Ethylenediamine → HCID 59648633, compound

HRID 1363270Notes

Reaction equation

HRID 1363270 reaction equation
[F:1][C:2]1[C:3]2[S:21][CH:20]=[CH:19][C:4]=2[N:5](COCC[Si](C)(C)C)[C:6]=1[C:7]([O:9][CH3:10])=[O:8].CCCC[N+](CCCC)(CCCC)CCCC.[F-].C(N)CN.COC1C=CC(C=O)=CC=1>CN(C=O)C.CCCCCCC.CCOC(C)=O>[F:1][C:2]1[C:3]2[S:21][CH:20]=[CH:19][C:4]=2[NH:5][C:6]=1[C:7]([O:9][CH3:10])=[O:8]

Participants

8

Reactant 4

HCID 3301EthylenediamineHCID 312444-MethoxybenzaldehydeHCID 2724141Tetrabutylammonium FluorideHCID 59648543HCID 59648543, compound

Product 1

HCID 59648633HCID 59648633, compoundYield 94%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent2×HCID 8900HeptaneSolvent2×

Conditions

Temperature
80 °C

Procedure

Methyl 6-fluoro-4-((2-(trimethylsilyl)ethoxy)methyl)-4H-thieno[3,2-b]pyrrole-5-carboxylate (16 mg, 0.0485 mmol) was dissolved in 3 mL anhydrous DMF. TBAF (1.0 M in THF, 0.485 mL, 10 equiv) and ethylenediamine (0.10 mL, 87.45 mg, 1.455 mmol, 30 equiv) were added, and the reaction was heated to 80° C. for 1 h and then allowed to cool to rt overnight. TLC (1/1 EtOAc in heptane, visualized with anisaldehyde and heat) indicated complete reaction. The product was partitioned with LiCl saturated solution and EtOAc, dried (Na2SO4), filtered, evaporated in vacuo the organic layer to give a residue. The residue was passed through a 5 g silica gel cartridge (1/1 EtOAc in heptane) to give methyl 6-fluoro-4H-thieno[3,2-b]pyrrole-5-carboxylate (9 mg, 94% yield) as a white solid. The regiochemistry of fluorine was determined via NMR-NOE experiments. 1H NMR (400 MHz, (CD3)2CO) δ ppm 3.86 (s, 3H) 7.03 (dd, J=5.27, 2.29 Hz, 1H) 7.55 (d, J=5.27 Hz, 1H) 10.81 (br. s., 1H). 19F NMR (376 MHz, (CD3)2CO) δ ppm −155.88 (dd, J=27.47, 2.29 Hz, 1F).

Workup

  1. temperatureto cool to rt overnight
  2. customreaction
  3. customThe product was partitioned with LiCl saturated solution and EtOAc
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. customevaporated in vacuo the organic layer
  7. customto give a residue

Sources & evidence

ORD record
ord-ef7304a2d4904d8991da9ef6a9f296e6
Source dataset
uspto-grants-2011_02
Patent number
US07884124B2

Reaction notes

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