Sodium hydride → HCID 20090666, compound

HRID 275181Notes

Reaction equation

HRID 275181 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.[Cl-].[NH4+]>CS(C)=O>[CH3:25][C:21]1([CH3:26])[CH2:20][CH2:19][C:18]([CH3:28])([CH3:27])[C:17]2[CH:16]=[C:15]([CH2:14][O:12][C:11]3[CH:10]=[CH:9][CH:8]=[C:5]([CH:6]=[O:7])[C:4]=3[OH:3])[CH:24]=[CH:23][C:22]1=2

Participants

6

Reactant 4

HCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 905792,3-DihydroxybenzaldehydeHCID 28008916-(Chloromethyl)-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene

Product 1

HCID 20090666HCID 20090666, compound

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent2×

Procedure

Sodium hydride (2.54 g., 0.106 mol, 2.5 equiv.; 80% dispersion, unwashed) is suspended in 75 mL of DMSO. A solution of 2,3-dihydroxybenzaldehyde (5.84 g., 42.3 mmol, 1 equiv.) in 30 mL of DMSO is added dropwise with water bath cooling, and the mixture allowed to stir 1 hr. at room temperature. A solution of 2-chloromethyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene (18a) (10 g., 42.3 mmol, 1 equiv.) is added and the mixture is allowed to stir overnight at room temperature. The mixture is then poured into half-saturated ammonium chloride solution, and extracted with EtOAc. The aqueous phase is saturated with sodium chloride, and then extracted twice with EtOAc. The combined organic phase is washed with brine, dried (MgSO4), and evaporated. Chromatography on silica gel using 50% CH2Cl2 /hexane affords 3-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-2-naphthalenyl)methoxy-salicylaldehyde (19a) as a yellow oil (6.02 g., 17.8 mmol, 44%) which occasionally crystallizes upon standing: UVmax (CHCl3) 268 nm (ε=9894), 240 nm (ε=6181), 350 nm (ε=2513); 1H NMR (300 MHz, CDCl3) δ 11.01 (s, 1H, OH), 9.91 (s, 1H, CHO), 7.33 (d, J=2 Hz, 1H, ArH), 7.29 (d, J=8 Hz, 1H, ArH), 7.21-7.13 (m, 3H, ArH), 6.90 (dd, J=8, 8 Hz, 1H, ArH), 5.10 (s, 2H, ArCH2O), 1.66 (s, 4H, CH2CH2), 1.25 (s, 12H, 4×CH3); 13C NMR (75 MHz, CDCl3) δ 196.45 (C=O), 152.31, 147.46, 145.07, 144.86, 133.33, 126.93, 125.90, 125.12, 125.01, 121.06, 120.97, 119.46, 71.78, 35.03, 35.00, 34.26, 34.16, 31.83; IR (film) 2960, 2926, 2860, 1658, 1456, 1388, 1364, 1276, 1252, 1216, 750, 736 cm-1 ; MS (DCI) m/e 339 (MH+), 201 (C15H21+). Anal. Calcd for C22H26O3.0.4 H2O: C, 76.45; H, 7.81. Found: C, 76.62; H, 7.62.

Workup

  1. temperaturecooling
  2. customat room temperature
  3. stirringto stir overnight at room temperature
  4. extractionextracted with EtOAc
  5. extractionextracted twice with EtOAc
  6. washThe combined organic phase is washed with brine
  7. dry with materialdried (MgSO4)
  8. customevaporated

Sources & evidence

ORD record
ord-75371053ab3246d5bc7000f720350fdd
Source dataset
uspto-grants-1995_02
Patent number
US05391817

Reaction notes

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