Ethyl orthoformate → 4-t-Butyldimethylsilyloxymethyl-2-ethoxy-1,3-dithiolane

HRID 481716Notes

Reaction equation

HRID 481716 reaction equation
[Si:1]([O:8][CH2:9][CH:10]([SH:13])[CH2:11][SH:12])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH2:14]([O:16][CH:17](OCC)OCC)[CH3:15].C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1>C1(C)C=CC=CC=1>[Si:1]([O:8][CH2:9][CH:10]1[CH2:11][S:12][CH:17]([O:16][CH2:14][CH3:15])[S:13]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 31214Ethyl orthoformateHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 212558391-t-BUTYLDIMETHYLSILYLOXY-2,3-DIMERCAPTOPROPANE

Product 1

HCID 212558444-t-Butyldimethylsilyloxymethyl-2-ethoxy-1,3-dithiolaneYield 94%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 1-t-butyldimethylsilyloxy-2,3-dimercaptopropane (example 47) (32.00 g, 134 mmol) in toluene (400 mL) were added triethylorthoformate (29.0 mL, 174 mmol, 1.3 eq) and pyridinium p-toluenesulfonate (200 mg). The solution was strirred at 120°-130° C. for 6 hr then was quenched at room temperature with a solution of saturated sodium bicarbonate. The aqueous phase was extracted with dichloromethane and the organic layer was dried with magnesium sulfate and evaporated under reduced pressure. The crude product was obtained in 94% yield (37.17 g) as a 1:1 mixture and was used without further purification. 1H NMR (300 MHz, CDCl3) δ: 0.06 and 0.07 (2s, 6H, CH3), 0.89 (s, 9H, t-butyl), 1.22 and 1.23 (2t, 3H, J=7.0 Hz, CH3), 3.28-3.70 (m, 5H, H-5, CH2O, H-4), 3.75-4.00 (m, 2H, CH2O), 6.19 and 6.20 (2s, 1H, H-2).

Workup

  1. customthen was quenched at room temperature with a solution of saturated sodium bicarbonate
  2. extractionThe aqueous phase was extracted with dichloromethane
  3. dry with materialthe organic layer was dried with magnesium sulfate
  4. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-6c23c1aa1346429cbefb51e9cbab30c7
Source dataset
uspto-grants-1998_08
Patent number
US05789394

Reaction notes

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