Synthesis of blue-red emissive amido-substituted di(het)aryl and tri(het)aryl amine derivatives via chemoselective N-mono and N,N-diarylation of (het) aryl amino amides using benzyne/arynes

Article abstract of DOI:10.1039/C8NJ05823G

Herein, via chemoselective N-mono and N,N-diarylation of an aryl/hetaryl amino amide reaction using benzyne or arynes, an amide-substituted triaryl amine derivative and diaryl amine derivatives were afforded. The scope and limitation of the present study have been studied. The products thus obtained were synthetically transformed to highly functionalized biphenyl bridged heterocycles via Suzuki coupling and condensation with 4,4′-biphenyl dialdehyde. Evaluation of the photophysical properties has revealed that the triaryl amine derivatives are blue emissive with high quantum yields, whereas the heterocyclic triaryl amine derivatives are blue-red emissive. The benzofuran-derived compound 4i was found to be blue emissive with high quantum yield, whereas the pyridine-derived compound 5j was found to be red emissive with low quantum yield.

Full text of DOI:10.1039/C8NJ05823G

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The role of atropisomers on the photo-reactivity and fatigue of
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Synthesis of blue-red emissive amido substituted di(het)aryl and
tri(het)aryl amine derivatives via chemoselective N-mono and N,
N-diarylation of (het) aryl amino amides using benzyne/arynes
Received 00th January 20xx,
Accepted 00th January 20xx
Ramakrishnan Suseela Meerakrishnaa and Ponnusamy Shanmugama*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Chemoselective N-mono and N, N-diarylation of aryl/hetaryl amino amide reaction using benzyne or arynes afforded
amide substituted triaryl amine derivative and diaryl amine derivatives. Scope and limitation of the research work has
been studied. The products thus obtained were synthetically transformed to highly functionalized biphenyl bridged
heterocycles via Suzuki coupling and condensation with 4,4’-biphenyl dialdehyde. Evaluation of photophysical properties
revealed that the triaryl amine derivatives are blue emmisive with high quantum yields while heterocyclic triaryl amine
derivatives are blue-red emmisive. The benzofuran derived compound 4i found as blue emissive with high quantum yiled
whereas pyridine derived compound 5j found as red emissive with low quantum yield.
Introduction
group substitution and position in the aryl groups. Thus, to
tune the properties and development of TPA and DPA based
organic molecules with different functional groups by
minimum synthetic steps is of great potential for practical
applications.
The propeller-shaped triphenylamine (TPA) and its derivatives
are a key resource for both theoretical and synthetic chemists
due to their promising optical and electrical properties.1 The
notable properties of TPA include easy oxidation of amine and
excellent positive charge carrier2 and the transformation of
TPA to free radicals has remarkably utilized as a good electron
donor unit in hole transport material applications.3 TPA and its
derivatives are extensively used in electrochromic materials4,
dye-sensitized solar cells (DSSCs)5, organic field effect
transistors, and solid state fluorescent materials for organic
light-emitting diode (OLED) device applications.6 Owing to the
semiconducting property of TPA derivatives, these are utilized
in many studies related to organic electronics.7 Utility of TPA
molecule as smart fluorescent material is foreseen, as shown
in figure 1, compounds (A-E) exhibit an array of functional
properties such as fluorescence switching, mechanochromism,
polymorphism, nano-fabrication, halochromism, compound (F)
found to show piezo fluorochromism (G) illustrate an example
for non-doped red emitters for OLED.8 Significant synthetic
Aryl triflate has been employed to generate arynes in situ
to undergo
a
variety of electrophilic, nucleophilic,
cycloaddition reactions11 and extensively used for N-arylation
reactions.12 To the best of our knowledge the reaction of
(het)aryne with aryl and heteroaryl amino-amides has not
been reported. Thus, herein we report the reactivity profile of
(het)arynes towards various positionally placed amino-amides,
sulphone amide and photophysical properties of selected
fluorescent molecules obtained.
O
O
O
CONH2
CHO
NC
N
O
O
N
N
N
N
N
(A)
(B)
(C)
(D)
(E)
CHO
O
N
R3 = H, R4 = diphenylamino
R3 = R4 = diphenylamino
R3 = R4 = carbazol-9-yl
approaches for TPA include Ullmann reaction, Suzuki and Heck
N
1(c),7,9
N
reaction.
Diphenylamine (DPA) derivatives are most
(F)
R4
R3
commonly used as stabilizers in nitrocellulose-containing
explosives and propellants, in the perfumery, as antioxidants,
for production of dyes, pharmaceuticals, photography
1 include few biologically active
diphenylamine based compounds (H-K).10 It should be noted
(G)
O
O
N
O2N
Cl
NO2
N
NH2
NH
NH2
S
O
NH
F
Cl
NH
chemicals etc. Figure
Cl
O
NO2
SIRT1 Inhibitor
Sirtuin-2-Selective Inhibitor
Anticancer
Fungiside
(K)
(H)
(I)
that the material functional and biological properties of TPA
(J)
and DPA are prominently depends on the nature of functional Figure 1 Examples of TPA based smart fluorescent materials and
DPA based bio-active compounds
Initial reaction between 1 equiv. of 2-aminobenzamide 1 in
dry acetonitrile and 1.2 equiv. of benzyne 2 generated in situ
from o-(trimethylsilyl) phenyl triflate and CsF under argon
atmosphere at RT for 24 h afforded N- mono and N, N-di
a. Organic and Bio-Organic Chemistry Division, CSIR-Central Leather Research
Institute (CLRI), Adyar, Chennai-600020, India; Fax: (+) 91-44-24911589; Phone:
(+91)-44-24437130; E-mail: shanmu196@rediffmail.com
Electronic Supplementary Information (ESI) available: [Copies of 1H NMR, 13C NMR,
DEPT-135, and HRMS of all the new compound and absorption and emission
spectra for selected compounds are provided.]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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arylated products 3a and 4a in 65% and 16% yield, respectively and a number of positionally placed amido-amidVeiesw, hAretictleerOonlione-
(Scheme 1).
amino-amides and o-amino sulphonamiDdOeI:a1s0.s10h3o9w/Cn8NinJ0f5i8g2u3rGe
3.
