Sodium Hydroxide → (3-Phenoxyphenyl)hydrazine

HRID 601005Notes

Reaction equation

HRID 601005 reaction equation
[O:1]([C:8]1[CH:9]=[C:10]([NH:14]C2C=CC=CC=2)[CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N:21]([O-])=O.[Na+].O.O.[Sn](Cl)(Cl)(Cl)Cl.[OH-].[Na+].C(=O)(O)[O-].[Na+]>CO.O.Cl>[O:1]([C:8]1[CH:9]=[C:10]([NH:14][NH2:21])[CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

9

Reactant 5

HCID 14798Sodium HydroxideHCID 516892Sodium BicarbonateHCID 189707563-Phenoxy-phenylanilineHCID 23668193Sodium NitriteHCID 85782573Tin tetrachloride dihydrate

Product 1

HCID 21697795(3-Phenoxyphenyl)hydrazineYield 71.1%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolvent2×HCID 887MethanolSolventHCID 962WaterSolvent2×

Procedure

To a solution of 3-phenoxy-phenylaniline (2.32 g, 12.5 mmol) in methanol (5 mL), water (10 mL) and concentrated HCl (3 mL) at 0° C. was added in rapid drops a solution of sodium nitrite (0.87 g, 12.7 mmol) in water (2 mL). The reaction was stirred 10 min then treated in rapid drops with a 0° C. solution of tin chloride dihydrate (6.77 g, 30 mmol) in concentrated HCl (25 mL). The reaction was stirred for 1 h, then adjusted to ˜pH 7 with 6N NaOH and sodium bicarbonate, then filtered through Celite, washing with 1:3 methanol:dichloromethane. The filtrate was separated, the aqueous phase was extracted with 1:3 methanol:dichloromethane (2×). The combined organic layer was dried over sodium sulfate, evaporated, then purified by flash chromatography (SiO2) eluted with 35:65 ethyl acetate:hexanes to provide (3-phenoxy-phenyl)-hydrazine (1.78 g, 71% yield) as an orange oil. 1H-NMR (CDCl3, 500 MHz) 7.30 (m, 2H), 7.14 (t, 1H), 7.08 (t, 1H), 7.00 (m, 2H), 6.52 (m, 1H), 6.47 (m, 1H), 6.45 (m, 1H) 5.2 (br 1H), 3.5 (br 2H) ppm; MS (FIA) 201.1 (M+H); HPLC (method A) 2.887 min.

Workup

  1. stirringThe reaction was stirred for 1 h
  2. filtrationfiltered through Celite
  3. washwashing with 1:3 methanol
  4. customThe filtrate was separated
  5. extractionthe aqueous phase was extracted with 1:3 methanol
  6. dry with materialThe combined organic layer was dried over sodium sulfate
  7. customevaporated
  8. custompurified by flash chromatography (SiO2)
  9. washeluted with 35:65 ethyl acetate

Sources & evidence

ORD record
ord-03dae21656ce4560bc5f9c301609b011
Source dataset
uspto-grants-2011_03
Patent number
US07902239B2

Reaction notes

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