Abstract
The structural investigation of synthesized compounds can be carried out by various spectroscopic techniques. It is an important prospect in order to elucidate the structure of the desired products before being further utilized. The preparation of new p-nitro stilbene Schiff base derivatives as an electrochemical DNA potential spacer was synthesized using (E)-4-(4-nitrostyryl)aniline from Heck reaction with aldehydes in ethanolic solution. The data presented here in this article contains FTIR, UV-Vis and 1H and 13C NMR of (E)-4-(4-nitrostyryl)aniline and nitrostyryl aniline derivatives.
Keywords: Aldehyde, Imine, Heck reaction, Schiff base derivatives, Stilbene, Spacer
Specifications table
| Subject | Chemistry |
| Specific subject area | Spectroscopy |
| Type of data | Table Figure Scheme |
| How data were acquired | FTIR (Shimadzu IRTracer-100 Fourier Transform Infrared Spectrometer) ranges from 400 to 4000 cm−1 by using single reflection ATR; UV-Vis (double beam Shimadzu UV-1800 spectrophotometer) ranges from 190 to 800nm by using acetonitrile as solvent in 1cm3 cuvette; 1H and 13C nuclear magnetic resonance (NMR) spectra (Bruker Avance II 400 spectrophotometer) using deuterated dimethylsulfoxide (DMSO-d6) as solvent. |
| Data format | Raw and analysed |
| Parameters for data collection | All compounds were synthesized at room temperature. |
| Description of data collection | The synthesized compounds from Heck and Schiff base reactions were characterized by spectroscopic method for establishing the structure of compounds. |
| Data source location | Faculty of Science and Marine Environment, Universiti Malaysia Terengganu, 21030 Kuala Nerus, Terengganu, Malaysia. |
| Data accessibility | http://dx.doi.org/10.17632/fw86ngty6c.1 |
Value of the data
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The following data shows new derivatives synthesized from (E)-4-(4-nitrostyryl)aniline, which are important in structure elucidation and are useful to researchers who are developing spacer to be applied on substrate used in electrochemical DNA sensor.
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For future investigations, the details in these data could be used for comparison study with previous spacers, which in turn could help in further understanding of the significant role of substituent attached at the (nitrostyryl)aniline terminal end.
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The details in this data could be extended towards other field such as for antibacterial study and other biological application as many studies has reported that imine structure could inhibit the bacterial growth.
1. Data
Previously, Hassan et al. (2018) had synthesized several stilbene Schiff base derivatives with various alkyl chain lengths [1], [2], [3]. This paper deals about the identification and characterization of Heck product and three (nitrostyryl)aniline derivatives of the same length but with different terminal end as a comparison with alkyl terminal end. This paper deals about the identification and characterization of Heck product and three (nitrostyryl)aniline derivatives. It describes the preparation of samples prior the spectroscopy measurements which presented accordingly. Scheme 1 describes the overall reaction involved in producing (E)-N-(4-ethylbenzylidene)-4-((E)-4-nitrostyryl)aniline (NO2Et), (E)-N-(4-methylbenzylidene)-4-((E)-4-nitrostyryl)aniline (NO2Me) and (E)-N-(4-methoxybenzylidene)-4-((E)-4-nitrostyryl)aniline (NO2OMe), which includes Heck and Schiff base reactions. Table 1 and Fig. 1 describe the comparative assessment of FTIR of all the samples. Whereas, Table 2 and Fig. 2 describe the UV-vis data comparison of four products produced. Tables 3 and 4 tabulate the 1H and 13C NMR of (E)-4-(4-nitrostyryl)aniline (Heck 1) and three imine products. Figs. 4, 6, 8 and 10 display the images of NMR spectra of Figs. 3, 5, 7 and 9 that are being studied, respectively.
Scheme 1.
Overall reaction scheme.
Table 1.
