Dimethylformamide → Methylhydrazine

HRID 2387138Notes

Reaction equation

HRID 2387138 reaction equation
C[N:2]([CH:4]=O)[CH3:3].O=P(Cl)(Cl)[Cl:8].[CH3:11][N:12]1[C:16]([OH:17])=[CH:15][C:14]([CH3:18])=[N:13]1.[OH-].[Na+]>ClCCCl.ClC(Cl)C.O>[Cl:8][C:4]1[N:2]([CH3:3])[N:13]=[C:14]([CH3:18])[C:15]=1[CH:16]=[O:17].[CH3:11][NH:12][NH2:13]

Participants

9

Reactant 4

HCID 6228DimethylformamideHCID 14798Sodium HydroxideHCID 24813Phosphorus oxychlorideHCID 178429390HCID 178429390, compound

Product 2

HCID 6061MethylhydrazineHCID 27773975-Chloro-1,3-dimethylpyrazole-4-carboxaldehyde

Reagents, catalysts & solvents 3

HCID 111,2-DichloroethaneSolventHCID 962WaterSolvent2×HCID 63651,1-DichloroethaneSolvent

Conditions

Temperature
0 °C

Procedure

To DMF (33.29 mL, 0.456 mol) was carefully added POCl3 (134.16 g, 81.5 mL 0.874 mol,) at 0° C. The reaction mixture was diluted with 1,2-dichloroethane (100 mL), then treated with a solution of crude 1,3-dimethyl-1H-pyrazol-5-ol (50 g, from Step 1) in dichloroethane (100 mL) under continued stirring at 0° C. The mixture was refluxed for 3 h, then left to stir overnight at room temperature. In order to decompose the formylating reagent, to the reaction mixture was added a solution of sodium hydroxide (91.2 g, 2.28 mol) in water (200 mL) dropwise at 0° C. The reaction mixture was diluted with water and extracted with dichloromethane (3×250 mL). The organic extracts were washed with water to neutral pH, washed with water, then dried with sodium sulfate. The solvent was removed under vacuum to afford the title product (31.1 g, 51% overall from methylhydrazine) as a yellow crystalline substance.

Workup

  1. customat 0° C
  2. temperatureThe mixture was refluxed for 3 h
  3. waitleft
  4. stirringto stir overnight at room temperature
  5. extractionextracted with dichloromethane (3×250 mL)
  6. washThe organic extracts were washed with water to neutral pH
  7. washwashed with water
  8. dry with materialdried with sodium sulfate
  9. customThe solvent was removed under vacuum

Sources & evidence

ORD record
ord-5d192f7b719b41ec9940468b9949c2b8
Source dataset
uspto-grants-2012_09
Patent number
US08268835B2

Reaction notes

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