Carbon Tetrachloride → HCID 68675195, compound

HRID 1993065Notes

Reaction equation

HRID 1993065 reaction equation
[F:1][C:2]([F:32])([F:31])[C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH:10]=[C:11]([CH:28]=[CH:29][CH:30]=2)[CH2:12][O:13][C:14]2[CH:19]=[CH:18][C:17]([CH:20]([CH3:27])[C:21]([NH:23]CC=C)=O)=[CH:16][CH:15]=2)=[CH:5][CH:4]=1.[CH:33]1[CH:38]=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=C[CH:34]=1.CCN(CC)CC.C(Cl)(Cl)(Cl)Cl>ClCCl>[F:32][C:2]([F:1])([F:31])[C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH:10]=[C:11]([CH:28]=[CH:29][CH:30]=2)[CH2:12][O:13][C:14]2[CH:19]=[CH:18][C:17]([C:20]([CH3:27])([CH2:38][CH:33]=[CH2:34])[C:21]#[N:23])=[CH:16][CH:15]=2)=[CH:5][CH:4]=1

Participants

6

Reactant 4

HCID 5943Carbon TetrachlorideHCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 68675319HCID 68675319, compound

Product 1

HCID 68675195HCID 68675195, compoundYield 80.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

The 3-aza-claisen reaction was carried out according to the method of Walters et al. (1991) Tetrahedron Lett. 2: 179-182. Amide 49.3 (15.9 g, 36.2 mmol) and PPh3 (21 g, 80 mmol) were dissolved in anhydrous dichloromethane (160 mL). Et3N (12 g, 119.5 mmol) and CCl4 (18.4 g, 119.5 mmol) were added dropwise. The resulting mixture was stirred at room temperature overnight. The reaction was quenched with saturated brine (250 mL). The organic phase was extracted with ethyl acetate (50 mL×3). The combined organic phases were dried over MgSO4 and concentrated under reduced pressure. The resulting residue was purified via flash chromatography (25% ethyl acetate in hexanes) to yield 12.3 g of 49.4. 1H NMR (400 MHz) (CDCl3) δ 7.73 (4H, s); 7.70 (1H, s); 7.61-7.51 (3H, m); 7.41 (2H, d, J=8.9 Hz); 7.05 (2H, d, J=8.9 Hz); 5.76-5.72 (1H, m); 5.21-5.17 (4H, m); 2.71-2.59 (2H, m); 1.72 (3H, s).

Workup

  1. customThe 3-aza-claisen reaction
  2. customThe reaction was quenched with saturated brine (250 mL)
  3. extractionThe organic phase was extracted with ethyl acetate (50 mL×3)
  4. dry with materialThe combined organic phases were dried over MgSO4
  5. concentrationconcentrated under reduced pressure
  6. customThe resulting residue was purified via flash chromatography (25% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-784fc3c5bba24355b57eeac46fd125d7
Source dataset
uspto-grants-2010_01
Patent number
US07649110B2

Reaction notes

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