Dimethylformamide → HCID 16103450, compound

HRID 83960Notes

Reaction equation

HRID 83960 reaction equation
Br[C:2]1[CH:6]=[CH:5][S:4][C:3]=1[CH2:7][C:8](=O)[CH2:9][CH2:10][CH2:11][CH2:12][CH3:13].C([O-])([O-])=O.[K+].[K+].CN(C)C=O.[SH:26][CH2:27][C:28]([O:30][CH2:31][CH3:32])=[O:29]>C1OCCOCCOCCOCCOCCOC1.O>[CH2:8]([C:7]1[C:3]2[S:4][CH:5]=[CH:6][C:2]=2[S:26][C:27]=1[C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH2:9][CH2:10][CH2:11][CH2:12][CH3:13]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 12185Ethyl ThioglycolateHCID 66925162HCID 66925162, compound

Product 1

HCID 16103450HCID 16103450, compoundYield 84.5%

Reagents, catalysts & solvents 2

HCID 2855718-Crown-6CatalystHCID 962WaterSolvent

Procedure

Compound 59 (35.4 g, 0.13 mol) and K2CO3 (27.6 g, 0.2 mol) are mixed with N,N-dimethylformamide (100 mL). A catalytic amount (˜25 mg) 18-crown-6 is added, and to this mixture, ethyl 2-mercaptoacetate (14.0 mL, 0.13 mol) is added dropwise at 60° C. The mixture is stirred overnight and poured into water (500 mL). The organic component is extracted with ethyl acetate (3×80 mL). The combined organic layers are washed with brine (2×100 mL) and water (100 mL). The organic layer is then dried over MgSO4. After evaporation of the solvent, the crude compound 61 is obtained and purified by column chromatography (SiO2/5% ethyl acetate in hexanes) to yield pure compound 61 (32.1 g, 84.5%). GC/MS: 296 g/mol (M). 1H NMR (CD2Cl2): δ 7.56 (d, 1H), 7.24 (d, 1H), 4.34 (q, 2H), 3.15 (t, 2H), 1.71 (m, 2H), 1.32 (m, 6H), 0.88 (m, 6H). 13C NMR: 163.24, 143.31, 141.85, 141.09, 131.13, 128.44, 120.35, 61.25, 31.99, 29.72 (overlap), 22.98, 14.52, 14.23.

Workup

  1. extractionThe organic component is extracted with ethyl acetate (3×80 mL)
  2. washThe combined organic layers are washed with brine (2×100 mL) and water (100 mL)
  3. dry with materialThe organic layer is then dried over MgSO4
  4. customAfter evaporation of the solvent
  5. customthe crude compound 61 is obtained
  6. custompurified by column chromatography (SiO2/5% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-4580d396f9ff455bb0d3e3855d677267
Source dataset
uspto-grants-2014_09
Patent number
US08846855B2

Reaction notes

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