SUPPLEMENTARY MATERIAL TO Solvatochromism of isatin based Schiff bases: An LSER and LFER study

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J. Serb. Chem. Soc. 8 (9) S258S266 (26) Supplementary material SUPPLEMENTARY MATERIAL TO Solvatochromism of isatin based Schiff bases: An LSER and LFER study DOMINIK R. BRKIĆ, ALEKSANDRA R.

DRMANIĆ3 Belgrade Polytechnic, Brankova 7, Belgrade, Serbia, 2Faculty of Chemistry, University of Belgrade, Studentski trg 26, Belgrade, Serbia and 3Department of Organic Chemistry, Faculty of

1 J. Serb. Chem. Soc. 8 (9) S258S266 (26) Supplementary material SUPPLEMENTARY MATERIAL TO Solvatochromism of isatin based Schiff bases: An LSER and LFER study DOMINIK R. BRKIĆ, ALEKSANDRA R. BOŽIĆ, VESNA D. NIKOLIĆ2, ALEKSANDAR D. MARINKOVIĆ3, HANA ELSHAFLU3, JASMINA B. NIKOLIĆ3* and SAŠA Ž. DRMANIĆ3 Belgrade Polytechnic, Brankova 7, Belgrade, Serbia, 2Faculty of Chemistry, University of Belgrade, Studentski trg 26, Belgrade, Serbia and 3Department of Organic Chemistry, Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 2 Belgrade, Serbia J. Serb. Chem. Soc. 8 (9) (26) GENERAL METHOD FOR THE PREPARATION OF ISATIN DERIVATIVES The isatin derivatives were synthesized according to a literature method. Isatin (5 mmol) was dissolved in methanol (4 ml), and the corresponding reactants (substituted anilines or arylamines (5 mmol) and glacial acetic acid ( ml) were added. The reaction mixture was refluxed at 7 C for 6 h using a magnetic stirrer. Subsequently, the mixture was left overnight without stirring at room temperature. The obtained crystals were filtered off, dried and recrystallized from methanol or an appropriate solvent mixture (Table S-I). The average yield was about 779 %. TABLE S-I. Solvent parameters used in KamletTaft Equation2 Solvent π* β Ethanol Methanol Propanol Butanol Cyclohexanol Benzyl alcohol (BnOH).7 2-Methoxyethanol 2-Chloroethanol ,2-dimethoxyethane (DME) Toluene Dichloromethane (DCM) Tetrahydrofuran (THF) Acetonitrile (ACN).75.3 α * Corresponding author. jasmina@tmf.bg.ac.rs S258 (CC) 26 SCS. All rights reserved.

2 S259 SUPPLEMENTARY MATERIAL TABLE S-I. Continued Solvent Formamide Dimethylacetamide (DMAc) Dimethylformamide (DMF) -Methyl-2-pyrrolidinone (NMP) Ethyl acetate (EtOAc) 2-Pyrrolidone Dimethyl sulfoxide (DMSO) Acetone Cyclohexanone π* β α MATERIALS AND INSTRUMENTATION All commercially available chemicals were purchased from SigmaAldrich (St. Louis, MO, USA). The NMR spectral measurements were performed on a Varian 2 (2 MHz for H- and 5 MHz for 3C-NMR). The spectra were recorded at room temperature in deuterated dimethyl sulfoxide (DMSO-d6). The chemical shifts are expressed in ppm values referenced to δh = 2.5 ppm and δc = 39.5 ppm in the H- and 3C-NMR spectra, respectively. UV data were recorded on a Shimadzu 7 UVVis spectrophotometer in ethanol as solvent at a concentration of 5 5 mol dm-3. Fourier-transform infrared (FTIR) spectra were obtained of the samples in the form of KBr pellets using an FTIR Bomem MB instrument. The FTIR spectra were recorded in the transmission mode between 4 and 4 cm with a resolution of 4 cm. The results of H- and 3C-NMR, FTIR spectra and elemental analysis of the studied compounds are given in Table S-II, and the general structure of,3-dihydro-3-(arylimino)-2h-indol-2-one with labelling of the atoms is given in Fig. S-. Fig. S-. General formula of,3-dihydro-3-(arylimino)-2h-indol-2-one with labelling of the atoms. (CC) 26 SCS. All rights reserved.

