Sodium ethanethiolate → 8-(Ethylthio)naphthalene-2-sulfonamide

HRID 528798Notes

Reaction equation

HRID 528798 reaction equation
I[C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[CH:10]=[C:9]([S:12]([NH2:15])(=[O:14])=[O:13])[CH:8]=[CH:7]2.[CH2:16]([S-:18])[CH3:17].[Na+]>CN(C=O)C.[Li+].[Cl-].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:16]([S:18][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[CH:10]=[C:9]([S:12]([NH2:15])(=[O:14])=[O:13])[CH:8]=[CH:7]2)[CH3:17]

Participants

6

Reactant 2

HCID 4459711Sodium ethanethiolate2×HCID 697221528-Iodonaphthalene-2-sulfonamide2×

Product 1

HCID 710611118-(Ethylthio)naphthalene-2-sulfonamideYield 30%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst2×HCID 6228DimethylformamideSolventHCID 433294Lithium ChlorideSolvent

Conditions

Temperature
50 °C

Procedure

A solution of 8-iodonaphthalene-2-sulfonamide (Intermediate 7, 100 mg, 0.30 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (12 mg, 0.015 mmol) and sodium ethanethiolate (50 mg, 0.60 mmol) in DMF (2 mL) was purged with argon. The reaction mixture was heated to 50° C. for 12 h. Additional sodium ethanethiolate (25 mg, 0.30 mmol) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (240 mg, 0.30 mmol) were added, and the reaction mixture was heated at 125° C. for 12 h. The reaction mixture was cooled to room temperature, diluted with 10% aq. LiCl solution and extracted with EtOAc (3×). The combined organic extracts were dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by preparative HPLC to give the title compound (24 mg, 30%). 1H NMR (CD3OD) δ 9.02-8.98 (m, 1H), 8.08-8.03 (m, 1H), 8.00-7.95 (m, 1H), 7.86 (d, J=8.4 Hz, 1H), 7.73 (dd, J=7.4, 1.0 Hz, 1H), 7.64-7.57 (m, 1H), 3.09 (q, J=7.3 Hz, 2H), 1.34 (t, J=7.4 Hz, 3H); MS(ESI−) m/z 266.2 (M−H)−.

Workup

  1. temperaturethe reaction mixture was heated at 125° C. for 12 h
  2. temperatureThe reaction mixture was cooled to room temperature
  3. extractionextracted with EtOAc (3×)
  4. dry with materialThe combined organic extracts were dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by preparative HPLC

Sources & evidence

ORD record
ord-fd5d94836c0346a9b3c2e275d73c45e7
Source dataset
uspto-grants-2016_05
Patent number
US09346795B2

Reaction notes

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