Sodium Carbonate → HCID 86626549, compound

HRID 1895573Notes

Reaction equation

HRID 1895573 reaction equation
[CH3:1][N:2]=[S:3]([CH:11]([C:13]1[CH:14]=[CH:15][C:16]([C:19]([F:22])([F:21])[F:20])=[N:17][CH:18]=1)[CH3:12])([C:5]1[S:6][CH:7]=[C:8](Br)[N:9]=1)=[O:4].[CH3:23][C:24]1[CH:29]=[CH:28][C:27](B(O)O)=[CH:26][CH:25]=1.C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][N:2]=[S:3]([CH:11]([C:13]1[CH:14]=[CH:15][C:16]([C:19]([F:22])([F:21])[F:20])=[N:17][CH:18]=1)[CH3:12])([C:5]1[S:6][CH:7]=[C:8]([C:27]2[CH:28]=[CH:29][C:24]([CH3:23])=[CH:25][CH:26]=2)[N:9]=1)=[O:4]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 79799Tolylboronic acidHCID 86626550HCID 86626550, compound

Product 1

HCID 86626549HCID 86626549, compoundYield 70%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

A suspension of 5-{1-[methyl(4-bromo-1,3-thiazol-2-yl)sulfonimidoyl]ethyl}-2-(trifluoromethyl)pyridine (13) (0.055 g, 0.133 mmol), 4-methylphenyl boronic acid (0.027 g, 0.199 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.006 g, 0.005 mmol) in dioxane (0.9 ml) and 2M Na2CO3 (0.070 g, in 0.33 ml of water) was heated at reflux for 2 hours. The reaction mixture was cooled and filtered. The filtrate was evaporated in vacuo and the residue was dissolved in EtOAc, and subsequently washed with water and brine. The combined organic layers were dried (MgSO4), filtered and concentrated to dryness. The crude product was purified by column chromatography (SiO2, with a gradient of 50% EtOAc/hexanes) to give 5-{1-[methyl(4-(4-methylphenyl)-1,3-thiazol-2-yl)sulfonimidoyl]ethyl}-2-(trifluoromethyl)pyridine (19) as a dark yellow semi-solid (0.039 g, 70%). 1:1 mixture of two diastereomers 1H NMR (300 MHz, CDCl3) δ 8.85 (d, 1H), 8.75 (d, 1H), 8.1 (m, 2H), 7.7 (m, 6H), 7.2 (m, 4H), 6.9 (d, 2H), 5.4 (m, 1H), 5.2 (m, 1H), 3.3 (s, 3H), 3.1 (s, 3H), 2.4 (d, 6H), 2.0 (d, 3H), 1.9 (d, 3H); LC-MS (ESI): Mass calcd for C19H18F3N3OS2 [M+H]+, 426. Found 426.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 2 hours
  3. temperatureThe reaction mixture was cooled
  4. filtrationfiltered
  5. customThe filtrate was evaporated in vacuo
  6. dissolutionthe residue was dissolved in EtOAc
  7. washsubsequently washed with water and brine
  8. dry with materialThe combined organic layers were dried (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated to dryness
  11. customThe crude product was purified by column chromatography (SiO2

Sources & evidence

ORD record
ord-88e24342ba374218b7c4942acbab9775
Source dataset
uspto-grants-2013_08
Patent number
US08513462B2

Reaction notes

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