TMS
OTf
O
N
O
Br
Me
OMe
CsF
NH2
O
NH2
Dry CH3CN, Ar
NH2
NH
+
NH
RT, 24 hrs
+
NH2
2a
N-Arylation
2b
2c
2d
2e
10
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60
2
1
82%
4a
3a
8:2
O
NH2
O
O
O
NH2
I
Scheme 1 Synthesis of N- mono and N, N- di arylated products
of 2-aminobenzamide
NH2
NH2
NH2
NH2
O
NH2
1a
1b
1c
1d
NH2
O
O
O
The structure of products 3a and 4a was confirmed by
spectroscopic data (See SI) and structure of representative
product 4a was confirmed by single-crystal X-ray analysis
(Figure 2).14
SO2NH2
NH2
S
NH2
NH2
NH2
NH2
NH2
N
NH2
1e
1f
1h
1g
Figure 3. Various arynes, hetarynes, and amino-amides
screened
Under optimized condition, all the reactions underwent
smoothly to give rise to corresponding arylated products
(Figure 4 and Table 2). To understand the positional effect of
functional group on arylation meta and para amine substituted
benzamide substrates 1c and 1d were chosen to react with
benzyne 2a and gave rise to both mono arylated 3b, 3c and
diarylated 4b, 4c products in excellent combined yield.
Comparing the yield of the reaction, amine on meta position
directed diarylated product in higher yield (Table 2, entries 2
and 3). To examine the diversity of the arynes, Me and OMe
substituted arynes 2c and 2d were subjected to react with 2-
Figure 2 ORTEP diagram of compound 4a (CCDC 1814895)
In order to optimize the synthesis of compounds 3a and 4a,
an optimization study was undertaken by varying source of
fluoride for the generation of benzyne, mole equivalents of
aryne precursor, temperature and time. The reaction aminobenzamide, however, an inseparable mixture of
performed using 1.2 equiv. of benzyne using CsF as fluoride
regioisomer of mono-arylated products 3d and 3e, respectively
was obtained (Table 2, entries 4 and 5). The ratio of
regioisomer of the products were established from the 1H
NMR spectrum of compounds 3d and 3e (See foot note table 2
entries 4 and 5). Reaction of compound 1a with hetaryne
indolyne 2e gave rise to corresponding single regioisomer N-
mono and N, N- diarylated products 3f and 4f, respectively
(Table 2, entry 6). The reaction of benzyne 2a with 5-iodo
anthranilamide 1b and 3-aminothiophene-2-carboxamide 1e
yielded only mono arylated products 3g and 3h, respectively
(Table 2, entries 7 and 8). Further exploration on reaction of
heterocyclic amino amides 1f and 1g with aryne 2a yielded
exclusively diarylated products 4i and 4j (Table 2, entries 10
and 11). Reaction of compound 1g with halogen and methoxy
substituted arynes 2b and 2d also gave rise to only diarylated
products 4k and 4l (Table 2, entries 12 and 13). Formation of
sole diarylated or mono arylated products may be due to
varying electronic nature of heteroatom involved resonance
stability of intermediates and electron donating substituent at
meta position. When 2-amino benzenesulfonamide 1h was
chosen as a substrate, amine triarylated product 4g was
obtained in 78 % yield and amide diarylated product 4h was
obtained in 13 % yield amide and (Table 2, entry 9).
o
source in dry ACN under argon atmosphere at 60 C (Table 1,
entry 2) found completed in 3h to afford compounds 3a and 4a
in 63 and 27% yield, respectively. Increasing the mole equiv. of
the aryne precursor lead to improved yield of compound 4a
(Table 1, entry 3). The experiment using 2.4 equiv. of aryne
precursor and KF, 18-Crown-6 as fluoride source for the
generation of benzyne at RT the reaction completed within 0.5
h with an improved yield of compound 4a (Table 1, entry 4)
which later found as the optimized condition. Further
increment in equivalence of aryne precursor did not improve
the yield (Table 1, entry 5).
Table 1 Optimization of Synthesis of 3a and 4a
Equiv. of
Aryne
Precursor
1.2
1.2
2.4
% Yield
of
Temp.
F-
Time
hr
o
entry
Sourcea
3a/4ab
65/16
63/27
12/73
C
1
2
3
CsF
CsF
CsF
24
3
3
rt
60
60
KF, 18
Crown-6
KF, 18
crown-6
4
2.4
0.5
rt
14/79c
5
4
3
rt
13/76
a2.0 equiv. of the fluoride ion source was used for 1 equiv. of
aryne precursor; bIsolated Yield; cOptimized condition.
To demonstrate generality of the method, we investigated
the substrate scope by selecting various arynes and hetarynes
2 | J. Name., 2018, 00, 1-3
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Table 2. Synthesized heterocycles 3a-h and 4a-l
ARTICLE
1
2
3
4
5
6
7
8
To explain the formation of products 3 and 4, a plausible
View Article Online
DOI: 10.1039/C8NJ05823G
mechanism is proposed in scheme 4. Nucleophilic attack of
Sl No.
1
2
3
4
5
6
7
8
Aryne
2a
2a
2a
2c
2d
2e
2a
2a
2a
Substrates
Product(s) (% Yield)a
2-aminobenzamide 1 on benzyne 2 followed by proton
abstraction from HF (generated insitu from the initial
abstraction of hydrogen by fluoride ion) led to mono N-
arylated product 3. Second arylation is feasible on product 3 in
presence of excess of benzyne which led to formation of N, N-
diarylated compound 4.
