Dimethyl Sulfoxide → HCID 69769063, compound

HRID 1529841Notes

Reaction equation

HRID 1529841 reaction equation
C[O-].[Na+].CS(C)=O.CO[C:10](=[O:24])[CH2:11][CH2:12][C:13]([CH2:15][CH2:16][CH2:17][CH2:18][O:19][CH2:20][CH2:21][O:22][CH3:23])=[O:14]>C1(C)C=CC=CC=1>[CH3:23][O:22][CH2:21][CH2:20][O:19][CH2:18][CH2:17][CH2:16][CH:15]1[C:10](=[O:24])[CH2:11][CH2:12][C:13]1=[O:14]

Participants

5

Reactant 3

HCID 679Dimethyl SulfoxideHCID 10942334Sodium Methoxide2×HCID 86601513HCID 86601513, compound

Product 1

HCID 69769063HCID 69769063, compoundYield 82.5%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

In a 5 L 3-neck round bottom flask fitted with mechanical stirrer, a distillation system, a 2 L dropping funnel, and an argon inlet, was poured sodium methoxide solution (25 wt. % solution in methanol, 200 mL). Toluene (1.0 L) was added and methanol was removed off by distillation with an heating mantle. To the sodium methoxide suspension, methyl sulfoxide (13.4 mL, 0.4 eq) was added and a solution of 44 (121.0 g, 0.46 mol) in toluene (2.0 L) was slowly added over a period of 2 h. The distillation was continued during the addition and additional 30 minutes (until 0.5 L residual toluene). The reaction mixture was cooled and water (1 L) was added. Toluene was extracted and thrown away. The aqueous phase was acidified with 10% HCl until pH 1 and extracted with dichloromethane (4×800 mL). The combined organic phase was washed with brine, dried over magnesium sulfate, and rotary evaporated to give the cyclopentanedione 45 (81.3 g, 75%) as a brown heavy oil. 1H NMR (400 MHz, CD3OD) δ 2.42 (t, J=7.1 Hz, 2H), 2.51 (s, 4H), 3.38 (s, 3H), 3.55-3.61 (m, 4H), 3.67 (m, 2H), 4.68 (s, 2H) ppm.

Workup

  1. customIn a 5 L 3-neck round bottom flask fitted with mechanical stirrer
  2. custommethanol was removed off by distillation with an heating mantle
  3. distillationThe distillation
  4. additionwas continued during the addition and additional 30 minutes (until 0.5 L residual toluene)
  5. temperatureThe reaction mixture was cooled
  6. additionwater (1 L) was added
  7. extractionToluene was extracted
  8. extractionextracted with dichloromethane (4×800 mL)
  9. washThe combined organic phase was washed with brine
  10. dry with materialdried over magnesium sulfate
  11. customrotary evaporated

Sources & evidence

ORD record
ord-1b9ed78539d044f9afa6777d498682e6
Source dataset
uspto-grants-2015_07
Patent number
US09090651B2

Reaction notes

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