Pyridine → N,N-diethyl-1-methyl-2-(2-(2-methyl-2-(phenylcarbonothioyl)hydrazinyl)-2-oxoethylsulfanyl)hydrazinecarbothioamide

HRID 1190936Notes

Reaction equation

HRID 1190936 reaction equation
Cl[S:2]([CH2:5][C:6](Cl)=[O:7])(=O)=O.[CH3:9][N:10]([C:12](=[S:19])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[NH2:11].[CH2:20]([N:22]([CH2:28][CH3:29])[C:23]([N:25]([CH3:27])[NH2:26])=[S:24])[CH3:21].N1C=CC=CC=1>C1COCC1>[CH2:20]([N:22]([CH2:28][CH3:29])[C:23]([N:25]([CH3:27])[NH:26][S:2][CH2:5][C:6]([NH:11][N:10]([CH3:9])[C:12]([C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)=[S:19])=[O:7])=[S:24])[CH3:21]

Participants

6

Reactant 4

HCID 1049PyridineHCID 77642(Chlorosulphonyl)acetyl chlorideHCID 12206211N-methylbenzothiohydrazideHCID 86762305N,N-diethyl-1-methylhydrazinecarbothioamide

Product 1

HCID 86762304N,N-diethyl-1-methyl-2-(2-(2-methyl-2-(phenylcarbonothioyl)hydrazinyl)-2-oxoethylsulfanyl)hydrazinecarbothioamide

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

44 mg (0.25 mmol) 2-(chlorosulfonyl)acetyl chloride dissolved in 1 ml dry THF was treated with 42 mg (0.25 mmol) N-methylbenzothiohydrazide dissolved in 0.5 ml THF at 0° C. over 15 min. The reaction was stirred for 15 min and then checked by TLC if the thiohydrazide has completely reacted. Now 40 mg (0.25 mmol) N,N-diethyl-1-methylhydrazinecarbothioamide dissolved in 0.5 ml THF was added and the mixture stirred at 0° C. for 15 min. Then 60 μl (0.75 mmol) pyridine was added and the reaction allowed to warm up to r.t. overnight. The reaction was quenched with 5 ml water, the pH adjusted to 11 and extracted with 5 ml ethyl acetate. The pH was reduced to 4-5 and the aqueous phase extracted 2 times with 5 ml ethyl acetate. The latter extracts were dried over MgSO4 and concentrated. If the purity was not satisfactory (<90%) it was purified on silica with DCM/MeOH (5-20%)/NH4OH (1%). ESMS (C16H25N5O3S3): calc'd. 431.11. Found: 432.2 [M+H+].

Workup

  1. customhas completely reacted
  2. additionwas added
  3. stirringthe mixture stirred at 0° C. for 15 min
  4. customThe reaction was quenched with 5 ml water
  5. extractionextracted with 5 ml ethyl acetate
  6. extractionthe aqueous phase extracted 2 times with 5 ml ethyl acetate
  7. dry with materialThe latter extracts were dried over MgSO4
  8. concentrationconcentrated
  9. customwas purified on silica with DCM/MeOH (5-20%)/NH4OH (1%)

Sources & evidence

ORD record
ord-839173589abb44b19b4dc86531afe3a9
Source dataset
uspto-grants-2014_03
Patent number
US08680100B2

Reaction notes

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