2-Cyanobenzaldehyde → HCID 67044515, compound

HRID 2367101Notes

Reaction equation

HRID 2367101 reaction equation
I[C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[N:7]([Si:11]([CH:18]([CH3:20])[CH3:19])([CH:15]([CH3:17])[CH3:16])[CH:12]([CH3:14])[CH3:13])[N:6]=[CH:5]2.C([Li])CCC.[C:26]([C:28]1[CH:35]=[CH:34][CH:33]=[CH:32][C:29]=1[CH:30]=[O:31])#[N:27]>O1CCCC1>[OH:31][CH:30]([C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[N:7]([Si:11]([CH:12]([CH3:14])[CH3:13])([CH:18]([CH3:20])[CH3:19])[CH:15]([CH3:16])[CH3:17])[N:6]=[CH:5]2)[C:29]1[CH:32]=[CH:33][CH:34]=[CH:35][C:28]=1[C:26]#[N:27]

Participants

5

Reactant 3

HCID 1012092-CyanobenzaldehydeHCID 67044267HCID 67044267, compoundHCID 178418339Butyllithium

Product 1

HCID 67044515HCID 67044515, compoundYield 9.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 5-iodo-1-[tris(1-methylethyl)silyl]-1H-indazole (1.8 g, 4.6 mmol) in tetrahydrofuran (9.2 mL) was cooled to −78° C., and n-butyllithium was added (1.6M in hexanes, 3.4 mL, 5.5 mmol). After 15 min., 2-cyanobenzaldehyde (0.78 g, 6.0 mmol) in 2.0 mL tetrahydrofuran was added quickly and the solution was allowed to warm to room temperature. The reaction mixture was quenched with an excess of saturated aqueous ammonium chloride solution, then partitioned between water and ethyl acetate. The layers were separated and the aqueous layer was extracted (2×100 mL ethyl acetate). The combined organic layers were dried (sodium sulfate), filtered and concentrated in vacuo. Column chromatography (silica gel, 3:1 hexanes/ethyl acetate) gave 0.17 g (9%) of 2-(hydroxy{1-[tris(1-methylethyl)silyl]-1H-indazol-5-yl}methyl)benzonitrile. 1H NMR (400 MHz, CDCl3): 8.20 (s, 1H), 7.95 (m, 1H), 7.69 (s, 1H), 7.51 (m, 3H), 7.23 (m, 1H), 7.09 (m, 1H), 6.50 (s, 1H), 1.77 (m, 3H), 1.06 (m, 18H); MS (EI) for C24H31N3OSi: 250 (M−SiiPr3).

Workup

  1. customThe reaction mixture was quenched with an excess of saturated aqueous ammonium chloride solution
  2. custompartitioned between water and ethyl acetate
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted (2×100 mL ethyl acetate)
  5. dry with materialThe combined organic layers were dried (sodium sulfate)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-b9b933dd1fa54150b93253d2219a6e8f
Source dataset
uspto-grants-2014_04
Patent number
US08697737B2

Reaction notes

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