Phenyl(pyridazin-4-yl)methanone → 4-methyl-N'-[phenyl(pyridazin-4-yl)methylidene]piperazine-1-carbothiohydrazide

HRID 1258115Notes

Reaction equation

HRID 1258115 reaction equation
[C:1]1([C:7]([C:9]2[CH:14]=[CH:13][N:12]=[N:11][CH:10]=2)=O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:15][N:16]1[CH2:21][CH2:20][N:19]([C:22]([NH:24][NH2:25])=[S:23])[CH2:18][CH2:17]1>C(O)C.C(Cl)Cl>[CH3:15][N:16]1[CH2:17][CH2:18][N:19]([C:22](=[S:23])[NH:24][N:25]=[C:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[C:9]2[CH:14]=[CH:13][N:12]=[N:11][CH:10]=2)[CH2:20][CH2:21]1

Participants

5

Reactant 2

HCID 12486783Phenyl(pyridazin-4-yl)methanoneHCID 152917424-Methylpiperazine-1-carbothiohydrazide

Product 1

HCID 749273984-methyl-N'-[phenyl(pyridazin-4-yl)methylidene]piperazine-1-carbothiohydrazideYield 99.3%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
65 °C

Procedure

A mixture of phenyl-pyridazin-4-yl-methanone (12; Synthon A, 2.3 g, 12.4 mmol) and 4-Methylpiperazine-1-carbothioic acid hydrazide (6; Synthon B, 2.82 g, 16.18 mmol) in ethanol (7.5 mL) was heated to 65° C. for 5 h under N2 in a 50 mL pyrex tube equipped with a screw cap. The mixture remained heterogeneous during the heating and a brown suspension resulted at the end of the reaction. The mixture was diluted with CH2Cl2 (7.5 mL) and was chromatographed on silica gel that was eluted with MeOH/CH2Cl2 (2.5-5%) to give 1.8 g of a yellow foamy solid 1A (99.3% pure by HPLC); m.p. 141-143° C. (m.p. of a crystalline sample 143-145). TLC (CH2Cl2/MeOH/NH4OH:95/5/0.5): Rf=0.6, product is visibly yellow, UV and Dragendorff stain active. MS (ESI+): [M+H]+=340.93. HRMS: m/z calcd. for C17H21N6S ([M+H]+): 341.15429; found: 341.15501. 1H NMR (300 MHz, CDCl3), δ ppm: 2.38 (s, 3H), 2.61 (t, 4H, J=5.0 Hz), 4.12 (t, 4H, J=5.0 Hz), 7.29 (m, 3H), 7.63 (m, 3H), 8.64 (s, 1H), 9.14 (dd, 1H, J=5.7 Hz, J′=1.5 Hz), 9.44 (dd, 1H, J=2.4 Hz, J′=1.5 Hz). 13C NMR (75.4 MHz, CDCl3), δ ppm: 45.75, 51.64, 54.75, 123.30, 128.29, 128.39, 130.40, 131.10, 134.86, 143.94, 148.31, 151.31, 181.49.

Workup

  1. customequipped with a screw
  2. customcap
  3. customresulted at the end of the reaction
  4. customwas chromatographed on silica gel that
  5. washwas eluted with MeOH/CH2Cl2 (2.5-5%)

Sources & evidence

ORD record
ord-85633d584bea4fabbf3b4f254caf657d
Source dataset
uspto-grants-2013_06
Patent number
US08466151B2

Reaction notes

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