Citric Acid → Benzoic acid, 2-chloro-6-(trimethylsilyl)-
Reaction equation
[Cl:1][C:2]1[CH:10]=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].CN(CCN(C)C)C.[Li]C(CC)C.C1CCCCC1.[CH3:30][Si:31](Cl)([CH3:33])[CH3:32].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C1COCC1>[Cl:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]([Si:31]([CH3:33])([CH3:32])[CH3:30])[C:3]=1[C:4]([OH:6])=[O:5]Participants
8
Reactant 6
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- -100 °C
Procedure
2-Chlorobenzoic acid (3.91 g, 25 mmol), THF (60 mL), and TMEDA (8.6 mL, 57 mmol) were stirred under nitrogen and cooled to -100° C. 1.3M s-BuLi in cyclohexane (0.055 mol, 42.3 mL) was added dropwise keeping the temperature below -80° C. After the addition was complete, TMSCl (2.7 g, 25 mmol) was added dropwise and the resulting mixture was allowed to stir and slowly warm to -30° C. 25% citric acid (100 mL) was added and the mixture was extracted with two 50 mL portions of ether, which were then combined and washed three times with water, dried (MgSO4) and concentrated. The crude product was purified by HPLC, eluting with 2:3 ethyl acetate/hexanes. The product was recovered as a white solid in 63% yield. m.p. 129°-131° C.
Workup
- customthe temperature below -80° C
- additionAfter the addition
- temperatureslowly warm to -30° C
- extractionthe mixture was extracted with two 50 mL portions of ether, which
- washwashed three times with water
- dry with materialdried (MgSO4)
- concentrationconcentrated
- customThe crude product was purified by HPLC
- washeluting with 2:3 ethyl acetate/hexanes
- customThe product was recovered as a white solid in 63% yield
Sources & evidence
- ORD record
- ord-4ea87d788f4b476e8cd285e5f051c57a
- Source dataset
- uspto-grants-1996_03
- Patent number
- US05498630
Reaction notes
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