Ethyl Acetate → 8-Ethyl-1-methyl-thienyl[3',4':6,5]dipyrido[2,3-b:3',2'-f]azepine

HRID 580820Notes

Reaction equation

HRID 580820 reaction equation
[CH3:1][CH2:2][N:3]1[C:16]2[N:17]=[CH:18][CH:19]=[CH:20][C:15]=2[C:14]2[C:10](=[CH:11][S:12][CH:13]=2)[C:5]2[CH:6]=[CH:7][CH:8]=[N:9][C:4]1=2.[CH:21]([N-]C(C)C)(C)C.[Li+].C(O[CH2:33][CH3:34])(=O)C>O1CCCC1.IC>[CH3:1][CH2:2][N:3]1[C:16]2[N:17]=[CH:18][CH:19]=[CH:20][C:15]=2[C:14]2[C:10](=[CH:11][S:12][C:13]=2[CH3:21])[C:5]2[CH:6]=[CH:7][CH:8]=[N:9][C:4]1=2.[CH3:1][CH2:2][N:3]1[C:4]2[N:9]=[CH:8][CH:7]=[CH:6][C:5]=2[C:10]2[C:14](=[C:33]([CH3:34])[S:12][C:11]=2[CH3:21])[C:15]2[CH:20]=[CH:19][CH:18]=[N:17][C:16]1=2

Participants

7

Reactant 3

HCID 8857Ethyl AcetateHCID 4746208-Ethyl-thienyl[3',4':6,5]dipyrido[2,3-b:3',2'-f]azepineHCID 2724682Lithium diisopropylamide

Product 2

HCID 4746238-Ethyl-1-methyl-thienyl[3',4':6,5]dipyrido[2,3-b:3',2'-f]azepineHCID 4746248-Ethyl-1,3-dimethyl-thienyl[3',4':6,5]dipyrido[2,3-b:3',2'-f]azepine

Reagents, catalysts & solvents 2

HCID 6328Methyl iodideCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 8-ethyl-thienyl[3',4':6,5]dipyrido[2,3-b:3',2'-f]azepine (0.025 g) in tetrahydrofuran (2 mL) cooled to -78° C. was added lithium diisopropylamide (1.5M in cyclohexane, 0.1 mL). After 10 minutes, iodomethane (2 drops) was added, and the mixture was allowed to warm to room temperature. The mixture was diluted with ethyl acetate, washed with water, dried, filtered and evaporated. The residue was dissolved in tetrahydrofuran (2 mL) cooled to -78° C., and lithium diisopropylamide (1.5M in cyclohexane, 0.1 mL) was added. After 10 minutes, iodomethane (0.05 mL) was added, and the mixture was allowed to warm to room temperature. The mixture was diluted with ethyl acetate, washed with water, dried, filtered and evaporated. The residue was fractionated by HPLC to give 8-ethyl-1-methyl-thienyl[3',4':6,5]dipyrido[2,3-b:3',2'-f]azepine (0.010 g) mp 106-108° C. and 8-ethyl-1,3-dimethyl-thienyl[3',4':6,5]dipyrido[2,3-b:3',2'-f]azepine (0.003 g) mp 176-178° C.

Workup

  1. washwashed with water
  2. customdried
  3. filtrationfiltered
  4. customevaporated
  5. dissolutionThe residue was dissolved in tetrahydrofuran (2 mL)
  6. temperaturecooled to -78° C.
  7. additionlithium diisopropylamide (1.5M in cyclohexane, 0.1 mL) was added
  8. waitAfter 10 minutes
  9. additioniodomethane (0.05 mL) was added
  10. temperatureto warm to room temperature
  11. additionThe mixture was diluted with ethyl acetate
  12. washwashed with water
  13. customdried
  14. filtrationfiltered
  15. customevaporated

Sources & evidence

ORD record
ord-bda48862a9c4471eab1c497175f5e668
Source dataset
uspto-grants-1999_07
Patent number
US05919779

Reaction notes

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