Ethylbenzene → HCID 23497591, compound

HRID 1837044Notes

Reaction equation

HRID 1837044 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(C1C=CC=CC=1)C.[C:37]1([S:43]([O:46][C:47]2[CH:48]=[CH:49][C:50]([CH2:53]Br)=[N:51][CH:52]=2)(=[O:45])=[O:44])[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1>C1COCC1.CCOCC.CCCCCC>[C:1]1([C:7]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[N:8][CH:9]([CH2:53][C:50]2[CH:49]=[CH:48][C:47]([O:46][S:43]([C:37]3[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=3)(=[O:45])=[O:44])=[CH:52][N:51]=2)[C:10]([O:12][CH2:13][CH3:14])=[O:11])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

7

Reactant 4

HCID 7500EthylbenzeneHCID 319508Ethyl 2-(diphenylmethyleneamino)acetateHCID 2724682Lithium diisopropylamideHCID 10639974HCID 10639974, compound

Product 1

HCID 23497591HCID 23497591, compoundYield 72.8%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 21584099Diethylether hexaneSolvent

Procedure

A solution of ethyl N-(diphenylmethylene)glycinate (1.71 g, 6.40 mmol) in dry THF (10 ml) was added to a stirrred solution of LDA (2M in heptane/TNF/ethylbenzene, 320 ml, 6.40 mmol) in dry THF 910 ml) at −70° under nitrogen. After stirring at this temperture for 0.75 h, a solution of 5-benzenesulphonyloxy-2-bromomethylpyridine (2.00 g, 6.01 mmol); [prepared as described by Myers et al, J.O.C. 61, 813 (1996)] 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 910 ml) then partitioned between EtOAc (70 ml) and bring (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. Chromatography (silica: 60-75% Et2O/Hexane) afforded the title compound as a tan-coloured solid (2.25 g, 72%). δ H (CDCl3) 8.02 (1H, d, J 2.8 Hz), 7.72 (2H, d, J 8.0 hz), 7.59 (1H, t, J 8.0 hz), 7.50 (2H, dd, J 8.4 Hz), 7.40-7.27 (8H, m), 7.19 (1H, dd, J 8.5, 2.8 Hz), 7.11 (1H, d, J 8.5 Hz), 6.67 (2H, br, d, J 8.0 Hz), 4.50 (1H, dd, J 9.0, 4.6 Hz), 4.25-4.10 (2H, m), 3.50-3.33 (2H, m) and 1.24 (3H, t, J 7.2 Hz), m/z (ES+, 70V) 515 (MH+).

Workup

  1. additionwas added
  2. stirringThe reaction mixture was stirred at −70° for 1 h
  3. waitat room temperature for 18 h
  4. customThe reaction was quenched with water 910 ml)
  5. customthen partitioned between EtOAc (70 ml)
  6. customThe phases were separated
  7. extractionthe aqueous phase re-extracted with EtOAc (2×40 ml)
  8. washThe combined organic extracts were washed with brine (10 ml)
  9. dry with materialdried (Na2SO4)
  10. customevaporated in vacuo
  11. customto afford the crude product as a dark oil

Sources & evidence

ORD record
ord-94be6830ac5949eca9d2d5938dabd046
Source dataset
uspto-grants-2004_08
Patent number
US06780874B2

Reaction notes

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