Hydroxylamine → HCID 22625132, compound

HRID 635446Notes

Reaction equation

HRID 635446 reaction equation
NO.[CH:3]1([CH:6]=[O:7])[CH2:5][CH2:4]1.C([Zn][CH2:11][CH3:12])C.[C:13](OC(=O)C)(=[O:15])[CH3:14]>CCCCCC.CCOCC.C1(C)C=CC=CC=1>[C:13]([O:7][CH:6]([CH:3]1[CH2:5][CH2:4]1)[CH2:11][CH3:12])(=[O:15])[CH3:14]

Participants

8

Reactant 4

HCID 787HydroxylamineHCID 7918Acetic AnhydrideHCID 123114CyclopropanecarboxaldehydeHCID 178418750HCID 178418750, compound

Product 1

HCID 22625132HCID 22625132, compoundYield 54%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Procedure

To a vial containing aminoalcohol A (0.05 g, 0.21 mmol) prepared as in Example 13 was added a solution containing cyclopropanecarboxaldehyde (0.21 g, 3.0 mmol), toluene (3.0 mL), and 1 M diethylzinc in hexane (6.0 mL). After 3 days at room temperature, acetic anhydride (1.2 mL, 13 mmol) was added. After 2 additional days the mixture was diluted in ether (50 mL) and the reaction was quenched by dropwise addition of half-saturated aqueous ammonium chloride (50 mL). The ether layer was separated and the aqueous layer was further extracted with ether (2×50 mL). The combined ether layers were dried over magnesium sulfate whereupon the solvent was removed at reduced pressure. The residue was purified by flash chromatography on 220-400 mesh silica with 90% hexane and 10% ether as eluant. The product (+)-1-(cyclopropyl)propyl acetate (0.23 g, 54%) was isolated as a colorless liquid by distillation at reduced pressure. Anal. for C11H20O2. Calcd: C, 71.70; H, 10.94; found: C, 71.41; H, 10.69. 1H NMR (CDCl3/TMS): δ0.23 (m, 1 H), 0.36 (m, 1 H), 0.43 (m, 1 H), 0.52 (m, 1 H), 1.00-1.09 (m+t, 4 H total), 1.69 (m, 2 H), 2.05 (s, 3 H), 4.20 (m, 1 H); 13C NMR (CDCl3/TMS): δ2.66, 2.82, 9.57, 14.57, 21.03, 27.45, 79.62, 170.66. [α]D25=+26.2, c=1.04 g/100 mL chloroform. Chiral capillary gas chromatographic analysis at 55° C. on Cyclodex B stationary phase (J & W Scientific) indicated that the enantiomeric excess of the product was 96%.

Workup

  1. customA (0.05 g, 0.21 mmol) prepared as in Example 13
  2. additionwas added a solution
  3. customthe reaction was quenched by dropwise addition of half-saturated aqueous ammonium chloride (50 mL)
  4. customThe ether layer was separated
  5. extractionthe aqueous layer was further extracted with ether (2×50 mL)
  6. dry with materialThe combined ether layers were dried over magnesium sulfate whereupon the solvent
  7. customwas removed at reduced pressure
  8. customThe residue was purified by flash chromatography on 220-400 mesh silica with 90% hexane and 10% ether as eluant

Sources & evidence

ORD record
ord-294fb649e812492db26407532c1c6c73
Source dataset
uspto-grants-2001_02
Patent number
US06187918B1

Reaction notes

Loading…