Growth of (e)-(3-chloro-2-nitroprop-1-enyl)benzene using Nitro Olefin derivatives Crystal

 

M.N. Sivakumar¹*, A. Vidya²

¹Assistant Professor, Department Chemistry, AMET University Kanathur Chennai 603 112, India

²Assistant Professor, Department of Chemistry, Madras University.

 

ABSTRACT:

For the first time Baylis–Hillman adducts derived from nitro olefins have been conveniently transformed into a novel class of building blocks, (E)-(3-chloro-2-nitroprop-1-enyl)benzene. The large second order optical nonlinearities, short transparency cut-off wavelength and stable physiochemical performance, which are needed in the realization of most of the recent electronic applications, are also considered in the present study.

 

 

 

 

1.   INTRODUCTION:

The search for suitable materials^1,2,3 and crystals that display excellent nonlinear optical properties is increased day by day because of  the varied inherent applications in the field of optical computing, optical information processing, optical disk data storage, laser remote sensing, laser driven fusion, colour display, medical diagnostic etc. The above said the important application ignited us to search for good and efficient NLO materials^{4, 5} and that is the objective of the present work. Since there is a high demand for crystals in the revolution of electronic phase, it is required that both the technical and economical aspects^{6, 7} of crystal growth have to be improved. This analysis focuses on pure organic materials in the emerging field of optoelectronics.

 

The present materials are selected to increase the electron transformation, which increases the Cl and CH₂ stretching vibration, and also to reduce the NO₂^- bending vibration for obtaining better nonlinear optical activities.

 

This work specially concentrates on higher environmental stability and greater diversity of tuneable electronic properties for economic and eco-friendly operations^{8, 9}. In the present chapter synthesis growth and characterization of new NLO crystal (E)-(3-chloro-2-nitroprop-1-enyl) benzene is discussed in detail

 

2.   EXPERIMENTAL METHOD:

2.1 X-Ray diffraction analysis:

Characterization of a material can be defined as a complete description of its physical and chemical properties. A through and extensive characterization of a single crystal is very difficult because it requires variety of tests using a number of sophisticated instruments and accurate analysis of the results^{10, 11} of these tests and confirmation.

 

Characterization of the grown crystals facilitates an understanding of the quality of crystals and their feasibility for technical applications. More over characterization of the grown crystals forms an integral part of the growth studies to be performed by the crystal grower.

 

Characterization of a crystal essentially consists of an evaluation of the chemical composition. In addition to the evaluation of these parameters characterization also involves the determination of their effect on the physical properties of the crystal.

 

The discovery of X-rays by crystals led to the development of a powerful and precise method for the exploration of the internal arrangement of atoms in a crystal.

 

A crystal might be regarded as a three dimensional diffraction grating for energetic electromagnetic waves of wavelength comparable with the atomic spacing and that a diffraction pattern should provide information about the regular arrangement of atoms ^{12, 13}.

 

X-rays are still the principal source of new information about the crystallography of solids and are supplemented by electron and neutron diffraction, 2-Bromo-1-(1-phenylsulfonyl-1H-indol-3-yl) propan-1-one explained.

 

It is well known that when a beam of light passes through a screen containing a regular pattern of holes interference phenomenon may be observed if the distance between the holes is of the same as the wavelength of the light employed.

 

The diffraction of X-rays by the atoms in a solid is a completely analogous phenomenon the wavelength of electromagnetic radiation in the case being of the order of inter-atomic distance in solids, which is 1Å.

 

The structure of the compound was confirmed by IR, ¹H NMR and ¹³C NMR spectral data.  The ¹H NMR spectrum shows that the CH₂ protons appeared at δ 4.23 and Aromatic protons appeared in the region of δ 7.25-7.52.  The olefinic proton appeared at δ 8.26.  Encouraged by this results we prepared variety of Baylis-Hillman adducts and successfully transformed them into their corresponding applications.

 

2.2 Powder x-ray diffraction method:

The powder method is applicable to finely divided crystalline powder or to a very fine-grained polycrystalline spectrum. This is also Debye-Schrerrer method. In this method single crystals are not required and it is used for accurate determination of lattice parameters in crystals of known structure and for the identification of elements and compounds. The powdered sample is kept inside a small capillary tube, which does not undergo diffraction by X-rays.