1a
1c
1d
1a
1a
1a
1b
1e
1h
1f
3a (14)
3b (20)
3c (40)
3d (20)b,c
3e (19)b,d
3f (44)
3g (96)
3h (92)
4g (78)
--
4a (79)
4b (67)
4c (53)
4d (71)
4e (73)
4f (47)
--
9
10
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O
O
O
--
NH2
NH2
NH2
NH
9
4h (13)
4i (96)
4j (98)
4k (97)
4l (93)
NH2
H+
10
11
12
13
2a
2a
2b
2d
N
1
H+
1g
1g
1g
--
--
--
3
4
TMS
OTf
F-
2
aIsolated Yield; bIsolated as mixture of regioisomers; Ratio of
regioisomers of 3d was found to 1:0.4 as evidenced from 1H
NMR; d.Ratio of regioisomers of 3e was found to 1:0.6 as
evidenced from 1H NMR.
c.
Scheme 4. Plausible Mechanism for the Formation of
Compounds 3 and 4.
In order to demonstrate the synthetic utilities of
compounds synthesized, initially dibenzofuran and pyrene
substituted N-aryl anthranilamide 6a and 6b were prepared by
Suzuki coupling of 5-iodo N-aryl anthranilamide 3g using
O
NH2
O
O
O
NH2
NH2
NH
O
NH2
NH
NH2
+
NH
NH
NH
respective boronic acids in excellent yield (Scheme 5).
3a
3b
3c
3d
O
pyren-1-yl
NH2
O
O
O
O
O
boronic acid
O
NH
I
NH2
S
NH2
NH
NH2
NH
NH2
NH
O
NH2
NH
I
NH2
6b
I
NH
+
NH2
NH
90 % yield
a.
NH2
85 % Yeild
O
3g
3f
3h
3e
OMe
NH2
NH
dibenzo[b,d]furan-4-yl
boronic acid
OMe
O
HN
NH2
3g
O
O
O
NH2
a. Pd(OAc)2 (20 mol%), 2N NaOH
Reflux, 12 hr. Etahnol:toluene
6a
NH2
O
NH2
93 % yield
N
N
N
N
Scheme 5. Synthesis of Dibenzofuran and pyrene substituted
N-aryl anthranilamide
4d
4c
4a
4b
O
O
Further, a microwave assisted Mont.K10 clay catalysed
condensation reaction of N-aryl anthranilamide 3a with 4, 4’
biphenyl dicarboxaldehyde was envisaged to the formation of
structurally unique products. The reaction afforded mono
condensed 5a and bis condensed 5b hydroquinazolinone
derivatives in 32% and 43% yield, respectively. dibenzofuran
appended hydroquinazolinone derivatives 7a and 7b were
prepared in 35% and 47% yields, respectively by microwave
assisted Mont. K10 clay catalysed condensation of compound
6a and 4, 4’ biphenyl dicarboxaldehyde (Scheme 6).
O
S
NH2
N
NH2
O
N
S
O
N
O
N
NH
OMe
NH
NH2
4g
4e
4h
4f
HN
OMe
O
O
O
N
O
N
O
NH2
NH2
NH2
OMe
NH2
Br
N
N
N
N
N
4j
4l
4k
MeO
Br
4i
Figure 4 Synthesized di and triaryl amine derivatives from
various amino amides and arynes.
O
O
O
NH
N
CHO
NH2
NH2
NH2
NH
a.
Wangs et al. reported13 selective N-arylation of secondary
amide in presence of primary amine. However, there is no
report on primary amide arylation in the presence of amine
using aryne. Our attempt for primary amide arylation using
diphenyliodonium hexafluorophosphate as aryne precursor for
substrate 1a was found to be unreactive and starting material
was recovered (Scheme 3). `
5a
32 % yield
1a
3a
+
O
NH
N
N
HN
O
5b
43 % yield
O
NH
N
CHO
O
O
O
7a
NH2
NH
a.
KOtBu
O
35 % yield
PF6
O
+
N
H
N
I
Ph
THF, 0 
C
Ph
Ph
NH2
NH2
+
O
78 %
6a
O
O
NH
N
N
KOtBu
No reaction
Starting material recovered
NH2
PF6
+
HN
I
Ph
THF, 0 
C
Ph
7b
O
NH2
a. MW 200 W, MK-10, 5 min,
4,4'-Biphenyl biscarboxaldehyde
O
1a
47 % yield
Scheme
3.
Attempted
amide
arylation
using
Scheme 6. Synthesis of quinazolinones via Suzuki coupling and
diphenyliodoniumhexafluorophosphate as aryne precursor
MW assisted condensation
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Notably, the compound 4a in solution appeared yellow solvent polarity from dichloromethane to MeOH value of
under visible light irradiation and blue under UV (365 nm) compound 4j showed a blue shift in absorption maxima λmax,abs
irradiation driven us to evaluate its photophysical properties. value whereas the emission maxima value λmax, emi showed a
Compound 4a showed two UV absorption maxima at 377 nm decrease from hexane to acetonitrile and increase in the case
and 397 nm. Upon excitation of the longer wavelength, of DMSO and MeOH(See SI).
compound 4a shows a redshifted emission band (Δν˜ = 2253
and 2147 cm–1) with two emission maxima at 411 nm and 435 Table 3 Photophysical data for selected compounds (recorded
nm, which lies in the blue region (Figure 5, Table 3, Entry 1). in MeOH at 25 °C)
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The quantum yield of 4a was measured in MeOH by using
quinine sulphate in 0.5 M H2SO4 as a reference and showed a
significantly high quantum yield Φ = 0.812. This data confirms
that compound 4a is a promising fluorescent triphenylamine
based material. Compounds 4j and 4k showed UV absorption
maxima in the visible region at 519 nm and 504 nm and red
shifted emission maxima at 586 and 610 nm, respectively. The
compounds showed Stokes shifts Δν˜=1754 and 3447 cm–1
(Figure 5, Table 3, Entries 6 and 7). However, the quantum
yield of 4j and 4k measured in MeOH (Φ = 0.0006 and 0.0013)
by using rhodamine 6G as a reference found to be very low.
