N,N,N',N'-Tetramethylethylenediamine → HCID 516472, compound

HRID 1263456Notes

Reaction equation

HRID 1263456 reaction equation
C([Li])CCC.CCCCCC.CN(CCN(C)C)C.[CH3:20][C:21]1[S:25][C:24]2[C:26](=O)[CH2:27][CH2:28][C:23]=2[CH:22]=1.[CH2:30]([N:32]1[C:41]2[C:36](=[CH:37][C:38]([CH:42]([CH3:44])[CH3:43])=[CH:39][CH:40]=2)[C:35](=[O:45])C=C1C1OC=CC=1)[CH3:31]>C1COCC1.[Cl-].[NH4+]>[CH2:30]([N:32]1[C:41]2[C:36](=[CH:37][C:38]([CH:42]([CH3:44])[CH3:43])=[CH:39][CH:40]=2)[C:35](=[O:45])[C:27]2[CH2:28][C:23]3[CH:22]=[C:21]([CH3:20])[S:25][C:24]=3[C:26]1=2)[CH3:31]

Participants

8

Reactant 5

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 8058HexaneHCID 516434HCID 516434, compoundHCID 12416658HCID 12416658, compoundHCID 178418339Butyllithium

Product 1

HCID 516472HCID 516472, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 25517Ammonium ChlorideSolvent

Procedure

To a 1.53M solution of n-butyl lithium in hexane (0.47 mL, 0.72 mmol) were added under argon atmosphere TMEDA (0.11 mL, 0.72 mmol) at room temperature and then 2-methyl-4,5-dihydro-6H-cyclopenta[b]thiophen-6-one (0.11 g, 0.72 mmol) in anhydrous THF dropwise with ice cooling and stirring. The reaction mixture was stirred at room temperature for 1 hour and ice-cooled again. To this was added dropwise a solution of 1-ethyl-6-isopropylisatoic anhydride (Example 6, step 1) (0.11 g, 0.48 mmol) in anhydrous THF. The reaction mixture was stirred at room temperature for 2 hours and diluted with saturated aqueous solution of ammonium chloride. The organic layer was concentrated to dryness and the residue was dissolved in ethyl acetate. This solution was washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated again. The residue was subjected to silica gel-chromatography (chloroform: acetone=9:1) and crystallization from diethyl ether to give the title compound. 1H-NMR(CDCl3) δ 1.33(6H,d,CH(CH3)2), 1.58(3H,t,CH2CH3), 2.64(3H,s,CH3), 3.10(1H,septet,CH), 3,78(2H,s,H-4), 4,49(2H,q,NCH3), 6.97(1H,s,H-3), 7.49(1H,d,H-9), 7.56(1H,dd,H-8), 8.45(1H,d,H-6)

Workup

  1. temperatureice-cooled again
  2. stirringThe reaction mixture was stirred at room temperature for 2 hours
  3. concentrationThe organic layer was concentrated to dryness
  4. dissolutionthe residue was dissolved in ethyl acetate
  5. washThis solution was washed with saturated sodium chloride solution
  6. dry with materialdried with sodium sulfate
  7. customevaporated again
  8. customThe residue was subjected to silica gel-chromatography (chloroform: acetone=9:1) and crystallization from diethyl ether

Sources & evidence

ORD record
ord-59b0ee803f754595a5e739387a5e3803
Source dataset
uspto-grants-2003_04
Patent number
US06541470B1

Reaction notes

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