Azelaic Acid → Nonanedioic acid, bis[(2,2-dimethyl-1-oxopropoxy)methyl] ester

HRID 1866485Notes

Reaction equation

HRID 1866485 reaction equation
[C:1](=[O:4])([O-])[O-].[Cs+].[Cs+].[C:7]([OH:19])(=[O:18])[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][C:15]([OH:17])=[O:16].[C:20]([O:26][CH2:27]Cl)(=[O:25])[C:21]([CH3:24])([CH3:23])[CH3:22].[Na+].[I-].CN(C)[CH:33]=[O:34]>>[CH3:22][C:21]([CH3:24])([CH3:23])[C:20]([O:26][CH2:27][O:16][C:15](=[O:17])[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][C:7]([O:19][CH2:1][O:4][C:33](=[O:34])[C:21]([CH3:23])([CH3:22])[CH3:20])=[O:18])=[O:25]

Participants

6

Reactant 5

HCID 2266Azelaic AcidHCID 5238Sodium IodideHCID 6228DimethylformamideHCID 10796Cesium carbonateHCID 87885Chloromethyl pivalate

Product 1

HCID 9953710Nonanedioic acid, bis[(2,2-dimethyl-1-oxopropoxy)methyl] ester

Conditions

Temperature
40 °C

Procedure

Caesium carbonate (32.6 g; 0.120 mol) was added to a stirred solution of nonanedioic acid (9.4 g; 50.0 mmol), chloromethyl pivalate (15.1 g; 0.10 mmol), and NaI (0,5 g; 3.3 mmol) in dry N,N-dimethylformamide (50 mL). The mixture was stirred for 2 days at ca. 40° C. (bath temperature) under argon. Excess solvent was evaporated off at ca. 35° C. (bath temperature) and 5 to 1 mm Hg. The residue was dissolved in water (50 mL) and diethyl ether (25 mL). The aqueous portion was extracted with ether (1×15 mL) and the combined ether solutions were washed with saturated NaCl solution (1×10 mL) and dried (Na2SO4). Filtration and evaporation left 12.34 g (59%) after pumping out to 0.2 mm Hg. 1H NMR (200 MHz; CDCl3): δ 1.20 (20H, s), 1.32 (4H, s), 1.63 (4H, m), 2.35 (4H, t, J=7.4 Hz), 5.76 (4H, d, J=2.8 Hz). 13C NMR (50 MHz; CDCl3): δ 24.58, 26.84, 28.80, 29.01, 33.92, 38.73, 79.22, 164.87, 172.29, MS(ES):439.3 [M+Na]+.

Workup

  1. customExcess solvent was evaporated off at ca. 35° C. (bath temperature) and 5 to 1 mm Hg
  2. dissolutionThe residue was dissolved in water (50 mL)
  3. extractionThe aqueous portion was extracted with ether (1×15 mL)
  4. washthe combined ether solutions were washed with saturated NaCl solution (1×10 mL)
  5. dry with materialdried (Na2SO4)
  6. filtrationFiltration and evaporation
  7. waitleft 12.34 g (59%)

Sources & evidence

ORD record
ord-9a6f855ccbb74211978155e7a74ad9ad
Source dataset
uspto-grants-2009_12
Patent number
US07629383B2

Reaction notes

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