Hydrochloric Acid → 2-(5-Fluoro-2-nitro-phenylamino)-5-methyl-thiophene-3-carbonitrile

HRID 131342

Reaktionsgleichung

Reaktionsgleichung von HRID 131342
[NH2:1][C:2]1[S:3][C:4]([CH3:9])=[CH:5][C:6]=1[C:7]#[N:8].F[C:11]1[CH:16]=[C:15]([F:17])[CH:14]=[CH:13][C:12]=1[N+:18]([O-:20])=[O:19].O.[OH-].[Li+].Cl>O.CS(C)=O>[F:17][C:15]1[CH:14]=[CH:13][C:12]([N+:18]([O-:20])=[O:19])=[C:11]([NH:1][C:2]2[S:3][C:4]([CH3:9])=[CH:5][C:6]=2[C:7]#[N:8])[CH:16]=1

Komponenten

7

Edukt 4

HCID 313Hydrochloric AcidHCID 679672,4-DifluoronitrobenzeneHCID 168937Lithium hydroxide, monohydrateHCID 6890562-Amino-5-methyl-3-thiophenecarbonitrile

Produkt 1

HCID 586259392-(5-Fluoro-2-nitro-phenylamino)-5-methyl-thiophene-3-carbonitrileAusbeute 62 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 679Dimethyl SulfoxideLösungsmittelHCID 962WaterLösungsmittel

Versuchsvorschrift

Add 2-amino-5-methyl-thiophene-3-carbonitrile (10.0 g, 72.4 mmol) and 2,4-difluoro-1-nitro-benzene (8.00 mL, 73.0 mmol) to DMSO (130 mL) and stir under nitrogen at ambient temperature. Add lithium hydroxide monohydrate (6.10 g, 145 mmol) in one portion and stir at ambient temperature. After 18 hours, add deionized water (390 mL) dropwise at 10-20° C. Adjust the pH to 7-8 with concentrated HCl (˜6 mL) and stir for 4 hours. Filter the crude product and rinse with 3:1/water: DMSO, then water. Dry at 50° C. to constant weight. Purify by flash chromatography, eluting with methylene chloride to give the title compound 10.3 g (62%): 1H NMR (400 MHz, DMSO-d6) δ 9.83 (bs, 1H), 8.28 (m, 1H), 7.12 (s, 1H), 6.91 (m, 1H), 6.73 (m, 1H), 2.53 (s, 3H). HRMS (ES) exact mass M+H calcd for C12H8FN3O2S 300.0219; found 300.0219.

Aufarbeitung

  1. stirringstir for 4 hours
  2. filtrationFilter the crude product
  3. washrinse with 3:1/water
  4. customDry at 50° C. to constant weight
  5. customPurify by flash chromatography
  6. washeluting with methylene chloride

Quellen und Nachweise

ORD-Eintrag
ord-4acee4ebf9f04702ae3394d9518dbba9
Quelldatensatz
uspto-grants-2008_06
Patentnummer
US07384934B2

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