1,2-Dichloroethane → HCID 11960790, compound

HRID 1172861Notes

Reaction equation

HRID 1172861 reaction equation
Cl.[NH2:2][CH2:3][C:4]1[CH:5]=[CH:6][C:7]2[S:11][C:10]([C:12]([O:14]CC)=O)=[CH:9][C:8]=2[CH:17]=1.[C:18]1([CH2:24][C:25](Cl)=[O:26])[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.CCN(CC)CC.[Li+].[OH-].C(Cl)CCl.[CH:41]1[CH:42]=[CH:43][C:44]2[N:49](O)N=[N:47][C:45]=2[CH:46]=1.C1(N)C=CC=CC=1N>CN(C=O)C.CCOC(C)=O>[NH2:47][C:45]1[CH:46]=[CH:41][CH:42]=[CH:43][C:44]=1[NH:49][C:12]([C:10]1[S:11][C:7]2[CH:6]=[CH:5][C:4]([CH2:3][NH:2][C:25](=[O:26])[CH2:24][C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)=[CH:17][C:8]=2[CH:9]=1)=[O:14]

Participants

10

Reactant 7

HCID 111,2-DichloroethaneHCID 3939Lithium HydroxideHCID 7243O-PhenylenediamineHCID 7679Phenylacetyl chlorideHCID 8471TriethylamineHCID 757711-HydroxybenzotriazoleHCID 68696706HCID 68696706, compound

Product 1

HCID 11960790HCID 11960790, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent3×

Procedure

A mixture of ethyl 5-(aminomethyl)-1-benzothiophene-2-carboxylate hydrochloride (75 mg, 0.28 mmol), phenylacetyl chloride (0.045 mL, 0.34 mmol) and NEt3 (0.20 mL, 1.4 mmol) in 1 mL of DMF was stirred for 3 h, poured into EtOAc, washed with sat'd NaHCO3, dried (Na2SO4) and concentrated. Next, the residue was dissolved in 2:1:1 THF/MeOH/water (2 mL) and stirred for 3 h in the presence of LiOH (35 mg, 0.83 mmol), then finally poured into EtOAc and washed with 2 N HCl, dried (Na2SO4) and concentrated. The residue was dissolved in DMF (2 mL) and treated with EDC (100 mg, 0.524 mmol), HOBt (50 mg, 0.37 mmol) and 1,2-phenylenediamine (60 mg, 0.56 mmol). After stirring overnight the reaction mixture was poured into EtOAc, washed with sat'd NaHCO3, dried (Na2SO4) and concentrated. Trituration with ether gave the desired product: 1H NMR (600 MHz, DMSO-d6) δ 9.86 (s, 1H), 9.11 (t, J=5.9 Hz, 1H), 8.26 (s, 1H), 7.97 (d, J=8.5 Hz, 1H), 7.88 (d, J=7.0 Hz, 2H), 7.85 (s, 1H), 7.52 (t, J=7.3 Hz, 1H), 7.43-7.47 (m, 3H), 7.14 (d, J=7.0 Hz, 1H), 6.96 (t, J=7.0 Hz, 1H), 6.75 (d, J=7.9 Hz, 1H), 6.57 (t, J=7.3 Hz, 1H), 4.95 (s, 2H), 4.59 (d, J=5.9 Hz, 2H); MS cal'd 416 (MH+), exp 416 (MH+).

Workup

  1. washwashed with sat'd NaHCO3
  2. dry with materialdried (Na2SO4)
  3. concentrationconcentrated
  4. dissolutionNext, the residue was dissolved in 2:1:1 THF/MeOH/water (2 mL)
  5. washwashed with 2 N HCl
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated
  8. dissolutionThe residue was dissolved in DMF (2 mL)
  9. stirringAfter stirring overnight the reaction mixture
  10. washwashed with sat'd NaHCO3
  11. dry with materialdried (Na2SO4)
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-a43c596075084669b99e4a79b677f96c
Source dataset
uspto-grants-2010_11
Patent number
US07834034B2

Reaction notes

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