Sodium hydride → 1-(6-Chloro-3-pyridylmethyl)-1-formyl-3,3-dimethyl-2-nitroguanidine

HRID 2395682Notes

Reaction equation

HRID 2395682 reaction equation
[Cl:1][C:2]1[N:7]=[CH:6][C:5]([CH2:8][NH:9][C:10]([N:15]([CH3:17])[CH3:16])=[N:11][N+:12]([O-:14])=[O:13])=[CH:4][CH:3]=1.[H-].[Na+].[CH:20](OC(=O)C)=[O:21]>C1COCC1>[Cl:1][C:2]1[N:7]=[CH:6][C:5]([CH2:8][N:9]([CH:20]=[O:21])[C:10]([N:15]([CH3:17])[CH3:16])=[N:11][N+:12]([O-:14])=[O:13])=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 75269Acetic-formic anhydrideHCID 1362181971-(6-Chloro-3-pyridylmethyl)3,3-dimethyl-2-nitroguanidine

Product 1

HCID 545004451-(6-Chloro-3-pyridylmethyl)-1-formyl-3,3-dimethyl-2-nitroguanidineYield 34.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a mixture of 0.26 g of 1-(6-chloro-3-pyridylmethyl)3,3-dimethyl-2-nitroguanidine (Compound No. 6) and 3 ml of dry THF was added 0.08 g of 60% sodium hydride (in mineral oil) in a water bath of 20° C., followed by stirring for 30 minutes. A solution of 0.26 g of acetic formic anhydride in 0.5 ml of THF was added to the reaction mixture in one minute, and then stirred for 12 hours after the bath was removed. After adding 0.5 ml of acetic acid, the reaction mixture was concentrated. The residue was purified by a column chromatography [developing solvent: dichloromethanemethanol (30:1)] to obtain 0.10 g of 1-(6-chloro-3-pyridylmethyl)-1-formyl-3,3-dimethyl-2-nitroguanidine (Compound No. 22) as a syrup. 1H NMR(CDCl3): 3.03(6H,s), 4.70(2H,s), 7.36(1H,d,J=8.7 Hz), 7.74(1H,dd,J=8.7, 2.7 Hz), 8.40(1H,d,J=2.7 Hz), 8.44(1H,s)

Workup

  1. stirringstirred for 12 hours after the bath
  2. customwas removed
  3. additionAfter adding 0.5 ml of acetic acid
  4. concentrationthe reaction mixture was concentrated
  5. customThe residue was purified by a column chromatography [developing solvent: dichloromethanemethanol (30:1)]

Sources & evidence

ORD record
ord-dc9aeaa1688f4a89b3286be9b5d6d4e1
Source dataset
uspto-grants-1996_02
Patent number
US05489603

Reaction notes

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