Chlorine → HCID 69518704, compound

HRID 854863Notes

Reaction equation

HRID 854863 reaction equation
[F:1][C:2]1[CH:27]=[C:26]([N+:28]([O-])=O)[CH:25]=[CH:24][C:3]=1[O:4][C:5]1[CH:14]=[C:13]2[C:8]([CH:9]=[C:10]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH:11]([C:15]([F:18])([F:17])[F:16])[O:12]2)=[CH:7][CH:6]=1.[Cl:31]Cl>C(O)(=O)C.[Zn]>[NH2:28][C:26]1[CH:25]=[CH:24][C:3]([O:4][C:5]2[CH:14]=[C:13]3[C:8]([CH:9]=[C:10]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH:11]([C:15]([F:18])([F:17])[F:16])[O:12]3)=[CH:7][C:6]=2[Cl:31])=[C:2]([F:1])[CH:27]=1

Participants

5

Reactant 2

HCID 24526Chlorine2×HCID 69519487HCID 69519487, compound

Product 1

HCID 69518704HCID 69518704, compound

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 176Acetic AcidSolvent2×

Procedure

A solution of the ester from Step 1 (0.5 g, 1.17 mmole) in acetic acid was stirred at 10° C. The pre-prepared solution of Cl2 (gas) in acetic acid (10 mL, 4.0 mmole was added to the above solution. The mixture was stirred for 2 hour. After Cl2 (gas) was blown away, Zn powder (5 eq) was added to the mixture and stirred for 30 min. The Zn salts were removed by filtration and the filtrate was evaporated to dryness. The residue was purified by normal phase silica chromatography with 20% ethyl acetate in hexane to give the ester as a yellow oil, which solidified upon standing (0.43 g, 85%): LCMS m/z 431.75 (M+H). 1NMR (CDCl3/400 MHz) 7.61 (s, 1H), 7.27 (s, 1H), 6.95 (dd, 1H, J=8.4 Hz), 6.50 (dd, 1H, J=12, 2.4 Hz ), 6.42 (m, 1H), 5.61 (q, 1H, J=6.8 Hz), 4.30 (q, 2H, J=7.2 Hz), 1.33 (t, 3H, J=7.2 Hz).

Workup

  1. stirringstirred for 30 min
  2. customThe Zn salts were removed by filtration
  3. customthe filtrate was evaporated to dryness
  4. customThe residue was purified by normal phase silica chromatography with 20% ethyl acetate in hexane

Sources & evidence

ORD record
ord-b5c5c85961e74ac689fa5a5d35f12224
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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