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Chemical Structure| 81576-57-0

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Product Details of [ 81576-57-0 ]

CAS No. :81576-57-0
Formula : C14H20O2
M.W : 220.31
SMILES Code : C[C@H](C1=CC=C(CC(C)C)C=C1)C(OC)=O
MDL No. :MFCD00869922

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Application In Synthesis of [ 81576-57-0 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 81576-57-0 ]

[ 81576-57-0 ] Synthesis Path-Downstream   1~10

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  • 5
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YieldReaction ConditionsOperation in experiment
In diethyl ether; at -5℃; A solution of (R) (-) -ibuprofen (3.45 g) in ethyl ether, cooled to 5°C, is treated, dropwise, with a 0.6 M solution of diazomethane in ethyl ether, up to a persistent yellow colour. The solvent is removed under vacuum; the residual oil is purified by flash chromatography to yield 3.3 g of methyl (R) (-) 2- (4APOS;-ISOBUTYLPHENYL)-PROPIONATE. Alternatively, 2.6 g of CARBONYLDIIMIDAZOLE are added under stirring to a solution of R (-) ibuprofen (3. 45 G) in LOML of THF. The mixture is stirred for 1 h, the solvent is evaporated under vacuum, and the residual oil is purified by flash chromatography to yield 4.05 g of (R) (-) 2- (4APOS;-ISOBUTYLPHENYL)-PROPIONYLIMIDAZOLIDE. In an inert-gas atmosphere, a solution of butyl lithium (1. 56 M ; 13. 3 ML, 0. 027 mol) in hexane is added dropwise to a solution of dimethyl methylphosphonate (3.69 g; 0.03 mol) in anhydrous THF (10 ML) cooled TO-70°C. The mixture is stirred for 15MIN before addition, dropwise, of a solution in anhydrous THF (10 ML) of methyl ester or of imidazolide, prepared as previously described. Upon completion of the dripping step, the reaction mixture is kept, under stirring, for 1 h at - 70°C and then for 1 h at room temperature. The mixture is then cooled TO-10°C, and 1.8 mL of glacial acetic acid is added dropwise. The solvent is removed under vacuum, the residue is diluted with water, and the mixture is repeatedly extracted with dichloromethane (4X50 mL). The organic extracts are dried on sodium sulfate; after evaporation of the solvent, the residue is purified on silica gel, eluted with AcOEt to yield, as a colourless oil, 3.02 g of (R) (-)-dimethyl 3- (4-ISOBUTYL)-2-OXOBUTAN-L-PHOSPHONATE. [A] D=-171° (C=L ; CH30H) ;APOS;H-NMR (CDC13) : 5 7.03 (s, 4H); 4.1-3. 9 (dd, 2H, J1=15HZ, J2=8HZ) ; 3.8 (s, 3H); 3.70 (m, 1H) ; 3.65 (s, 3H); 2.55 (d, 2H, J=8Hz); 1.75 (m, 1H); 1.50 (d, 3H, J=8Hz); 0.85 (d, 6H, J=7Hz).
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  • 8
  • [ 5445-17-0 ]
  • [ 2051-99-2 ]
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YieldReaction ConditionsOperation in experiment
General procedure: To a 50-mL two-neck round-bottom flask equipped with a cannula were added magnesium turnings (608 mg, 25 mmol), and the flask was heated at 80 C in vacuo for 1 h. A solution of the <strong>[2051-99-2]4-isobutylphenyl bromide</strong> (426 mg, 2.0 mmol) in THF (5 mL) was added dropwise over 3 min under argon. The mixture was heated at 50 C until the reaction was initiated. Additional <strong>[2051-99-2]4-isobutylphenyl bromide</strong> (1.71 g, 8.0 mmol) in THF (11.6 mL) was then added slowly via cannula over 15 min. The reaction mixture was heated at reflux for 3 h, after which a solution of 4-isobutylphenyl magnesium bromide 5 was obtained. To a separate 50-mL Schlenk tube was added anhydrous CoBr2 (21.9mg, 0.10mmol), and the tube was heated at 50C in vacuo for 2h. After cooling to room temperature, the cyclopropane-based bisoxazoline ligand 2 (0.12mmol) in THF (3mL) was added under argon. The resulting mixture was stirred for 1h at the same temperature, with 2-bromopropanoate 6 (1mmol) being added via syringe. The mixture solution was cooled to -80C, and the prepared Grignard reagent 5 (2.8mL, 0.5M in THF, 1.4mmol) was then added over 1h via syringe. The reaction mixture was stirred for another 6h at -80C and then quenched with saturated NH4Cl solution (5mL). The aqueous phase was extracted with diethyl ether (4×10mL). The combined organic phases were dried over anhydrous Na2SO4, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (n-hexane/ethyl acetate 100:1). 4.4.2 (S)-Methyl 2-(4-isobutylphenyl)propanoate 7b Colorless oil, 86% yield, 86:14 er. The enantiomeric ratio was determined by HPLC with a Daicel Chiralcel OJ-H column (0.5% 2-propanol in n-hexane, 0.5 mL/min, 220 nm, major tr = 16.75 min (S), minor tr = 20.48 min (R)). [alpha]D20 = +50.5 (c 1.0, CHCl3). Lit. 25 [alpha]D29 = +59.5 (c 1.1, CHCl3, 97:3 er). 1H NMR (300 MHz, CDCl3) delta: 7.21-7.18 (m, 2H), 7.09 (d, J = 8.1 Hz, 2H), 3.70 (q, J = 7.1 Hz, 1H), 3.66 (s, 3H), 2.45 (d, J = 7.2 Hz, 2H), 1.89-1.80 (m, 1H), 1.49 (d, J = 7.2 Hz, 3H), 0.90 (d, J = 6.6 Hz, 6H). 13C NMR (75 MHz, CDCl3) delta: 175.1, 140.5, 137.7, 129.3, 127.1, 51.9, 45.01, 45.00, 30.1, 22.3, 18.6. HRMS (APCI-TOF): calcd for C14H21O2 [M+H]+ 221.1542, found 221.1549.
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YieldReaction ConditionsOperation in experiment
With Yarrowia lipolytica Lip2p lipase; In decane; at 20℃; for 100h;Enzymatic reaction;Kinetics; General procedure: In a 2 mL reactor (Eppendorf), 750 lL of culture supernatant (or the concentrate supernatant) containing the enzyme and 750 lL ofracemic ethyl ibuprofen, naproxen or ketoprofen (50 mM indecane) were added. The reactors were stirred in a vortex Genie2 (D. Dutscher, Brumat, France) at room temperature for 100 h.At regular time intervals, the progress of the reaction was monitored by analyzing the organic phase composition after phase separationby centrifugation (dilution 1, 10 and 30 in hexane for the ibuprofen, naproxen and ketoprofen ester, respectively).
 

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