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8th March 2012 @ 13:52
This experiment is synthesising 4-substituted methylidene oxindole from oxindole and their corresponding aromatic aldehydes.

GENERAL PROCEDURE FOR THE SYNTHESIS OF FIVE 4-SUBSTITUTED METHYLIDENE OXINDOLES FROM OXINDOLE AND THEIR CORRESPONDING AROMATIC ALDEHYDES


CHEMICALS AND SOLVENTS: The solvents and chemicals were reagent grade and used as received. All the respective benzaldehydes, oxindole, piperidine were supplied by Sigma
Aldrich while propan-2-ol was supplied by Fisher Scientific.


Amount of Chemical/ solvents used(3E)-3-(4-Chlorobenzylidene)-1,3-dihydro-2H-indol-2-one(3E)-3-(4-Bromobenzylidene)-1,3-dihydro-2H-indol-2-one (3E)-3-(4-Methoxybenzylidene)-1,3-dihydro-2H-indol-2-one (3E)-3-(4-Methylbenzylidene)-1,3-dihydro-2H-indol-2-one(3E)-3-(4-Nitrobenzylidene)-1,3-dihydro-2H-indol-2-oneBatch No. Grade (%)
Oxindole (g)1.371.371.371.371.37-97
4-chloro benz-aldehyde
(g)
1.43----S010728-13997
4-bromo benz-aldehyde
(g)
-1.86----99
4-Anis-aldehyde
(g)
--1.54---98
4-methyl-benz-aldehyde
(g)
---1.86--97
4-nitro-benz-aldehyde
(g)
----1.54S0652-44398
Propan-2-ol(ml)10241015100872337-
Piperidine (ml)0.50.51.00.50.5-99


General Procedure:
Oxindole (1.37g, 10mmol) and 4-chlorobenzaldehyde (1.43g, 10mmol) were accurately weighed into 50ml round bottom flask of weight 54.47g using an analytical weighing balance. Propan-2-ol (10ml, 100mmol) and piperidine (0.5ml, 5mmol) were correctly measured into it using measuring cylinder and calibrated micro pipette respectively.
The resulting mixtures of these starting materials were gently and thoroughly stirred till perfect dissolution was achieved. Anti bump was then introduced into the mixture before it was carefully transferred to electronic hot plate mounted with reflux condensers before heat was supplied. The condensation reaction was stopped after three (3) hours reflux with the temperature of the electronic hot plate set at 100°C and revolution per minute at 625.
The reaction conditions or completion was monitored using Thin Layer Chromatography (TLC). The stock solution of methylidene oxindoles of 4-chlorobenzaldehyde re-crystallized under cooling. This was isolated by vacuum filtration, washed using about 5ml of propan-2-ol and dried under suction.

(3E)-3-(4-Chlorobenzylidene)-1,3-dihydro-2H-indol-2-one(3E)-3-(4-Bromobenzylidene)-1,3-dihydro-2H-indol-2-one (3E)-3-(4-Methoxybenzylidene)-1,3-dihydro-2H-indol-2-one (3E)-3-(4-Methylbenzylidene)-1,3-dihydro-2H-indol-2-one(3E)-3-(4-Nitrobenzylidene)-1,3-dihydro-2H-indol-2-one
InChiKeyCIXKMQYKNWKSNZ-UKTHLTGXSA-NINAOSTJXLBNFMV-UKTHLTGXSA-NSOHLANGNFXOOEF-GXDHUFHOSA-NJEZSEMYAZZHQIB-GXDHUFHOSA-NWPZSQSSOBHCYOZ-UKTHLTGXSA-N
Yield (%)75.654.064.568.467.6
Melting Point
(°C)
181.48192.52152.2180.12226.98


The residue (product) was weighed and analyzed using range of analytical techniques such as Nuclear Magnetic Resonance Spectroscopy (NMR), High Performance Liquid Chromatography (HPLC), Electrospray Ionization Mass Spectrometer (MS) Analysis, Differential Scanning Calorimeter (DSC), Hot Stage Microscopy, Attenuated Total Internal Reflectance (ATIR) Fourier Transform Infrared (FT-IR) Spectroscopy, Powder X-Ray Diffraction (PXRD), X-Ray Crystallography and solubility test.

Experimental Set up


Sublimation Purifcation:

APPARATUS: Thermometer, electric hot plate with stirrer, 1 vacuum tubing, condenser, 2 condenser tubing, oil bath, analytical weighing balance, weighing boat, spatula, retort stand, clamp and Aldrich Sublimation Apparatus
Batch Number: 310
Model Number: Z221163-1EA
Supplier: Sigma Aldrich
PROCEDURE: The various quantities of five 4-substituted methylidene oxindoles listed in the table below were accurately weighed into the sublimation apparatus and carefully immersed in oil bath which contains approximately 500ml of paraffin oil. The oil bath was placed on the electric hot plate and clamp attached to retort stand was used to hold the sublimation apparatus at a fixed position. The vacuum and condenser tubes were connected, thermometer carefully inserted into the bath oil before heat was supplied. The temperature of the paraffin oil was maintained at 10°C below the melting point of each of the samples.

List of chemicals used for Sublimation Purifcation:
ChemicalsQuantity UsedBatch Number
(3E)-3-(4-Chlorobenzylidene)-1,3-dihydro-2H-indol-2-one
0.88g38
(3E)-3-(4-Bromobenzylidene)-1,3-dihydro-2H-indol-2-one1.18g38
(3E)-3-(4-Nitrobenzylidene)-1,3-dihydro-2H-indol-2-one
0.35g39
(3E)-3-(4-Methylbenzylidene)-1,3-dihydro-2H-indol-2-one1.82g38
(3E)-3-(4-Methoxybenzylidene)-1,3-dihydro-2H-indol-2-one0.77g39
Paraffin oil500ml0927659

Aldrich Sublimation Apparatus
Attached Files