Methoxyacetic Acid → N-ethyl-2-(methoxyacetyl)hydrazinecarbothioamide

HRID 732029Notes

Reaction equation

HRID 732029 reaction equation
[CH3:1][O:2][CH2:3][C:4]([OH:6])=O.[CH2:7]([NH:9][C:10](=[S:13])[NH:11][NH2:12])[CH3:8].C(N=C=NC(C)C)(C)C.OC1C2N=NNC=2C=CC=1.N(C(=S)N)N.C(=O)(O)[O-].[Na+]>CN(C)C=O.O>[CH2:7]([NH:9][C:10]([NH:11][NH:12][C:4](=[O:6])[CH2:3][O:2][CH3:1])=[S:13])[CH3:8]

Participants

9

Reactant 6

HCID 12251Methoxyacetic AcidHCID 12734DiisopropylcarbodiimideHCID 516892Sodium BicarbonateHCID 15517804-Ethyl-3-thiosemicarbazideHCID 2723789ThiosemicarbazideHCID 178418300HCID 178418300, compound

Product 1

HCID 3274176N-ethyl-2-(methoxyacetyl)hydrazinecarbothioamideYield 47%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

Methoxyacetic acid 360 mg, 3.99 mmol), 4-ethyl-3-thiosemicarbazide (581 mg, 4.87 mmol), diisopropylcarbodiimide (615 mg, 4.87 mmol) and hydroxybenzotriazole (69.6 mg, 0.51 mmol) were mixed in dimethylformamide (10 ml) and stirred under argon at ambient temperatures for 19 h. After evaporation to dryness the crude was used directly in the next step. MS (ESI) m/z 192 (M+1). Step 2: 4-Ethyl-5-methoxymethyl-2,4-dihydro-[1,2,4]triazole-3-thione: N-Ethyl-2-(methoxyacetyl(hydrazinecarbothioamide (760 mg crude, 4 mmol) and sodium bicarbonate (560 mg, 6.6 mmol) were suspended in water (15 ml) and refluxed for 5 h. After cooling and filtration the filtrate was acidified with concentrated hydrochloric acid, followed by extraction with ethyl acetate. After evaporation to dryness the crude was recrystallized in ethyl acetate/heptane. Filtration and recrystallization of the mother liquor gave a combined yield of 325 mg (47%) of the title compound. 1H NMR (CDCl3), δ (ppm): 4.47 (s, 2H), 4.13 (q, 2H), 3.37 (s, 3H), 1.38 (t, 3H).

Workup

  1. customAfter evaporation to dryness the crude
  2. temperaturerefluxed for 5 h
  3. temperatureAfter cooling
  4. filtrationfiltration the filtrate
  5. extractionfollowed by extraction with ethyl acetate
  6. customAfter evaporation to dryness the crude
  7. customwas recrystallized in ethyl acetate/heptane
  8. filtrationFiltration and recrystallization of the mother liquor

Sources & evidence

ORD record
ord-b7a079693fad4ce4b900f5573574d456
Source dataset
uspto-grants-2009_09
Patent number
US07585881B2

Reaction notes

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