Absorption
Emission
λmax(nm)(Ф)
Entry Product
Δῡ(cm-1)[d]
λmax(nm)[a]
412,
434 2253,
1
4a
377, 397
(0.812)[b]
416,
2147
433 2557
2350
2
3
4
4d
4e
4f
376, 393
294
(0.386)[b]
371 (0.0137)[b] 7059
385,
450 11761
265, 315
(0.0342)[b]
401,423
(0.706)[b]
586
9523
2016
2000
5
6
4i
4j
371, 390
519
1754
(0.00060)[c]
7
8
4k
6b
504
352
610 (0.0013)[c] 3444
463 (0.0043)[b] 6810
[a] Absorption recorded at a concentration of 10–5 mol L–1. [b]
Quinine sulphate in 0.5 M H2SO4 solution was used as the
standard to determine the quantum yield. [c] Rhodamine 6G in
ethanol was used as the standard to determine the quantum yield.
4a
Absorbance max= 377, 397 nm
1.0
Emission max= 411, 435 nm
0.8
0.6
0.4
0.2
0.0
[d] Stokes shift = λmax abs – λmax,emi
[cm–1].
,
In conclusion, an efficient procedure for the synthesis of
blue and red emissive amido substituted triaryl amine
derivatives with high quantum yield via addition of arynes has
been established. Scope of the reaction is demonstrated using
various aryl amino amides and substituted arynes and
hetarynes. N-mono arylated product have been synthetically
transformed to distinctly functionalized structurally important
heterocycles bridged with biphenyl ring. The amido
substituted triaryl amine derivatives showed promising
fluorescence materials. Further, photo physical properties of
the products are valid to extend the research work for
practical applications are underway.
400
450
500
Wavelength (nm)
4j
Absorbance max= 519 nm
Emission max= 586 nm
1.0
0.8
0.6
0.4
0.2
0.0
Experimental Section
General remarks
All the reactions were carried out in oven-dried glassware.
Unless otherwise specified, all reactions were carried out
under an atmosphere of argon. Commercially obtained dry
CH3CN was stored under nitrogen over 4 Å molecular sieves.
The symmetrical unsymmetrical and hetaryne precursors,
amino amides were purchased from Sigma Aldrich and used as
received, without any further purification. CsF was dried and
stored under nitrogen atmosphere. Progress of reactions was
monitored by Thin Layer Chromatography (TLC) using Merck
pre-coated TLC plates (Merck 60 F254) and compounds were
visualized with a UV light at 254 nm. Further visualization was
achieved by staining with iodine. Purification of products was
accomplished by column chromatography packed with silica
gel 230-400 mesh. The NMR spectra were recorded on Bruker-
400
450
500
550
600
650
700
750
800
Wavelength (nm)
Figure 5 Normalised Absorption and Emission spectrum of
compounds 4a and 4j
Considerable fluorescence material property showed by
compound 4a and 4j prompted us to evaluate the
photophysical data of the selected compounds 4a, 4d, 4e, 4f,
4i, 4k, and 6b and the results are reported in Table 3. All of
these compounds shows significant absorption and emission
behaviour and few compounds shows excellent quantum yield
(table 3, entries 1, 2 and 5). Overall, most of the synthesised
amido substituted triaryl amine derivatives showed promising
fluorescence materials. The solvatochromic effect of
compound 4j in various solvents indicates with increase in the
1
400 MHz NMR spectrometer (400 MHz for H NMR and 125
MHz for 13C NMR) with CDCl3 as the solvent and TMS as
internal reference. Integrals are in accordance with
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assignments; Coupling constants were reported in Hertz (Hz). product. The product was characterised usiVniegw AdrtiicflfeeOrnelinnet
All 13C spectra are proton-decoupled. Multiplicity is indicated spectroscopic techniques.
DOI: 10.1039/C8NJ05823G
as follows: s (singlet), d (doublet), t (triplet), q (quartet), m
(multiplet), dd (doublet of doublet), dt (doublet triplet), td
2-(phenylamino)benzamide(3a): Colourless powder: 62
(triplet of doublet), br s (broad singlet). FTIR spectra were mg, 80% yield (when 1.1 equiv. of aryne was used); Rf (30%
recorded on a Perkin-Elmer RX-IFT-IR spectrometer and EtOAc-Hexane):0.42 FTIR (KBr) λmax: 3454, 3416, 3339, 3169,
absorbencies are reported in cm-1. ESI HRMS were done on a 2885, 2735, 1623, 1585, 1513, 1443, 1391, 1316, 1289, 1158,
Waters(R) Micromass(R) Q-TOF MicroTM Mass Spectrometer. 1078, 889, 743, 693, 625, 560, 500 cm-1; 1H NMR (400 MHz,
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Yields refer to quantities obtained after chromatography.
CDCl3) δ 9.43 (s, 1H), 7.39 (dd, J = 7.9, 1.4 Hz, 1H), 7.28 – 7.17
Absorption spectra were recorded using Cary100 Bio UV-Vis (m, 4H), 7.15 – 7.12 (m, 2H), 6.98 – 6.93 (m, 1H), 6.67 (ddd, J =
spectrophotometer. Steady-state fluorescence spectra were 8.1, 6.9, 1.4 Hz, 1H), 5.92 (s, 2H).13C NMR (CDCl3/TMS, 100
recorded on HORIBA JOBIN YVON Fluoromax spectrometer by MHz): δ 115.3, 116.0, 117.5, 121.5, 122.8, 128.3, 129.3, 132.9,
excitation at the respective absorption maxima. We estimated 141.2, 146.9, 171.9. HRMS-ESI: Calcd. for C13H12N2O [M+H]+
the quantum yields of our compounds by comparison with the m/z: 213.0910; Found 213.0892.
known quantum yields of Quinine sulphate in 0.5 M H2SO4
solution (Q=0.54) or Rhodamine 6G in Ethanol (Q=0.94) at an
excitation wavelength of 466 nm or 488 nm respectively, using mg, 22% yield; Rf (30% EtOAc-Hexane):0.43; FTIR (KBr) λmax
3-(phenylamino)benzamide (3b): Colourless powder: 16
:
the following equation.
