Triethylamine → methyl N-[(3-chloro-4'-nitrobiphenyl-4-yl)carbonyl]-L-valinate

HRID 2356833Notes

Reaction equation

HRID 2356833 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:11]2[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][CH:12]=2)[CH:5]=[CH:6][C:7]=1[C:8]([OH:10])=O.C(Cl)(=O)C(Cl)=O.Cl.[CH3:27][O:28][C:29](=[O:35])[C@H:30]([CH:32]([CH3:34])[CH3:33])[NH2:31].C(N(CC)CC)C>C(Cl)Cl.CN(C=O)C>[Cl:1][C:2]1[CH:3]=[C:4]([C:11]2[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][CH:12]=2)[CH:5]=[CH:6][C:7]=1[C:8]([NH:31][C@H:30]([C:29]([O:28][CH3:27])=[O:35])[CH:32]([CH3:34])[CH3:33])=[O:10]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 111190Methyl valinate hydrochlorideHCID 593853313-Chloro-4'-nitrobiphenyl-4-carboxylic acid

Product 1

HCID 59385306methyl N-[(3-chloro-4'-nitrobiphenyl-4-yl)carbonyl]-L-valinate

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
50 °C

Procedure

3-Chloro-4′-nitrobiphenyl-4-carboxylic acid (0.31 g, 1.12 mmol) was dissolved in methylene chloride (10 mL), and then oxalyl chloride (0.15 mL, 1.7 mmol) was added, followed by one drop of DMF. The resulting mixture was stirred at 50° C. for 45 min and then concentrated under reduced pressure. The residue was dissolved in methylene chloride (5 mL) and added dropwise to an ice-cold mixture of L-valine methyl ester hydrochloride (0.22 g, 1.3 mmol), methylene chloride (10 mL), and triethylamine (0.62 mL, 4.5 mmol). The resulting solution was stirred at rt for 18 h and then concentrated under reduced pressure. The residue was taken up in EtOAc, passed through a plug of silica gel, and concentrated under reduced pressure. This yielded 0.305 g (70%) of the title compound. LC/MS m/z 390.9 (MH+), retention time 3.30 min. 1H NMR (400 MHz, CD2Cl2) δ 1.06 (dd, 6H), 2.32-2.39 (m, 1H), 3.80 (s, 3H), 4.71-4.78 (m, 1H), 6.33 (d, 1H), 6.76 (d, 2H), 7.58-7.80 (m, 5H), 8.35 (d, 2H).

Workup

  1. concentrationconcentrated under reduced pressure
  2. dissolutionThe residue was dissolved in methylene chloride (5 mL)
  3. stirringThe resulting solution was stirred at rt for 18 h
  4. concentrationconcentrated under reduced pressure
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-0c6e048c5359443e9f896bd2db458a4a
Source dataset
uspto-grants-2010_07
Patent number
US07759376B2

Reaction notes

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