Chlorotrimethylsilane → HCID 10539357, compound

HRID 235081Notes

Reaction equation

HRID 235081 reaction equation
[CH2:1]([N:3]([CH2:11][CH3:12])[C:4]([C:6]1[CH:10]=[CH:9][S:8][CH:7]=1)=[O:5])[CH3:2].CC([Li])CC.C1CCCCC1.Cl[Si:25]([CH3:28])([CH3:27])[CH3:26]>C1COCC1.C(OCC)(=O)C.O>[CH2:11]([N:3]([CH2:1][CH3:2])[C:4]([C:6]1[CH:10]=[CH:9][S:8][C:7]=1[Si:25]([CH3:28])([CH3:27])[CH3:26])=[O:5])[CH3:12]

Participants

8

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 8078CyclohexaneHCID 11389776N,N-diethylthiophene-3-carboxamideHCID 178418400CID 53628100

Product 1

HCID 10539357HCID 10539357, compoundYield 38%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 3 g (16.4 mmol) of 3-thiophenecarboxylic acid, N,N-diethylamide, from step 2a above, in 20 mL of THF cooled to -78° C. and stirred under N2 was added 1.68 g (2.1 mL, 16.4 mmol) of N,N,N',N'-tetramethylenediamine (TMEDA), followed by 12.6 mL of a 1.3M solution of 2-butyl lithium in cyclohexane (16.4 mmol), and the reaction was stirred for 1 hour. Chlorotrimethylsilane (1.78 g, 2.1 mL, 16.4 mmol) was added, and the solution was stirred for 45 min, then poured into 100 mL of water. The mixture was extracted 3× with methylene chloride, and the solvent was washed with brine, dried over MgSO4, concentrated, and purified by flash chromatography, eluting with 3:1 hexane:ethyl acetate to afford 1.4 g (38% yield) of the title product as an oil. MS 256 (M+H)+. NMR (CDCl3) δ:7.51 (d, 1 H, J=5 Hz), 7.10 (d, 1 H, J=5 Hz), 3.60-3.50 (bm, 2H), 3.3-3.10 (bm, 2H), 1.30-1.20 (bm, 3H), 1.15-1.05 (bm, 3H), 0.34 (s, 9H).

Workup

  1. stirringthe reaction was stirred for 1 hour
  2. stirringthe solution was stirred for 45 min
  3. extractionThe mixture was extracted 3× with methylene chloride
  4. washthe solvent was washed with brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. custompurified by flash chromatography
  8. washeluting with 3:1 hexane

Sources & evidence

ORD record
ord-e73218c3a5654320b2ac75d27a064fcc
Source dataset
uspto-grants-1997_01
Patent number
US05597832

Reaction notes

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