Sodium hydride → HCID 23557313, compound

HRID 1639568Notes

Reaction equation

HRID 1639568 reaction equation
[H-].[Na+].[C:3]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])(=[O:12])[CH2:4][C:5]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:6].Br[CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25]>C1COCC1>[CH2:27]([O:26][C:24](=[O:25])[CH2:23][CH2:22][CH2:21][CH2:20][CH2:19][CH:4]([C:5]([O:7][C:8]([CH3:9])([CH3:10])[CH3:11])=[O:6])[C:3]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH3:28]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 68324Di-tert-butyl malonateHCID 117544Ethyl 6-bromohexanoate

Product 1

HCID 23557313HCID 23557313, compoundYield 74%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a suspension of sodium hydride (0.11 g, 2.78 mmol) in THF (5 mL) at 0° C. was added a solution of di-tert-butyl malonate (0.53 mL, 0.5 g, 2.31 mmol) in THF (1.5 mL). The mixture was warmed to room temperature and stirred for 10 min. To the mixture was slowly added a solution of ethyl 6-bromohexanoate (0.42 mL, 0.52 g, 2.31 mmol) in THF (0.5 mL) and the mixture was stirred at 70° C. for 10 hours. After dilution of the mixture with ethyl acetate (10 mL), the solution was washed with water (20 mL) and brine (20 mL), dried over MgSO4 and evaporated. The residue was purified by chromatography on silica gel (80:20 petroleum ether 60-80° C.:ethyl acetate) to give the 2-tert-butoxycarbonyloctanedioate 1-tert-butyl ester 8-ethyl ester (14a) as a clear oil (0.61 g, 74%); Rf=0.33 (5:1 petroleum ether 60-80° C.:ethyl acetate); 1H NMR (300 MHz, CDCl3): δ 4.11 (2H, q, J=7.2 Hz, OCH2CH3), 3.37 (1H, t, J=5.7 Hz, COCH), 2.27 (2H, t, J=7.1 Hz, CH2CO), 1.87 (2H, br m, CHCH2CH2CH2CH2), 1.46 (2H, t, J=7.6 Hz, CHCH2), 1.37 (4H, br m, CHCH2CH2CH2), 1.22 (3H, t, J=7.2 Hz, OCH2CH3), 1.43 (18H, s, C(CH3)3); 13C NMR (75 MHz, CDCl3): δ 173.93 (CO), 173.93 (CO), 171.15 (CO), 61.14 (OCH2CH3), 51.66 (COCH), 33.89 (CH2CO), 29.44 (CH(CH3)3), 28.91 (CHCH2CH2CH2), 28.27 (CHCH2CH2), 26.83 (CHCH2CH2CH2CH2), 24.46 (CHCH2), 14.17 (OCH2CH3).

Workup

  1. stirringthe mixture was stirred at 70° C. for 10 hours
  2. washAfter dilution of the mixture with ethyl acetate (10 mL), the solution was washed with water (20 mL) and brine (20 mL)
  3. dry with materialdried over MgSO4
  4. customevaporated
  5. customThe residue was purified by chromatography on silica gel (80:20 petroleum ether 60-80° C.:ethyl acetate)

Sources & evidence

ORD record
ord-6b6f8316ccde4e1f9ccda39e72da32d9
Source dataset
uspto-grants-2012_02
Patent number
US08110577B2

Reaction notes

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