Acetic Anhydride → HCID 178471965, compound

HRID 1859488

Reaction equation

HRID 1859488 reaction equation
[F:1][C:2]1[C:15]([F:16])=[C:14]([F:17])[C:13]([F:18])=[CH:12][C:3]=1[C:4]([CH2:6][C:7]([O:9][CH2:10][CH3:11])=[O:8])=[O:5].[CH3:19]C(OCC1C2C(=CC=CC=2)C(COC(C)=O)=C2C=1C=CC=C2)=O.C(OC(OCC)OCC)C.C(OC(=O)C)(=O)C.Cl.[NH2:61][C:62]1[C:71]2[C:66](=[CH:67][CH:68]=[CH:69][CH:70]=2)[CH:65]=[CH:64][C:63]=1[OH:72]>ClCCl.N1C=CC=CC=1>[OH:72][C:63]1[CH:64]=[CH:65][C:66]2[C:71](=[CH:70][CH:69]=[CH:68][CH:67]=2)[C:62]=1[NH:61][CH:19]=[C:6]([C:4]([C:3]1[CH:12]=[C:13]([F:18])[C:14]([F:17])=[C:15]([F:16])[C:2]=1[F:1])=[O:5])[C:7]([O:9][CH2:10][CH3:11])=[O:8]

Participants

8

Reactant 5

HCID 7918Acetic AnhydrideHCID 31214Ethyl orthoformateHCID 5184691-Amino-2-naphthol hydrochlorideHCID 600916Ethyl 3-oxo-(2,3,4,5-tetrafluorophenyl)propanoate2×HCID 613145Acetic acid 10-acetoxymethyl-anthracen-9-ylmethyl ester

Product 1

HCID 178471965HCID 178471965, compoundYield 93%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolvent2×HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
130 °C

Procedure

Ethyl 2,3,4,5-tetrafluorobenzoylacetate was treated with triethyl orthofomate and acetic anhydrate, then with different aminonaphthols in the presence of pyridine to generate an aminoketoacid. The solution of ethyl 2,3,4,5-tetrafluorobenzoylacetate (1.10 g, 4.18 mmol) in triethylorthoformate (1 ml, 6.06 mmol) and acetic anhydride (1.8 ml, 19 mmol) was heated and stirred at 130° C. for 4 h. During the process, the formed ethyl acetate was removed. The mixture was then distilled under vacuum to yield an orange oil, which was dissolved in 30 ml dichloromethane. 1-aminonaphthalen-2-ol hydrogen chloride (90% pure from Aldrich) (1.36 g, 6.26 mmol), premixed with 2 equivalent of pyridine, was added to the dichloromethane solution, and the mixture was stirred overnight at 22° C. After the solvent was removed under reduced pressure, the remaining residue was absorbed on silica gel and subjected to flash column chromatography (gradient ethylacetate:hexanes=8:4) that yield a bright yellow powder (1.69 g). Yield=93%. 1H NMR (CDCl3) δ 1.02 (t, J=7.2 Hz, 3H), 4.01 (q, J=7.2 Hz, 2H), 4.10 (m, 1H), 7.34 (d, J=9.0 Hz, 1H), 7.41 (m, 1H), 7.60 (m, 2H), 7.82 (8, 2H), 7.91 (d, J=8.1 Hz, 1H), 8.54 (b, 1H).

Workup

  1. customDuring the process, the formed ethyl acetate was removed
  2. distillationThe mixture was then distilled under vacuum
  3. customto yield an orange oil, which
  4. stirringthe mixture was stirred overnight at 22° C
  5. customAfter the solvent was removed under reduced pressure
  6. customthe remaining residue was absorbed on silica gel

Sources & evidence

ORD record
ord-90f4cdb0eb8140d2bacc64d5a78b5d63
Source dataset
uspto-grants-2003_03
Patent number
US06528517B1

Linked notes

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