Dimethylformamide → HCID 86718318, compound

HRID 1852323Notes

Reaction equation

HRID 1852323 reaction equation
S(Cl)([Cl:3])=O.CN(C)C=O.O[CH2:11][N:12]1[CH:17]=[C:16]([Cl:18])[CH:15]([Cl:19])[C:14](=O)[NH:13]1.C([O-])(O)=O.[Na+]>O.C(Cl)Cl>[Cl:18][C:16]1[C:15]([Cl:19])=[CH:14][NH:13][N:12]([CH2:11][Cl:3])[CH:17]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 24386Thionyl ChlorideHCID 516892Sodium BicarbonateHCID 86718319HCID 86718319, compound

Product 1

HCID 86718318HCID 86718318, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
0 °C

Procedure

4,5-dichloripyridazine-3(2H)-one (60 g, 364 mmol) and distilled water 350 mL) were stirred at room temperature for 10 minutes. A formaldehyde solution (36%, 70 mL) were added and refluxed for 1.5 hours. The resulting material was cooled down to 5-10° C., and the produced precipitate was filtered, washed with cold water (0-5° C., 200 mL), and dried in the air to obtain N-hydroxymethyl-4,5-dichloropyridazine-3(2H)-one. A methylene chloride solution (50 mL) of thionyl chloride (357 mmol) and dimethyl formamide (360 mmol) was slowly added to a mixture of the N-hydroxymethyl-4,5-dichloropyridazine-3(2H)-one and methylene chloride (550 mL) and methylene chloride (550 mL) at room temperature for 30 minutes with stirring. The mixture was stirred at room temperature for 2 hours. After the mixture was cooled down to 0° C., water (200 mL) was slowly added. The solution was neutralized to pH 6.7-7.4 by using NaHCO3 saturated solution. An organic layer was separated and dried on anhydrous magnesium sulfate. The organic solution was evaporated to concentrated under reduced pressure. The residue was washed with n-hexane (100 mL) to obtain 4,5-dichloro-2-chloromethylpyridazine)-3(2H)-one (71.2 g, 92%). White crystal (diethyl ether/n-hexane=1:5, v/v). mp 69-70° C. TLC (CH2Cl2) Rf=0.65. IR (KBr) 3046, 2984, 1670, 1292, 1122, 964 cm-1; 1H NMR (CDCl3): δ 5.83 (s, 2H), 7.88 ppm (s, 1H); 13C NMR (CDCl3) δ 58.40, 134.87, 137.23, 137.34, 155.58 ppm. Elemental analysis calcd. for C5H3Cl3N2O: C, 28.13; H, 1.42; N, 13.12. Found: C, 28.10; H, 1.41; N, 13.09.

Workup

  1. stirringThe mixture was stirred at room temperature for 2 hours
  2. customAn organic layer was separated
  3. dry with materialdried on anhydrous magnesium sulfate
  4. customThe organic solution was evaporated
  5. concentrationto concentrated under reduced pressure
  6. washThe residue was washed with n-hexane (100 mL)

Sources & evidence

ORD record
ord-92bef028d46942ec82c9cd882b0a6d2a
Source dataset
uspto-grants-2015_02
Patent number
US08961937B2

Reaction notes

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