Chlorodimethylaluminum → HCID 66756365, compound

HRID 1177301Notes

Reaction equation

HRID 1177301 reaction equation
[NH2:1][C:2]1[CH:6]=[CH:5][N:4]([CH3:7])[N:3]=1.[Al](Cl)(C)C.[CH3:12][C:13]1[S:14][C:15]2[C:21]([O:22][C@@H:23]([CH3:31])[CH2:24][C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)=[CH:20][C:19]([C:32](OCC)=[O:33])=[CH:18][C:16]=2[CH:17]=1>ClCCCl>[CH3:12][C:13]1[S:14][C:15]2[C:21]([O:22][CH:23]([CH3:31])[CH2:24][C:25]3[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=3)=[CH:20][C:19]([C:32]([NH:1][C:2]3[CH:6]=[CH:5][N:4]([CH3:7])[N:3]=3)=[O:33])=[CH:18][C:16]=2[CH:17]=1

Participants

5

Reactant 3

HCID 79147ChlorodimethylaluminumHCID 1372541-Methyl-3-aminopyrazoleHCID 59560301HCID 59560301, compound

Product 1

HCID 66756365HCID 66756365, compoundYield 57.1%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

3-Amino-1-methylpyrazole (649 mg, 6.69 mmol) was dissolved in DCE (10 mL) at 0° C., then Al(CH3)2Cl (6.69 mL, 1M in hexanes) was added drop wise. After the addition, the ice-bath was removed, and the mixture was stirred for 30 min at room temperature. Ethyl 2-methyl-7-[(1S)-1-methyl-2-phenylethoxy]-1-benzothiophene-5-carboxylate (237 mg, 0.669 mmol) was added and the stirring was continued for 14 h. The reaction was quenched with potassium sodium tartrate tetrahydrate (20% w/w) cautiously. The product was extracted with CHCl3, washed with brine and dried over MgSO4. The product was purified by reverse phase HPLC to give the title compound (155 mg, 57%) as a white solid. 1H NMR (300 MHz, CHLOROFORM-D) δ ppm 1.38 (d, J=6.03 Hz, 3 H) 2.59 (s, 3 H) 2.95 (dd, J=13.75, 6.22 Hz, 1 H) 3.16 (dd, J=13.75, 6.03 Hz, 1 H) 3.74 (s, 3 H) 4.78-5.01 (m, 1 H) 6.89 (d, J=2.26 Hz, 1 H) 7.00 (d, J=1.13 Hz, 1 H) 7.12-7.23 (m, 1 H) 7.26-7.42 (m, 6 H) 7.81 (d, J=1.13 Hz, 1 H) 9.60 (s, 1 H). LCMS m/z 406.0 (M+H)+.

Workup

  1. additionAfter the addition
  2. customthe ice-bath was removed
  3. waitthe stirring was continued for 14 h
  4. customThe reaction was quenched with potassium sodium tartrate tetrahydrate (20% w/w) cautiously
  5. extractionThe product was extracted with CHCl3
  6. washwashed with brine
  7. dry with materialdried over MgSO4
  8. customThe product was purified by reverse phase HPLC

Sources & evidence

ORD record
ord-5fb7d1caf6e94e4298716fd3fd3ee510
Source dataset
uspto-grants-2010_11
Patent number
US07842713B2

Reaction notes

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