Allyl Alcohol → HCID 178439549, compound

HRID 348025Notes

Reaction equation

HRID 348025 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

5

Reactant 4

HCID 7858Allyl AlcoholHCID 11194Diallyl etherHCID 24758Sodium hydrideHCID 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).

Workup

  1. concentrationThe reaction was concentrated, in vacuo
  2. customto give a residue which
  3. customwas partitioned between ethyl acetate and water
  4. additionThe organic layer which contained dispersed solids
  5. customwas separated
  6. washwashed with brine
  7. filtrationthe solids then collected by vacuum filtration
  8. customto give product I-15A-1a (1.24 g, 68%) as a solid

Sources & evidence

ORD record
ord-b5e6ca2846ba40aa860816d431cfb8ea
Source dataset
uspto-grants-2007_02
Patent number
US07176210B2

Reaction notes

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