Thiophenol → 6-(Benzylsulfanyl)-2,3-dimethoxypyridine

HRID 709058Notes

Reaction equation

HRID 709058 reaction equation
I[C:2]1[N:7]=[C:6]([O:8][CH3:9])[C:5]([O:10][CH3:11])=[CH:4][CH:3]=1.C1([SH:18])C=CC=CC=1.CCN(C(C)C)C(C)C.C[C:29]1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)O[C:31]2[C:32](P(C3C=CC=CC=3)C3C=CC=CC=3)=[CH:33][CH:34]=[CH:35][C:30]1=2>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:29]([S:18][C:2]1[N:7]=[C:6]([O:8][CH3:9])[C:5]([O:10][CH3:11])=[CH:4][CH:3]=1)[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1

Participants

7

Reactant 4

HCID 7969ThiophenolHCID 81531DiisopropylethylamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 453617466-Iodo-2,3-dimethoxypyridine

Product 1

HCID 711859196-(Benzylsulfanyl)-2,3-dimethoxypyridineYield 765.3%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

To a solution of 6-iodo-2,3-dimethoxypyridine (0.3 g, 1.13 mmol) in toluene (10 ml) was added phenyl mercaptan (0.21 g, 1.7 mmol) and DIPEA (0.32 g, 2.5 mmol). The reaction mass was degassed before Pd2(dba)3 (0.04 g, 0.05 mmol) and Xantphos (0.05 g, 0.1 mmol) were added and the whole was subjected to microwave irradiation at 120° C. with stirring for 2 hours. The resulting mixture was filtered through a pad of celite and the filtrate was added to water (60 ml) and extracted with ethyl acetate (2×30 ml). The combined organic layers were dried (Na2SO4) and then concentrated. The crude product was purified by column chromatography (SiO2; 0-5% ethyl acetate/petrol) and product fractions concentrated to yield 6-(benzylsulfanyl)-2,3-dimethoxypyridine (0.2 g, 68%).

Workup

  1. additionwere added
  2. customirradiation at 120° C.
  3. filtrationThe resulting mixture was filtered through a pad of celite
  4. additionthe filtrate was added to water (60 ml)
  5. extractionextracted with ethyl acetate (2×30 ml)
  6. dry with materialThe combined organic layers were dried (Na2SO4)
  7. concentrationconcentrated
  8. customThe crude product was purified by column chromatography (SiO2; 0-5% ethyl acetate/petrol) and product fractions
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-93eddf5e01d34ce4a799fd1ce44bb5b8
Source dataset
uspto-grants-2015_11
Patent number
US09180122B2

Reaction notes

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