1,3-Propanediol → HCID 22722527, compound

HRID 442990Notes

Reaction equation

HRID 442990 reaction equation
N(C(OCC)=O)=NC(OCC)=O.[CH3:13][C:14]1[CH:15]=[C:16]([O:21][S:22]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=2[S:31]([CH3:34])(=[O:33])=[O:32])(=[O:24])=[O:23])[CH:17]=[C:18]([OH:20])[CH:19]=1.[CH2:35](O)[CH2:36][CH2:37][OH:38].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1.CCCCCC>[CH3:13][C:14]1[CH:15]=[C:16]([O:21][S:22]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=2[S:31]([CH3:34])(=[O:33])=[O:32])(=[O:24])=[O:23])[CH:17]=[C:18]([CH:19]=1)[O:20][CH2:35][CH2:36][CH2:37][OH:38]

Participants

7

Reactant 4

HCID 104421,3-PropanediolHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 17871262HCID 17871262, compound

Product 1

HCID 22722527HCID 22722527, compoundYield 99.9%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

Diethyl azodicarboxylate (0.46 mL, 2.9 mmol) was added slowly to a solution of 1.0 g (2.9 mmol) of 5-methyl-3-[2-(methylsulfonyl)phenylsulfonyloxy]phenol, as prepared in the preceding step, 0.21 mL (2.9 mmol) of 1,3-propanediol, and 760 mg (2.9 mmol) of triphenylphosphine in anhydrous tetrahydrofuran (25 mL). The reaction mixture was stirred at ambient temperature overnight. The reaction mixture was evaporated to dryness. The residue was triturated with hexane under sonification, and the solvent was decanted (4 times). The residue was dissolved in dichloromethane and diluted with hexane to produce a crystalline material which was discarded. The filtrate was diluted with hexane to give an oil, and the solvent was decanted. The oil was dissolved in a minimum of methanol and diluted with water to initiate crystallization. The solid was collected by filtration to afford the title compound (1.16 g, quantitative yield). 1H-NMR (300 MHz, CDCl3) δ 8.45 (dd, 1H, J=1.3, 7.8 Hz), 8.12 (dd, 1H, J=1.2, 7.8 Hz), 7.88 (td, 1H, J=1.3, 7.7 Hz), 7.74 (td, 1H, J=1.3, 7.7 Hz), 6.61-6.56 (m, 3H), 4.00 (t, 2H, J=6 Hz), 3.81 (t, 3H, J=5.9 Hz), 3.45 (s, 3H), 2.24 (s, 3H), and 1.97 (pentet, 2H). Mass spectrum (MALDI-TOF, α-cyano-4-hydroxycinnamic acid matrix) calcd. for C17H20O7S2 : 423.1 (M+Na). Found: 423.1.

Workup

  1. customThe reaction mixture was evaporated to dryness
  2. customThe residue was triturated with hexane under sonification
  3. customthe solvent was decanted (4 times)
  4. dissolutionThe residue was dissolved in dichloromethane
  5. additiondiluted with hexane
  6. customto produce a crystalline material which
  7. customto give an oil
  8. customthe solvent was decanted
  9. dissolutionThe oil was dissolved in a minimum of methanol
  10. additiondiluted with water
  11. customcrystallization
  12. filtrationThe solid was collected by filtration

Sources & evidence

ORD record
ord-ba41430028984c5e99f77e5dcf49b213
Source dataset
uspto-grants-1999_04
Patent number
US05891909

Reaction notes

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