Allyl Alcohol → HCID 178439549, compound

Reaction equation

Cl[C:2]1[N:7]2[N:8]=[C:9]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=3[Cl:24])[C:10]([C:11]3[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=3)=[C:6]2[N:5]=[CH:4][CH:3]=1.[H-].[Na+].[CH2:27](OCC=C)[CH:28]=[CH2:29].C([OH:37])C=C>>[CH2:29]([C:3]1[CH:4]=[N:5][C:6]2[N:7]([N:8]=[C:9]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=3[Cl:24])[C:10]=2[C:11]2[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][CH:12]=2)[C:2]=1[OH:37])[CH:28]=[CH2:27]

Participants

Reactant 4

HCID 7858Allyl Alcohol

HCID 11194Diallyl ether

HCID 24758Sodium hydride

HCID 21083723HCID 21083723, compound

Product 1

HCID 178439549HCID 178439549, compound

Procedure

To a suspension of 7-chloro-3-(4-chlorophenyl)-2-(2-chlorophenyl)-pyrazolo[1,5-a]pyrimidine (I-13A-1a; 1.72 g, 4.6 mmol) in allyl alcohol (50 ml) at 0° C. was added NaH (60% dispersion in oil, 0.28 g, 6.9 mmol), portionwise over 3 minutes. After warming to room temperature, the reaction was stirred overnight. The resultant allyl ether was then heated at 125° C. for 1.5 hours to facilitate the rearrangement. The reaction was concentrated, in vacuo, to give a residue which was partitioned between ethyl acetate and water adjusted to pH=4 with 1M aqueous HCl. The organic layer which contained dispersed solids was separated, washed with brine, and the solids then collected by vacuum filtration to give product I-15A-1a (1.24 g, 68%) as a solid: +ESI MS (M+1) 396.4; 1H NMR (400 MHz, CD3OD) δ 7.64 (s 1H), 7.52–7.48 (m, 1H), 7.43–7.48 (m, 3H), 7.30 (d, J=8.7 Hz, 2H), 7.15 (d, J=8.7 Hz, 2H), 6.06–5.92 (m, 1H), 5.21–5.14 (m, 1H), 5.12–5.07 (m, 1H).