 

A narrow pencil of monochromatic X-ray is diffracted from the powder and recorded by photographic films as a series of lines of varying curvature. The full opening angle of the diffraction cone 4Ɵ is determined by measuring the distance S between two corresponding arch on the power photographs symmetrically displaced about the exit point of the direct beam. The distance S on the film between two diffraction lines corresponding to a particular plan is related to the Bragg’s angle by the equation.

4Ɵ=S/R radians=S/R (180/π) degree

 

Where R is distance from the specimen to the film that is usually the radius of the camera housing the film.

 

From the measured values of S a list of Ɵ and intensity gives a list of spacing d, each spacing is the distance between neighbouring planes (hkl).

 

2.3 Fourier transform infrared spectroscopy:

FT-IR stands for Fourier Transform Infrared Spectroscopy which provides the structural information, from the observed diffraction patterns is obtained through a mathematical manipulation known as Fourier Transformation.

 

In FT-IR spectroscopy^14,15, IR radiation is passed through a sample, some of the radiation is absorbed by the sample and some of it is passed through (transmitted). The resulting spectrum represents the molecular absorption and transmission of the sample. Like a finger print, no two unique molecular structures produce the infrared spectrum. This makes infrared spectroscopy useful for several types of analysis.

 

The advent of Fourier Transform Spectroscopy has made the far infrared much more accessible, and has considerably speeded and improved spectroscopy in the infrared region in general.

 

There are a number of advantages to be gained by using Fourier Transform rather than dispersive measurements in the infrared.

•        It is a non-destructive technique

•        It provides a precise measurement method which requires no external calibration

•        It has greater optical throughput

•        The total scanning time for FTIR is considerably less than that required time to produce a dispersive spectrum of the same sensitivity and resolution

•        The whole spectrum is obtained across the entire frequency range at once. In dispersive IR spectroscopy, it is common to change the dispersing grating during the scan, as one grating is not usually able to function sufficient well over the whole range.

 

2.4 Principle of fourier transform infrared spectroscopy:

The FT-IR spectra of most of the samples are recorded.

1615, 1528, 1325 cm^-1.

 

 

The principle of interferometer is the simple interference of radiation where the absorption spectrum is obtained through the interference technique.

 

Two radiation beams with same wavelength and amplitude leads to optical interference.

·        If the radiation beams are in phase, the beam will interfere constructively and the resultant amplitude will be twice as high

·        If the radiation beams are out of phase by ½(2n+1)λ (half integral number of wavelengths). The beams will interfere destructively cancelling out each other.

·        At intermediate phase differences, the amplitude is given by ½(1±cos2πθ/λ). Where θ is the phase difference.

 

A typical inter ferogram, which is a plot of the intensity (amplitude) versus path length difference (phase) for the interference of two radiation beams of identical wavelength is obtained.

A complex interference pattern is obtained when two radiation beams of different wavelengths are interfere.

 

3.   RESULTS AND DISCUSSIONS:

To a stirred solution of (E)-2-nitro-3-phenylprop-2-en-1-ol (0.72 g, 4 mmol) in THF (15 ml), rt. The mixture was cooled to 0°C and then TiCl₄ (0.05mL) was added drop wise. The mixture was stirred well at rt. for about 1 h. On completion of the reaction (TLC analysis), the mixture was poured into H₂O and the aqueous layer was extracted with EtOAc (3×10mL). The combined organic layers were washed with brine (10 mL) and concentrated. The crude product thus obtained was purified by column chromatography (EtOAc–hexanes) to provide (0.60 g, 68%) as a colorless crystalline solid; mp 76–78°C. is represented in the following equation:

 

 

 

By using the low temperature solution growth method, large single crystal (E)-(3-chloro-2-nitroprop-1-enyl)benzene was successfully grown from supersaturated solution. The grown single crystals has been harvested and subjected to different characterization methods.

 

4.   CONCLUSION:

Baylis–Hillman adducts derived from nitroolefins have been suitably transformed into a novel class of building blocks, (E)-(3-chloro-2-nitroprop-1-enyl)benzene. The large second order optical nonlinearities, short transparency cut-off wavelength and stable physiochemical performance, which are needed in the realization of most of the recent electronic applications.

 

5.   ACKNOWLEDGMENTS:

We thank AMET University for the financial support. We also thank University of Madras for the NMR facility. Indian institute of Technology, Chennai for IR, and  Mass Spectrascopy.

 

6.   REFERENCES:

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Accepted on 21.08.2017        © RJPT All right reserved