Frequencies of selected bands of diagnostic importance from the IR spectra of Heck 1 and nitrostyryl aniline Schiff bases derivatives.
| Compound frequency (cm−1) |
Assignment | |||
|---|---|---|---|---|
| Heck 1 | NO2Et | NO2Me | NO2OMe | |
| 3483 & 3383 | - | - | - | NH2 |
| 1496 & 1307 | 1458 & 1334 | 1419 & 1338 | 1458 & 1338 | N=O |
| 3070-2900 | 3074-2877 | 3097-2868 | 3074-2843 | C-H stretching |
| - | 1458 | - | - | CH2 bending |
| - | 1373 | 1377 | 1373 | CH3 bending |
| - | 1681 | 1681 | 1681 | C=N |
| - | - | - | 1253 & 1022 | C-O stretching |
| 1581 | 1516 | 1516 | 1508 | C=C alkene |
Fig. 1.
Infrared spectra of compounds formed. (A) Heck 1, (B) NO2Et, (C) NO2Me and (D) NO2OMe.
Table 2.
Wavelengths of UV-visible spectra values of Heck 1 and nitrostyryl aniline Schiff bases derivatives.
| Peak | Compound wavelength, nm (absorbance) |
Assignment | |||
|---|---|---|---|---|---|
| Heck 1 | NO2Et | NO2Me | NO2OMe | ||
| 1 | 408.0 (0.42) | 381.50 (0.399) | 382.5 (0.413) | 384.5 (0.242) | R-NO2 and C=N (n → π*) |
| 2 | 288.0 (0.27) | 276.50 (0.355) | 277.0 (0.389) | 276.5 (0.306) | C=C aromatic (π → π*) |
Fig. 2.
UV-Visible spectra of Heck 1, NO2Et, NO2Me and NO2OMe in acetonitrile, respectively.
Table 3.
Chemical shifts of 1H NMR values of Heck 1 and nitrostyryl aniline Schiff bases derivatives.
| Signal |
1H NMR chemical shifts of compounds (ppm) |
Assignment | |||
|---|---|---|---|---|---|
| Heck 1 | NO2Et | NO2Me | NO2OMe | ||
| 2 | 8.17, 8.19 (d) | 8.15, 8.17 (d) | 8.24, 8.26 (d) | 8.23, 8.26 (d) | Aromatic |
| 3 | 7.72, 7.75 (d) | 7.82, 7.84 (d) | 7.87, 7.89 (d) | 7.90, 7.92 (d) | Aromatic |
| 5 | 7.03, 7.07 (d) | 7.01, 7.05 (d) | 7.56, 7.60 (d) | 7.55, 7.59 (d) | C=C |
| 6 | 7.34 (s) | 6.58, 6.61 (d) | 7.41, 7.45 (d) | 7.40, 7.44 (d) | C=C |
| 8 | 7.36, 7.38 (d) | 7.72, 7.74 (d) | 7.84, 7.86 (d) | 7.89, 7.87 (d) | Aromatic |
| 9 | 6.59, 6.61 (d) | 7.33 (s) | 7.32 (s) | 7.30, 7.32 (d) | Aromatic |
| 11 | 5.57 (s) | 9.95 (s) | 8.64 (s) | 8.60 (s) | NH2 |
| 13 | - | 7.36, 7.38 (d) | 7.41, 7.45 (d) | 7.72, 7.74 (d) | Aromatic |
| 14 | - | 7.43, 7.45 (d) | 7.34, 7.36 (d) | 7.08, 7.10 (d) | Aromatic |
| 16 | - | 2.68, 2.70 (d) | 2.39 (s) | 3.85 (s) | Alkane |
| 17 | - | 1.20 (s) | - | - | Alkane |
Table 4.
