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19th September 2014 @ 01:01

 

Procedure

AEW 200-1 (~6.9 mmol) was stirred into CH2Cl2 (100 mL). PhI(OAc)(2.2 g, 6.9 mmol) was added and the resulting grey suspension was stirred at room temperature.

After 2h30, reaction mixture is red with a couple of grams of suspension. 16 hours into reaction - deeper red but still suspension.  

The reaction was stopped and the organic layer washed with saturated NaHCO3 solution (20 mL). The inorganic layer was extracted with DCM (3 x 20mL). The combined organic layers were dried over MgSO4, filtered and the solvent removed by rotary evaporation before the crude product was dried in vacuo (

 

For comparison:
 
JU 14-1 crude 400 MHz.pdf
 
JU14-1.zip 
JU 14-1_arch.pdf
 
JU 14-1 pure 200 MHz.pdf
 
JU 14-1 pure.zip

 

IR data 

JU 14-1.pdf
 

HIRAC

HIRAC JU 14-1.pdf

 

InChI strings

InChI=1S/C10H8ClN5/c11-9-6-13-7-10(15-9)16-14-5-8-1-3-12-4-2-8/h1-7H,(H,15,16)/b14-5+

to

InChI=1S/C10H6ClN5/c11-8-5-13-6-9-14-15-10(16(8)9)7-1-3-12-4-2-7/h1-6H

SMILES

ClC1=CN=CC(N/N=C/C2=CC=NC=C2)=N1

to

ClC1=CN=CC2=NN=C(C3=CC=NC=C3)N21

17th September 2014 @ 13:18

Procedure

AEW 199-1 (~6.9 mmol (1.8 g)) was stirred into CH2Cl2 (100 mL). PhI(OAc)(2.2 g, 6.9 mmol) was added and the resulting brown suspension was stirred at room temperature.

The flask smashed in half and left around 20 mL of the reaction mixture in the bottom part. This was recovered and stirred overnight. The remainder of the reaction mixture was spilt all over the bench. Recovery by scratching with spatula returned 2.7 g of a brown solid which was dissolved in CH2Cl2 (80 mL) [a lot of black floaters] and left to stir at rt with fingers tightly crossed.

AFter 2.5 h, both suspensions had dissolved to give orange soln. Too late to work up so TLC ref taken.

Data:

Disaster Pics:

2014-09-17 20.41.21.jpg
2014-09-17 20.11.18.jpg
2014-09-17 20.10.08.jpg

After 2.5 h

2014-09-17 23.20.26.jpg

TLC:

Crude NMR:

 

Hazard and Risk Assessment:

See JU 14-1

InChi:

InChI=1S/C10H8ClN5/c11-9-6-13-7-10(15-9)16-14-5-8-2-1-3-12-4-8/h1-7H,(H,15,16)/b14-5+

to

InChI=1S/C10H6ClN5/c11-8-5-13-6-9-14-15-10(16(8)9)7-2-1-3-12-4-7/h1-6H

 

Smiles:

ClC1=CN=CC(N/N=C/C2=CN=CC=C2)=N1

to

ClC1=CN=CC2=NN=C(C3=CN=CC=C3)N21

Attached Files
17th September 2014 @ 13:09

Procedure

AEW 198-1 (~6.9 mmol) was stirred into CH2Cl2 (100 mL). PhI(OAc)(2.2 g, 6.9 mmol) was added and the resulting grey suspension was stirred at room temperature.

After 2h30, reaction mixture is black and all of the suspension has dissolved. Too late to work up so TLC taken and left until morning. 

Data:

Reaction mixture after 2.5 h

2014-09-17 23.20.24.jpg

TLC:

Crude NMR:

 

Hazard and Risk Assessment:

See JU 14-1

InChi:

InChI=1S/C10H8ClN5/c11-9-6-12-7-10(15-9)16-14-5-8-3-1-2-4-13-8/h1-7H,(H,15,16)/b14-5+

to

InChI=1S/C10H6ClN5/c11-8-5-12-6-9-14-15-10(16(8)9)7-3-1-2-4-13-7/h1-6H


Smiles:

ClC1=CN=CC(N/N=C/C2=NC=CC=C2)=N1

to

ClC1=CN=CC2=NN=C(C3=NC=CC=C3)N21

Attached Files
16th September 2014 @ 02:02

scheme

Following the procedure given in DOI:10.1021/jo800907e, and performed in parallel to TM 58 (a direct repetition of a reaction from the paper).

Potassium carbonate (208 mg, 1.50 mmol) and molecular sieves (4 Å, powdered, 150 mg) were combined in a 2-neck RBF equipped with one ground glass gas adapted + stopcock and one septum (effectively a Schlenk flask), and heated with a heatgun under vacuum for ~5 minutes. The flask was cooled to RT under vacuum, then refilled with nitrogen.

A septum was briefly removed, and palladium acetate (4.5 mg, 0.02 mmol), dcpp•2HBF4 (1,3-bis(dicyclohexylphosphino)propane bis(tetrafluoroborate): 24.4 mg, 0.04 mmol), and TM 37 (from Repeat synthesis of 5-chloro-[1,2,4]triazolo[4,3-a]pyrazine (TM 37-14): 154 mg, 1 mmol) added. The flask was then evacuated and refilled with nitrogen, and a standard solution of phenol in DMF (1 mL, 1.2 M, 1.2 mmol) added by syringe. 

Two nested ballons were attached to a short length of vacuum tubing with a cable tie, sealed with parafilm. This was attached to a valve, and a second short length of tubing. The balloon apparatus was filled with CO, the valve closed, and attached to the flask's gas adapter. The flask was evacuated and backfilled with CO three times, then filled with CO and the valve to the balloon left open.

The flask was then heated in an oil bath at 100 oC for 6 h with rapid stirring.

Attached Files
15th September 2014 @ 13:32

Incorrect SM used. Reaction abandoned and repeated as: Synthesis of (E)-2-chloro-6-(2-(pyridin-2-ylmethylene)hydrazinyl)pyrazine (AEW 198-2)

 

AEW 85 (crude, 1 g, 6.9 mmol) was stirred into MeCN (12 mL). 2-Pyridinecarboxaldehyde (0.74 g, 6.9 mmol, density 1.137 g/mL) was added and the reaction mixture (light brown suspension) was stirred at room temperature for 40 hours. (NB May have been finished earlier but meetings prevented progress being followed). TLC indicates no starting hydrazine.

Pale brown solid used as crude in next reaction. MASS ?

Data:

TLC

AEW 198-2 100% EtOAc.jpg

SM

Hydrazine SM 200 MHz.pdf

Crude Product

AEW 198-2 Crude 200 MHZ.pdf

Hazard and Risk Assessment:

HIRAC AEW 198-1.pdf


InChi:

InChI=1S/C4H5ClN4/c5-3-1-7-2-4(8-3)9-6/h1-2H,6H2,(H,8,9)

and

InChI=1S/C6H5NO/c8-5-6-3-1-2-4-7-6/h1-5H

to

InChI=1S/C10H8ClN5/c11-9-6-12-7-10(15-9)16-14-5-8-3-1-2-4-13-8/h1-7H,(H,15,16)/b14-5+ 


Smiles

ClC1=CN=CC(NN)=N1

and

O=C([H])C1=CC=CC=N1

to

ClC1=CN=CC(N/N=C/C2=NC=CC=C2)=N1

Linked Posts
Attached Files