Carbon Tetrachloride → Methyl 3-[2-benzyloxy-5-(2-chloroethyl)-4-nitroanilino]-4,4,4-trifluoro-2-butenoate

HRID 431725Notes

Reaction equation

HRID 431725 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:20]([Cl:24])(Cl)(Cl)Cl.[CH2:25]([O:32][C:33]1[CH:49]=[C:48]([N+:50]([O-:52])=[O:51])[C:47]([CH2:53]CO)=[CH:46][C:34]=1[NH:35][C:36]([C:42]([F:45])([F:44])[F:43])=[CH:37][C:38]([O:40][CH3:41])=[O:39])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1>C(Cl)Cl>[CH2:25]([O:32][C:33]1[CH:49]=[C:48]([N+:50]([O-:52])=[O:51])[C:47]([CH2:53][CH2:20][Cl:24])=[CH:46][C:34]=1[NH:35][C:36]([C:42]([F:43])([F:44])[F:45])=[CH:37][C:38]([O:40][CH3:41])=[O:39])[C:26]1[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=1

Participants

5

Reactant 3

HCID 5943Carbon TetrachlorideHCID 11776TriphenylphosphineHCID 69547699Methyl 3-[2-benzyloxy-5-(2-hydroxyethyl)-4-nitroanilino]4,4,4-trifluoro-2-butenoate

Product 1

HCID 69546885Methyl 3-[2-benzyloxy-5-(2-chloroethyl)-4-nitroanilino]-4,4,4-trifluoro-2-butenoate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Triphenylphosphine (2.57 g, 9.77 mmol), CCl4 (2.83 mL, 29.3 mmol), and dry CH2Cl2 (55 mL) were added to methyl 3-[2-benzyloxy-5-(2-hydroxyethyl)-4-nitroanilino]4,4,4-trifluoro-2-butenoate (2.10 g, 4.89 mmol) in a round bottom flask. The yellow solution was flushed with N2 and stirred overnight. The solution was checked by TLC (20% ethyl acetate/petroleum ether) and then concentrated under reduced pressure. The residue was purified on a silica gel column run in 10% ethyl acetate/petroleum ether solvent system to give methyl 3-[2-benzyloxy-5-(2-chloroethyl)-4-nitroanilino]-4,4,4-trifluoro-2-butenoate. Total yield: 1.25 g (2.71 mmol, 57%). M.p.=105-110° C. TLC (20% ethyl acetate /petroleum ether) Rf320.69.500 MHz 1H-NMR (CDCl3) 10.04 (s, 1H), 7.72 (s, 1H), 7.48 (d, 7.5, 2H), 7.41 (t, 7.5, 2H), 7.35 (t, 7.5, 1H), 7.14 (s, 1H), 5.63 (s, 1H), 5.23 (s, 2H), 3.80 (t, 6.5, 2H), 3.75 (s, 3H), 3.33 (t, 6.5, 2H). IR (neat) 2415, 3050, 2956, 1730, 1687, 1640, 1615, 1585, 1530, 1334, 1296, 1215, 1143, 1024, 815, 739, 696. EI-MS (relative intensity) 458 (M+, 6). Accurate mass for C20H18O5N235ClF3: calcd. 458.0856, obsd. 458.0853.

Workup

  1. customThe yellow solution was flushed with N2
  2. concentrationconcentrated under reduced pressure
  3. customThe residue was purified on a silica gel column

Sources & evidence

ORD record
ord-b3123db0852d438b995a63447463b3d3
Source dataset
uspto-grants-2003_12
Patent number
US06660742B2

Reaction notes

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