Chemical shifts of 13C NMR values of Heck 1 and nitrostyryl aniline Schiff bases derivatives.
| Signal |
13C NMR chemical shifts of compounds (ppm) |
Assignment | |||
|---|---|---|---|---|---|
| Heck 1 | NO2Et | NO2Me | NO2OMe | ||
| 1 | 150.48 | 161.01 | 146.55 | 146.50 | Aromatic |
| 2 | 124.51 | 120.83 | 124.54 | 124.54 | Aromatic |
| 3 | 129.18 | 129.18 | 129.27 | 129.35 | Aromatic |
| 4 | 145.83 | 150.40 | 144.67 | 144.69 | Aromatic |
| 5 & 6 | 126.67 | 124.51 | 127.68 | 127.65 | C=C |
| 7 | 120.80 | 145.80 | 134.54 | 134.26 | Aromatic |
| 8 | 134.84 | 130.19 | 129.95 | 131.08 | Aromatic |
| 9 | 114.26 | 114.31 | 122.13 | 122.08 | Aromatic |
| 10 | 207.00 | 193.24 | 152.13 | 152.34 | Aromatic |
| 11 | - | 207.38 | 161.02 | 160.43 | Imine |
| 12 | - | 134.81 | 133.94 | 128.63 | Aromatic |
| 13 | - | 129.06 | 133.31 | 133.35 | Aromatic |
| 14 | - | 126.69 | 126.26 | 114.79 | Aromatic |
| 15 | - | 151.80 | 142.19 | 162.51 | Aromatic |
| 16 | - | 28.84 | 21.67 | 55.90 | Alkane |
| 17 | - | 15.79 | - | - | Alkane |
Fig. 4.
(A) 1H and (B) 13C NMR of Heck 1.
Fig. 6.
(A) 1H and (B) 13C NMR of NO2Et.
Fig. 8.
(A) 1H and (B) 13C NMR of NO2Me.
Fig. 10.
(A) 1H and (B) 13C NMR of NO2OMe.
Fig. 3.
Heck 1.
Fig. 5.
NO2Et.
Fig. 7.
NO2Me.
Fig. 9.
NO2Ome.
2. Experimental Design, Materials, and Methods
2.1. Materials
4-vinylaniline, 4-ethylbenzaldehyde, p-tolualdehyde and p-anisaldehyde (98%) were purchased from Acros Organics; N,N-dimethylformamide and dichloromethane were from Fisher Scientific, while 1-iodo-4-nitrobenze (98%), trimethylamine and ethanol absolute were purchased from Sigma-Aldrich, R&M Chemicals and HmbG Chemicals, respectively. All chemicals were used as received.
2.2. Instrumentation
The structure of synthesized products was established by spectral data obtained by different spectroscopic instruments. FTIR, UV-Vis and NMR were recorded by Shimadzu IRTracer-100 Fourier Transform Infrared Spectrometer, double beam Shimadzu UV-1800 spectrophotometer and Bruker Avance II 400 spectrophotometer, respectively. Reaction progresses of the compounds were monitored by Thin layer chromatography (TLC) using silica gel 60 F254, 0.25 mm thick plastic plates [1,3].
2.3. Synthesis of (E)-4-(4-nitrostyryl)aniline
A substituted aryl halide (1 mol) was added to a mixture of N, N-dimethylformamide (3 ml) and 4-vinylaniline (1 mol, 0.4 g), trimethylamine (3 ml) as base and bis(triphenylphosphine)palladium chloride (40 mg) as catalyst in a three-neck round bottom flask. The resulting mixture was stirred well and refluxed for 24 hours at 70-80°C. The completion of reaction was monitored by TLC. The reaction mixture was filtered and thoruoghly washed by dichloromethane. Next, the solvent was evaporated by the rotary evaporator and run for column chromatography in order to obtain the the product of (E)-4-(4-nitrostyryl)aniline (Heck 1) (Fig. 3) as previously produced by [3].
2.4. Synthesis of Schiff bases derivatives
Schiff base method of [4] was modified to produce imine compounds. In a Dean-stark flask 1 mol of the synthesized product from Heck reaction dissolved in ethanol (50 ml), 0.1 ml of commercial aldehyde (p-tolualdehyde or p-ansaldehyde) in ethanol (10 ml) was added at 60°C. The reaction mixture was refluxed for 2 hours at 80°C. The reaction mixture was cooled down and the product was precipitated. The yielded product was filtered off and recrystallized from hot acetonitrile [5]. Nitrostyryl aniline derivatives (Figs. 2, 7, 9) produced were weighed and the percentage yield was recorded.
