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8th August 2016 @ 01:10

Reference:

http://malaria.ourexperiment.org/triazolopyrazine_se/8947/Synthesis_of_methyl_234difluorophenyl2tetrahydro2Hpyran2yloxyacetate_AEW_1092.html

http://malaria.ourexperiment.org/triazolopyrazine_se/11404/Synthesis_of_methyl_2phenyl2tetrahydro2Hpyran2yloxyacetate_AEW_2191.html

 

Procedure: Reaction started at 15:17 2nd Aug

methyl 2-hydroxy-2-phenylacetate(5.0 g, 30.09 mmol, 1 equiv.) and DHP (4.12 mL, 3.8g, 45.13 mmol, 1.5 equiv.) were dissolved in anhydrous CH2Cl2 (5 mL) under Argon and cooled to 0 ˚C. TsOH (259.06mg, 1.5mmol, 0.05 eq.) was added and the reaction mixture was stirred at 0 ˚C for 3 h (black solution) and then at rt. 

CH2Cl(80 mL) was added and the resulting solution was shaken with portions of ice-cold water (3 x 10 mL) and once with saturated NaHCO(10 mL). The organic phase was dried (MgSO4) and filtered, and the solvent was removed under reduced pressure.


HIRAC:

 See http://malaria.ourexperiment.org/triazolopyrazine_se/14343/Synthesis_of_methyl_2phenyl2tetrahydro2Hpyran2yloxyacetateHM_51.html

String:

InChI=1S/C9H10O3/c1-12-9(11)8(10)7-5-3-2-4-6-7/h2-6,8,10H,1H3

to

InChI=1S/C14H18O4/c1-16-14(15)13(11-7-3-2-4-8-11)18-12-9-5-6-10-17-12/h2-4,7-8,12-13H,5-6,9-10H2,1H3

 

Log

8th Aug

The reaction was started at 10:50am.The reacting mixture began with a yellow solution and remained the same for an hour. TLC was performed at 11:40. New compound was formed, though there was still lots of SM. Ice bath was removed.

    

TLC was performed again at 2:00 pm. No obvious difference. Finally found out that tosylic acid hadn't been added to the solution.(Oh......). Tosylic acid was added. The reacting mixture turned brown immediately.

At 4:00pm, TLC was performed(10% of ethyl acetate in petroleum), which showed that product was formed, and small amount of SM was still there. 0.5 more equiv of DHP was added.The reaction was left overnight.

9th Aug

NMR was performed, the spectrum looks much like HM 5-1 frac1's which is the product of the reaction.But in the region between 5.0 to 5.5ppm,the peaks didn't match. I'm not confident about the product, it probably needs column.

NMR data(300MHz CDCl3)

HM 5-2.zip
HM 5-2.png

11th Aug

product was purified by column. Fraction 1 was combined and 2.31g product was attained(yield:30%). The product is colorless viscous oil. NMR indicated that there was some ethyl acetat left in the product. 

NMR data(300MHz CDCl3)

HM 5-2 f1.png
HM 5-2f1.zip


 



Attached Files
HM 5-1.png
QQ图片20160808121557.jpg
IMG_2486.JPG
IMG_2491.JPG
IMG_2493.JPG
HM 5-2.png
HM 5-2.zip
HM 5-2 f1.png
HM 5-2f1.zip