Stannous chloride dihydrate → (5-chloro-2-methoxyphenyl)hydrazine

HRID 1166219Notes

Reaction equation

HRID 1166219 reaction equation
O.O.[Sn](Cl)Cl.[CH3:6][O:7][C:8]1[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][C:9]=1[N+:15]#[N:16].[Cl-].COC1C=CC(Cl)=CC=1N>Cl.COC1C=CC(Cl)=CC=1[N+]#N.COC1C=CC(Cl)=CC=1[N+]#N.[Cl-].[Cl-].Cl[Zn]Cl>[Cl:14][C:11]1[CH:12]=[CH:13][C:8]([O:7][CH3:6])=[C:9]([NH:15][NH2:16])[CH:10]=1

Participants

6

Reactant 3

HCID 61436Stannous chloride dihydrateHCID 66730Benzenediazonium, 5-chloro-2-methoxy-, chloride (1:1)HCID 667635-Chloro-2-methoxyaniline

Product 1

HCID 408926(5-chloro-2-methoxyphenyl)hydrazineYield 84%

Reagents, catalysts & solvents 2

HCID 16212471HCID 16212471, compoundCatalystHCID 313Hydrochloric AcidSolvent

Conditions

Temperature
0 °C

Procedure

Tin(II)chloride dihydrate (SnCl2.2H2O, 121 g, 0.54 mol) was dissolved in 300 ml concentrated HCl at −72° C. Diazo Red RC (Azoic Diazo No. 10, C.I. 37120, Fast Red RC Salt, Aldrich Chemical Co., 50 g, 0.18 mole) was added in portions with vigorous mechanical stirring. After the addition was complete, the reaction was stirred at 0° C. for three hours. The tan solid was filtered and washed with concentrated HCl, then stirred for 30 minutes in a mixture of 500 ml of dichloromethane and 500 ml 2N NaOH. The organic layer was separated, dried over sodium sulfate, concentrated under vacuum, and the resulting oil crystallized from 100 ml of diethyl ether to yield (5-chloro-2-methoxyphenyl)hydrazine (26.4 g, 84%). 1H NMR (300 MHz, CDCl3) δ6.96 (1H, d, J=2.4 Hz), 6.70 (1H, dd, 8.4, 2.4 Hz), 6.65 (1H, d, J=8.4 Hz), 3.81 (3H, s).

Workup

  1. addition, 50 g, 0.18 mole) was added in portions with vigorous mechanical stirring
  2. additionAfter the addition
  3. filtrationThe tan solid was filtered
  4. washwashed with concentrated HCl
  5. stirringstirred for 30 minutes in a mixture of 500 ml of dichloromethane and 500 ml 2N NaOH
  6. customThe organic layer was separated
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated under vacuum
  9. customthe resulting oil crystallized from 100 ml of diethyl ether

Sources & evidence

ORD record
ord-8d18fb50e9d442679598b9ad1e910427
Source dataset
uspto-grants-2003_09
Patent number
US06613786B2

Reaction notes

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