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29th October 2016 @ 03:39

Scheme:

Following procedure outlined in [Synlett, Issue 18, 2823-2825, 2005, ISSN:0936-5214, DOI:10.1055/s-2005-918948]

 

Procedure:

Under inert atmosphere, step 3 product [rxn 3-2] (0.4416 g, 1.489 mmol, 1 eq) was disolved in dry benzene (10.0 mL) in a 20 mL microwave reaction vial. Phenyl acetylene (0.20 mL, 1.8 mmol, 1.2 eq) and InCl3 (33 mg, 0.15 mmol, 0.10 eq). The reaction vial was placed in a microwave synthesizer, and was heated to 100°C for 1 hour.

 

TLC:

The crude reation mixture was spotted on a TLC plate (silica gel), developed in 1:1 EtOAc/hexanes, and visualized with UV. The TLC indicated that no reaction had occured. Lanes from top to bottom are [rxn 3-2] product, phenyl acetylene, cospot, workup mixture.

Attached Files
20th October 2016 @ 19:38

Scheme:

Following procedure outlined in [Synlett, Issue 18, 2823-2825, 2005, ISSN:0936-5214, DOI:10.1055/s-2005-918948]

 reaction scheme

Procedure:

 All glassware was dried on the high vacuum and flushed with argon. Starting material from [rxn 3-1] (0.3649 g, 1.23 mmol, 1 eq) was disolved in dry benzene (15 mL). Phenyl acetylene (0.18 mL, 1.623 mmol, 1.3 eq) and InCl3 (~0.03 g, 0.14 mmol, 0.1 eq) were added and the mixture was stirred. The reaction was heated to 80°C and stirred at reflux (5h).

Workup:

 Benzene was removed on the rotary evaporator and the resulting solid was partitioned between EtOAc and water (50 mL ea). The organic layer was washed with water (3 x 50 mL) and then filtered through celite. The organic layer was washed with two additional portions of water. No product was found using TLC or GC/MS.

TLC:

The organic layer from the workup was spotted on a TLC plate (silica gel), developed in 1:1 EtOAc/hexanes, and visualized with UV.

TLC Sonogashira product v1 10_4_16.JPG

Lanes from top to bottom are [rxn 3-1] product, phenyl acetylene, cospot, workup mixture.

GC/MS:

The mixture from workup was concentrated and injected on the GC/MS. The fraction at 12.5 min has a MS consistent with the MS of [rxn 3-3] product, indicating that no product formed.

rxn4r1_GCMS.pdf

InChI:

InChI=1S/C12H7ClF2N4O/c13-9-5-16-6-10-17-18-11(19(9)10)7-1-3-8(4-2-7)20-12(14)15/h1-6,12H

Attached Files
8th October 2016 @ 04:16

Reaction Scheme

 


Procedure

1.48 g (4.955 mmol, 1 eq) of 2-Chloro-6-hydrazinylpyrazine (product from reaction 2-4), were dissolved in 25 mL DCM to form a brown suspension/sludge. Approximately 1.9 g (5.7 mmol, 1.2 eq) of PhI(OAc)2 were added, and the solution was stirred under inert atmosphere. As the reaction proceded, the solution cleared and became redidish-brown. After stirring for 2 days, the solution was yellow.

 

Workup

The reaction was quenched with 25 mL saturated NaHCO3 solution, then transfered to a seperatory funnel, and diluted with 10 mL DCM. The organic layer was removed, and the aqueous layer was extracted with 20 mL DCM thrice. The organic layers were combined, and washed with 20 mL saturated NaHCO3, then washed with 20 mL brine. MgSO4 was added, and the solution was filtered. Solvent was removed via rotory evaporation and high vac.  The product was then left to sit in an open flask in the hood for 1 week, over which the product changed from light brown to red-brown. The product was dissolved again in DCM, transfered to another round bottom flask, rotory evaporated and placed on the hi vac to give a yield of 2.0541 g (6.9241 mmol, 139.7% yield).


InChI

InChI=1S/C12H9ClF2N4O/c13-10-6-16-7-11(18-10)19-17-5-8-1-3-9(4-2-8)20-12(14)15/h1-7,12H,(H,18,19)/b17-5+

to 

InChI=1S/C12H7ClF2N4O/c13-9-5-16-6-10-17-18-11(19(9)10)7-1-3-8(4-2-7)20-12(14)15/h1-6,12H


SMILES

ClC1=CN=CC(N([H])/N=C/C2=CC=C(OC(F)F)C=C2)=N1

to
 
ClC1=CN=CC2=NN=C(C3=CC=C(OC(F)F)C=C3)N21
Attached Files
8th October 2016 @ 03:56

 Following [AEW 205-6]

 

Reaction Scheme

 


Procedure

1.3101 g (4.386 mmol, 1 eq) of 2-Chloro-6-hydrazinylpyrazine, were dissolved in 25 mL DCM to form a dark-yellow suspension/sludge. Approximately 1.6 g (5.0 mmol, 1.1 eq) of PhI(OAc)2 were added, and the solution was stirred under inert atmosphere. As the reaction proceded, the solution cleared and became red-brown.

 

Workup

The reaction was quenched with 25 mL saturated NaHCO3 solution, then transfered to a seperatory funnel. The organic layer was removed, and the aqueous layer was extracted with 20 mL DCM four times. The organic layers were combined, and washed with 20 mL saturated NaHCO3, then washed with 20 mL brine. Drying agent was added, and the solution was filtered. Solvent was removed via rotory evaporation and high vac. The product was then left to sit in an open flask in the hood for 1 week, over which the product changed from light brown to red-brown.The product was dissolved again in DCM, transfered to another round bottom flask, rotory evaporated and placed on the hi vac to give a yield of 1.1852 g (3.9951 mmol, 91.09% yield).


InChI

InChI=1S/C12H9ClF2N4O/c13-10-6-16-7-11(18-10)19-17-5-8-1-3-9(4-2-8)20-12(14)15/h1-7,12H,(H,18,19)/b17-5+

to 

InChI=1S/C12H7ClF2N4O/c13-9-5-16-6-10-17-18-11(19(9)10)7-1-3-8(4-2-7)20-12(14)15/h1-6,12H


SMILES

ClC1=CN=CC(N([H])/N=C/C2=CC=C(OC(F)F)C=C2)=N1

to
 
ClC1=CN=CC2=NN=C(C3=CC=C(OC(F)F)C=C3)N21
Attached Files
8th October 2016 @ 03:24

Scheme:

Following [AEW 204-x]

 reaction scheme

Procedure:

A sample of the Reaction 1 product, 2-Chloro-6-hydrazinylpyrazine (1.17g, 8.125mmol, 1eq) was dissolved in ethanol (35 mL, 95% v/v). 4-(difluoromethoxy)benzaldehyde (1.1 mL, 8.125mmol, 1eq) was added to the reaction mixture and the resulting solution was stirred under argon. A white precipitate formed and 20 mL of ethanol was added to the reaction mixture. The reaction was allowed to stir for 72 hours.

Workup (10-2-16)


The precipitate was recovered by vacuum filtration and washed with cold ethanol (30 mL, 95% v/v) and was connected to the high vacuum for 1 hour. A yellow-white powder (1.68 g, 6.38mmol, 79%) was recovered. This crude product was not further purified.

 

InChi:

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

and

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

to

InChI=1S/C12H9ClF2N4O/c13-10-6-16-7-11(18-10)19-17-5-8-1-3-9(4-2-8)20-12(14)15/h1-7,12H,(H,18,19)/b17-5+

Attached Files