3 S26 BRKIĆ et al. TABLE S-II. Yields, melting points, and FTIR, H- and compounds No. R 3C-NMR H-NMR data of the synthesized (2 MHz, DMSO-d6, δ / ppm) Yield: 76 %; 3344, 74, 6.65 (H, d, H4), 6.74 Exp.: , 254. (H, t, H5), 6.95 (H, d, H4 ), 7.4 (2H, d, H2 C (methanol) & H6 ), 7.26 (H, t, Lit.: 29.7 H6), 7.3 (H, t, H7), 2.4 C (2H, t, H3 & H5).76 (H, s, H8). Yield and m.p. IR (cm-) 2 Yield: 69 %; 3342, 746, Exp.: , 252. C (methanol) Lit.: C3 3 Yield: 66 %; 334, 744, Exp.: , 25. C (methanol) Lit.: C3 4 Yield: 8 %; 3342, 745, Exp.: , 25 C (methanol) Lit.: C3 3C-NMR (5 MHz, DMSO-d6, δ / ppm) 2. (C7), 6.4 (C3a), 8. (C2 & 6 ), 23. (C5), 25.7 (C4), 26.6 (C4 ), 29.7 (C3 & 5 ), 34.6 (C6), 46. (C7a), 5.88 (C ), 56.2 (C3), (H, d, H4), (C2 ),.6 (H, td, H5), 6.78 (H, (C7), 6.74 (C3a), d, H6 ), 6.94 (H, d, 9.58 (C6 ), 22.2 H6), 7.34 (H, d, H4 ), (C5), 23.4 C4 ), (2H, m, H (C4), 27.3 & H5 ), 7.62 (H, d, (C5 ), 33.2 (C3 ), H3 ),.66 (H, s, H8). 35. (C6), (C ), 48.4 (C7a), 52. (C3), (H, d, H4), (C3 ),.8 (H, td, H5), 6.88 (H, (C7), 6.7 (C3a), d, H6 ), 6.9 (H, d, 9.69 (C6 ), H6), 7.28 (H, d, H5 ), (C5), 23.4 C2 ), 7.37 (H, dd, H7), (C4), (2H, m, H2 (C4 ), 35.6 (C6), & H4 ),.84 (H, s, 36.2 (C5 ), 47.6 H8). (C ), 48.2 (C7a), 52.3 (C3), (H, d, H4), (C4 ),.9 (H, td, H5), 6.83 (2H, (C7), 5.87 (C3a), d, H2, 6 ), 6.9 (H, d, 9.69 (C2, C6 ), H6), 7.35 (H, dd, H7), 22.8 (C5), (2H, td, H3 & 5 ), (C4), 35. (C6),.8 (H, s, H8) (C3 & C5 ), (C7a), (C ), 52.9 (C3), 64. (CC) 26 SCS. All rights reserved.

