Stannous Chloride → 3-hydrazino-N-methoxy-4-methyl-benzamide

HRID 251332

Reaktionsgleichung

Reaktionsgleichung von HRID 251332
[NH2:1][C:2]1[CH:3]=[C:4]([CH:10]=[CH:11][C:12]=1[CH3:13])[C:5]([NH:7][O:8][CH3:9])=[O:6].[N:14]([O-])=O.[Na+].[Sn](Cl)Cl>O1CCOCC1.O.Cl>[NH:1]([C:2]1[CH:3]=[C:4]([CH:10]=[CH:11][C:12]=1[CH3:13])[C:5]([NH:7][O:8][CH3:9])=[O:6])[NH2:14]

Komponenten

7

Edukt 3

HCID 24479Stannous ChlorideHCID 207670003-Amino-N-methoxy-4-methylbenzamideHCID 23668193Sodium Nitrite

Produkt 1

HCID 116153463-hydrazino-N-methoxy-4-methyl-benzamideAusbeute 81,8 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 313Hydrochloric AcidLösungsmittel2×HCID 962WaterLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

To a stirred solution of 3-amino-4-methylbenzoic acid 1 (5.64 g, 31.2 mmol, 1.0 eq) in 100 mL of dioxane and 100 mL of water at 0° C. was added 100 mL of conc. HCl followed by the portionwise addition of sodium nitrite (2.82 g, 40.9 mmol, 1.1 eq) as a solid at a rate to control gas evolution and foaming over 45 minutes. A clear brown solution resulted. Anhydrous tin(II)chloride (15.62 g, 83.7 mmol, 2.25 eq) was dissolved in conc. HCl (25 mL) and added dropwise over 25 mL at 0° C. After 1 hour, the precipitate was filtertered and washed with dioxanes then dried under vacuum to provide 3-hydrazino-4-methyl-benzoic acid hydrochloride 2 as a tan solid (4.98 g, 66%): HPLC (4 minute gradient) tR 0.97 min; MS m/z 167 [M+H]+; 1H (300 MHz, DMSO-d6) δ 10.03 (s, 1 H, COOH), 7.89 (s, 1 H), 7.51 (s, 1 H), 7.27 (d, J=8.0, 1 H), 3.38 (s, 3 H, NHNH2), 2.23 (s, 3 H) ppm.

Aufarbeitung

  1. customA clear brown solution resulted
  2. additionadded dropwise over 25 mL at 0° C
  3. waitAfter 1 hour
  4. washwashed with dioxanes
  5. customthen dried under vacuum

Quellen und Nachweise

ORD-Eintrag
ord-8eddd532014a481d9a2efac60b3329ae
Quelldatensatz
uspto-grants-2011_01
Patentnummer
US07863314B2

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