Hexane → 2-Chloropyrazolo[1,5-a]pyridine-3-carbonitrile

HRID 530022Notes

Reaction equation

HRID 530022 reaction equation
[Cl:1][C:2]1[C:10](I)=[C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][N:4]2[N:3]=1.C([Li])CCC.CCCCCC.C1(C)C=CC(S([C:32]#[N:33])(=O)=O)=CC=1>O1CCCC1>[Cl:1][C:2]1[C:10]([C:32]#[N:33])=[C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][N:4]2[N:3]=1

Participants

6

Reactant 4

HCID 8058HexaneHCID 87946p-Toluenesulphonyl cyanideHCID 717433402-Chloro-3-iodopyrazolo[1,5-A]pyridineHCID 178418339Butyllithium

Product 1

HCID 894717052-Chloropyrazolo[1,5-a]pyridine-3-carbonitrile

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a cooled −78° C. solution of the title compound from Example 1 Step A (0.20 g, 0.718 mmol) in tetrahydrofuran (3.59 ml) was added a solution of n-butyllithium in hexane (1.6 M, 0.494 ml, 0.790 mmol). After 5 minutes, p-toluenesulfonyl cyanide (0.169 g, 0.934 mmol) was added, and the resulting reaction mixture was allowed to warm to room temperature. After 18 hours, the mixture was concentrated under reduced pressure. Purification by column chromatography on silica gel (0-30% ethyl acetate in hexanes) provided the title compound: LCMS m/z 177.91 [M+H]+, 179.86 [M+2+H]+; 1H NMR (500 MHz, CDCl3) δ 8.47 (d, J=6.9 Hz, 1 H), 7.70 (d, J=9.0 Hz, 1 H), 7.52 (dd, J=8.0, 8.0 Hz, 1 H), 7.26-7.20 (m, 1 H).

Workup

  1. customthe resulting reaction mixture
  2. waitAfter 18 hours
  3. concentrationthe mixture was concentrated under reduced pressure
  4. customPurification by column chromatography on silica gel (0-30% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-87f22f4c6c224983bda9c8ab3c9befe9
Source dataset
uspto-grants-2016_05
Patent number
US09351973B2

Reaction notes

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