Citric Acid → HCID 86663139, compound

HRID 1025970Notes

Reaction equation

HRID 1025970 reaction equation
[Li]CCCC.[C:6]([Si:10]([CH3:16])([CH3:15])[O:11][CH2:12][C:13]#[CH:14])([CH3:9])([CH3:8])[CH3:7].[F:17][C:18]([F:25])([F:24])[C:19](OCC)=[O:20].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C1(C)C=CC=CC=1>[Si:10]([O:11][CH2:12][C:13]#[C:14][C:19](=[O:20])[C:18]([F:25])([F:24])[F:17])([C:6]([CH3:8])([CH3:9])[CH3:7])([CH3:15])[CH3:16]

Participants

6

Reactant 4

HCID 311Citric AcidHCID 9794Ethyl trifluoroacetateHCID 3445622tert-Butyl(dimethyl)[(prop-2-yn-1-yl)oxy]silaneHCID 178418339Butyllithium

Product 1

HCID 86663139HCID 86663139, compoundYield 75.4%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
-10 °C

Procedure

To 50 mL of a 1.6M solution of n-BuLi (0.080 mol, 1 equ) in hexanes was added dropwise tert-butyldimethyl(prop-2-ynyloxy)silane (13.57 g; 0.080 mol; 1 equ) with dry ice acetone cooling. After addition the dry ice acetone bath was replaced by an ice acetone bath. When the mixture became difficult to stir toluene (25 mL) was added. The mixture became clear and was stirred at −10° C. for 15 min. To the resulting slightly yellow solution was added ethyl 2,2,2-trifluoroacetate (11.3 g; 0.080 mol; 1 equ) with cooling in a dry ice acetone bath (ca<−40° C.). After addition the dry ice acetone bath was replaced by an ice acetone bath and the mixture was stirred with thawing to room temperature for 18 h. The reaction mixture was poured onto ice mixed with 10% aqueous citric acid. The phases were separated and the organic phase was washed with 10% aqueous sodium bicarbonate and brine and purified by filtration over ca 350 g silica gel using heptane:dichloromethane=1:1 as eluent. The product fractions (dichloromethane:heptane 1:1; r.f.:0.3 KMnO4 staining) were pooled and evaporated to yield the title compound as an orange yellow oil (16.0 g, 75.4% Th), MS 266.277 (M)+.

Workup

  1. customwas replaced by an ice acetone bath
  2. additionwas added
  3. temperaturewith cooling in a dry ice acetone bath (ca<−40° C.)
  4. customwas replaced by an ice acetone bath
  5. stirringthe mixture was stirred with thawing to room temperature for 18 h
  6. additionThe reaction mixture was poured onto ice
  7. customThe phases were separated
  8. washthe organic phase was washed with 10% aqueous sodium bicarbonate and brine
  9. filtrationpurified by filtration over ca 350 g silica gel
  10. customevaporated

Sources & evidence

ORD record
ord-ad986bbecd1e4ffebd59f5c1ad434e7c
Source dataset
uspto-grants-2014_05
Patent number
US08729105B2

Reaction notes

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