Sodium borohydride → Ethyl {4-[2-(allyloxy)-4-methylphenyl]-2-methyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl}(hydroxy)acetate

HRID 2406383Notes

Reaction equation

HRID 2406383 reaction equation
Cl.[CH2:2]([O:4][C:5](=[O:33])[C:6]([C:8]1[C:9]([C:22]2[CH:27]=[CH:26][C:25]([CH3:28])=[CH:24][C:23]=2[O:29][CH2:30][CH:31]=[CH2:32])=[C:10]2[C:17]3[CH2:18][CH2:19][CH2:20][CH2:21][C:16]=3[S:15][C:11]2=[N:12][C:13]=1[CH3:14])=[O:7])[CH3:3].[BH4-].[Na+]>C(O)C>[CH2:2]([O:4][C:5](=[O:33])[CH:6]([C:8]1[C:9]([C:22]2[CH:27]=[CH:26][C:25]([CH3:28])=[CH:24][C:23]=2[O:29][CH2:30][CH:31]=[CH2:32])=[C:10]2[C:17]3[CH2:18][CH2:19][CH2:20][CH2:21][C:16]=3[S:15][C:11]2=[N:12][C:13]=1[CH3:14])[OH:7])[CH3:3]

Participants

4

Reactant 2

HCID 4311764Sodium borohydrideHCID 69672800Ethyl {4-[2-(allyloxy)-4-methylphenyl]-2-methyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl}(oxo)acetate hydrochloride salt

Product 1

HCID 69672380Ethyl {4-[2-(allyloxy)-4-methylphenyl]-2-methyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl}(hydroxy)acetateYield 95.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a stirred solution of [4-(2-Allyloxy-4-methyl-phenyl)-2-methyl-5,6,7,8-tetrahydro-benzo[4,5]thieno[2,3-b]pyridin-3-yl]-oxo-acetic acid ethyl ester hydrochloride (1.1 g, 2.56 mmols) in ethanol (20 mL) was added sodium borohydride (145 mg, 1.5 eq, 3.84 mmols), and the reaction was stirred at room temperature for 5 minutes. The reaction was concentrated in vacuo, and the residue was partitioned between ethyl acetate (20 mL) and hydrochloric acid (aqueous, 1 N, 30 mL). The organics were separated, washed with brine (10 mL), dried (MgSO4), filtered and concentrated in vacuo to give crude [4-(2-allyloxy-4-methyl-phenyl)-2-methyl-5,6,7,8-tetrahydro-benzo[4,5]thieno[2,3-b]pyridin-3-yl]-hydroxy-acetic acid ethyl ester as a pale orange gum 1.1 g (91% yield). LCMS (2 min acidic) 1.53 min 52-81% pure by UV, ES+/AP+ 452. HNMR (CDCl3)>80% pure 7.02 (d, J=7.4 Hz, 1H) 6.81-6.85 (m, 1H) 6.79 (s, 1H) 5.86 (m, 1H) 5.18 (s, 1H) 5.08-5.17 (m, 2H) 4.47-4.51 (m, 2H) 4.08-4.22 (m, 2H) 2.81 (t, J=6.2 Hz, 2H) 2.63 (s, 3H) 2.43 (s, 3H) 1.71-1.87 (m, 4H) 1.53-1.64 (m, 2H) 1.17-1.21 (m, 3H).

Workup

  1. concentrationThe reaction was concentrated in vacuo
  2. customthe residue was partitioned between ethyl acetate (20 mL) and hydrochloric acid (aqueous, 1 N, 30 mL)
  3. customThe organics were separated
  4. washwashed with brine (10 mL)
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-f3624e3b2c584b12988a1494d511db74
Source dataset
uspto-grants-2014_08
Patent number
US08809363B2

Reaction notes

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