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31st October 2013 @ 10:19

Repeat of Synthesis of 2-Chloro-6-hydrazinylpyrazine (AEW 85-1), see also Synthesis of 2-Chloro-6-hydrazinylpyrazine (AEW 85-2)

Started 8.30 am 

2,6-Dichloropyrazine (4 g, 27.0 mmol) was vigorously stirred in ethanol (40 mL) and hydrazine hydrate (1.32 mL, 1.36 g, 27.0 mmol) was added. The resulting mixture was heated at 80 ˚C for 12 h. Reaction incomplete. Stirred overnight and still SM. Stirred over the weekend..with a TLC check...couldn't see SM. Solvent evaporated - still SM by NMR. Resubmitted to the reaction conditions.

 

Data:

1H NMR (200 MHz, CDCl3): incomplete

 

AEW 85-3 200 mhz incomplete.pdf
AEW 85-3.zip

1H NMR (300 MHz, CDCl3):

 

AEW 85-3.pdf
AEW 85-3.zip

Hazard and Risk Assessment:

See Synthesis of 2-Chloro-6-hydrazinylpyrazine (AEW 85-1)

InChi Strings:

InChI=1S/C4H2Cl2N2/c5-3-1-7-2-4(6)8-3/h1-2H

to

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

 

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31st October 2013 @ 10:12

Started 20:30

To a well stirred solution of AEW 95-1 (500 mg,  1.94 mmol) in CH2Cl2 (15 mL) was added PhI(OAc)2 (625 mg, 1.94 mmol) and the resulting reaction mixture was stirred at room temperature for 1 h.

Solvent was evaporated in vacuo.The crude residue was purified by column chromatography (using silica gel 100-200 and gradient elution of 100% EA) to afford the 

 

Data:

 

Hazard and Risk Assessment:

See 4-(5-chloro-[1,2,4]triazolo[4,3-a]pyrazin-3-yl)benzonitrile (AEW 97-1) 

InChi:

InChI=1S/C12H8ClN5/c13-11-7-15-8-12(17-11)18-16-6-10-3-1-9(5-14)2-4-10/h1-4,6-8H,(H,17,18)/b16-6+

to

InChI=1S/C12H6ClN5/c13-10-6-15-7-11-16-17-12(18(10)11)9-3-1-8(5-14)2-4-9/h1-4,6-7H

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29th October 2013 @ 01:02

Repeat of AEW 97-3 on 1g scale.

To a well stirred solution of AEW 95-1 (1 g, 3.9 mmol) in CH2Cl2 (30 mL) was added PhI(OAc)2 (1.25 g, 3.9 mmol) and the resulting reaction mixture was stirred at room temperature for 1 h. Still SM on TLC plate so stirred for a 1 h further. Before crude NMR aliquot removed.

Solvent was evaporated in vacuo.The crude residue was purified by column chromatography (using silica gel 100-200 and gradient elution of 100% EA) to afford the desired product as a mustard solid (120 mg, 0.47 mmol, ~12% yield). 

N.B the Rf of the product in EtOAc is 0.6, not 0.1 as reported in CRO report.

 Data:

AEW 97-4 (EtOAc) column.jpg

Hazard and Risk Assessment:

See 4-(5-chloro-[1,2,4]triazolo[4,3-a]pyrazin-3-yl)benzonitrile (AEW 97-1) 

InChi:

InChI=1S/C12H8ClN5/c13-11-7-15-8-12(17-11)18-16-6-10-3-1-9(5-14)2-4-10/h1-4,6-8H,(H,17,18)/b16-6+

to

InChI=1S/C12H6ClN5/c13-10-6-15-7-11-16-17-12(18(10)11)9-3-1-8(5-14)2-4-9/h1-4,6-7H

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28th October 2013 @ 14:37

 

To a well stirred solution of AEW DS 2-1 (100 mg, 1.94 mmol), CH2Cl2 (3 mL) and PhI(OAc)2 (125 mg, 1.94 mmol) was added and the resulting reaction mixture was stirred at room temperature for 1h. A TLC of the solution was taken, in 100% EtOAc, and an NMR was also done.

The slvent was then removed using a rotary evaporator and the crude residue was purified by column chromatography (using silica gel 40-63μm and gradient elution of 100% EtOAc). The solvent was then removed using a rotary evaporator.

14.43mg of product was recovered.

Data:

3ORProject10_DS3-2_281013_1H_bi600.tar

Hazard and Risk Assessment:

Risk Assessment

TLC:

TLC 3-2

NMR:

NMR DS 3-2.pdf
Attached Files
25th October 2013 @ 10:26

 

A well stirred sample of EO 2-1 (0.1018 g) was mixed with CH2Cl2 (3 mL) and Phl(OAc)2 (0.1252 g) and the mixture was stirred for 25 hours after which a TLC analysis was carried out using 30% EtOAc in Hexane ( EO 3-1 TLC). No spot was observed for the sample material, i.e. EO 2-1,  so the mixture was stirred for another 24 hours and NMR analysis was carried out ( EO 3-1A 1H NMR)

The solution was then washed with CH2Cl2 (50 mL), NaHCO3 (40 mL) and CH4 (5 mL) to dissolve  majority of the solid, with some solid remaining undissolved. Upon 5 consecutive washings with CH2Cl2 (10 mL), during which the bottom layer was consecutively collected, the collceted solution was dried using magnesium sulphate, after which the solvent was removed under vacuum. NMR analysis of the resultant solid was derived. (EO 3-1B 1H NMR) 

 

Hazards and Risk Assesment

 

Risk Assessment

 

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