, 3H, 2.69 (q, 4H, J ¼ 6.3 Hz), 3.11 (dd, 1H, J1 ¼ 18.5 Hz, J2 ¼ 5.0 Hz,
6-Me), 2.77 (q, 4H, J ¼ 6.2 Hz), 3.11 (dd, 1H, J1 ¼ 19.0 Hz, J2 ¼ 5.2 pyrazole 4-Ha), 3.51 (d, 1H, J ¼ 16 Hz), 3.67 (dd, 1H, J1 ¼ 12.0 Hz,
Hz, pyrazole 4-Ha), 3.68 (d, 1H, J ¼ 16 Hz), 3.94 (dd, 1H, J1 ¼ 12.0 J2 ¼ 19.0 Hz, pyrazole 4-Hb), 3.97 (d, 1H, J ¼ 16.0 Hz), 5.64 (dd,
Hz, J2 ¼ 19.0 Hz, pyrazole 4-Hb), 4.11 (d, 1H, J ¼ 16.0 Hz), 5.65 (dd, 1H, J1 ¼ 12.0 Hz, J2 ¼ 5.0 Hz, pyrazole 5-H), 7.06–7.41 (m, 8H,
1H, J1 ¼ 12.0 Hz, J2 ¼ 5.2 Hz, pyrazole 5-H), 6.88–7.51 (m, 7H, ArH ArH and chromen H). Anal. calcd for C27H30ClN3O3: C, 67.56; H,
and chromen H), 8.43 (s, 1H, chromen C4–H). ESI-MS: 525.04 6.30; N, 8.75%. Found: C, 67.85; H, 5.95; N, 9.01%.
(C27H30BrN3O3, [M + H]+); anal. calcd for C27H30BrN3O3: C, 61.83;
H, 5.77; N, 8.01%. Found: C, 62.05; H, 6.02; N, 7.72%.
10c. 3-(3-(2-Bromophenyl)-1-(2-(dipropylamino)acetyl)-4,5-
dihydro-1H-pyrazol-5-yl)-4-chloro-2H-chromen-2-one, colorless
4k. 3-(1-(2-(Dipropylamino)acetyl)-5-(3-(triuoromethyl)phenyl)- crystals, yield, 57%; mp 182–183 ꢁC; 1H NMR (500 MHz, CDCl3)
4,5-dihydro-1H-pyrazol-3-yl)-2H-chromen-2-one, colorless d (ppm): 0.85 (t, 6H, J ¼ 7.5 Hz), 1.49 (t, 4H, J ¼ 7.5 Hz), 2.72 (q,
5614 | RSC Adv., 2014, 4, 5607–5617
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