Supporting Information
Study on Synthesis and Fluorescence of Novel Benzofused phenazine π-conjugated skeleton
with coumarin and isophoron cores
Amol S. Choudhary, Sharad R. Patil, Nagaiyan Sekar*
a
Tinctorial Chemistry Group, Institute of Chemical Technology, Matunga, Mumbai-
400019 (India).
Email: nethisekar@gmail.com
Tel.: +91 22 3361 1111/ 2707
1. General Information
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2. Typical Procedure
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3. Spectral Data
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4. Supporting figure
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__________________________________________________________
S1. General Information
S.1. Materials and instrumentation
2-Hydroxy-1, 4-napthaquinone, substituted o-phenylenediamine, o-aminothiophenol, and
malononitrile were procured from Sigma Aldrich. 2-(3,5,5-trimethylcyclohex-2-en-1-
ylidene)malononitrile and 2-(1-(2-oxo-2H-chromen-3-yl)ethylidene) malononitrile were
synthesized by the reported method. The reaction was monitored by TLC using 0.25 mm EMerck silica gel 60 F254 percolated plates, which were visualized with UV light. Melting
points were measured on standard melting point apparatus from Sunder industrial
product Mumbai, and are uncorrected. The FTIR spectra were recorded on a PerkinElmer Spectrum 100 FTIR Spectrometer. 1HNMR spectra were recorded on VXR 300
MHz instrument using TMS as an internal standard. The visible absorption spectra of the
compounds were recorded on a Spectronic Genesys 2 UV-Visible spectrophotometer.
Emission and excitation spectra of the compounds are measured on Varian Cary eclipse
spectrofluorimeter.
S.2. Computational methods
Gaussian 09 program package was used to optimize geometry and to study the synthesized
azo dyes in their azo and hydrazone tautomeric forms [12]. Ground state (S0) geometry of
the dyes in gas and solvent was optimized in their C1 symmetry using DFT [13]. The
Becke’s three parameter exchange functional (B3) [14] combining with nonlocal correlation
functional by Lee, Yang and Parr (LYP) [15] and basis set6-31G (d)was used for all atom.
Same method was used for vibrational analysis to verify that the optimized structures
correspond to local minima on the energy surface. Time Dependent Density Functional
Theory (TD- DFT) computations were used to obtain the vertical excitation energies and
oscillator strengths at the optimized ground state equilibrium geometries at the same
hybrid functional and basis set [16]. All the computations in solvents of different polarities
were carried out using the Self-Consistent Reaction Field (SCRF) under the Polarizable
Continuum Model (PCM) [17].
S.3. Synthetic strategy
S.3.1. General method for the synthesis and characterization of 3
2-Hydroxy-1, 4-napthaquinone 1 (2 mmol) and substituted o-phenylenediamine 2 (2 mmol)
were stirred in a mixture of AcOH: EtOH (50:50) (20 ml) at 80 oC for 1-1.5 h. Completion
of the reaction was monitored by TLC. After completion of the reaction, the reaction mass
was poured in crushed ice and stirred for 30 minute at room temperature. The reaction
mass was filtered and the product was purified by column chromatography using silica gel
100-200 mesh and ethyl acetate: hexane (50:50) as eluent system.
S.3.2. General procedure for the synthesis of 4a
POCl3 (0.015 mmol) was added to DMF (0.20 mmol) at 0 0C within 15 min and stirred for
30 minutes at 0 o C. Naphtho [1,2-a]phenazin-5-ol 3 (0.01 mmol) dissolved in DMF (5 ml)
was added slowly at 0-5 0C and stirred for 2-3 hr at room temperature. The completion of
the reaction was monitored by TLC. The reaction mass was poured in ice and stirred,
neutralized with sodium bicarbonate, filtered and dried. The crude aldehyde was
recrystallized from ethanol. The product was purified by column chromatography using
silica gel 100-200 mesh and ethyl acetate: hexane (10:90) as eluent system. Yield = 69 %,
Melting point: 163-168 oC
FT-IR (KBr, cm-1): 3100 (-OH), 2930 (COH), 1600 (CO), 1577 (C=N), 1200 (C-O).
Mass: m/z 274 [M+1].1H NMR (CDCl3, 300 MHz) = δ 3.67 (t, 4H, J = 6.9, 4.7 Hz), 3.83 (t,
4H, J = 7.4, 5.1 Hz), 7.29 (m, 4H), 8.60 (bs, 1H), 8.5 (s, 1H) ppm.
S.3.3. Procedure for the synthesis of 4b
POCl3 (0.015 mmol) was added to DMF (0.20 mmol) at 0 0C within 15 min and stirred for
30 minutes at 0 0C. naphtho [1,2-a]phenazin-5-ol 17 (0.01 mmol) dissolved in DMF (5 ml)
was added slowly at 0-5 0C and stirred and heated up to 90 0 C for 2-3 hr. The completion
of the reaction was monitored by TLC. The reaction mass was poured in ice and stirred,
neutralized with sodium bicarbonate, filtered and dried. The crude aldehyde was
recrystallized from ethanol. The product was purified by column chromatography using
silica gel 100-200 mesh and hexane as eluent system. Yield = 58 %, Melting point: 173-178
oC
FT-IR (cm-1) = 1701 (C=O), 1586 (C=C, aromatic). Mass = m/z = 292.08, M+1= 293.08
M+2 = 294.08, (M+1).1H NMR (CDCl3, 300 MHz) = δ 10.24 (s, 1H) 7.66-7.80 (m, 4H), 7.837.95 (m, 4H).
