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6th October 2016 @ 02:16

 

AEW 319-1 (155 mg, 0.90 mmol, 1.0 equiv.) was dissolved in CH2Cl2 (1 mL) and a drop of AcOH was added. Dimethylamine (0.18 mL, 1.0 equiv., 33% in abs ethanol) was added and the reaction mixture stirred at rt for 15 mins (yellow to orange soln).

NaCNBH3 (86 mg, 0.45 mmol, 0.5 equiv.) was added in a single portion at rt and the reaction mixture stirred at rt for...

 

Hazard Identification Risk Assessment and Controls

HIRAC AEW 320-1.doc
HIRAC AEW 320-1.pdf

Strings

FC1=C(F)C=C(C(CO)=O)C=C1

to

FC1=C(F)C=C(C(N(C)C)CO)C=C1

 

InChI=1S/C8H6F2O2/c9-6-2-1-5(3-7(6)10)8(12)4-11/h1-3,11H,4H2

to

InChI=1S/C10H13F2NO/c1-13(2)10(6-14)7-3-4-8(11)9(12)5-7/h3-5,10,14H,6H2,1-2H3

Attached Files
6th October 2016 @ 02:13

Procedure


Strings

FC1=C(F)C=C(C(OC)(OC)CO)C=C1

to

FC1=C(F)C=C(C(CO)=O)C=C1

 

InChI=1S/C10H12F2O3/c1-14-10(6-13,15-2)7-3-4-8(11)9(12)5-7/h3-5,13H,6H2,1-2H3

to

InChI=1S/C8H6F2O2/c9-6-2-1-5(3-7(6)10)8(12)4-11/h1-3,11H,4H2

Attached Files
28th September 2016 @ 01:03

 

Reference: https://www.google.com/patents/US6159990


Procedure:

KOH (3.77 g, 67.3 mmol, 10.0 equiv.) was dissolved in MeOH (35 mL) and stirred at 0 ˚C. AEW 316-1 (1.05 g, 6.73 mmol, 1.00 equiv.) was added dropwise at 0 ˚C and then stirred at this temperature for 15 mins. PIDA (4.33 g, 13.5 mmol, 2.00 equiv.) was added portionwise over 20 min and the reaction mixture was stirred at rt for 20 h.

Clear and colourless solution, to clear yellow solution to cloudy yellow mixture.

Solvent was removed in vacuo to provide






Strings:

FC1=C(F)C=C(C(C)=O)C=C1

to

FC1=C(F)C=C(C(OC)(OC)CO)C=C1

InChI=1S/C8H6F2O/c1-5(11)6-2-3-7(9)8(10)4-6/h2-4H,1H3

to

InChI=1S/C10H12F2O3/c1-14-10(6-13,15-2)7-3-4-8(11)9(12)5-7/h3-5,13H,6H2,1-2H3

Attached Files
21st September 2016 @ 02:36

NB used crude AEW 232-3 prior to NMR owing to time constraints - will check validity of SM asap.

 

 

AEW 232-3 (based on 1.96 mmol) was dissolved in EtOH (8 mL). CuCl2.2H2O (17 mg, 0.08 mmol, 5 mol%) was added and the reaction heated at reflux for 40 mins. TLC no SM

The solvent was removed and the crude black oil was columned using the Biotage Isolera - EtOAc then 10-20% MeOH in DCM. Multiple black fractions collected.

 

Data:

TLC

AEW 317-1 (EtOAc).JPG

AEW 317-1 Frac 2 NMR 300 MHz

problem accessing NMR data but looks promising

Strings:

FC(OC(C=C1)=CC=C1C2=NN=C3N2C(OCC(COC4OCCCC4)C5=CC=CC=C5)=CN=C3)F

to

OCC(C1=CC=CC=C1)COC2=CN=CC3=NN=C(C4=CC=C(OC(F)F)C=C4)N32

InChI=1S/C21H18F2N4O3/c22-21(23)30-17-8-6-15(7-9-17)20-26-25-18-10-24-11-19(27(18)20)29-13-16(12-28)14-4-2-1-3-5-14/h1-11,16,21,28H,12-13H2

to

InChI=1S/C21H18F2N4O3/c22-21(23)30-17-8-6-15(7-9-17)20-26-25-18-10-24-11-19(27(18)20)29-13-16(12-28)14-4-2-1-3-5-14/h1-11,16,21,28H,12-13H2

Attached Files
20th September 2016 @ 23:14

 

Procedure:

To a solution of oxalyl chloride (5.42 mL, 63.2 mmol, 5 equiv.) and 3 Å MS in CH2Cl2 (13 mL) at -78 °C under N2 was added dropwise a solution of DMSO (8.98 mL, 126 mmol) in CH2Cl2 (1 mL). After 15 min a solution of the alcohol (2.00 g, 12. 7 mmol, 1 equiv.) in CH2Cl2 (40 mL) was slowly added dropwise. After 30 min, Et3N (26.4 mL, 190 mmol) was added dropwise. The reaction was stirred 30 min at -78 °C then slowly allowed to warm to rt whilst stirring for 20 h.

TLC inconclusive

Reaction partioned with 1M HCl (aq) and organic layers extracted and then washed with 1M HCl (aq) x 2, a saturated aqueous solution of NaHCO(x 3), water, brine and then dried over MgSO4 filtered and evaporated to give a yellow oil. Crude NMR shows mixture of products.

TLC of crude shows one major product and faint other spots - one that can be seen more clearly when visualised with KMnO4.

Purified using the Biotage Isolera (10% EtOAc in Hexane gradient, 50 g handpacked column) to yield two products:

Frac 1 - bright yellow liquid - desired product

Frac 2 - bright yellow oil - starting material

 

Data:

TLC: AEW 316-1 (10% EtOAc in Hex) after work-up

AEW 316-1 (10% EtOAc in Hex) after work-up.JPG

Crude NMR 300 MHz:

 

Strings:

FC1=C(F)C=C(C(O)C)C=C1

to

FC1=C(F)C=C(C(C)=O)C=C1

InChI=1S/C8H8F2O/c1-5(11)6-2-3-7(9)8(10)4-6/h2-5,11H,1H3

to

InChI=1S/C8H6F2O/c1-5(11)6-2-3-7(9)8(10)4-6/h2-4H,1H3


Literature Reference:

http://www.ochemonline.com/Swern_oxidation

Attached Files