Sodium hydride → HCID 20090668, compound

HRID 275187Notes

Reaction equation

HRID 275187 reaction equation
[H-].[Na+].[OH:3][C:4]1[C:11]([OH:12])=[CH:10][CH:9]=[CH:8][C:5]=1[CH:6]=[O:7].Cl[CH2:14][C:15]1[CH:24]=[CH:23][C:22]2[C:21]([CH3:26])([CH3:25])[CH2:20][CH2:19][C:18]([CH3:28])([CH3:27])[C:17]=2[CH:16]=1>CS(C)=O>[OH:12][C:11]1[C:4]([O:3][CH2:14][C:15]2[CH:24]=[CH:23][C:22]3[C:21]([CH3:26])([CH3:25])[CH2:20][CH2:19][C:18]([CH3:28])([CH3:27])[C:17]=3[CH:16]=2)=[C:5]([CH:8]=[CH:9][CH:10]=1)[CH:6]=[O:7]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 905792,3-DihydroxybenzaldehydeHCID 28008916-(Chloromethyl)-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene

Product 1

HCID 20090668HCID 20090668, compoundYield 56%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent3×

Procedure

Sodium hydride (0.139 g., 4.60 mmol, 1.1 equiv.; 80% in oil washed with pentane) is suspended in 6 mL of DMSO. 2,3-Dihydroxybenzaldehyde (0.580 g., 4.20 mmol, 1 equiv.) dissolved in 2.8 mL of DMSO is added dropwise via cannula, and the mixture is allowed to stir for 1 hour. 2-Chloromethyl-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene) (18a) (1.00 g., 4.20 mmol, 1 equiv.) dissolved in 8 mL of DMSO is added dropwise via cannula, and the mixture allowed to stir 26.5 hours. The mixture is partitioned between saturated aqueous ammonium chloride solution and EtOAc. Salt is added to the aqueous phase, which is then extracted twice with EtOAc. The combined extracts are washed with brine, dried (MgSO4), and treated with charcoal before filtering through a pad of silica gel. The filtrate is evaporated, and the crude material is chromatographed on silica gel using EtOAc/hexane to afford 3-hydroxy-2-[5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthalenyl]methoxy benzaldehyde (45) (0.786 g., 2.33 mmol, 56%) as an oil: 1H NMR (300 MHz, CDCl3) δ 10.14 (s, 1H, CHO), 7.35 (m, 2H, ArH), 7.22-7.09 (m, 4H, ArH), 5.77 (s, 1H, OH), 5.00 (s, 2H, ArCH2O), 1.67 (s, 4H, CH2CH2), 1.27 (s, 6H, 2×CH3), 1.22 (s, 6H, 2×CH3); 13C NMR (75 MHz, CDCl3) δ 189.40 (C=0), 149.74, 148.00, 146.20, 145.64, 132.58, 129.63, 127.36, 127.11, 126.00, 125.12, 121.64, 121.34, 79.18, 34.92, 34.90, 34.27, 31.80, 31.75; IR (KBr) 3226, 2958, 2926, 1662, 1604, 1580, 1470, 1294, 1284, 1222, 934, 786 cm-1 ; MS (DCI) m/e 339 (MH+), 201 (C15H21+).

Workup

  1. additionis added dropwise via cannula
  2. additionis added dropwise via cannula
  3. stirringto stir 26.5 hours
  4. customThe mixture is partitioned between saturated aqueous ammonium chloride solution and EtOAc
  5. additionSalt is added to the aqueous phase, which
  6. extractionis then extracted twice with EtOAc
  7. washThe combined extracts are washed with brine
  8. dry with materialdried (MgSO4)
  9. additiontreated with charcoal
  10. filtrationbefore filtering through a pad of silica gel
  11. customThe filtrate is evaporated
  12. customthe crude material is chromatographed on silica gel

Sources & evidence

ORD record
ord-0ecc53d10d9845b5b0be581436fd4b0c
Source dataset
uspto-grants-1995_02
Patent number
US05391817

Reaction notes

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