3453, 3420, 3343, 3201, 2885, 2363, 1657, 1598, 1521, 1416,
1378, 1303, 1289, 1258, 1063, 788, 653, 615, 560 cm-1; 1H
Q = QR . I/IR . ODR/OD . n2/n2
R
where Q is the quantum yield, I is the integrated intensity, OD NMR (400 MHz, CDCl3) δ 7.44 – 7.43 (m, 1H), 7.25 – 7.18 (m,
is the optical density, and n is the refractive index. The 4H), 7.17 – 7.12 (m, 2H), 7.04 – 7.01 (m, 2H), 6.91 (t, J = 7.4 Hz,
subscript R refers to the Quinine sulphate or Rhodamine 6G.
1H), 5.91 (s, 2H); 13C NMR (CDCl3/TMS, 100 MHz): δ 114.0,
115.9, 116.1, 118.8, 118.9, 120.2, 122.0, 123.5, 124.0, 124.6,
129.5, 134.5, 139.2, 142.1, 144.0, 169.6; HRMS-ESI: Calcd. for
C13H12N2O [M+H]+ m/z: 213.0910; Found 213.0862.
Experimental procedures
a. Typical experimental procedure for the preparation of N-
Arylated Products:
4-(phenylamino)benzamide (3c): Colourless powder: 31
2-aminobenzamide 1 was subjected to react with benzyne mg, 40% yield; Rf (30% EtOAc-Hexane):0.40; FTIR (KBr) λmax
:
2 which is generated from 2.2 equivalence of 2-(trimethylsilyl) 3553, 3473, 3343,2976, 2635, 2360, 1652, 1554, 1501, 1444,
phenyl trifluoromethanesulfonate using 4 equiv. of KF and 18- 1388, 1329, 1279, 1248, 1043, 712, 623, 625, 573 cm-1; 1H
crown 6 as fluoride source in dry acetonitrile under nitrogen NMR (400 MHz, CDCl3) δ 7.66 – 7.62 (m, 2H), 7.28 – 7.23 (m,
atmosphere at 70 ˚C. The reaction was monitored with TLC. 2H), 7.09 (ddd, J = 3.0, 2.5, 1.4 Hz, 2H), 7.00 – 6.92 (m, 3H),
After the completion of the reaction the crude mixture was 5.98 (s, 1H), 5.74 (s, 2H); 13C NMR (CDCl3/TMS, 100 MHz): δ
purified by silica gel column chromatography to obtain pure 115.0, 120.1, 122.9, 124.1, 129.2, 129.5, 141.0, 147.3, 168.9;
compound 3 and 4. The compounds were characterised by HRMS-ESI: Calcd. For C13H12N2O [M+H]+ m/z: 213.0910; Found
spectroscopic techniques.
b. Typical experimental procedure for Suzuki coupling
reaction
213.0892.
2-(p-tolylamino)benzamide (3d) : Colourless powder: 17
A mixture of 5-iodo-2-(phenylamino)benzamide 3g (1 mg, 20% yield; Rf (30% EtOAc-Hexane): 0.46; FTIR (KBr) λmax
:
equiv.), boronic acid (2 equiv.) Pd(OAc)2 (20 mol%,) and 2N 3363, 3327, 3149, 1650, 1601, 1556, 1508, 1467, 1273, 766,
Na2OH (1 mL) in 5 mL of Ethanol:toluene (1:3) mixture was 686, 675, 653, 637, 503 cm-1; 1H NMR (400 MHz, CDCl3) δ 9.50
refluxed for 12 hr. After the completion of reaction monitored (d, J = 7.3 Hz, 1H), 8.02 (dtd, J = 5.8, 4.4, 1.7 Hz, 1H), 7.36 –
by TLC, the solvent was removed in vacuo, and then residue 7.29 (m, 2H), 7.21 – 7.05 (m, 4H), 7.04 – 6.96 (m, 5H), 6.93 –
was extracted with ethyl acetate and washed with dilute HCl 6.90 (m, 3H), 6.80 – 6.71 (m, 4H), 6.69 – 6.52 (m, 4H), 6.37 (s,
followed by brine and distilled water. The crude mixture was 3H), 2.33 (s, 3H), 2.28 (d, J = 3.1 Hz, 3H), 2.24 (d, J = 2.8 Hz,
dried over Na2SO4 and solvent was removed under reduced 3H); 13C NMR (CDCl3/TMS, 100 MHz): δ 20.7, 20.9, 21.5, 114.8,
pressure. The crude mixture was purified by silica gel column 115.3, 115.5, 116.2, 117.0, 117.4, 118.4, 119.2, 119.8, 122.2,
chromatography. The product was characterised using 122.3, 122.5, 123.0, 123.6, 125.6, 125.8, 125.9, 128.5, 129.1,
different spectroscopic techniques.
c. Typical experimental procedure for the synthesis of 5a, 139.3, 141.3, 145.0, 145.3, 145.4, 145.6, 145.7, 146.5, 147.2,
129.2, 129.8, 129.9, 130.0, 131.6, 132.7, 132.8, 138.6, 139.1,
5b, 7a and 7b
147.5, 147.8, 168.5, 172.3; HRMS-ESI: Calcd. for C14H14N2O
The substrate 3a or 6a (1 equiv.) and 4,4' biphenyl [M]+ m/z: 226.0586; Found 226.0605.
