1,2-Dichloroethane → HCID 57550276, compound

HRID 1642257Notes

Reaction equation

HRID 1642257 reaction equation
[Cl:1][C:2]1[CH:15]=[CH:14][C:5]([O:6][C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=2[NH2:13])=[CH:4][CH:3]=1.[CH3:16][CH2:17][O:18][C:19]([N:21]1[C@@H:25]2[CH2:26][C:27]([CH2:29][C@H:22]1[CH2:23][CH2:24]2)=O)=[O:20].C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].[Cl:48]CCCl>>[Cl:48][C:14]1[CH:15]=[C:2]([Cl:1])[CH:3]=[CH:4][C:5]=1[O:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[NH:13][CH:27]1[CH2:29][CH:22]2[N:21]([C:19]([O:18][CH2:17][CH3:16])=[O:20])[CH:25]([CH2:24][CH2:23]2)[CH2:26]1

Participants

6

Reactant 5

HCID 111,2-DichloroethaneHCID 176Acetic AcidHCID 760102-(4-Chlorophenoxy)anilineHCID 5049666Sodium triacetoxyborohydrideHCID 10954505HCID 10954505, compound

Product 1

HCID 57550276HCID 57550276, compoundYield 22%

Procedure

To a solution of 2-(4-chlorophenoxy)phenylamine (130 mg, 0.51 mmol), N-(ethoxycarbonyl)-tropinone (201 mg, 1.02 mmol) and acetic acid (153 mg, 2.55 mmol) in DCE (4 ml), was added sodium triacetoxyborohydride (270 mg, 1.28 mmol). The reaction mixture was allowed to stir at room temperature for 10 days. On return, the reaction was quenched with saturated aqueous sodium sodium bicarbonateonate (15 ml) and extracted with ethyl acetate (2×15 ml). The combined organics were dried (MgSO4), filtered and concentrated in vacuo. Purification by flash chromatography then proceeded (eluent; 9:1 hexane:ethyl acetate to ethyl acetate) to afford the title compound as a pale yellow oil (49.7 mg, 22%). 1H NMR (270 MHz, CDCl3): δ 1.24 (3H, t, J=7.2 Hz, CH3), 1.63-1.86 (6H, m, 2×CH2, 2×CH), 2.03-2.18 (2H, m, 2×CH), 3.69-3.72 (1H, m, CH), 4.05-4.30 (3H, m, CH2, NH), 4.39 (1H, d, J=4.5 Hz, CH), 6.57-6.68 (2H, m, Ar—H), 6.77 (1H, d, J=8.9 Hz, Ar—H), 6.82-6.86 (1H, dd, J=1.5, 7.9 Hz, Ar—H), 7.04-7.07 (1H, d, J=1.5, 7.5 Hz, Ar—H), 7.09-7.13 (1H, dd, J=2.2, 8.8 Hz, Ar—H), 7.44-7.45 ppm (1H, d, J=2.5 Hz, Ar—H). 13C NMR (67.93 MHz, CDCl3): δ 14.9, 28.0, 28.3, 35.0, 35.6, 44.5, 52.4, 61.0, 111.5, 116.8, 118.1, 120.1, 125.9, 128.0, 130.3, 132.0, 138.9, 142.0, 152.0, 153.9 ppm. LCMS: M+H, 435.44 HPLC: 95.62% (5.044 min, isocratic 90% acetonitrile, 10% water at 1 ml/min).

Workup

  1. customOn return, the reaction was quenched with saturated aqueous sodium sodium bicarbonateonate (15 ml)
  2. extractionextracted with ethyl acetate (2×15 ml)
  3. dry with materialThe combined organics were dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customPurification by flash chromatography

Sources & evidence

ORD record
ord-92c24c01627542b8a197ac2918d947dd
Source dataset
uspto-grants-2012_02
Patent number
US08119627B2

Reaction notes

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