4 SUPPLEMENTARY MATERIAL S26 TABLE S-II. Continued C R Yield and m.p. IR (cm-) 5 Yield: 64 %; 3445, 39, Exp.: , 729, 625, Yield: 72 %; 3444, 39, Exp.: , 73, 627, 254. Lit.: 2426 C 7 Yield: 6 %; 3447, 393, Exp.: , 733, 626, Yield: 7 %; 3447, 39, Exp.: , 73, 626, 253. methanol) H-NMR (2 MHz, 3C-NMR (5 MHz, DMSO-d6, δ / ppm) DMSO-d6, δ / ppm) 2.3 (3H, s, CH3), (CH3),.88 (H, d, H4), 6.72 (H, (C7), 5.98 (C3a), td, H5), 6.96 (H, d, 8.73 (C4 ), 22.9 H6), 7.6 (H, d, H4 ), (C5), (C4), 7.38 (H, dd, H7), (C3 ), 35.2 (H, dd, H5 ), 8.36 (H, (C6), (C5 ), dd, H3 ),.5 (H, s, (C7a), 5.64 H8). (C3 ), 52.6 (C3), 58.3 (C ), (3H, s, CH3), (CH3),.9 (H, d, H4), 6.68 (H, (C7), 5.99 (C3a), td, H5), 6.93 (H, d, 7.9 (C6 ), 22.9 H6), 7. (H, d, H6 ), (C5), (C4), 7.38 (H, dd, H7), (C4 ), 35.3 (H, dd, H4 ), 8.42 (H, (C6), (C7a), dd, H3 ),.4 (H, s, (C5 ), 5.44 H8). (C3 ), (C3), (C ), (3H, s, CH3), (CH3),.88 (H, d, H4), 6.72 (H, (C7), 6. (C3a), td, H5), 6.88 (H, d, 7.73 (C6 ), H6 ), 6.95 (H, d, H6), (C5), (C4), 7.37 (H, H, H7), (C4 ), 35. (H, dd, H5 ), 8.33 (H, (C6), (C5 ), dd, H3 ),.7 (H, s, 47.4 (C7a), 5.74 H8). (C3 ), 52.2 (C3), 54.4 (C ), (3H, s, CH3), (CH3),.92 (H, d, H4), 6.74 (td, (C7), 6. (C3a), H, 5), 6.88 (d, H, 6), 4.73 (C6 ), (H, d, H6 ), 7.4 (C5), (C4 ), (H, dd, H7), 7.68 (H, 25.9 (C4), dd, H5 ), 7.72 (H, dd, (C6), 37.5 (C5 ), H4 ),.3 (H, s, H8) (C7a), 5.62 (C3 ), 52.8 (C3), (C ), 63.5 (CC) 26 SCS. All rights reserved.

5 S262 BRKIĆ et al. TABLE S-II. Continued C R Yield and m.p. IR (cm-) 9 Yield: 59 %; 348,742, Exp.: 33 64, 3, 254. Lit.: 3334 C4 Yield: 64 %; 36,742, Exp.: , 32, 254. Yield: 7 %; 345, 356, Exp.: , 626, C (DMSO/ 32. H-NMR (2 MHz, 3C-NMR (5 MHz, DMSO-d6, δ / ppm) DMSO-d6, δ / ppm) 6.33 (H, d, H4), (C7), 6.2 (H, td, H5), 6.92 (H, (C3a), (C5), d, H6), 7. (H, t, (C4), H6 ), 7.35 (H, dd, H7), (C6 ), 28. (C4 ), (2H, dtdd, 28.3 (C5 ), 28.5 H4 & H5 ), (C8 ), 29.2 (C7 a), (2H, m, H7 & H8 ), 35. (C7 ), (H, dd, H2 ), (C6), 43. (C2 ),.3 (H, s, H8) (C ), (C3 a), 47.7 (C7a), (C3), (H, d, H4), (C7), 5.9 (H, td, H5), 6.94 (H, (C3a), (C5), d, 6H), 7.3 (H, t, (C4), H7 ), 7.37 (H, dd, H7), (C2 ), (C4 ), (2H, m, H4 28. (C8 ), 29.8 & H8 ), (2H, (C2 a), 33. (C7 ), m, H2 & H3 ), (C3 ), (H, dd, H5 ),.6 (C6), (C6 a), (H, s, H8) (C7a), 49. (C5 ), 5. (C ), 54.3 (C3), (H, d, H4), (C7). 2. (H, t, H5), 6.92 (H, d, (C6 ), 6.3 (C3a). H6), 7.35 (H, t, H5 ), 7.7 (C4 ), (3H, m, H7, (C2 ), 22.4 (C5), H4 & H6 ), 8.4 (H, (C4), d, H3 ), 8.35 (H, d, (C5 ), 28.7 (C3a ), H2 ), 9.8 (H, d, H8 ), 35.4 (C6), (H, s, H8). (C3 ), 38. (C7a ), 47.7 (C7a), (C ), (C3), (C2), (C7 ). (CC) 26 SCS. All rights reserved.

