1,3-Propanediol → HCID 53811499, compound

HRID 442953Notes

Reaction equation

HRID 442953 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:20])=[C:6]([S:8]([O:11][C:12]2[CH:13]=[C:14]([OH:19])[CH:15]=[C:16]([CH3:18])[CH:17]=2)(=[O:10])=[O:9])[CH:7]=1.[CH2:21](O)[CH2:22][CH2:23][OH:24].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[F:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:20])=[C:6]([S:8]([O:11][C:12]2[CH:13]=[C:14]([CH:15]=[C:16]([CH3:18])[CH:17]=2)[O:19][CH2:21][CH2:22][CH2:23][OH:24])(=[O:10])=[O:9])[CH:7]=1

Participants

6

Reactant 4

HCID 104421,3-PropanediolHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 54447329HCID 54447329, compound

Product 1

HCID 53811499HCID 53811499, compoundYield 100.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To 458 mg (1.49 mmol) 3-(5-fluoro-2-methylphenylsulfonyloxy)-5-methylphenol, as prepared in the preceding step, 1.08 mL (14.9 mmol) of 1,3-propanediol and 782 mg (2.98 mmol) of triphenylphosphine in 10 mL of anhydrous tetrahydrofuran was added 0.470 mL (2.98 mmol) of diethyl azodicarboxylate dropwise over 15 min. After stirring at ambient temperature for 2 h, the reaction mixture was concentrated to a semisolid. The resulting mixture was flash chromatographed on 50 g of silica gel with 8-10% ethyl acetate-dichloromethane. Impure fractions were re-chromatographed on 40 g of silica gel with 50-100% ethyl acetate-hexane. Material from the two purifications was combined to afford 530 mg (97% yield) of the title compound as a colorless oil: 1H-NMR (300 MHz; CDCl3) δ 7.59 (dd, 1H, J=8.3, 2.8 Hz), 7.38 (dd, 1H, J=8.4, 5.3 Hz), 7.25 (td, 1H, J=8.4, 2.8 Hz), 6.62 (m, 1H), 6.1 (m, 1H), 6.37 (t, 1H, J=2.1 Hz), 4.00 (t, 2H, J=6.0 Hz), 3.83 (dd, 2H, J=11.3, 5.8 Hz), 2.73 (s, 3H), 2.24 (s, 3H) and 1.99 (pentet, 2H, J=6.0 Hz). Mass spectrum (MALDI-TOF, α-cyano-4-hydroxycinnamic acid matrix) calcd. for C17H19FO5S: 377.1 (M+Na). Found: 377.0.

Workup

  1. concentrationthe reaction mixture was concentrated to a semisolid
  2. customchromatographed on 50 g of silica gel with 8-10% ethyl acetate-dichloromethane
  3. customImpure fractions were re-chromatographed on 40 g of silica gel with 50-100% ethyl acetate-hexane

Sources & evidence

ORD record
ord-ec8957246a1e4e5695b003a5ecea0489
Source dataset
uspto-grants-1999_04
Patent number
US05891909

Reaction notes

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