Ethyl formate → HCID 67113850, compound

HRID 1879087Notes

Reaction equation

HRID 1879087 reaction equation
[CH3:1][C:2]1([C:9]#[C:10][Si:11]([CH3:14])([CH3:13])[CH3:12])[CH2:7][CH2:6][C:5](=[O:8])[CH:4]=[CH:3]1.[CH:15](OCC)=[O:16].C[O-].[Na+]>C1C=CC=CC=1.C(Cl)Cl.CCOCC>[OH:16][CH:15]=[C:4]1[C:5](=[O:8])[CH:6]=[CH:7][C:2]([CH3:1])([C:9]#[C:10][Si:11]([CH3:12])([CH3:14])[CH3:13])[CH2:3]1

Participants

6

Reactant 3

HCID 8025Ethyl formateHCID 10942334Sodium MethoxideHCID 57523557HCID 57523557, compound

Product 1

HCID 67113850HCID 67113850, compoundYield 94.3%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 21881112Ethyl ether methylene chlorideSolvent

Procedure

To a solution of 8 (139 mg, 0.67 mmol) in dry benzene (7.8 mL) were added ethyl formate (97%, 244 mg, 3.2 mmol) and sodium methoxide (176 mg, 3.3 mmol), successively. The mixture was stirred at room temperature for 1 h. The mixture was diluted with methylene chloride/ether (1:2, 40 mL). The mixture was washed with 5% aqueous HCl solution (15 mL×2). The acidic washings were extracted with methylene chloride/ether (1:2, 20 mL×1). The original organic solution and the extract were combined. The combined solution was washed with water (15 mL×2) and brine (15 mL×1), dried over MgSO4, and filtered. The filtrate was evaporate in vacuo to give 6-(hydroxymethylene)-4-methyl-4-((trimethylsilyl)-ethynyl)cyclohex-2-enone (148 mg, 94%): 1H NMR (CDCl3) δ 13.69 (1H, brs), 7.53 (1H, s), 6.64 (1H, d, J=9.9 Hz), 6.00 (1H, d, J=9.9 Hz), 2.78 (1H, d, J=14.6 Hz), 2.47 (1H, d, J=14.6 Hz), 1.38 (3H, s), 0.14 (9H, s); 13C NMR (CDCl3) δ 187.7, 168.0, 152.3, 126.8, 110.2, 109.5, 106.1, 37.2, 37.1, 26.9, 0.2. This material was used without further purification for the next step.

Workup

  1. washThe mixture was washed with 5% aqueous HCl solution (15 mL×2)
  2. extractionThe acidic washings were extracted with methylene chloride/ether (1:2, 20 mL×1)
  3. washThe combined solution was washed with water (15 mL×2) and brine (15 mL×1)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. customThe filtrate was evaporate in vacuo

Sources & evidence

ORD record
ord-08e959e52f3b4158abc94e9e8658fe83
Source dataset
uspto-grants-2012_11
Patent number
US08314137B2

Reaction notes

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