Triethylamine → HCID 46932515, compound

HRID 1192083Notes

Reaction equation

HRID 1192083 reaction equation
C(Cl)(=O)C(Cl)=O.[Cl:7][C:8]1[CH:9]=[N:10][CH:11]=[C:12]([Cl:26])[C:13]=1[S:14][C:15]1[S:19][C:18]([C:20]([OH:22])=O)=[CH:17][C:16]=1[N+:23]([O-:25])=[O:24].[CH3:27][S:28][CH2:29][CH2:30][NH2:31].C(N(CC)CC)C>ClCCl.O1CCCC1.C(OC(=O)C)C>[Cl:26][C:12]1[CH:11]=[N:10][CH:9]=[C:8]([Cl:7])[C:13]=1[S:14][C:15]1[S:19][C:18]([C:20]([NH:31][CH2:30][CH2:29][S:28][CH3:27])=[O:22])=[CH:17][C:16]=1[N+:23]([O-:25])=[O:24]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 87697(2-(Methylthio)ethyl)amineHCID 602073175-((3,5-Dichloropyridin-4-yl)thio)-4-nitrothiophene-2-carboxylic acid

Product 1

HCID 46932515HCID 46932515, compoundYield 24.9%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Oxalyl chloride (0.934 g, 3.92 mmol) followed by N,N-dimethylformide (0.1 mL) was added dropwise to a suspension of 5-[(3,5-dichloro-4-pyridyl)sulfanyl]-4-nitro-thiophene-2-carboxylic acid (0.60 g, 1.71 mmol) in dichloromethane (30 mL) and the mixture was stirred at ambient temperature for 8 hour. After this time, TLC analysis showed no acid remaining so the mixture was allowed to be concentrated in vacuo to give a yellow solid. The resulting acid chloride solid was dissolved in dry tetrahydrofuran (10 mL). 2-(methylthio)ethanamine (0.047 g, 0.52 mmol) followed by triethylamine (0.066 g, 0.65 mmol) was added to a 2.5 mL aliquot of acid chloride solution in tetrahydrofuran at 0° C. The resulting mixture was stirred at ambient temperature for 3 hours. TLC analysis showed no acid chloride remaining so the mixture was diluted with ethylacetate and washed with water and brine. The organic layer was separated, dried (Na2SO4), filtered and the solvent was removed to afford a brown oil. The crude material was purified by silica gel chromatography using an 85:15 mixture of hexane and ethyl acetate as eluent to afford the title product as a brown solid (55 mg, 13% yield). 1H NMR (400 MHz, d6-DMSO) δ: 8.99 (1H, m), 8.98 (2H, m), 8.41 (1H, s), 3.39 (2H, m), 2.59 (2H, m), 2.08 (3H, s). MS m/z: 422.20, 424.21 [M+H]+.

Workup

  1. concentrationto be concentrated in vacuo
  2. customto give a yellow solid
  3. stirringThe resulting mixture was stirred at ambient temperature for 3 hours
  4. washwashed with water and brine
  5. customThe organic layer was separated
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. customthe solvent was removed
  9. customto afford a brown oil
  10. customThe crude material was purified by silica gel chromatography
  11. additionan 85:15 mixture of hexane and ethyl acetate as eluent

Sources & evidence

ORD record
ord-7e2337118ab547818004c1492397c90b
Source dataset
uspto-grants-2014_03
Patent number
US08680139B2

Reaction notes

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