S.3.4 General procedure for the synthesis of 6a-6d
5-Hydroxybenzo[a]phenazine-6-carbaldehyde 4a or 4b (1.8 mmol) and 2-(3, 5, 5trimethylcyclohex-2-en-1-ylidene) malononitrile 5a or 2-(1-(2-oxo-2H-chromen-3-yl)
ethylene) malononitrile 5b (2.0 mmol) were stirred in ethanol (20 ml). Catalytic amount of
piperidine was added to the mixture and refluxed for 2 h. Completion of the reaction was
monitored by TLC. The compound precipitated out was filtered and purified by column
chromatography using silica 100-200 mesh and ethyl acetate: hexane as eluent.
(E)-2-(3-(2-(5-hydroxybenzo[a]phenazin-6-yl)vinyl)-5,5-dimethylcyclohex-2-en-1ylidene)malononitrile 6a
Yield = 54%; Melting point = 283-285 ºC.
FT-IR (cm-1) = 3029 (Ar-H), 3201 (-OH), 2920 (CH3), 1610 (C=C, aromatic), 1558 (C=N),
2110 (-CN). Mass = m/z = 442.12, M+2 = 443.6.1H NMR (CDCl3, 300 MHz) = δ 1.4 (s, 3H, CH3) δ 1.7 (s, 3H, -CH3), δ 2.7 (d, 2H,-CH2), δ 3.3(s,2H,-CH2),7.3(s,1H), δ
7.1(dd,1H),7.7(s,1H) δ 7.9-8.1(m,4H,Ar), δ 8.2-8.4(m,4H, Ar), δ 9.4 (br,s,1H, -OH).
(E)-2-(3-(5-hydroxybenzo[a]phenazin-6-yl)-1-(2-oxo-2H-chromen-3-yl)allylidene)
malononitrile 6b
Yield = 64%; Melting point = 278-281 ºC. 73
FT-IR (cm-1) = 3013 (Ar-H), 3207 (-OH), 2910 (CH3), 1605 (C=C, aromatic), 1545 (C=N),
2210 (-CN). Mass = m/z = 492.12, M+2 = 493.6.1H NMR (CDCl3, 300 MHz) = δ 5.4 (s, 1H, OH) δ 6.8 (d, 1H, =CH), δ 7.2 (d, 1H,=CH), δ 7.5(s,1H, pyrano ring proton), δ 7.2-7.4 (m,
4H, Ar-H), δ 7.5-7.8 (m,4H, Ar-H), 8.0-8.4 (m,4H,Ar-H).
(E)-2-(3-(2-(5-chlorobenzo[a]phenazin-6-yl)vinyl)-5,5-dimethylcyclohex-2-en-1ylidene)malononitrile 6c
Yield = 45%; Melting point = 278-280 ºC.
FT-IR (cm-1) = 3029 (Ar-H), 3201 (-OH), 2920 (CH3), 1610 (C=C, aromatic), 1558 (C=N),
786 (Ar-Cl) 2110 (-CN). Mass = m/z = 442.12, M+2 = 443.6.1H NMR (CDCl3, 300 MHz) = δ
1.4 (s, 3H, -CH3) δ 1.7 (s, 3H, -CH3), δ 2.7 (d, 2H,-CH2), δ 3.3(s,2H,-CH2),7.3(s,1H), δ
7.1(dd,1H),7.7(s,1H) δ 7.9-8.1(m,4H,Ar), δ 8.2-8.4(m,4H, Ar).
(E)-2-(3-(5-chlorobenzo[a]phenazin-6-yl)-1-(2-oxo-2H-chromen-3-yl)allylidene)malononitrile
6d
Yield = 74%; Melting point = 278-280 ºC.
FT-IR (cm-1) = 3013 (Ar-H), 3207 (-OH), 2910 (CH3), 1605 (C=C, aromatic), 1545 (C=N),
2210 (-CN). Mass = m/z = 492.12, M+2 = 493.6.1H NMR (CDCl3, 300 MHz) = δ 6.8 (d, 1H,
=CH), δ 7.2 (d, 1H,=CH), δ 7.5(s,1H, pyrano ring proton), δ 7.2-7.4 (m, 4H, Ar-H), δ 7.5-7.8
(m,4H, Ar-H), 8.0-8.4 (m,4H,Ar-H).
S4 Supporting copy of NMR and Mass spectra
Mass and 1NMR spectra copy of some compound
Mass spectra of 4a
Intensity
100
118.55
150
148.72
200
186.21
A1_120530113218 #6 RT: 0.08 AV: 1 NL: 1.38E6
F: + c ESI Full ms [ 90.00-450.00]
1350000
1300000
1250000
1200000
1150000
1100000
1050000
950000
1000000
900000
850000
800000
750000
700000
650000
600000
550000
500000
450000
400000
350000
300000
250000
200000
150000
50000
100000
0
228.39
m/z
314.32
300
293.09
274.81
265.01
246.70
250
351.13
359.45
350
398.82
400
426.67
449.54
450
1HNMR of 6a
1HNMR of 6b