2-(Methyldithio)isobutyraldehyde → HCID 86671286, compound

HRID 58012Notes

Reaction equation

HRID 58012 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([CH2:10][OH:11])[CH:5]=[C:6]([CH2:8][OH:9])[CH:7]=1.[CH3:12][S:13][S:14][C:15]([CH3:19])([CH3:18])[CH:16]=O.[BH4-].[Na+]>C(O)C>[CH3:16][C:15]([S:14][S:13][CH3:12])([CH3:19])[CH2:18][NH:1][C:2]1[CH:3]=[C:4]([CH2:10][OH:11])[CH:5]=[C:6]([CH2:8][OH:9])[CH:7]=1

Participants

5

Reactant 3

HCID 1062172-(Methyldithio)isobutyraldehydeHCID 4311764Sodium borohydrideHCID 13401257HCID 13401257, compound

Product 1

HCID 86671286HCID 86671286, compoundYield 65%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
0 °C

Procedure

(5-amino-1,3-phenylene)dimethanol (2.5 g, 16.32 mmol) and 2-(methyldithio)isobutyraldehyde (2.347 ml, 16.32 mmol) were stirred at ambient temperature in absolute ethanol (82 ml) until completely dissolved (3 hours). The mixture was cooled to 0° C. in an ice bath and sodium borohydride (0.741 g, 19.59 mmol) was added. The reaction was stirred for 1 hour at 0° C., and was then quenched slowly with cold 5% HCl solution. The mixture was diluted with dichloromethane and the pH was adjusted to pH=8 with saturated sodium bicarbonate solution then extracted with dichloromethane and then washed with brine. The organic extracts were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. Purification by silica gel chromatography (MeOH/DCM) yielded (5-(2-methyl-2-(methyldisulfanyl)propylamino)-1,3-phenylene)dimethanol (3g, 65%) as a white solid. 1H NMR (400 Hz, CDCl3): δ6.62 (s, 1H), 6.54 (s, 2H), 4.53 (s, 4H), 3.13 (s, 2H), 2.30 (s, 3H), 1.32 (s, 6H). See FIG. 47.

Workup

  1. dissolutionuntil completely dissolved (3 hours)
  2. customwas then quenched slowly with cold 5% HCl solution
  3. additionThe mixture was diluted with dichloromethane
  4. extractionthen extracted with dichloromethane
  5. washwashed with brine
  6. dry with materialThe organic extracts were dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customPurification by silica gel chromatography (MeOH/DCM)

Sources & evidence

ORD record
ord-f709423753a444f3bd1dde25f5a7ed8f
Source dataset
uspto-grants-2016_09
Patent number
US09434748B2

Reaction notes

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