Ozone → HCID 67513432, compound

HRID 1519553Notes

Reaction equation

HRID 1519553 reaction equation
[F:1][C:2]1[C:9]([CH2:10][CH:11]=C)=[CH:8][C:5]([C:6]#[N:7])=[C:4]([O:13][CH3:14])[CH:3]=1.[O:15]=[O+][O-].[BH4-].[Na+]>CO.CCOCC.O>[F:1][C:2]1[C:9]([CH2:10][CH2:11][OH:15])=[CH:8][C:5]([C:6]#[N:7])=[C:4]([O:13][CH3:14])[CH:3]=1

Participants

6

Reactant 3

HCID 24823OzoneHCID 4311764Sodium borohydrideHCID 675133654-Fluoro-2-methoxy-5-(2-propen-1-yl)benzonitrile

Product 1

HCID 67513432HCID 67513432, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 21584184Diethylether waterSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 4-fluoro-2-methoxy-5-(prop-2-en-1-yl)benzonitrile (1.2 g, 6.0 mmol) in methanol (50 mL) was cooled in a dry ice acetone bath and treated with ozone. Since the starting material was contaminated with some tributylstanane residue from the previous reaction, the reaction turned brown at first. The mixture was flushed with nitrogen and quenched with dimethylsulfide (4 mL). The solution was allow to warm to about 0° C. which resulted in a clear yellow solution and then sodium borohydride (0.27 g, 7.2 mmol) was added under nitrogen and the reaction was stirred for 30 minutes at room temperature. TLC of an aliquot in ether/water (30% ethyl acetate in hexanes) indicated a product band without evidence of starting material. After a total of 1 hour, the reaction was quenched with 18% aqueous citric acid and concentrated in vacuo to remove the methanol. The residue was partitioned between ethyl acetate and 18% citric acid, washed with brine, dried over sodium sulfate and evaporated. Purification of the residue with a Biotage 40+M column (10 to 60% ethyl acetate in hexanes) gave the title alcohol as a white solid. 1H-NMR (500 MHz, CDCl3) δ ppm 1.60 (br s, 1H), 2.842 (t, J=6.5 Hz, 2H), 3.853 (t, J=6.5 Hz, 2H), 3.904 (s, 3H), 6.682 (d, J=11.2 Hz, 1H), 7.487 (d, J=8.1 Hz, 1H).

Workup

  1. customSince the starting material was contaminated with some tributylstanane residue from the previous reaction
  2. customThe mixture was flushed with nitrogen
  3. customquenched with dimethylsulfide (4 mL)
  4. customresulted in a clear yellow solution
  5. customAfter a total of 1 hour, the reaction was quenched with 18% aqueous citric acid
  6. concentrationconcentrated in vacuo
  7. customto remove the methanol
  8. customThe residue was partitioned between ethyl acetate and 18% citric acid
  9. washwashed with brine
  10. dry with materialdried over sodium sulfate
  11. customevaporated
  12. customPurification of the residue with a Biotage 40+M column (10 to 60% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-0dc5b02b53ef40dba883864147e68d97
Source dataset
uspto-grants-2015_07
Patent number
US09073882B2

Reaction notes

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