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18th January 2017 @ 21:35

synthesis of NA-04-01.png


Reagents

Equivalents

Quantity
 (mg / mL)

mmol

Molecular Weight g/mol

(E)-2-chloro-6-(2-(2-(pyrrolidin-1-yl)benzylidene)hydrazineyl)pyrazine

1

424.8 mg
 

1.41 mmol

301.7780

PIDA

1

454.2 mg

1.41 mmol

322.10

DCM
(density 1.325 g/mL)

-

(26.5 g)
20 mL

312
mmol

84.93


Procedure:

Part 1: crude product

To the RBF containing NA-03-01 (424.8 mg, 1.41 mmol, 1 eqv) 20 mL of DCM was added while stirring the mixture. PIDA (454.2 mg, 1.41 mmol, 1 eqv.) was added and the solution was left to stir over night at room temperature.

A miniwork up was done first for TLC analysis (50% EtOAc/pet. Ether). A full work-up was done by washing the reaction mixture with NaHCO3 (15 mL) and then extracting it with DCM (3x 10mL). The combined organic phases were collected in a conical flask and dried (MgSO4). The dried solution was filtered and the solvent removed in vacuo to give an oil. The crude product [NA-04-01] was weighed (491.2 mg, 1.64 mmol, 116.2% yield) and a sample was analysed by 1H NMR.

 

Rf value= 0.6

 

Part 2: pure product fractions

To remove the solvent ethyl acetate and silica were added to the crude product [NA-04-01] and rotary evaporated. The product was then purified in column chromatography using varying EtOAc-Pet. Ether eluents of increasing polarity. 

The first eluent concentration was at 5% of EtOAc-Pet.Ether and was used up to fraction 42. The polarity was then increased to 15% EtOAc-Pet.Ether from fractions 43 till 50 and then again to 20% EtOAc-Pet.Ether after fraction 51.

All the fractions were analysed by TLC (50% EtOAc/pet. Ether) and then viewed under short (254nm) and long (366nm) UV waves.  Each collection of fractions that were thought to be similar was collected and placed in vacuo to remove the solvents and produce oily products. The 5 RBF containing the pure reaction mixtures were analysed by TLC (50% EtOAc/pet. Ether) and samples of these fractions were analysed for 1H NMR using a CDCl3 solvent.

Notes:

 

Notes and observations:

RBF fraction collection
NA-04-01-(#)

Short wave
 (254nm)

Long wave
 (366nm)

Observations under long wave (numbers refer to the fraction number)

6-11

Very faintly

-

Considered to not contain any product

12-15

Showed

-

Saved as a collection and checked for product

16-24

Showed

Showed

Only16 showed two different colors under long wave (blue and green) and
20 showed (only green). The fluorescence decreased from 16 until 21 were it was very strong to a faint 24 (only blue on top).

25-43

Showed

Showed

25 to 43 showed as green but changed position to green on the lower side with the exception of 43 which showed it on top.

 

(Quick UV look without tlc showed yellow Fluorescence until 38 then and increasing blue fluorescence from 38 till 48)

44-54

Showed
(faintly
after 49)                 

Showed
(rainbow)

44 till 51 showed three fluorescent colors combined as a spherical shape (orange on top, yellow in the middle, and blue at the bottom).
52 till 54 showed the separation and spacing out of these three colors.

 

(Quick UV look without tlc showed 47 & 48 as strong blue and a combination of blue and green specs from 49 till 54)

55- (unknown)

Showed
(faintly)

Showed
(rainbow-partly)

55 showed both the separation of three colors as well as a very strong blue spot very low on the plate in comparison.

56 showed a longer blue spot (strong)

 

NA-04-01-RBF collection #

Weight, Yield

12-15

21.9 mg,  5.18%

16-24

64.4 mg,  15.24%

25-43

218.9 mg,  51.79%

44-54

87.6 mg,  20.72%

55-(unknown)

63.8 mg,  15.09%


Pictures of RM:


RM.JPG
     
RM after drying.JPG

 

TLC PLATES

TLC of RM.JPG

Rf value = 0.6 


TLC comparisons.jpg

comparisons between this TLC and former TLC plates from NA-03-01 experiment. 


TLCs of the fractions 

22-11-IMG_0690.JPG
 
22-11-IMG_0688.JPG


22-11-IMG_0692.JPG
 
22-11-IMG_0691.JPG


21-11-IMG_0665.JPG
 
TLC of fractions.jpeg

 


It can be seen that there are multiple colours of fluorescences that appear in the TLC plates of the fractions

 

all fractions TLC notes.jpg


all TLCs.jpg

 

NA-04-01.JPG


NMR COLLECTION DATA


CRUDE sample NA-04-01

NA-04-01-CRUDE.jpeg

 

 

PURE FRACTIONS OF SAMPLE NA-04-01

 

NA-04-01-1215.jpeg

 FRACTIONS 12-15

 

NA-04-01-1624.jpeg

 FRACTIONS 16-24

 

NA-04-01-2543.jpeg

FRACTIONS 25-43 

 

NA-04-01-4454.jpeg

FRACTIONS 44-54 

 

NA-04-01-55XX.jpeg

 FRACTIONS 55-unknown

 

NMR proved to be inconclusive as to the formation of the desired product. 

Attached Files
synthesis of NA-04-01.png
NA-04-01-CRUDE.jpeg
NA-04-01-1215.jpeg
NA-04-01-1624.jpeg
NA-04-01-2543.jpeg
NA-04-01-4454.jpeg
NA-04-01-55XX.jpeg
22-11-IMG_0690.JPG
22-11-IMG_0688.JPG
22-11-IMG_0691.JPG
22-11-IMG_0692.JPG
21-11-IMG_0665.JPG
TLC comparisons.jpg
TLC of fractions.jpeg
TLC of RM.JPG
NA-04-01.JPG
all TLCs.jpg
all fractions TLC notes.jpg
RM after drying.JPG
RM.JPG