1,3-Propanediol → HCID 54075637, compound

HRID 442931Notes

Reaction equation

HRID 442931 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH3:9])=[CH:5][C:4]=1[S:10]([O:13][C:14]1[CH:15]=[C:16]([OH:21])[CH:17]=[C:18]([CH3:20])[CH:19]=1)(=[O:12])=[O:11].[CH2:22](O)[CH2:23][CH2:24][OH:25].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH3:9])=[CH:5][C:4]=1[S:10]([O:13][C:14]1[CH:15]=[C:16]([CH:17]=[C:18]([CH3:20])[CH:19]=1)[O:21][CH2:22][CH2:23][CH2:24][OH:25])(=[O:11])=[O:12]

Participants

6

Reactant 4

HCID 104421,3-PropanediolHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 54409244HCID 54409244, compound

Product 1

HCID 54075637HCID 54075637, compoundYield 97.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To 458 mg (1.49 mmol) 3-(2-methoxy-5-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 7.95 (d, 1 H, J=2.2 Hz), 7.40 (dd, 1 H, J=8.5, 2.3 Hz), 6.97 (d, 1 H, J=8.5 Hz), 6.59 (br s, 1 H), 6.53 (br s, 1 H), 6.47 (t, 1 H, J=2.1 Hz), 4.01 (t, 2 H, J=6.0 Hz), 3.98 (s, 3 H), 3.81 (q, 2 H, J=5.7 Hz), 2.29 (s, 3 H), 2.25 (s, 3 H) and 1.98 (m, 2 H).

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-fa8d547ca3e640818ca2fe0dc54658a3
Source dataset
uspto-grants-1999_04
Patent number
US05891909

Reaction notes

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