2-Methylcinnamic aldehyde → HCID 53837773, compound

HRID 1906397Notes

Reaction equation

HRID 1906397 reaction equation
C1(C)C=CC(S(O)(=O)=O)=CC=1.[CH2:12]([O:19][C:20]([CH2:22][CH2:23][CH2:24][CH2:25][NH2:26])=[O:21])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[OH-].[Na+].[CH3:29][C:30](=[CH:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[CH:31]=O.[BH4-].[Na+]>C(OCC)(=O)C.O.ClCCl>[CH2:12]([O:19][C:20]([CH2:22][CH2:23][CH2:24][CH2:25][NH:26][CH2:29][C:30]([CH3:31])=[CH:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)=[O:21])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

7

Reactant 4

HCID 75572-Methylcinnamic aldehydeHCID 14798Sodium HydroxideHCID 4311764Sodium borohydrideHCID 567770174-Methylbenzene-1-sulfonic acid--benzyl 5-aminopentanoate (1/1)

Product 1

HCID 53837773HCID 53837773, compoundYield 15%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 22728543Water ethylacetateSolvent

Procedure

13.7 g (36 mM) of 4-(benzyloxycarbonyl)butylamine para toluene sulphonate salt was stirred vigorously in ethyl acetate-water whilst being treated with aqueous sodium hydroxide to pH 9.5. The organic phase was washed with saturated brine, dried (anhydrous magnesium sulphate), benzyl alcohol (100 cm3) added, and the ethyl acetate evaporated. The solution was treated with one equivalent of α-methylcinnamaldehyde and stirred for 1/2 hour. Dichloromethane (50 cm3) was added and the reaction mixture treated with excess sodium borohydride. The mixture was filtered and the filtrate diluted with dichloromethane (100 cm3), washed with saturated brine (4×150 cm3) and dried (anhydrous magnesium sulphate). The dichloromethane was removed by evaporation under reduced pressure and the residue diluted with diethyl ether (300 cm3). This solution was treated with excess para toluene sulphonic acid in ether. The resultant crystals were filtered off, washed with ether and dried to yield 2.7 g (15%) of the title compound as a para-toluene sulphonate salt. This salt was extracted into ethyl acetate with aqueous sodium hydroxide (pH 9-10). The organic phase was washed with saturated brine, dried (anhydrous magnesium sulphate) and evaporated to an oil, yield=1.85 g (15%), (film) 3330, 1735, 1450, 1155, 750, 700 cm-1 ; (CDCl3) 1.35-2.00 (5H, m), 1.85 (3H, d, J 1 Hz), 2.37 and 2.62 (4H, 2 x t, J 6.5 Hz), 3.27 (2H, s), 5.10 (2H, s), 6.42 (1H, broad s), 7.26 and 7.34 (10H, 2×s).

Workup

  1. washThe organic phase was washed with saturated brine
  2. dry with materialdried (anhydrous magnesium sulphate), benzyl alcohol (100 cm3)
  3. additionadded
  4. customthe ethyl acetate evaporated
  5. filtrationThe mixture was filtered
  6. additionthe filtrate diluted with dichloromethane (100 cm3)
  7. washwashed with saturated brine (4×150 cm3)
  8. dry with materialdried (anhydrous magnesium sulphate)
  9. customThe dichloromethane was removed by evaporation under reduced pressure
  10. additionthe residue diluted with diethyl ether (300 cm3)
  11. additionThis solution was treated with excess para toluene sulphonic acid in ether
  12. filtrationThe resultant crystals were filtered off
  13. washwashed with ether
  14. customdried

Sources & evidence

ORD record
ord-544d433151394831aa8ca7d140b6bfef
Source dataset
uspto-grants-1987_03
Patent number
US04652560

Reaction notes

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