Ethyl 2-(diphenylmethyleneamino)acetate → HCID 23497591, compound

HRID 841048Notes

Reaction equation

HRID 841048 reaction equation
[C:1]1([C:7]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[N:8][CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Li+].CC([N-]C(C)C)C.[C:29]1([S:35]([O:38][C:39]2[CH:40]=[CH:41][C:42]([CH2:45]Br)=[N:43][CH:44]=2)(=[O:37])=[O:36])[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1>C1COCC1>[C:1]1([C:7]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[N:8][CH:9]([CH2:45][C:42]2[CH:41]=[CH:40][C:39]([O:38][S:35]([C:29]3[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=3)(=[O:37])=[O:36])=[CH:44][N:43]=2)[C:10]([O:12][CH2:13][CH3:14])=[O:11])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

5

Reactant 3

HCID 319508Ethyl 2-(diphenylmethyleneamino)acetateHCID 2724682Lithium diisopropylamideHCID 10639974HCID 10639974, compound

Product 1

HCID 23497591HCID 23497591, compoundYield 72.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of ethyl N-(diphenylmethylene)glycinate (1.71 g, 6.40 mmol) in dry THF (10 ml) was added to a stirred solution of LDA (2M in heptane/THF/ethylbenzene, 3.20 ml, 6.40 mmol) in dry THF (10 ml) at −70° under nitrogen. After stirring at this temperature for 0.75 h, a solution of 5-benzenesulphonyloxy-2-bromomethyl-pyridine [2.00 g, 6.01 mmol; prepared as described by Myers et al, J.Org.Chem. (1996), 61, 813] in dry THF (10 ml) was added. The reaction mixture was stirred at −70° for 1 h then at room temperature for 18 h. The reaction was quenched with water (10 ml) then partitioned between EtOAc (70 ml) and brine (30 ml). The phases were separated and the aqueous phase re-extracted with EtOAc (2×40 ml). The combined organic extracts were washed with brine (10 ml), dried (Na2SO4) and evaporated in vacuo to afford the crude product as a dark oil. Purification by flash chromatography (silica, 60% to 75% Et2O/hexane; applied as DCM solution) afforded the title compound as a tan-coloured solid (2.25 g, 72%). δH (CDCl3) 8.02 (1H, d, J 2.8 Hz, pyr-H(6), 7.72 (2H, d, J˜8 Hz, ortho-Ar—H), 7.59 (1H, t, J˜8 Hz, para-Ar—H), 7.50 (2H, dd, J 8.4, 1.4 Hz, phenyl-H), 7.40-7.27 (8H, ms, Ar and phenyl-H), 7.19 (1H, dd, J 8.5, 2.8 Hz, pyr-H(4), 7.11 (1H, d, J 8.5 Hz, pyr-H(3), 6.67 (2H, br d, J˜8 Hz, phenyl-H), 4.50 (1H, dd, J 9, 4.6 Hz, CH-α), 4.24-4.10 (2H, sym.m. CH2CH3), 3.50-3.33 (2H, m, pyr-CH2), 1.24 (3H, t, J 7.2 Hz, CH2CH3); m/z (ESI) 515 (MH+).

Workup

  1. stirringThe reaction mixture was stirred at −70° for 1 h
  2. waitat room temperature for 18 h
  3. customThe reaction was quenched with water (10 ml)
  4. customthen partitioned between EtOAc (70 ml) and brine (30 ml)
  5. customThe phases were separated
  6. extractionthe aqueous phase re-extracted with EtOAc (2×40 ml)
  7. washThe combined organic extracts were washed with brine (10 ml)
  8. dry with materialdried (Na2SO4)
  9. customevaporated in vacuo
  10. customto afford the crude product as a dark oil
  11. customPurification by flash chromatography (silica, 60% to 75% Et2O/hexane; applied as DCM solution)

Sources & evidence

ORD record
ord-d7b4cc7fafce451a9463486c8a628a74
Source dataset
uspto-grants-2002_04
Patent number
US06369229B1

Reaction notes

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