dicarboxaldehyde (0.5 equiv.) was microwave irradiated at 200
W in presence of Mont K-10 clay (100 w/w %) for 5 min. The
progress of the reaction was monitored by TLC. After the colured liquid: 19 mg, 19% yield; Rf (40% EtOAc-Hexane): 0.46;
completion of the reaction the crude mixture was filtered FTIR (KBr) λmax: 3465, 3328, 3137, 2829, 1566, 1503, 1489,
through celite pad and Silica gel column purified to obtain pure 1368, 1313, 1254, 1148, 1125, 878, 810, 764, 754, 675, 653,
2-((3-methoxyphenyl)amino)benzamide
(3e):
Brown
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637, 503 cm-1; 1H NMR (400 MHz, CDCl3) δ 9.41 (s, 1H), 9.31
Journal Name
3-(diphenylamino)benzamide (4b): Yellow powder: 70 mg,
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(s, 1H), 7.40 – 7.34 (m, 3H), 7.31 – 7.29 (m, 2H), 7.23 – 7.06 (m, 67% yield; Rf (30% EtOAc-Hexane): 0.48;DFOTII:R10(.K10B3r9)/Cλ8mNaxJ:035852231G,
8H), 6.97 – 6.94 (m, 1H), 6.82 – 6.80 (m, 2H), 6.74 – 6.72 (m, 3429, 3343, 3235, 3132, 2943, 2854, 1845, 1691, 1488, 1448,
2H), 6.70 – 6.66 (m, 3H), 6.60 – 6.56 (m 1H), 6.52 – 6.50 (m, 1353, 1298, 1237, 1143, 1052, 1035, 919, 862, 820, 762, 752,
2H), 5.92 (s, 2H), 3.73 (s, 3H), 3.71 (s, 4H); 13C NMR (100 MHz, 684, 621, 506 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.43 (t, J = 1.9
CDCl3) δ 172.1, 71.9, 160.6, 156.3, 148.4, 146.1, 142.6, 133.9, Hz, 1H), 7.31 – 7.28 (m, 1H), 7.21 – 7.10 (m, 6H), 7.01 – 6.93
133.0, 130.0, 128.3, 125.2, 117.8, 116.3, 115.8, 114.6, 114.2, (m, 6H), 6.06 (s, 2H); 13C NMR (CDCl3/TMS, 100 MHz): δ 120.9,
113.6, 108.3, 106.8, 55.5, 55.2; HRMS-ESI: Calcd. for 122.0, 123.4, 124.5, 126.7, 129.4, 134.7, 147.3, 148.4, 169.5;
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C14H14N2O2Na [M+Na]+ m/z:265.0653; Found 265.0699.
HRMS-ESI: Calcd. for C19H16N2O [M+H]+ m/z: 289.1063; Found
289.1141.
2-((1H-indol-5-yl)amino)benzamide (3f): Brown powder:
41 mg, 44% yield; Rf (30% EtOAc-Hexane): 0.42; FTIR (KBr)
4-(diphenylamino)benzamide (4c): Yellow powder: 56 mg,
λmax: 3765, 3542, 3333, 3214, 2635, 1568, 1412, 1358, 1334, 53% yield; Rf (30% EtOAc-Hexane): 0.46; FTIR (KBr) λmax: 3411,
1273, 1138, 1125, 978, 868, 763, 673, 641, 630, 513 cm-1; H 3458, 3422, 3314, 3200, 2973, 2844, 1845, 1761, 1658, 1448,
NMR (400 MHz, CDCl3) δ 9.35 (s, 1H), 8.27 (s, 1H), 7.39 (s, 1H), 1353, 1228, 1156, 1072, 1055, 960, 919, 860, 822, 773, 752,
7.31 (d, J = 7.9 Hz, 1H), 7.22 (d, J = 8.4 Hz, 1H), 7.09 – 7.06 (m, 674, 623, 509 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.59 – 7.56 (m,
2H), 6.97 – 6.94 (m, 2H), 6.52 (t, J = 7.5 Hz, 1H), 6.38 (d, J = 0.6 2H), 7.24 – 7.20 (m, 4H), 7.07 – 7.01 (m, 6H), 6.95 – 6.93 (m,
Hz, 1H), 6.04 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 172.6, 149.2, 2H), 5.83 (s, 2H); 13C NMR (CDCl3/TMS, 100 MHz): δ 120.6,
133.8, 133.4, 133.2, 133.1, 132.9, 128.6, 128.3, 125.1, 122.5, 124.2, 125.3, 125.6, 128.6, 129.5, 146.8, 151.3, 168.9; HRMS-
120.2, 116.1, 114.4, 113.9, 111.8, 106.6, 102.4; HRMS-ESI: ESI: Calcd. for C19H16N2O [M+H]+ m/z: 289.1063; Found
Calcd. for C15H13N3ONa [M+Na]+ m/z: 274.0656; Found 289.1106.
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274.0675.