2.5. Complete characterization description of the four compounds
(E)-4-(4-nitrostyryl)aniline (Heck 1): Brick-red powder; ATR: 3483 & 3388 (NH2, stretching), 1496 & 1307 (N=O), 3070-2900 (C-H stretching,)1581 (C=C alkene); UV–Vis spectrum [ACN, λmax nm (log ɛ, L mol−1 cm−1)]: 408.00 (4.62), 288.00 (4.43); 1H NMR (400MHz, DMSO-d6): δ 8.19-6.59 (d, 10H), 5.57 (s, 2H); 13C NMR (100MHz, DMSO-d6): δ 207.0, 150.48, 145.83, 129.18, 126.67, 124.51, 120.80, 114.26.
(E)-N-(4-ethylbenzylidene)-4-((E)-4-nitrostyryl)aniline (NO2Et): Yellow flakes; ATR: 1458 & 1334 (N=O), 3074-2877 (C-H, stretching), 1458 (CH2, bending), 1373 (CH3, bending), 1681 (C=N), 1516 (C=C alkene): UV–Vis spectrum [ACN, λmax nm (log ɛ, L mol−1 cm−1)]: 381.50 (4.60), 276.50 (5.55); 1H NMR (400MHz, DMSO-d6): δ 9.95 (s, 1H), 8.17-6.58 (d, 14H), 2.70-2.68 (d, 2H), 1.20 (s, 3H);); 13C NMR (100MHz, DMSO-d6): δ 207.38, 193.24, 161.01, 151.80, 150.40, 145.80, 134.81, 130.19, 129.18, 126.69, 129.06, 124.51, 120.83, 114.31, 28.84, 15.79.
(E)-N-(4-methylbenzylidene)-4-((E)-4-nitrostyryl)aniline (NO2Me): Yellow flakes; ATR: 1419 & 1338 (N=O), 3097-2868 (C-H, stretching), 1377 (CH3, bending), 1681 (C=N), 1516 (C=C alkene); UV–Vis spectrum [ACN, λmax nm (log ɛ, L mol−1 cm−1)]: 382.50(4.62), 277.00 (4.59); 1H NMR (400MHz, DMSO-d6): δ 8.64 (s, 1H), 8.26-7.32 (d, 14H), 2.39 (s, 3H); 13C NMR (100MHz, DMSO-d6): δ 161.02, 152.13, 146.55, 144.67, 142.19, 134.54, 133.94, 133.31, 129.95, 129.97, 127.68, 126.26, 124.54, 122.13, 21.67.
(E)-N-(4-methoxybenzylidene)-4-((E)-4-nitrostyryl)aniline (NO2OMe): Yellow flakes; ATR: 1458 & 1338 (N=O), 3074-2843 (C-H, stretching), 1373 (CH3, bending), 1681 (C=N), 1253 & 1022 (C-O, stretching), 1508 (C=C alkene); UV–Vis spectrum [ACN, λmax nm (log ɛ, L mol−1 cm−1)]: 384.5 (4.38), 276.5 (4.49); 1H NMR (400MHz, DMSO-d6): δ 8.60 (s, 1H), 8.26-7.32 (d, 14H), 2.39 (s, 3H); 13C NMR (100MHz, DMSO-d6): δ 162.51, 160.42, 152.34, 146.50, 144.69, 134.26, 133.35, 131.08, 129.35, 128.63, 127.65, 124.54, 122.08, 14.79, 55.90.
Acknowledgments
Authors gratefully acknowledge Ministry of Higher Education, Malaysia, for their financial support through Fundamental research grant scheme (FRGS) (FRGS/1/2015/SG01/UMT/02/3). A sincere thanks to National Institute of Technology, Sendai College and also Giant Molecular Analysis, Tohoku University, Japan for their help in completing a part of this work.
Footnotes
Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.dib.2020.105568.
Appendix. Supplementary materials
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