7 S264 BRKIĆ et al. TABLE S-III. Absorption frequencies (νmax -3 / cm-) of isatin compounds in selected solvents (lower wavelength peak) Compound Methanol Ethanol Propanol Butanol 3.35 Cyclohexanol Benzyl alcohol (BnOH) Methoxyethanol (2-ME) Chloroethanol (2-CE) DME Toluene DCM Acetone Cyclohexanone EtOAc Formamide DMF DMAc NMP ACN DMSO THF Pyrrolidone Solvent TABLE S-IV. The results of the correlation analysis for the isatin derivatives (lower wavelength peak) according to the KamletTaft Equation; no statistically valuable correlations were obtained for compds. and Compd. ν ±.6.86 ± ±..66 ±.5 4 Pαd Solvent excluded from the correlation Butanol, cyclohexanol, BnOH, Acetone, ±.5 ±.8 ChO, 2-methoxyethanol, toluene, 2-pyrrolidone Butanol, cyclohex±.2 ±.7 anol, BnOH, acetone, ChO, ACN, DCM, NMP, DMF, methanol Butanol, cyclohexanol, BnOH, acetone, ±.4 ±.8 ChO, ACN, ethanol, THF, 2-methoxyethanol, 2-pyrrolidone s b -3 cm ±.3 ±.7 a Ra SDb Fc Pπd Pβd % (CC) 26 SCS. All rights reserved.

8 S265 SUPPLEMENTARY MATERIAL TABLE S-IV. Continued Compd. ν s b -3 cm- a Ra SDb Fc Pπd Pβd % ±.6.2 ± ±.6 ± ±.5.99 ± ±.4 ± ±.6.97 ± ±.6 ± ±.2. ± ±. ± ±.2.57 ± ±.8 ± ±.27. ± ±.22 ±.6 Pαd Solvent excluded from the correlation Butanol, cyclohexanol, BnOH, toluene, acetone, ChO, F, 2-methoxyethanol, 2-chloroethanol, ethanol Butanol, cyclohexanol, BnOH, toluene, acetone, ChO, 2-methoxyethanol, methanol Butanol, cyclohexanol, BnOH, toluene, acetone, ChO, methanol, 2-methoxyethanol Butanol, cyclohexanol, BnOH, toluene, acetone, ChO, methanol 26. Cyclohexanol, BnOH, acetone, ChO, 2-propanol, ACN, F, ethanol, toluene Butanol, cyclohexanol, BnOH, acetone, ChO, methanol, toluene, F, AcN acorrelation coefficient; bstandard deviation; cfisher test of significance; dthe percentage contribution of sol- vatochromic parameters obtained using the KamletTaft Equation (%) TABLE S-V. Substituent constants5 No X H 2-Br 3-Br 4-Br 3-Me-2-pyridyl 4-Me-2-pyridyl 5-Me-2-pyridyl 6-Me-2-pyridyl 3-Quinolinyl 6-Quinolinyl 8-OH-2-quinolinyl σ a.68a.58a.68a a a The σ constants were calculated as additive values; 4-NO2 (.78) and 4-CN (.66) were taken from the lite rature (CC) 26 SCS. All rights reserved.

9 S266 BRKIĆ et al. TD-DFT calculations In order to confirm validity of implemented theoretical consideration, theoretical absorption spectra of compound were calculated in acetone, acetonitrile, ethanol, tetrahydrofuran, dimethylsulfoxide, foramide and toluene. The calculated value for the higher wavelength peak are presented in Table S-VI and are in good agreement with experimental values. TABLE S-VI. Calculated and experimental absorption frequencies (νmax 3 / cm) of compound in selected solvents (higher wavelength peak) Solvent Acetone Acetonitrile Ethanol THF DMSO Formamide Toluene Calculated (TD-DFT) Experimetal REFERENCES G. M. Šekularac, J. B. Nikolić, P. Petrović, B. Bugarski, B. Đurović, S. Ž. Drmanić, J. Serb. Chem. Soc. 79 (24) 347 M. J. Kamlet, J. L. M. Abboud, M. H. Abraham, R. W. Taft, J. Org. Chem. 48 (983) 2877 J.-Y. Ma, Y.-C Quan, H.-G. Jin, X.-H. Zhen, X.-W. Zhang, L.-P. Guan, Chem. Biol. Drug Des. 85 (25) 54 F. D. Popp, J. Heterocycl. Chem. 2 (984) 64 C. Hansch, A. Leo, D. Hoekman, Exploring QSAR: Hydrophobic, Electronic and Steric Constants, ACS Professional Reference Book, American Chemical Society, Washington DC, 995. (CC) 26 SCS. All rights reserved.

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