2-(di-p-tolylamino)benzamide (4d): Yellow powder: 82 mg,
Colourless 71% yield; Rf (30% EtOAc-Hexane): 0.45; FTIR (KBr) λmax: 3323,
powder: 61 mg, 96% yield; Rf (30% EtOAc-Hexane): 0.43; FTIR 3253, 2935, 2845, 1733, 1673, 1513, 1462, 1441, 1356, 1314,
(KBr) λmax: 3428, 3380, 3177, 2813, 1688, 1627, 1593, 1503, 1268, 1164, 979, 754, 643, 625, 542 cm-1; H NMR (400 MHz,
1398, 1313, 1276, 1158, 1128, 1082, 889, 808, 785, 744, 695, CDCl3) δ 8.07 – 8.02 (m, 1H), 7.48 – 7.42 (m, 1H), 7.34 – 7.26
658, 627, 501 cm-1; H NMR (400 MHz, CDCl3) δ 9.46 (s, 1H), (m, 1H), 7.13 – 7.08 (m, 2H), 7.05 – 7.02 (m, 2H), 6.90 – 6.73
7.73 (d, J = 2.1 Hz, 1H), 7.49 (dd, J = 8.9, 2.1 Hz, 1H), 7.35 – (m, 5H), 5.73 (s, 1H), 2.28 (d, J = 3.2 Hz, 3H), 2.23 (d, J = 2.8 Hz,
7.30 (m, 2H), 7.18 (d, J = 7.5 Hz, 2H), 7.09 – 7.05 (m, 2H), 5.91 3H); 13C NMR (100 MHz, CDCl3) δ 168.0, 147.7, 147.5, 145.5,
(s, 2H); 13C NMR (CDCl3/TMS, 100 MHz): δ117.2, 117.9, 122.0, 145.4, 145.2, 145.0, 139.3, 132.8, 132.7, 132.7, 132.5, 131.7,
123.5, 129.4, 136.6, 140.4, 141.2, 146.2, 170.4; HRMS-ESI: 130.1, 130.0, 129.9, 129.8, 129.1, 126.0, 125.8, 123.8, 123.5,
123.1, 122.9, 122.6, 122.4, 119.7, 119.1, 21.4, 20.7; HRMS-ESI:
Calcd. for C21H20N2ONa [M+Na]+ m/z: 339.1173; Found
3-(phenylamino)thiophene-2-carboxamide (3h): Colourless 339.1149.
powder: 70 mg, 92% yield; Rf (30% EtOAc-Hexane): 0.45; FTIR
2-(bis(4-methoxyphenyl)amino)benzamide (4e): Brown
1459, 1403, 1335, 1279, 1164, 1103, 1029, 903, 848, 782, 741, coloured liquid: 93 mg, 73% yield; Rf (40% EtOAc-Hexane):
703, 636, 570, 538 cm-1; H NMR (400 MHz, CDCl3) δ H NMR 0.41; FTIR (KBr) λmax: 3443, 3312, 3261, 2845, 2742, 1919,
(400 MHz, CDCl3) δ 9.37 (s, 1H), 7.27 – 7.23 (m, 2H), 7.21 – 1728, 1612, 1573, 1448, 1326, 1315, 1247, 1144, 868, 742,
7.18 (m, 1H), 7.11 – 7.07 (m, 3H), 6.99 – 6.95 (m, 2H), 5.84 (s, 673, 632, 503 cm-1; H NMR (400 MHz, CDCl3) δ 7.89 (ddd, J =
2H); 13C NMR (CDCl3/TMS, 100 MHz): δ104.5, 119.2, 120.0, 7.7, 4.1, 1.5 Hz, 1H), 7.37 – 7.30 (m, 1H), 7.21 – 7.12 (m, 1H),
121.9, 122.6, 128.2, 129.3, 129.6, 141.8, 150.5, 167.2; HRMS- 7.05 (dd, J = 8.0, 0.9 Hz, 1H), 6.98 (dd, J = 7.9, 1.1 Hz, 1H), 6.92
ESI: Calcd. for C11H10N2OS [M+H]+ m/z: 218.0314; Found – 6.90 (m, 1H), 6.81 – 6.77 (m, 2H), 6.72 – 6.67 (m, 3H), 6.47
(dd, J = 9.0, 5.0 Hz, 1H), 6.41 – 6.33 (m, 1H), 5.99 (s, 1H), 3.66
(d, J = 3.8 Hz, 4H), 3.60 (d, J = 4.9 Hz, 2H); 13C NMR (100 MHz,
2-(diphenylamino)benzamide (4a): Colourless crystals: 79 CDCl3) δ 168.5, 168.4, 160.5, 156.2, 155.5, 149.6, 148.4, 146.2,
mg, 79% yield; Rf (30% EtOAc-Hexane): 0.40; FTIR (KBr) λmax 145.3, 144.9, 141.5, 140.1, 139.2, 132.7, 132.6, 132.5, 131.5,
3421, 3328, 3242, 3134, 3030, 2923, 2854, 1945, 1671, 1588, 130.6, 130.0, 129.6, 128.7, 126.3, 125.7, 125.1, 124.0, 115.1,
1486, 1448, 1373, 1278, 1247, 1153, 1082, 1035, 970, 919, 114.7, 114.7, 114.1, 113.3, 108.9, 108.1, 107.0, 106.9, 55.4,
880, 820, 783, 752, 694, 621, 509 cm-1; H NMR (400 MHz, 55.2; HRMS-ESI: Calcd. for C21H20N2O3 [M]+ m/z: 348.1274;
5-iodo-2-(phenylamino)benzamide
(3g):
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Calcd. for C13H11IN2O [M+H]+ m/z: 338.9616; Found 338.9642.
(KBr) λmax: 3364, 3327, 3190, 1687, 1633, 1585, 1551, 1489,
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218.0317.
:
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CDCl3) δ 7.94 (dd, J = 7.8, 1.3 Hz, 1H), 7.40 (td, J = 7.8, 1.5 Hz, Found 348.1203.
1H), 7.25 (t, J = 7.6 Hz, 2H), 7.17 (dd, J = 12.7, 4.3 Hz, 4H), 7.07
2-(di(1H-indol-5-yl)amino)benzamide (4f): Brown powder:
(CDCl3/TMS, 100 MHz): δ121.5, 122.4, 123.0, 126.1, 129.3, 63 mg, 47% yield; Rf (30% EtOAc-Hexane): 0.38; FTIR (KBr)
(d, J = 7.9 Hz, 1H), 6.93 (t, J = 8.9 Hz, 6H), 5.58 (s, 1H); 13C NMR
129.4, 130.3, 131.7, 132.8, 145.1, 147.4, 168.0; HRMS-ESI: λmax: 3825, 3652, 3453, 3326, 2743, 1656, 1583, 1448, 13674,
Calcd. for C19H16N2O [M]+ m/z: 288.1063; Found 288.0989.
