Sodium hydride → 2-(6,11-Dihydrodibenzo[b,e]thiepin-11-yloxy)-ethanol

HRID 394629Notes

Reaction equation

HRID 394629 reaction equation
[CH:1]1[C:11]2[CH:10]([OH:12])[C:9]3[CH:13]=[CH:14][CH:15]=[CH:16][C:8]=3[CH2:7][S:6][C:5]=2[CH:4]=[CH:3][CH:2]=1.[H-].[Na+].[C:19]([O:23]C(=O)CBr)(C)(C)[CH3:20].[H-].[Al+3].[Li+].[H-].[H-].[H-]>C1COCC1.CCOCC>[CH:1]1[C:11]2[CH:10]([O:12][CH2:20][CH2:19][OH:23])[C:9]3[CH:13]=[CH:14][CH:15]=[CH:16][C:8]=3[CH2:7][S:6][C:5]=2[CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 4

HCID 24758Sodium hydrideHCID 79177tert-Butyl bromoacetateHCID 6014316,11-Dihydrodibenzo[b,e]thiepin-11-olHCID 21226445Aluminium lithium hydride

Product 1

HCID 227277542-(6,11-Dihydrodibenzo[b,e]thiepin-11-yloxy)-ethanolYield 63%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

6,11-Dihydrodibenzo[b,e]thiepin-11-ol (1.14 g, 5 mmol) was dissolved in dry THF (25 mL) at 0° C. Sodium hydride (0.24 g of 50% mineral oil dispersion, 5 mmol) was added portionwise at 0° C. and then refluxed for 30 min. tert-Butylbromoacetate (980 mg, 5.0 mmol) in dry THF (10 mL) was added over a period of 20 min followed by a 30 min reflux. The reaction mixture was quenched with water at 0° C. and the product extracted with ether. The combined ex-extracts were dried (MgSO4), and concentrated in vacuo. The product was redissolved in ether and added dropwise to an ether (15 mL) suspension of lithium aluminium hydride (190 mg, 5.0 mmol). The reaction was stirred 16 h at room temperature, quenched with water, cooled, and filtered through Decalit. The ether solution was washed with saturated NaCl, dried, and purified by chromatography eluting with ethyl acetate/dichloromethan (1:10) to give 850 mg (63%) of 2-(6,11-dihydrodibenzo[b,e]thiepin-11-yloxy)-ethanol. 1H NMR (300 MHz, CDCl3) δ 3.55-3.70 (m, 2H), 3.75-3.85 (m, 2H), 4.00 (bs,1H), 4.85 (bs, 1H), 5.55 (bs, 1H), 7.03-7.13 (m, 3H), 7.13-7.48 (m, 5H).

Workup

  1. additionwas added over a period of 20 min
  2. temperaturereflux
  3. customThe reaction mixture was quenched with water at 0° C.
  4. extractionthe product extracted with ether
  5. dry with materialwere dried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. dissolutionThe product was redissolved in ether
  8. customquenched with water
  9. temperaturecooled
  10. filtrationfiltered through Decalit
  11. washThe ether solution was washed with saturated NaCl
  12. customdried
  13. custompurified by chromatography
  14. washeluting with ethyl acetate/dichloromethan (1:10)

Sources & evidence

ORD record
ord-796d0b6372864acd9938e9442263b01d
Source dataset
uspto-grants-2003_08
Patent number
US06602901B2

Reaction notes

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