Sodium Hydroxide → HCID 11674524, compound

HRID 1876463Notes

Reaction equation

HRID 1876463 reaction equation
C([O:5][C:6]([C:8]1([CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16](=[O:30])[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][C:22]([CH3:29])([CH3:28])[C:23]([O:25]CC)=[O:24])[CH2:10][CH2:9]1)=[O:7])(C)(C)C.[OH-].[Na+]>C(O)=O.CCO.O>[C:6]([C:8]1([CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16](=[O:30])[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][C:22]([CH3:28])([CH3:29])[C:23]([OH:25])=[O:24])[CH2:10][CH2:9]1)([OH:7])=[O:5]

Participants

6

Reactant 2

HCID 14798Sodium HydroxideHCID 21932034HCID 21932034, compound

Product 1

HCID 11674524HCID 11674524, compoundYield 64.2%

Reagents, catalysts & solvents 3

HCID 284Formic AcidSolventHCID 702EthanolSolvent2×HCID 962WaterSolvent

Procedure

A solution of ethyl 13-[1-(t-butoxycarbonyl)cyclopropyl]-2,2-dimethyl-8-oxotridecanoate (18.34 g, 43.3 mmol) in HCO2H (50 mL) was stirred for 1.5 h, evaporated in vacuo and coevaporated in vacuo from toluene (10 mL). The remaining residue was dissolved in a mixture of EtOH and H2O (2:1, 250 mL) and NaOH (9.68 g, 241 mmol) was added. The resulting clear solution was warmed to 80° C. and after 5 h EtOH was evaporated in vacuo. The remaining solution was diluted with H2O to ˜250 mL, extracted with Et2O (3×250 mL), acidified to pH ˜1 with conc aqueous HCl (˜18 mL) and extracted with Et2O (3×250 mL). The latter organic layers were combined, dried (Na2SO4) and evaporated in vacuo to give a yellow oil which solidified overnight. The remaining residue was recrystallized from iPr2O/heptane to give 13-(1-carboxycyclopropyl)-2,2-dimethyl-8-oxotridecanoic acid (9.47 g, 57%) as a white solid. The mother liquor was evaporated in vacuo and the remaining residue was purified by column chromatography (heptane:EtOAc=2:1 (containing 1% (v/v) HOAc)) and recrystallization from iPr2O/heptane to give a second batch 13-(1-carboxycyclopropyl)-2,2-dimethyl-8-oxotridecanoic acid (2.23 g, 14%) as a white solid. mp=65-66° C. 1H NMR: (CD3OD): δ=2.43 (t, J=7.2 Hz, 4H), 1.58-1.42 (m, 10H), 1.35-1.20 (m, 6H), 1.14 (s, 6H), 1.15-1.06 (m, 2H), 0.70 (dd, J=6.6, 3.9 Hz, 2H). 13C NMR: (CD3OD): δ=213.8, 181.6, 179.0, 43.6, 43.5, 43.1, 41.9, 35.1, 31.0, 30.6, 28.7, 26.2, 25.9 (2×), 25.02, 24.96, 24.4, 16.4 (2×). Anal. calcd for C19H32O5: C, 67.03; H, 9.47, found: C, 66.86; H, 9.50.

Workup

  1. customevaporated in vacuo
  2. additionwas added
  3. customwas evaporated in vacuo
  4. additionThe remaining solution was diluted with H2O to ˜250 mL
  5. extractionextracted with Et2O (3×250 mL)
  6. extractionextracted with Et2O (3×250 mL)
  7. dry with materialdried (Na2SO4)
  8. customevaporated in vacuo
  9. customto give a yellow oil which
  10. customThe remaining residue was recrystallized from iPr2O/heptane

Sources & evidence

ORD record
ord-598fd9e108724c5d8418045cd6185e69
Source dataset
uspto-grants-2012_11
Patent number
US08309604B2

Reaction notes

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