Triphenylphosphine → 2-(4-(4-Hydroxybutyl)phenyl methyl)thio 3-methyl chromen-4-one

HRID 1723985Notes

Reaction equation

HRID 1723985 reaction equation
[SH:1][C:2]1[O:3][C:4]2[C:9]([C:10](=[O:12])[CH:11]=1)=[CH:8][CH:7]=[CH:6][CH:5]=2.O[CH2:14][C:15]1[CH:20]=[CH:19][C:18]([CH2:21][CH2:22][CH2:23][CH2:24][OH:25])=[CH:17][CH:16]=1.[CH:26]1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1.O>[OH:25][CH2:24][CH2:23][CH2:22][CH2:21][C:18]1[CH:19]=[CH:20][C:15]([CH2:14][S:1][C:2]2[O:3][C:4]3[C:9]([C:10](=[O:12])[C:11]=2[CH3:26])=[CH:8][CH:7]=[CH:6][CH:5]=3)=[CH:16][CH:17]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 12475277HCID 12475277, compoundHCID 177561734-(4-Hydroxymethyl-phenyl)-butan-1-ol

Product 1

HCID 177558312-(4-(4-Hydroxybutyl)phenyl methyl)thio 3-methyl chromen-4-oneYield 46.1%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To solution of 2-mercapto-chromen-4-one (1.52 g, 7.90 mmol) and 4-(4-hydroxymethyl-phenyl)-butan-1-ol (1.90 g, 9.90 mmol) dissolved in anhydrous THF (80 mL) was added solid PPh3 (3.11 g, 11.90 mmol) and DIAD (2.30 mL, 11.90 mmol). After completion of addition the reaction mixture continued to stir at room temperature. After 20 hours, the reaction mixture was diluted with water. The aqueous layer was separated and extracted with ethyl acetate (3×). All combined organic layers were dried over Na2SO4, filtered, and concentrated to yield an oil. The crude material was purified using silica gel chromatography (1:1 pentane: ethyl acetate) to yield 2-[4-(4-hydroxy-butyl)-benzylsulfanyl]-3-methyl-chromen-4-one (1.29 g, 3.64 mmol) in moderate yield (46%). 1H (CDCl3, 600 MHz): δ 8.18 (1H, dd, J=7.9, 1.3 Hz), 7.60 (1H, ddd, J=8.6, 7.2, 1.7 Hz), 7.31 (2H, t, J=8.5 Hz), 7.29 (2H, d, J=8.1 Hz), 7.12 (2H, d, J=8.1 Hz), 4.36 (2H, s), 3.62 (2H, m), 2.61 (2H, t, J=7.5 Hz), 2.00 (3H, s),1.67 (2H, m), 1.56 (2H, m); 13C (CDCl3, 150 MHz): δ 174.9, 161.3, 156.0, 141.5, 133.2, 132.3, 128.3, 128.2, 125.7, 124.5, 122.2, 117.2, 116.3, 62.3, 34.7, 31.8, 29.2, 26.9, 10.1.; HRMS calcd for C21H22O3S 355.1363:, found 355.1364

Workup

  1. additionAfter completion of addition the reaction mixture
  2. customThe aqueous layer was separated
  3. extractionextracted with ethyl acetate (3×)
  4. dry with materialAll combined organic layers were dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto yield an oil
  8. customThe crude material was purified

Sources & evidence

ORD record
ord-db9374045d56418cad04c541963cad14
Source dataset
uspto-grants-2009_02
Patent number
US07485283B2

Reaction notes

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