Sodium Sulfide → 3-Fluoro-2-mercapto-benzoic acid ethyl ester

HRID 1816830Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1816830
C(ON)C.[CH2:5]([O:7][C:8](=[O:17])[C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([F:15])[C:10]=1F)[CH3:6].[S-2:18].[Na+].[Na+]>CN(C=O)C.C(OCC)(=O)C.O.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>[CH2:5]([O:7][C:8](=[O:17])[C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([F:15])[C:10]=1[SH:18])[CH3:6]

Komponenten

8

Edukt 3

HCID 14804Sodium SulfideHCID 69357Hydroxylamine, O-ethyl-HCID 2761174Benzoic acid, 2,3-difluoro-, ethyl ester

Produkt 1

HCID 229782253-Fluoro-2-mercapto-benzoic acid ethyl ester

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 311Citric AcidLösungsmittelHCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittelHCID 8857Ethyl AcetateLösungsmittel2×

Versuchsvorschrift

Example 37(a) was prepared in a similar manner to that described for Example 35(a) except that the starting material described below was employed and that ethoxyamine was used instead of propylamine: 1H NMR (300 MHz, CDCl3) δ 8.59 (m, 1H), 8.08 (d, 1H), 7.88 (d, 1H, J=16.4 Hz), 7.79 (t, 1H), 7.65 (d, 1H), 7.60 (m, 1H), 7.50 (d, 1H, J=16.4 Hz), 7.40 (t, 1H), 7.36 (d, 1H), 7.28 (s, 1H), 7.23 (m, 1H), 7.10 (d, 1H), 3.90 (q, 2H), 1.19 (t, 3H). LCMS (100% area) Rt=4.85 min, (pos) [M+H]/z Calc'd 435.1, found 435.1, (neg) [M−H]/z Calc'd 433.1, found 433.1. Analyzed with 0.35H2O, 0.07 EtOAc Calc'd, C (62.56), H (4.57), N (12.54), S (7.17). Found: C (62.61), H (4.55), N (12.49), S (7.11). Starting material was prepared as follows: A solution of ethyl-2,3 difluorobenzoate (1.07 g, 5.75 mmol) in DMF (10 mL) was treated with sodium sulfide (896 mg, 11.5 mmol, 2.0 equiv) at 23° C. The mixture was stirred under argon for 10 h. The solution was diluted with ethyl acetate (50 mL) and water (50 mL) and 10% citric acid (5 mL). The organic layer was washed with saturated aqueous sodium bicarbonate, dried over sodium sulfate, decanted and concentrated under reduced pressure to give 3-Fluoro-2-mercapto-benzoic acid ethyl ester. 1H NMR (300 MHz, CDCl3)57.71 (t, 1H), 7.38 (m, H), 7.12 (m, 1H), 4.41 (q, 2H), 1.40 (t, 3H); LCMS (100% area) Rt=4.53 min, (pos) [M+H]/z Calc'd 201.0, found 200.9.

Aufarbeitung

  1. customExample 37(a) was prepared in a similar manner to that
  2. customStarting material was prepared
  3. washThe organic layer was washed with saturated aqueous sodium bicarbonate
  4. dry with materialdried over sodium sulfate
  5. customdecanted
  6. concentrationconcentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-4bc1bd1e57c14288bfa0f0277d38a39f
Quelldatensatz
uspto-grants-2005_04
Patentnummer
US06884890B2

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