3-hydroxy-1,2,3-benzotriazin-4(3H)-one → (4-Nitro-2-phenylbenzoyl)methionine methyl ester

HRID 2121170Notes

Reaction equation

HRID 2121170 reaction equation
[N+:1]([C:4]1[CH:12]=[CH:11][C:7]([C:8]([OH:10])=O)=[C:6]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH:5]=1)([O-:3])=[O:2].ON1C(=O)C2C=CC=CC=2N=N1.Cl.CN(C)CCCN=C=NCC.Cl.[CH3:44][O:45][C:46](=[O:53])[C@H:47]([CH2:49][CH2:50][S:51][CH3:52])[NH2:48]>CN(C=O)C.C(N(CC)CC)C>[CH3:44][O:45][C:46](=[O:53])[C@H:47]([CH2:49][CH2:50][S:51][CH3:52])[NH:48][C:8](=[O:10])[C:7]1[CH:11]=[CH:12][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][C:6]=1[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

7

Reactant 4

HCID 730263-hydroxy-1,2,3-benzotriazin-4(3H)-oneHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 106578414-Nitro-2-phenylbenzoic acidHCID 11435579L-Methionine, methyl ester, hydrochloride

Product 1

HCID 18666764(4-Nitro-2-phenylbenzoyl)methionine methyl ester

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent2×

Procedure

4-Nitro-2-phenylbenzoic acid (50.0 g, 205 mmol) and 3-hydroxy1,2,3-benzotriazin-4(3H)-one (36.89 g, 226 mmol) were dissolved in 500 mL DMF. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (47.3 g, 247 mmol) and methionine methyl ester hydrochloride (53.37 g, 267 mmol) were added followed by triethylamine (31.5 mL, 226 mmol). Additional triethylamine was added to raise the pH to 6˜7. After 1 hour at ambient temperature, the reaction mixture was concentrated to 200 mL, diluted with 500 mL ethyl acetate, washed with 1 M HCl, 5% NaHCO3, and brine, and dried over Na2SO4 to provide (4-nitro-2-phenylbenzoyl)methionine methyl ester which was used directly without further purification. MS m/e 389 (M+H)+. 1H NMR (CDCl3, 300 MHz) δ 1.78 (m, 2H), 2.01 (s, 3H), 2.60 (m, 2H), 3.69 (s, 3H), 4.69 (m, 1H), 6.02 (d, J=8 Hz, 1H), 7.48,(m, 5H), 7.85 (m, 1H), 8.27 (m, 2H).

Workup

  1. temperatureto raise the pH to 6˜7
  2. concentrationthe reaction mixture was concentrated to 200 mL
  3. additiondiluted with 500 mL ethyl acetate
  4. washwashed with 1 M HCl, 5% NaHCO3, and brine
  5. dry with materialdried over Na2SO4

Sources & evidence

ORD record
ord-0c42984f4720439badd03ff4c1a6c548
Source dataset
uspto-grants-2004_02
Patent number
US06693123B2

Reaction notes

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