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18th January 2017 @ 21:35
[data]20501[/data] 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: [data]20636[/data]      [data]20634[/data]   TLC PLATES [data]20626[/data] Rf value = 0.6  [data]20622[/data] comparisons between this TLC and former TLC plates from NA-03-01 experiment.  TLCs of the fractions  [data]20582[/data]   [data]20584[/data] [data]20588[/data]   [data]20586[/data] [data]20590[/data]   [data]20624[/data]   It can be seen that there are multiple colours of fluorescences that appear in the TLC plates of the fractions   [data]20632[/data] [data]20630[/data]   [data]20628[/data] NMR COLLECTION DATA CRUDE sample NA-04-01 [data]20554[/data]     PURE FRACTIONS OF SAMPLE NA-04-01   [data]20556[/data]  FRACTIONS 12-15   [data]20558[/data]  FRACTIONS 16-24   [data]20560[/data] FRACTIONS 25-43    [data]20562[/data] FRACTIONS 44-54    [data]20564[/data]  FRACTIONS 55-unknown   NMR proved to be inconclusive as to the formation of the desired product. 
Attached Files
synthesis of NA-04-01.png
TLC comparisons.jpg
TLC of fractions.jpeg
all TLCs.jpg
all fractions TLC notes.jpg
RM after drying.JPG