1-Naphthaldehyde → Butanedione

HRID 1937163Notes

Reaction equation

HRID 1937163 reaction equation
C1C[C@@H:5]([NH2:7])[C@H:4](N)CC1.[C:9]1(C=O)[C:18]2C(=CC=CC=2)C=C[CH:10]=1.C1[O:25][C:24]2[CH:26]=[C:27]([CH:30]=O)[CH:28]=[CH:29][C:23]=2[O:22]1.C(C1(C)CCC2CC1C2(C)C)=O>>[C:24]1([C@H:5]([NH2:7])[CH3:4])[C:26]2[C:27](=[CH:30][CH:10]=[CH:9][CH:18]=2)[CH:28]=[CH:29][CH:23]=1.[CH3:26][C:24](=[O:25])[C:23](=[O:22])[CH3:29]

Participants

6

Reactant 4

HCID 61951-NaphthaldehydeHCID 8438PiperonalHCID 438061,2-Diaminocyclohexane, trans-HCID 18520735HCID 18520735, compound

Product 2

HCID 650ButanedioneHCID 2724264(+)-1-(1-Naphthyl)ethylamine

Procedure

10 g of toluene, 1 mmol of a zinc compound such as diethylzinc (Examples 1 to 6 and 9), phenylzinc hydride (Example 7) or zinc hydride (Example 8), and 1 mmol of one of the ligands of the secondary diimine type shown in Table 1 overleaf were added to a 100 ml three-necked flask. The mixture was stirred for 10 min at 20° C., following which 12 g (100 mmol) of acetophenone were added. 6.5 g (100 mmol) of PMHS were then added over a period of 10 minutes, and the solution was stirred continuously for 8 h at 20° C. The complete disappearance of the acetophenone was traced by chromatography. The reaction solution was slowly poured onto an aqueous 30% soda solution (0.15 mol of NaOH). The aqueous phase was decanted, the toluene was evaporated from the organic solution, and the alcohol produced was vacuum-distilled. The enantiomeric excess of the product was determined by chromatographic analysis in the gaseous phase on a chiral column of the Chirasil® type. The Schiff base diimine ligands were prepared by reacting 1 equivalent of commercially available (1R,2R)-(−)diaminocyclohexane with 2 equivalents of 1-naphthaldehyde (Example 1), heliotropin (Example 2), mesitylaldehyde (Example 3) and 2-formylpinane (Example 4) in accordance with Krasik and Alper's description, Tetrahedron, 1994, 50, 4347. The diimine ligands of Examples 5 to 8 were obtained by condensing 2 equivalents of (R)-α-naphthylethylamine (Example 5) or (R)-(α)-phenylethylamine with 1 equivalent of 2,3-butanedione in accordance with Dieck and Dietrich's description, Chem. Ber., 1984, 117, 694. The pyridinyl-imine ligand of Example 9 was prepared by condensing 2-pyridyl carboxaldehyde and (R)-α-phenylethylamine in accordance with Brunner, Reiter and Riepel's method, Chem. Ber., 1984, 117, 1130.

Workup

  1. distillationwas vacuum-distilled
  2. customThe Schiff base diimine ligands were prepared

Sources & evidence

ORD record
ord-de408b20524b48e198235157c3e0f5c8
Source dataset
uspto-grants-2002_05
Patent number
US06392103B1

Reaction notes

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