Sodium Carbonate → HCID 19365957, compound

HRID 850105Notes

Reaction equation

HRID 850105 reaction equation
C[O:2][C:3](=O)[C:4]1[CH:9]=[CH:8][C:7]([C:10](=[CH2:27])[C:11]([C:19]2[CH:24]=[CH:23][C:22]([F:25])=[CH:21][C:20]=2[F:26])([OH:18])[CH2:12][N:13]2[CH:17]=[N:16][CH:15]=[N:14]2)=[CH:6][CH:5]=1.C(Cl)(=O)C(Cl)=O.[NH2:35][NH:36][C:37]([NH2:39])=[S:38].C(=O)([O-])[O-].[Na+].[Na+]>ClCCl.CN(C)C=O>[F:26][C:20]1[CH:21]=[C:22]([F:25])[CH:23]=[CH:24][C:19]=1[C:11]([OH:18])([C:10]([C:7]1[CH:6]=[CH:5][C:4]([C:3]([NH:35][NH:36][C:37]([NH2:39])=[S:38])=[O:2])=[CH:9][CH:8]=1)=[CH2:27])[CH2:12][N:13]1[CH:17]=[N:16][CH:15]=[N:14]1

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 65578Oxalyl chlorideHCID 2723789ThiosemicarbazideHCID 54102178HCID 54102178, compound

Product 1

HCID 19365957HCID 19365957, compoundYield 47.2%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent

Procedure

A sample of the product from part (i) (370 mg, 1 mmol) was suspended in dichloromethane (15 ml), and was treated with dimethylformamide (1 drop) and oxalyl chloride (0.1 ml, 1.1 mmol). The solution was stirred at room temperature for1 hour and was evaporated under reduced pressure. The residue. was dissolved in dichloromethane (15 ml) and treated with thiosemicarbazide (0.1 g, 1 mmol) and sodium carbonate (0.1 g, 1 mmol). The mixture was stirred at room temperature for 24 hours then filtered. The filtrate was absorbed onto silica and chromatographed by gradient elution with ethyl acetate/methanol (97:3, 95:5, 94:6). Fractions containing the desired product were combined and evaporated under reduced pressure. The crude product was triturated with ether to give 4-{2-[2,4-difluorophenyl]-2-hydroxy-1-[1,2,4-triazol-1-yl]-3-buten-3-yl}benzoylthiosemicarbazide (0.21 g, 47%) as a colourless solid which was characterised by 1H-N.M.R. spectroscopy (300 MHz, DMSO). δ=4.83 (Abq, 2H), 5.32 (s,1H), 5.58 (s,1H), 6.57 (s,1H), 6.77 (m,1H), 6.98 (m,1H), 7.11 (m, 1H), 7.30 (d,2H), 7.58 (brs, 1H), 7.60 (s,1H), 7.62 (d,2H), 7.78 (brs, 1H), 8.19 (s, 1H), 9.22 (brs, 1H), 10.22 (brs,1H) ppm.

Workup

  1. customwas evaporated under reduced pressure
  2. dissolutionwas dissolved in dichloromethane (15 ml)
  3. stirringThe mixture was stirred at room temperature for 24 hours
  4. filtrationthen filtered
  5. customThe filtrate was absorbed onto silica
  6. customchromatographed by gradient elution with ethyl acetate/methanol (97:3, 95:5, 94:6)
  7. additionFractions containing the desired product
  8. customevaporated under reduced pressure
  9. customThe crude product was triturated with ether

Sources & evidence

ORD record
ord-f968ba1bcf3d48f1990a9be2c6de0fd5
Source dataset
uspto-grants-2000_01
Patent number
US06015825

Reaction notes

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