Hydroxylamine → HCID 22625130, compound

HRID 279404Notes

Reaction equation

HRID 279404 reaction equation
NO.C([Zn][CH2:6][CH3:7])C.[S:8]1[CH:12]=[CH:11][C:10]([CH:13]=[O:14])=[CH:9]1.[C:15](OC(=O)C)(=[O:17])[CH3:16]>CCCCCC.C1(C)C=CC=CC=1.CCOCC>[C:15]([O:14][CH:13]([C:10]1[CH:11]=[CH:12][S:8][CH:9]=1)[CH2:6][CH3:7])(=[O:17])[CH3:16]

Participants

8

Reactant 4

HCID 787HydroxylamineHCID 7918Acetic AnhydrideHCID 681353-ThiophenecarboxaldehydeHCID 178418750HCID 178418750, compound

Product 1

HCID 22625130HCID 22625130, compoundYield 81%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Procedure

To a roundbottom flask containing aminoalcohol 1 (0.05 g, 0.17 mmol) prepared as in Example 1 and 1 M diethylzinc in hexane (6.0 mL) was added dropwise a solution of 3-thiophenecarboxaldehyde (0.32 g, 3.0 mmol) in toluene (3.0 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% ethyl acetate as eluant. The product (+)-1-(3-thienyl)propyl acetate (0.45 g, 81%) was isolated as a colorless liquid by distillation at reduced pressure. Anal. for C9H12O2S. Calcd: C, 58.67; H, 6.56; found: C, 58.80; H, 6.75. 1H NMR (CDCl3/TMS): δ 1.86 (t, 3 H, J=7), 1.80-1.88 (m, 1 H), 1.88-1.97 (m, 1 H), 2.04 (s, 3 H), 5.81 (t, 1 H, J=7), 7.05 (m 1 H), 7.20 (m, 1 H), 7.26 (m, 1 H). 13C NMR (CDCl3/TMS): δ 9.85, 21.22, 28.58, 73.10, 122.34, 125.87, 126.04, 141.46, 170.39. [α]D25=+131.7, c=2.06 g/100 mL chloroform. Chiral capillary gas chromatographic analysis at 120° C. on Cyclodex B stationary phase (J & W Scientific) indicated that the enantiomeric excess of the product was 96%.

Workup

  1. additionTo a roundbottom flask containing
  2. customthe reaction was quenched by dropwise addition of half-saturated aqueous ammonium chloride (50 mL)
  3. customThe ether layer was separated
  4. extractionthe aqueous layer was further extracted with ether (2×50 mL)
  5. dry with materialThe combined ether layers were dried over magnesium sulfate whereupon the solvent
  6. customwas removed at reduced pressure
  7. customThe residue was purified by flash chromatography on 220-400 mesh silica with 90% hexane and 10% ethyl acetate as eluant

Sources & evidence

ORD record
ord-ce9c6d7cf71b4bad8a1515033dcb3fb8
Source dataset
uspto-grants-2002_03
Patent number
US06362344B1

Reaction notes

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