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30th January 2018 @ 14:22

Another experiment was set up in attempt to highlight if it was the electronic configuration of the starting material that was preventing succesful reaction. Efforts were made to replicate the same conditions as the other experiments but Bromobenzene was used in stead of SBM005.

Reaction Scheme

Bromobenzene (20mg) was added in degassed toluene (2ml). Morpholine (15ul) was added, followed by Spanphos (approx. 1mg), NaOtBu (16.38mg) and Pd(DBA)3 (approx. 0.6mg) and left stirring at 80-1000C. This was repeated with the same conditions but changing the ligand to DPPF, then JohnPhos, then BINAP.

TLCs (5% methanol, 95% DCM) were run at 1 day and 14 days. 

TLC BB Binap

At 14 days, the DPPF Reaction mixture was extracted with HCl (2ml) and EtOAc (3x3ml) and then dried with MgSO4 before being put under rotary evap.

NMR of crude products showed experiments were unsuccessful.

30th January 2018 @ 13:58

Reaction

SBM005 was dissolved in degassed toluene (2ml). Morpholine (15ul) was added, followed by Spanphos (approx. 1mg), NaOtBu (16.38mg) and Pd(DBA)3 (approx. 0.6mg) and left stirring at 800C. This was repeated with the same conditions but DPPF instead of Spanphos.

After one week, another two reaction mixtures were set up the same way, with JohnPhos (approx. 1mg) as the ligand and but one with Piperidine (15ul) intead of Morpholine.

JohnPhos Morpholine and JohnPhos Piperidine Reaction mixtures
Colour changes to a darker crimson as shown, became more apparent with time.

TLCs (5% methanol, 95% DCM) were run at 7 days and 14 days. 


At 14 days, reaction mixtures were extracted with HCl (2ml) and EtOAc (3x3ml) and then dried with MgSO4 before being put under rotary evap.

Rotary Evap.
Crude Product


NMR of crude products showed experiments were unsuccessful.

30th January 2018 @ 13:17

Reaction
SBM005 was dissolved in degassed toluene (2ml). Morpholine (4 drops, approx. 20ul) was added, followed by BINAP (approx. 0.5mg), NaOtBu (16.38mg) and Pd(DBA)3 (approx. 0.6mg) and left stirring at 800C. This was repeated with the same conditions but JohnPhos instead of BINAP.

Reaction Mixtures

TLCs (5% methanol, 95% DCM) were run at 2hrs, 22hrs, 7 days and 14 days. The JohnPhos reaction mixture dried out before reaching the 7 day point.


22 hr TLC
At 14 days, reaction mixture was extracted with HCl (2ml) and EtOAc (3x2ml) and then dried with MgSO4 before being put under rotary evap.

NMR of crude product showed reaction was unsuccesful.


Attached Files
23rd October 2017 @ 00:24

Reaction

Triazolopyrazine (507mg, 1.615mmol) was dissolved in THF (10ml) under nitrogen atmosphere followed by addition of NaH (60% purity, 0.1244g, 3.2mmol) and left stirring (2hr).

Reaction


A TLC (50/50 Ethyl Acetate/Pet. Ether) was run to display completion which showed presence of lowest ratio starting material suggesting that the reaction was not yet complete so it was left stirring (1hr).

Reaction


Another TLC was run with a more polar solvent system to increase separation (Ethyl Acetate) which suggested completion. A permanganate stain showed the TLC spot expected to be product as a light spot often suggesting presence of an alkyl.

Reaction


Reaction mixture was quenched with HCl (~20ml, 2M) and organic layer was separated with Ethyl Acetate (2x40ml).

Reaction


Organic layer was dried with MgSO4 and filtered on air before being put under the rotary evaporator to remove solvent.

Reaction


A column was run (Ethyl Acetate) to separate product, fractions were tested via TLC. Fractions 14-29 were collated and put under rotary evaporator to give product (0.4456g, 1.0791mmol) with a 66.82% Yield.

Reaction



ProductProduct is shown above.
Attached Files
23rd October 2017 @ 00:17

Hydrazone (2.0015g, 6.4239mmol) was added to CH2Cl2 (40ml) and PIDA/BIPA (2.0870g, 6.4793mmol) and left stirring overnight (18hr).

Reaction
Reaction

This resulted in a brown suspension which was tested with TLC (50/50 pet. Ether (60-800C)/ethyl acetate), suggesting absence of remaining Hydrazone and presence of a product.
Reaction

The solution was left stirring (40mins) before a saturated NaHCO3 solution (40ml) was added and the organic layer was separated (100ml + 50ml Ethyl Acetate, 50ml Brine) which initially gave three layers which then became two layers after the addition of brine and excess Ethyl Acetate.
The organic layer was dried with MgSO4 and filtered in air with an Ethyl Acetate wash (15ml). This gave a yellow liquid. The rotary evaporator was used to remove the solvent.
The crude product was pre-loaded onto silica and a column was run (50/50 pet. Ether (60-800C)/ethyl acetate), the solvent was changed to be more polar (70/30 Ethyl Acetate/Pet. Ether) once the product showed up in fractions. Fractions tested via TLC. Fractions 21-35 were collected, product had begun to crystallise within the fractions and was dissolved with additional solvent (DCM) and put under the rotary evaporator to give product (1.0844gg, 3.5031mmol) with a yield of 54.53%.

DSC_0291.JPG

Reaction
Attached Files