Acetaldehyde → HCID 68727908, compound

HRID 1941775Notes

Reaction equation

HRID 1941775 reaction equation
[O:1]([C:8]1[CH:9]=[C:10]([CH:12]=[CH:13][CH:14]=1)[NH2:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:15]([O:19][C:20]([N:22]1[CH2:28][CH2:27][CH2:26][C@@H:23]1[CH:24]=O)=[O:21])([CH3:18])([CH3:17])[CH3:16].[C:29](O[BH-](OC(=O)C)OC(=O)C)(=O)[CH3:30].[Na+].C(=O)C.C([BH3-])#N.[Na+].C([O-])(=O)C.[NH4+]>ClCCCl.CO.[Cl-].[Zn+2].[Cl-].O>[C:15]([O:19][C:20]([N:22]1[CH2:28][CH2:27][CH2:26][C@@H:23]1[CH2:24][N:11]([CH2:29][CH3:30])[C:10]1[CH:12]=[CH:13][CH:14]=[C:8]([O:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[CH:9]=1)=[O:21])([CH3:18])([CH3:17])[CH3:16]

Participants

11

Reactant 6

HCID 177AcetaldehydeHCID 771353-PhenoxyanilineHCID 517165Ammonium AcetateHCID 5003444Sodium cyanoborohydrideHCID 5049666Sodium triacetoxyborohydrideHCID 7009153N-(tert-Butoxycarbonyl)-D-prolinal

Product 1

HCID 68727908HCID 68727908, compoundYield 67%

Reagents, catalysts & solvents 4

HCID 3007855ZincchlorideCatalystHCID 111,2-DichloroethaneSolventHCID 887MethanolSolventHCID 962WaterSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of 3-phenoxyaniline (0.3 g, 1.62 mmol) in 1,2-dichloroethane (4 ml) were added N-(tert-butoxycarbonyl)-D-prolinal (0.322 g, 1.62 mmol) and sodium triacetoxyborohydride (0.480 g, 2.26 mmol). The resulting suspension was stirred overnight at 50° C. The mixture was then cooled to room temperature, water (8 ml) was added and extracted with ethyl acetate (3×20 ml). The combined organic layers were dried with magnesium sulphate, filtered and concentrated in vacuo. The residue was purified by flash chromatography (SiO2: heptane/ethyl acetate=70:30) to yield a light yellow oil that was dissolved in methanol (8 ml). Acetaldehyde (0.134 g, 3.05 mmol), zinc chloride (0.333 g, 2.44 mmol) and sodium cyanoborohydride (0.115 g, 1.83 mmol) were added and the mixture was stirred overnight at 40° C. Saturated ammonium acetate solution (10 ml) was added and extracted with ethyl acetate (3×30 ml). The combined organic layers were dried with magnesium sulphate, filtered and concentrated in vacuo. The residue was purified by flash chromatography (SiO2: heptane/ethyl acetate=70:30) to yield 0.43 g (67%) of a colourless oil; MS (ISP): 397.0 ((M+H)+.).

Workup

  1. temperatureThe mixture was then cooled to room temperature
  2. extractionextracted with ethyl acetate (3×20 ml)
  3. dry with materialThe combined organic layers were dried with magnesium sulphate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by flash chromatography (SiO2: heptane/ethyl acetate=70:30)
  7. customto yield a light yellow oil that
  8. stirringthe mixture was stirred overnight at 40° C
  9. extractionextracted with ethyl acetate (3×30 ml)
  10. dry with materialThe combined organic layers were dried with magnesium sulphate
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo
  13. customThe residue was purified by flash chromatography (SiO2: heptane/ethyl acetate=70:30)

Sources & evidence

ORD record
ord-88c46309a97941c9865ee650751cb61a
Source dataset
uspto-grants-2013_03
Patent number
US08389507B2

Reaction notes

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