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Chemical Structure| 1581735-04-7 Chemical Structure| 1581735-04-7

Structure of 1581735-04-7

Chemical Structure| 1581735-04-7

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Product Details of [ 1581735-04-7 ]

CAS No. :1581735-04-7
Formula : C15H23F3O4
M.W : 324.34
SMILES Code : O=C(O)[C@@H]([C@H](CC1CC1)C(OC(C)(C)C)=O)CCC(F)(F)F

Safety of [ 1581735-04-7 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P280-P301+P312-P302+P352-P305+P351+P338

Application In Synthesis of [ 1581735-04-7 ]

* 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 [ 1581735-04-7 ]

[ 1581735-04-7 ] Synthesis Path-Downstream   1~2

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  • [ 1401067-00-2 ]
  • [ 1581735-04-7 ]
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  • [ 1401067-00-2 ]
  • [ 93958-21-5 ]
  • [ 1581735-04-7 ]
  • [ 1581735-05-8 ]
YieldReaction ConditionsOperation in experiment
Diisopropylamine (6.64 ml, 46.6 mmol) was dissolved in 71.7 mL ofTHF andcooled to -78 C, then n-BuLi (I8.0 mL, 44.9 mmol, 2.5M in hexane) was addedI5 dropwise over a period of 5 minutes. After 5 minutes, the resulting 0.5 M LDA solutionwas kept at 0 C] In a separate flask, lithium chloride (2.62 g, 61.7 mmol) was dried under highvacuum with heating and cooled under nitrogen. Intermediate SIA (3.0 g, I1.23 mmol),azeotroped once with toluene, was transferred with I5.0 mL toluene to the flask20 containing LiCl, and cooled to -78 C. To this stirring suspension was added LDA (25.83mL, I2.9I mmol, l.I5 equiv., 0.5M LDA) dropwise via syringe over 5 min. The reactionmixture was stirred at -78 oc for I5 minutes, then at 0 oc for I 0 minutes and cooled to -78oc. In a separate flask, Intermediate SIB (3.44 g, 20.2I mmol) was dissolved in25 I5.0 mL toluene underN2 and cooled to -78 C. To this solution was added LDA (46.48mL, 23.24 mmol, l.I5 equiv., 0.5M LDA) dropwise and stirred at -78 oc and the flask was transferred to 40 oc water bath and swirled vigorously for I5 minutes,and quenched over 5% NH40H solution (20 mL saturated NH40H and IOO mL water),and extracted with ethyl acetate (2xiOO mL). The pooled organic phases were washedwith brine, dried (Na2S04), filtered, concentrated and purified by silica gel5 chromatography (hexanes/EtOAc) to afford a mixture of Intermediate SIC andIntermediate SID (1.58g, 32% yield) as an oil. 1H NMR showed this material to be aI.5:I mixture ofSIC:SID, by integration of the t-Bu peaks: 1H NMR of diastereoisomermixture (400MHz, CDCh) 8 4.53-4.4I (m, 2H), 4.39-4.19 (m, 5H), 4.I0-4.0I (m, IH),2.89-2.77 (m, 2H), 2.47-2.26 (m, 2H), 2.16-1.72 (m, 8H), I.47 (s, 9H, t-Bu of SIC,I 0 integrates for relative intensity of I.5), I.46 (s, 9H, t-Bu of SID, integrates for relativeintensity of I), 0.98-0.86 (m, I6H), 0.78-0.64 (m, 2H), 0.56-0.37 (m, 4H), 0.14-0.0I (m,4H). for 30 minutes,at which time this solution was added via cannula (fast negative pressure, all addedwithin 30 seconds) to the LiCl/oxazolidone solution at -78 C. After I minute followingtransfer, solid bis(2-ethylhexanoyloxy)copper (I 0.80 g, 30.9 mmol) was added at -78 C, To a cool (0 C), stirred solution of a mixture oflntermediates SIC:SID (3.4g,20 7.8I mmol) in THF (60mL) and water (20 mL) was added 30% H20 2 (4.82 mL, 79mmol)followed by LiOH (0.567g, 23.66mmol). The reaction mixture was allowed to graduallywarm up to room temperature and stirred at room temperature for 3h. To the reactionmixture was added saturated Na2S03 (20 mL) and saturated NaHC03 (40 mL), and thenstirred for 5 min. The reaction mixture was partially concentrated and extracted with25 DCM (80mL). The aqueous phase was acidified to pH ~2, saturated with NaCl, extractedwith EtOAc (2x). The combined extracts were dried (MgS04), filtered and concentratedto provide a mixture oflntermediate SI and Intermediate SIE (2.0Ig, 79%). 1H NMRshowed this material to be a I.4:I mixture ofSI:SIE, by integration ofthe t-Bu peaks: 1HNMR of mixture of diastereomers ( 400MHz, CDCh) 8 2.82-2.59 (m, 4H), 2.3I-2.03 (m, To a cold ( -78 C), stirred solution of a 1.4:1 mixture oflntermediate S 1 andSIE (2.00 g, 6.17 mmol) in THF (30 mL) under N2 was added LDA (7.54 mL, 13.57mmol, 1.8M) via syringe over 5 min, stirred for 15 min, warmed to room temperature (24oc water bath), stirred for 15 min, cooled to -78 oc for 15 min. To the reaction mixturewas added diethylaluminum chloride (12.95 mL, 12.95 mmol, 1M in hexane) via syringe,15 stirred for 10 min, warmed to room temperature (24 oc bath) for 15 min then back to -78oc for 25 min. MeOH (38.9 mL, 962 mmol) was rapidly added, removed from bath thenice and IN HCl (55.5 mL, 55.5 mmol) was gradually added was added slowly. Once gasevolution subsided, the mixture was extracted with EtOAc (2x), the combined organicswashed with a solution of potassium fluoride (3.26 g, 56.2 mmol) in water (106 mL, 589520 mmol) and IN HCl (15.72 mL, 15.72 mmol), brine then dried (Na2S04). The mixture was subsequently filtered and concentrated to afford a~ 2: 1 (S 1: S 1 E, as determined byintegration of the t-Bu peaks in the 1H NMR) enriched mixture oflntermediate Sl andIntermediate S 1 E ( 1. 79 g, 90% ). 1 H NMR of mixture of diastereomers ( 400MHz, CDCh)8 2.87-2.57 (m, 2H), 2.36-2.06 (m, 2H), 1.97-1.81 (m, 2H), 1.81-1.70 (m, IH), 1.70-1.5625 (m, IH), 1.47 (s, 9H, t-Bu ofSl, integrates for relative intensity of2.0), 1.45 (s, 9H, t-BuofSIE, integrates for relative intensity of 1), 0.99-0.87 (m, IH), 0.77-0.61 (m, IH), 0.54-0.38 (m, 2H), 0.16--0.01 (m, 2H).
 

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