Dichloromethane → HCID 72490842, compound

HRID 968952Notes

Reaction equation

HRID 968952 reaction equation
[Si:1]([O:8][CH2:9][CH:10]1[CH2:15][O:14][C:13]2[CH:16]=[CH:17][C:18]([C:21]([OH:23])=[O:22])=[C:19]([CH3:20])[C:12]=2[O:11]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[F:24][C:25]1[C:30](O)=[C:29]([F:32])[C:28]([F:33])=[C:27]([F:34])[C:26]=1[F:35].C1(N=C=NC2CCCCC2)CCCCC1.C(Cl)Cl>O.C(OCC)(=O)C>[F:24][C:25]1[C:30]([O:22][C:21]([C:18]2[CH:17]=[CH:16][C:13]3[O:14][CH2:15][CH:10]([CH2:9][O:8][Si:1]([C:4]([CH3:7])([CH3:5])[CH3:6])([CH3:3])[CH3:2])[O:11][C:12]=3[C:19]=2[CH3:20])=[O:23])=[C:29]([F:32])[C:28]([F:33])=[C:27]([F:34])[C:26]=1[F:35]

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 10868DicyclohexylcarbodiimideHCID 13041PentafluorophenolHCID 68780291HCID 68780291, compound

Product 1

HCID 72490842HCID 72490842, compoundYield 84%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a round bottom flask equipped with magnetic stirring and a nitrogen inlet was added 3-(tert-butyldimethylsilyloxymethyl)-5-methyl-2,3-dihydrobenzo[1,4]dioxine-6-carboxylic acid (0.72 g, 2.13 mmol) and ethyl acetate (11 mL). To this was added pentafluorophenol (0.82 g, 2.23 mmol) followed by 1 M dicyclohexylcarbodiimide in methylene chloride (2.34 mL, 2.34 mmol). This mixture was stirred at room temperature for four hours. A few milliliters of water were added and stirring continued for 10 min. The reaction was filtered, diluted with ethyl acetate, washed once with 1 N HCl, once with saturated aqueous sodium bicarbonate solution, once with saturated sodium chloride, dried over magnesium sulfate, filtered and evaporated to give an oil. This oil was flash chromatographed on silica gel eluting with hexanes to give a clear colorless oil, 3-(tert-butyldimethylsilyloxymethyl)-5-methyl-2,3-dihydrobenzo[1,4]dioxine-6-carboxylic acid pentafluorophenyl ester, (0.90 g, 1.78 mmol) in 84% yield. 1H-NMR (300 MHz, CDCl3) δ (ppm): 0.10 (s, 6H), 0.90 (s, 9H), 2.50 (s, 3H), 3.90 (m, 2H), 4.14 (m, 1H), 4.24 (m, 1H), 4.40 (m, 1H), 6.83, (d, 1H), 7.86, (d, 1H); TLC Rf=0.88 (1:1 ethyl acetate/hexane).

Workup

  1. customTo a round bottom flask equipped
  2. stirringThis mixture was stirred at room temperature for four hours
  3. stirringstirring
  4. filtrationThe reaction was filtered
  5. additiondiluted with ethyl acetate
  6. washwashed once with 1 N HCl, once with saturated aqueous sodium bicarbonate solution, once with saturated sodium chloride
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. customevaporated
  10. customto give an oil
  11. customchromatographed on silica gel eluting with hexanes

Sources & evidence

ORD record
ord-ca8ed7a920e140d1905291cfd9cd610d
Source dataset
uspto-grants-2007_12
Patent number
US07304161B2

Reaction notes

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