2-Chlorobenzaldehyde → 1-[(2-Chlorophenyl)-(6,7-dihydro-4H-thieno[3,2-c]pyridin-5-yl)-methyl]-1H-benzotriazole

HRID 1526439Notes

Reaction equation

HRID 1526439 reaction equation
[S:1]1[C:9]2[CH2:8][CH2:7][NH:6][CH2:5][C:4]=2[CH:3]=[CH:2]1.[NH:10]1[C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][C:13]=2[N:12]=[N:11]1.[Cl:19][C:20]1[CH:27]=[CH:26][CH:25]=[CH:24][C:21]=1[CH:22]=O>C(OCC)C>[Cl:19][C:20]1[CH:27]=[CH:26][CH:25]=[CH:24][C:21]=1[CH:22]([N:6]1[CH2:7][CH2:8][C:9]2[S:1][CH:2]=[CH:3][C:4]=2[CH2:5]1)[N:10]1[C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][C:13]=2[N:12]=[N:11]1

Participants

5

Reactant 3

HCID 69962-ChlorobenzaldehydeHCID 30850764,5,6,7-Tetrahydrothieno(3,2-c)pyridineHCID 178418385HCID 178418385, compound

Product 1

HCID 675165691-[(2-Chlorophenyl)-(6,7-dihydro-4H-thieno[3,2-c]pyridin-5-yl)-methyl]-1H-benzotriazoleYield 61.7%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

4,5,6,7-Tetrahydro-thieno[3,2-c]pyridine (0.5 g, 3.59 mmol), benzotriazole (428 mg, 3.59 mmol), and 2-chlorobenzaldehyde (504 mg, 3.59 mmol) were dissolved in diethyl ether and stirred for 3 days in the presence of molecular sieves (4 Å) under an argon atmosphere at room temperature. After 3 days, the ether was filtered and washed with saturated sodium bicarbonate solution (20 mL). The ether was dried over sodium sulfate, filtered and concentrated. The remaining colorless foam was dissolved in heptane/diethyl ether (5 mL/1 mL) and stored in a freezer (−10° C.) overnight. After 20 hours at −10° C., the heptane was decanted and the remaining oil was dried under high vacuum at room temperature until a constant weight was achieved to provide 1-[(2-Chlorophenyl)-(6,7-dihydro-4H-thieno[3,2-c]pyridin-5-yl)-methyl]-1H-benzotriazole (Compound IVa, 0.84 g, 61.7% yield) as a colorless foam that appeared to be an 80:20 mixture of isomers by NMR. 1H NMR (300 MHz, CDCl3/TMS): δ=8.08 (d, 1H, J=8.1 Hz), 7.91-7.79 (m, 2H), 7.55 (d, 1H, J=8.4 Hz), 7.53-7.24 (m, 4H), 7.11 (s, 1H), 7.04 (d, 1H, J=5.1 Hz), 6.61 (d, 1H, J=5.1 Hz), 3.90 (d, 1H, J=14.4 Hz), 3.69 (d, 14.4 Hz), 3.21-2.95 (m, 2H), 2.88 (m, 2H). (major isomer). 13C NMR (75 MHz, CDCl3/TMS): δ=145.48, 133.78, 133.45, 132.94, 132.65, 130.10, 129.40, 127.50, 126.98, 126.56, 124.97, 124.00, 122.79, 119.80, 110.39, 84.85, 49.59, 47.28, 25.50. (major isomer). MS (HR, DIP-CI): Calculated for (MH+): 379.0779. found 379.0752.

Workup

  1. waitAfter 3 days
  2. filtrationthe ether was filtered
  3. washwashed with saturated sodium bicarbonate solution (20 mL)
  4. dry with materialThe ether was dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. dissolutionThe remaining colorless foam was dissolved in heptane/diethyl ether (5 mL/1 mL)
  8. customstored in a freezer (−10° C.) overnight
  9. waitAfter 20 hours at −10° C.
  10. customthe heptane was decanted
  11. customthe remaining oil was dried under high vacuum at room temperature until a constant weight

Sources & evidence

ORD record
ord-e51003438fcc4319af56c511dcaf5add
Source dataset
uspto-grants-2015_07
Patent number
US09085585B2

Reaction notes

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