Dimethyl Sulfoxide → HCID 22507594, compound

HRID 985643Notes

Reaction equation

HRID 985643 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[C:11]([O:15][C:16](=[O:30])[N:17]([CH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[CH2:18][CH2:19][CH2:20][CH2:21][OH:22])([CH3:14])([CH3:13])[CH3:12]>ClCCl>[CH2:23]([N:17]([C:16]([O:15][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:30])[CH2:18][CH2:19][CH2:20][CH:21]=[O:22])[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1

Participants

5

Reactant 3

HCID 679Dimethyl Sulfoxide2×HCID 65578Oxalyl chlorideHCID 22006367tert-Butyl benzyl(4-hydroxybutyl)carbamate

Product 1

HCID 22507594HCID 22507594, compoundYield 63.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent4×

Conditions

Temperature
-78 °C

Procedure

A commercially available 2 M solution of oxalyl chloride in DCM solution (13.8 mL of 27.6 mmol), obtained from Aldrich Chemical Co., was diluted with anhydrous dichloromethane (50 mL). The solution was cooled to −78° C., and a solution of dimethyl sulfoxide “DMSO” (4.45 ml 62 mmol) in DCM (10 ml) was added over a 45 min period. After the addition was completed a solution of benzyl-(4-hydroxy-butyl)-carbamic acid tert butyl ester (6.9 g, 25 mmol) in DCM (20 mL) was added was added over a 30 min period resulting in a thick white suspension. The reaction mixture was stirred for an additional 15 min followed by the addition of triethylamine TEA (24 mL) over a 30 min period. The cooling bath was removed and stirring was continued for 1 h. The reaction mixture was quenched with water (200 mL) and the layers were separated. The aqueous layer was extracted with ethyl acetate (3×100 mL). The organic layer was washed with water, brine, and dried over Na2SO4. The crude yellow oil was purified by chromatography using a 8:2 ethyl acetate-hexane mixture as eluent to afford N-benzyl-N-(t-butoxycarbonyl)-4-amino-1-butanal (4.41 g, 63%) as a colorless, viscous oil. 1H NMR δ 9.74 (s, 1H); 7.24-7.36 (m, 5H); 4.41 (bs, 2H); 3.18 (bs, 2H); 2.42 (bs, 2H); 1.66 (bs, 2H); 1.50 (bs, 9H). ELSD/MS: m/z 278 [M+H]+.

Workup

  1. additionAfter the addition
  2. additionwas added
  3. additionwas added over a 30 min period
  4. customresulting in a thick white suspension
  5. customThe cooling bath was removed
  6. stirringstirring
  7. waitwas continued for 1 h
  8. customThe reaction mixture was quenched with water (200 mL)
  9. customthe layers were separated
  10. extractionThe aqueous layer was extracted with ethyl acetate (3×100 mL)
  11. washThe organic layer was washed with water, brine
  12. dry with materialdried over Na2SO4
  13. customThe crude yellow oil was purified by chromatography

Sources & evidence

ORD record
ord-96ca760dd6824c448cf4ba7fe759d3f7
Source dataset
uspto-grants-2005_03
Patent number
US06872827B2

Reaction notes

Loading…