Sodium Hydroxide → HCID 15858319, compound

HRID 342103Notes

Reaction equation

HRID 342103 reaction equation
[O:1]1[C:5]2[CH:6]=[CH:7][CH:8]=[C:9]([C@@H:10]3[CH2:12][C@H:11]3[CH:13]=O)[C:4]=2[CH2:3][CH2:2]1.Cl.[NH2:16]O.[OH-].[Na+].C(O)C.O>C1COCC1>[O:1]1[C:5]2[CH:6]=[CH:7][CH:8]=[C:9]([C@@H:10]3[CH2:12][C@H:11]3[CH2:13][NH2:16])[C:4]=2[CH2:3][CH2:2]1

Participants

6

Reactant 4

HCID 14798Sodium HydroxideHCID 443297Hydroxyamine hydrochlorideHCID 19096565Water ethanolHCID 22941134HCID 22941134, compound

Product 1

HCID 15858319HCID 15858319, compoundYield 70.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A mixture of (-)-(trans)-2-(2,3-dihydrobenzofuran-4-yl)cyclopropanecarboxaldehyde (1.98 g, 10.5 mmol), hydroxylamine hydrochloride (2.29 g, 33 mmol), and 30% NaOH (3.5 mL, 35 mmol), in 5:1 ethanol/water (50 mL) was heated on a steam bath for 2 h. The solution was concentrated in vacuo, and the residue mixed with water. The mixture was extracted with CH2Cl2. The organic extracts were dried and concentrated in vacuo to give a solid which NMR analysis showed to be a mixture of the cis and trans oximes. This material was dissolved in THF (20 mL) and added to solution of alane in THF [prepared from LAH (1.14 g, 30 mmol) and H2SO4 (1.47 g, 15 mmol) at 0° C.]. The reaction was stirred for 18 h, and quenched successively with water (1.15 mL), 15% NaOH (1.15 mL), and then water (3.45 mL). The mixture was filtered and the filtrate was concentrated in vacuo. The residue was mixed with ether and washed with water and then 1N HCl. The acid washes were made basic and extracted with CH2Cl2. The extracts were dried and concentrated in vacuo to give the amine product (1.4 g, 70.5%). The amine was converted to the fumarate salt in ethanol (mp: 197°-198° C.). Anal. Calc'd for C12H15NO.C4H4O4 : C, 62.94; H, 6.27; N, 4.59; Found: C, 62.87; H, 6.31; N, 4.52.

Workup

  1. concentrationThe solution was concentrated in vacuo
  2. additionthe residue mixed with water
  3. extractionThe mixture was extracted with CH2Cl2
  4. customThe organic extracts were dried
  5. concentrationconcentrated in vacuo
  6. customto give a solid which NMR analysis
  7. customquenched successively with water (1.15 mL), 15% NaOH (1.15 mL)
  8. filtrationThe mixture was filtered
  9. concentrationthe filtrate was concentrated in vacuo
  10. additionThe residue was mixed with ether
  11. washwashed with water
  12. extractionextracted with CH2Cl2
  13. customThe extracts were dried
  14. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-66bd2df2123a47e1bf9a50009b706d36
Source dataset
uspto-grants-1999_01
Patent number
US05856529

Reaction notes

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