Experiment 1

NAME: _______________________ BATCH:_________

ROLL NO:_____________________ SEM:___________
SIGNATURE:___________________ DATE:__________

SYNTHESIS OF NBD-OCTYL AMIINE & ABSORPTION AND EMISSION

SPECTROPHOTOMETRIC STUDY
AIM
(a) To synthesize NBD-Octylamine and (b) study the change in absorbance and emission spectra of
NBD-Octylamine in different solvents viz. (n-hexane, Acetonitrile, Ethylacetate, Methanol & DCM)

THEORY
Fluorescent molecule (NBD-Octylamine) can be synthesized by substitution reaction of NBD-Cl (4-
Chloro-7-nitrobenzofurazan) and n-Octylamine as shown below the reaction scheme & mechanism.
NBD-Cl + n-Octylamine NBD-Octylamine

MATERIAL REQUIRED
NBD-Cl, n-Octylamine, Alumina, n-Hexane, Ethylacetate, Methanol, Dichloromethane, Acetonitrile,
RB Flask, Magnetic stirrer, Clamp and stand, filtration apparatus, ice-bath, TLC plate, etc.

(a) Synthesis
Reaction Scale:
Compound Mol. Wt (gm/mol) Wt. Taken (gm) No. of Equivalents Millimoles
NBD-Cl 200 0.15 1 0.75
N-Octylamine 129 0.194 1.4 0.78

Procedure:
1. Dissolve 150 mg of NBD-Cl in DCM in a RBF and stir it well on a magnetic stirrer.
2. Keep the RBF over an ice-bath and ensure uniform cooling.
3. Dissolve 0.25 ml of n-Octylamine with 5 ml of DCM in a beaker and slowly add it dropwise to
the RBF.
4. The mixture was then allowed to react for 2 hours.
5. After completion of the reaction, perform TLC analysis to ensure formation of the product,
NBD-Octylamine. TLC will show a distinct spot of product when compared to the reactants.
6. Filter the reaction mixture on alumina bed; extract several times with DCM to obtain the
required product and keep it overnight to evaporate.
Analysis of the Product
Colour:
Solubility:
Melting Point:
 Experiment 1

(b) Solvatochromic study of NBD-Octylamine and comparison with Anthracene

UV-VISIBLE Spectroscopic determination:
For NBD-Otylamine
Dissolve the Synthesized NBD-Octylamine in five different organic solvents of varying polarity and
record its absorption. Shift in λmax can be seen, which is attributed to the polarity of the medium
referred to as micropolarity.
For Anthracene
Solvatochromic effect of NBD-Octylamine can be compared with a rigid molecule whose absorption
maxima are independent of solvent polarity. Regarding this dissolve anthracene in five different
organic solvents (as above) of varying polarity and record its absorption. From the results it can be
seen, the absorption maxima are independent of solvent polarity. No change in spectrum pattern is
observed for anthracene in different solvents.
Inference
Anthracene being a rigid molecule has well separated vibrational levels which give rise to many
different absorbance maxima. These different absorbance maxima correspond to different vibrational
excitations. Anthracene spectrum shows no dependence on solvent polarity which indicates lack of any
charge transfer process taking place within the molecule. This is as expected since structure of
anthracene molecule has no net dipole moment.
The effect of micropolarity can be observed in the case of NBD-Octylamine. From the UV-VIS
spectrum of NBD-Octylamine it can be clearly seen that absorbance maxima shifts towards higher
wavelength with increasing solvent polarity. This indicates that the presence of charge transfer
mechanism within the molecule. One can also infer that solvent plays a major role in stabilizing the
charged species. So in case of more polar solvent, energy levels are less apart due to stabilization effect
of solvents while in case of non-polar solvent the energy levels of NBD-Octylamine are far apart due to
lack of any support from solvents.
Fluorescence Spectroscopic determination
Investigations on emission pattern of NBD-Octylamine & Anthracene molecule will be performed in
solvents of varying polarity.
For NBD-Octylamine:
The effect of micropolarity can clearly be observed in the fluorescence spectrum of NBD-Octylamine
where emission maxima are red shifted with increasing solvent polarity.
For Anthracene:
From the spectrum it can be observed that emission from anthracene is independent of solvent polarity.
Three structured bands are observed at fixed wavelength irrespective of solvent polarity.
Inference
From the spectral pattern of anthracene it can be inferred that due to lack of any charge transfer
mechanism within the molecule, there is no shift in emission maxima with varying solvent polarity.
Presence of band structure in the spectrum indicates the rigid nature of the molecule. While in case of
NBD-Octylamine appreciable change in emission pattern is observed with changing solvent polarity,
thus indicating charge transfer mechanism within the molecule.
Results:
1. Report color, solubility and melting point of synthesized NBD-Octylamine.
2. Paste all the four spectra along with peak assignments.
3. Give a comparison table of the results (as shown in the example below) and comment on the results.
Example table:
Compound NBD-Octylamine Anthracene
Solvents ET30 Abs λ max (nm) Emis λ max (nm) ∆λ (nm) Abs λmax (nm) Emis λmax (nm) ∆λ (nm)
n-Hexane 31 424 498 -74 321 378 -57
Ethylacetate 38.1 456 522 -66 322 380 -58
Acetonitrile 45.6 463 533 -70 324 381 -57
Methanol 55.4 468 538 -70 321 378 -57