Methyl morpholine oxide → HCID 10193247, compound

HRID 1358100Notes

Reaction equation

HRID 1358100 reaction equation
[OH:1][CH2:2]/[CH:3]=[C:4](\[C:6]1[C:7]([O:20][CH2:21][CH2:22][CH3:23])=[CH:8][C:9]2[C:10]([CH3:19])([CH3:18])[CH2:11][CH2:12][C:13]([CH3:17])([CH3:16])[C:14]=2[CH:15]=1)/[CH3:5].C[N+]1([O-])CCOCC1>C(Cl)Cl.[Ru]([O-])(=O)(=O)=O.C([N+](CCC)(CCC)CCC)CC>[CH3:17][C:13]1([CH3:16])[CH2:12][CH2:11][C:10]([CH3:18])([CH3:19])[C:9]2[CH:8]=[C:7]([O:20][CH2:21][CH2:22][CH3:23])[C:6](/[C:4](/[CH3:5])=[CH:3]\[CH:2]=[O:1])=[CH:15][C:14]1=2

Participants

5

Reactant 2

HCID 82029Methyl morpholine oxideHCID 10567448HCID 10567448, compound

Product 1

HCID 10193247HCID 10193247, compoundYield 99.4%

Reagents, catalysts & solvents 2

HCID 178419074HCID 178419074, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

(2Z)-3-[5,6,7,8-Tetrahydro-5,5,8,8-tetramethyl-2-(n-propyloxy)naphthalen-3-yl]-but-2-en-1-al (Structure 9 of Schemes 1 and 2, where R1, R4, R6=H, R1and R3 together form a tetramethyl saturated six-membered carbocyclic ring, R5=methyl, R7=n-propyl). To an oven-dried 10-mL r.b. flask containing (2Z)-3-(4-hydroxy-2-buten-2-yl)-5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-(n-propyloxy)naphthalene (25.0 mg, 0.08 mmol) and N-methylmorpholine N-oxide (NMO, 14 mg, 0.12 mmol, 1.5 equiv) in 0.5 mL CH2Cl2 at 0° C. was added tetra-n-propylammonium perruthenate (TPAP, 1.3 mg, 5 mol%), and the mixture was allowed to warm to room temperature. After 1 h at room temperature, the reaction mixture was filtered through a pad of silica gel, washing with an additional 50 mL CH2Cl2. The solvent was then removed under reduced pressure to afford 25 mg (99%) of (2Z)-3-[5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-(n-propyloxy)naphthalen-3-yl]-but-2-en-1-al as a colorless low-melting solid. The aldehyde thus obtained was of greater than 98% purity as judged by the 1H NMR spectrum, and was used directly in the next step without further purification. 1H NMR (400 MHz, CDCl3) 9.36 (d, 1H, J=8.1 Hz), 6.99 (s, 1H), 6.79 (s, 1H), 6.09 (dd, 1H, J=8.4, 1.1 Hz), 3.90 (t, 2H, J=6.4 Hz), 2.29 (d, 3H, J=1.1 Hz), 1.76 (m, 2H), 1.68 (d, 4H, J=1.6Hz), 1.30 and 1.23 (2s, 2×3H) 1.00 (t, 3H, J=7.5Hz). 13C NMR (100 MHz, CDCl3) 194.0, 161.7, 153.3, 146.9, 136.6, 129.7, 128.6, 125.3, 109.5, 69.7, 35.1, 35.0, 34.6, 33.6, 31.9, 31.8, 25.9, 22.6, 10.7. IR (thin film) 2922 (br, m), 1674 (s), 1202 (s), 1147 (s).

Workup

  1. filtrationthe reaction mixture was filtered through a pad of silica gel
  2. washwashing with an additional 50 mL CH2Cl2
  3. customThe solvent was then removed under reduced pressure

Sources & evidence

ORD record
ord-5261c52db0f8495995a5f9b0ac393faa
Source dataset
uspto-grants-2003_07
Patent number
US06593493B1

Reaction notes

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