Cesium carbonate → HCID 69199557、化合物
反応式
[CH2:1]([O:3][C:4]([CH:6]([O:8][C:9](=[O:31])[C@H:10]([C:24]1[CH:25]=[C:26]([CH3:30])[CH:27]=[CH:28][CH:29]=1)[CH2:11][C:12]#[C:13][C:14]([C:16]1[CH:21]=[CH:20][C:19]([Cl:22])=[C:18]([Cl:23])[CH:17]=1)=O)[CH3:7])=[O:5])[CH3:2].C([O-])([O-])=O.[Cs+].[Cs+].Cl.[CH3:39][O:40][C:41]1[CH:46]=[CH:45][C:44]([NH:47][NH2:48])=[CH:43][CH:42]=1>C1COCC1>[CH2:1]([O:3][C:4]([CH:6]([O:8][C:9](=[O:31])[C@H:10]([C:24]1[CH:25]=[C:26]([CH3:30])[CH:27]=[CH:28][CH:29]=1)[CH2:11][C:12]1[CH:13]=[C:14]([C:16]2[CH:21]=[CH:20][C:19]([Cl:22])=[C:18]([Cl:23])[CH:17]=2)[N:47]([C:44]2[CH:45]=[CH:46][C:41]([O:40][CH3:39])=[CH:42][CH:43]=2)[N:48]=1)[CH3:7])=[O:5])[CH3:2]参加物
5
実験手順
To a stirred solution of (S)-6-(3,4-dichloro-phenyl)-6-oxo-2-m-tolyl-hex-4-ynoic acid 1-ethoxycarbonyl-ethyl ester from Example 502 (15.5 g, 0.0336 mol) in THF (150 mL) was added Cs2CO3 (8.8 g, 0.027 mol) followed by 4-methoxyphenyl hydrazine HCl (6.5 g, 0.037 mol). The resulting slurry was stirred at rt overnight and then slowly quenched with 1 N HCl until pH 2-3. The mixture was transferred to a separatory funnel and extracted with EtOAc (3×75 mL). The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated to an oil. The crude oil was purified by pad filtration on silica gel using EtOAc/hexanes to obtain the pyrazole as mixture of two regioisomers in 4:1 ratio (18.6 g, 95%). Chiral HPLC (Method S): Rt (R,S)=5.6 min; (S,S)=6.3 min. 1H NMR (400 MHz, CDCl3): 7.31-7.07 (m, 8H), 6.91-6.86 (m, 3H), 6.23 (s, 1H), 5.13 (dd, J=10.4, 7.0 Hz, 1H), 4.16 (m, 1H), 4.07 (dd, J=14.4, 7.2 Hz, 2H), 3.82 (s, 3H), 3.51 (dd, J=14.9, 9.6 1H), 3.04 (dd, J=14.9, 6.3 Hz, 1H), 2.37 (s, 3H), 1.42 (d, J=7.0 Hz, 3H), 1.12 (t, J=7.3 Hz, 3H).