Acetic Anhydride → HCID 14522075, compound

HRID 1192741Notes

Reaction equation

HRID 1192741 reaction equation
[CH2:1]([O:4][C:5]1[CH:6]=[C:7]([CH:10]=[CH:11][CH:12]=1)[CH2:8][OH:9])[C:2]#[CH:3].[C:13](OC(=O)C)(=[O:15])[CH3:14]>S(=O)(=O)(O)O.C(Cl)Cl>[C:13]([O:9][CH2:8][C:7]1[CH:10]=[CH:11][CH:12]=[C:5]([O:4][CH2:1][C:2]#[CH:3])[CH:6]=1)(=[O:15])[CH3:14]

Participants

5

Reactant 2

HCID 7918Acetic AnhydrideHCID 107970673-(2-Propyn-1-yloxy)benzenemethanol

Product 1

HCID 14522075HCID 14522075, compound

Reagents, catalysts & solvents 2

HCID 1118Sulfuric AcidCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A 5.0 L flange flask was charged with 3 (706 g, approx. 4.36 mol, 1 eq) and acetic anhydride (99.5%, ex. Fisher, 1300 ml, 1 mol) to give a clear solution. Sulfuric acid (conc. 98%, 150 drops, ˜3 ml, catalytic) was then added very slowly (dropwise) over 30 minutes, with cooling to 0° C. by aid of an ice/water bath to control the exotherm to give a very dark reaction mixture. Maximum internal temperature observed was 45° C. After the addition the reaction mixture was stirred for 30 min, then the reaction mixture was stirred at 99° C. for 3 h. TLC-examination (silica-gel plate, DCM eluent, PMA stain) showed that all the starting material had been consumed. The mixture was cooled to room temperature (r.t.) overnight to give a dark green solution, which was poured onto an ice-water mixture (2.5 L water and 2.5 Kg of ice) with vigorous stirring. The product was extracted with DCM (5.0 L×3), and the combined extracts washed with water (3.0 L×3), dried over Na2SO4, and evaporated to give a black/brown oily residue.

Workup

  1. customto give a clear solution
  2. customto give a very dark reaction mixture
  3. customobserved was 45° C
  4. additionAfter the addition the reaction mixture
  5. stirringthe reaction mixture was stirred at 99° C. for 3 h
  6. customhad been consumed
  7. temperatureThe mixture was cooled to room temperature (r.t.) overnight
  8. customto give a dark green solution, which
  9. extractionThe product was extracted with DCM (5.0 L×3)
  10. washthe combined extracts washed with water (3.0 L×3)
  11. dry with materialdried over Na2SO4
  12. customevaporated
  13. customto give a black/brown oily residue

Sources & evidence

ORD record
ord-75312b6558af4077b975a0ec19419a87
Source dataset
uspto-grants-2014_03
Patent number
US08680265B2

Reaction notes

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