Hydrochloric Acid → HCID 70204637, compound

HRID 611579Notes

Reaction equation

HRID 611579 reaction equation
C[C:2]1[N:7]=[C:6]2[CH:8]=[CH:9][S:10][C:5]2=[CH:4][CH:3]=1.[CH:11](NC(C)C)(C)C.[Li]CCCC.Cl([O-])(=O)(=O)=O.[CH2:28]1[C:35]2[CH2:34][CH2:33][CH2:32][N+:31]=2[CH2:30][CH2:29]1.Cl>C1COCC1>[CH2:28]1[C:35]2([CH:9]3[S:10][C:5]4[C:6]([N:7]([CH3:11])[CH:2]=[CH:3][CH:4]=4)=[CH:8]3)[N:31]([CH2:32][CH2:33][CH2:34]2)[CH2:30][CH2:29]1

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 7912DiisopropylamineHCID 591057HCID 591057, compoundHCID 10878400Pyrrolizinium, 1,2,3,5,6,7-hexahydro-, perchlorateHCID 178418339Butyllithium

Product 1

HCID 70204637HCID 70204637, compoundYield 32%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

5-Methylthieno[3,2-b]pyridine (285 mg, 1.91 mmol, prepared according to Gronowitz et al., Acta Chemica Scandinavica B, 29:233-238 (1975)), diisopropylamine (270 uL, 1.91 mmol) and nBuLi (2.5 M in hexanes, 765 uL, 1.91 mmol) were combined in THF (8 mL). After 20 minutes of stirring, 1,2,3,5,6,7-hexahydro-pyrrolizinium perchlorate from Example 15a (200 mg, 0.95 mmol) was added. The mixture was allowed to warm to ambient temperature and 2 N aqueous HCl was added. The reaction mixture was washed with Et2O and the aqueous phase was basified with 15% NaOH solution and extracted with CH2Cl2 (3×). The organic phases were combined, dried (MgSO4), concentrated and chromatographed (silica gel; CHCl3 /MeOH, 99:1) to afford a solid (79 mg, 32%): 1H NMR (CDCl3, 300 MHz) δ 1.80-1.94 (m, 4H), 1.98-2.07 (m, 2H), 2.16-2.24 (m, 2H), 2.64 (s, 3H), 2.64-2.71 (m, 2H), 3.22-3.28 (m, 2H), 7.02 (d, J=8 Hz, 1H), 7.16 (s, 1H), 7.92 (d, J=8 Hz, 1H); MS (CI/NH3) m/z: 259 (M+H)+.

Workup

  1. washThe reaction mixture was washed with Et2O
  2. extractionextracted with CH2Cl2 (3×)
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated
  5. customchromatographed (silica gel; CHCl3 /MeOH, 99:1)

Sources & evidence

ORD record
ord-27e817f89c714ba3b60f85937d9e7611
Source dataset
uspto-grants-1999_12
Patent number
US06001849

Reaction notes

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