1256, 1221, 1123, 933, 854, 724, 630, 508 cm-1; H NMR (400
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MHz, DMSO-d6) δ 11.00 (d, J = 20.1 Hz, 2H), 7.64 (d, J = 7.7 Hz, 178.5; HRMS-ESI: Calcd. for C18H15N3O [M]+ m/z: 289.0941;
1H), 7.59 (s, 1H), 7.38 (t, J = 7.4 Hz, 2H), 7.29 – 7.26 (m, 4H), Found 289.0940.
View Article Online
DOI: 10.1039/C8NJ05823G
7.20 (s, 1H), 7.14 (t, J = 7.5 Hz, 1H), 7.03 (s, 2H), 6.98 (d, J = 8.0
Hz, 1H), 6.78 (d, J = 8.7 Hz, 2H), 6.26 (s, 2H); 13C NMR (100
2-(bis(4-bromophenyl)amino)nicotinamide
(4k):Purple
MHz, DMSO-d6) δ 168.4, 162.8, 150.0, 147.7, 142.2, 132.8, powder: 125 mg, 97% yield; Rf (30% EtOAc-Hexane): 0.41; FTIR
132.4, 131.6, 130.7, 128.5, 126.2, 124.4, 123.7, 119.3, 114.8, (KBr) λmax: 3268, 3150, 3012, 2813, 1942, 1867, 1718, 1678,
112.2, 101.4; HRMS-ESI: Calcd. for C23H18N4O [M+Na]+ m/z: 1509, 1342, 1156, 1111, 1034, 867, 756, 648, 567, 504 cm-1;
389.1078; Found 389.1072.
1H NMR (400 MHz, CDCl3) δ 8.90 (dd, J = 7.4, 1.9 Hz, 1H), 8.04
(dd, J = 6.4, 1.9 Hz, 1H), 7.67 – 7.64 (m, 2H), 7.45 – 7.43 (m,
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N,N-diphenyl-2-(phenylamino)benzenesulfonamide (4g): 2H), 7.40 – 7.34 (m, 2H), 7.32 (d, J = 0.8 Hz, 4H), 7.29 – 7.25 (m,
Green powder: 91 mg, 78% yield; Rf (15% EtOAc-Hexane): 0.47; 1H), 6.89 – 6.85 (m, 1H); HRMS-ESI: Calcd. for C18H13Br2N3O
FTIR (KBr) λmax
:
3643, 3489, 3312, 3071, 2983, 1673, 1583, [M+H]+ m/z: 445.9025; Found 445.9041.
1343 1157, 976, 742, 687, 512 cm-1; 1H NMR (400 MHz, CDCl3)
δ 7.55 (d, J = 8.2 Hz, 1H), 7.40 (s, 1H), 7.21 (td, J = 7.6, 1.5 Hz,
2-(di-p-tolylamino)nicotinamide (4l): Red powder: 118 mg,
6H), 7.15 (t, J = 7.8 Hz, 2H), 7.12 – 7.08 (m, 4H), 7.06 – 7.02 (m, 93% yield; Rf (25% EtOAc-Hexane): 0.44; FTIR (KBr) λmax: 3463,
2H), 6.93 (d, J = 7.3 Hz, 1H), 6.88 (d, J = 8.4 Hz, 2H), 6.67 – 6.63 3214, 3128, 2868, 1865, 17033, 1657, 1548, 1432, 1256, 1192,
(m, 1H); 13C NMR (100 MHz, CDCl3) δ 143.0, 141.3, 140.4, 1142, 935, 783, 689, 613, 510 cm-1; 1H NMR (400 MHz, CDCl3)
134.3, 131.3, 129.3, 128.7, 127.7, 123.9, 123.2, 120.8, 118.5, δ 9.03 (dd, J = 7.4, 2.0 Hz, 1H), 8.03 (dd, J = 6.3, 2.0 Hz, 1H),
116.2; HRMS-ESI: Calcd. for C24H20N2O2SNa [M+Na]+ 7.71 (d, J = 3.0 Hz, 1H), 7.41 – 7.37 (m, 3H), 7.23 – 7.20 (m, 1H),
m/z:423.1043; Found 423.1087.
7.02 (d, J = 9.0 Hz, 3H), 6.79 (dd, J = 5.5, 2.0 Hz, 2H), 3.85 (s,
6H); 13C NMR (100 MHz, CDCl3) δ 177.8, 160.1, 155.5, 145.7,
2-amino-N,N-diphenylbenzenesulfonamide (4h): Green 144.9, 144.1, 134.2, 129.3, 128.1, 125.0, 121.7, 114.5, 107.9,
powder: 12 mg, 13% yield; Rf (15% EtOAc-Hexane): 0.37; FTIR 104.6, 55.6; HRMS-ESI: Calcd. for C20H19N3O3 [M]+
(KBr) λmax: 3475, 3338, 2654, 1765, 1442, 1334, 1222, 934, m/z:349.1126; Found 349.1144.
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726, 641, 523 cm-1; H NMR (400 MHz, CDCl3) δ 7.34 (dd, J =
8.1, 1.4 Hz, 1H), 7.30 – 7.26 (m, 4H), 7.23 (t, J = 1.7 Hz, 1H),
7.22 (d, J = 1.7 Hz, 2H), 7.20 (dd, J = 2.3, 1.6 Hz, 2H), 7.18 – [1,1'-biphenyl]-4-carbaldehyde (5a): Colourless powder: 30
7.17 (m, 1H), 7.16 – 7.14 (m, 1H), 6.61 (dd, J = 8.3, 0.9 Hz, 1H), mg, 32% yield; Rf (30% EtOAc-Hexane): 0.45; FTIR (KBr) λmax
4'-(4-oxo-1-phenyl-1,2,3,4-tetrahydroquinazolin-2-yl)-
:
6.54 (td, J = 7.1, 3.6 Hz, 1H), 4.79 (s, 2H); 13C NMR (100 MHz, 3170, 3056, 2914, 2846, 2740, 2360, 1937, 1729, 1663, 1600,
CDCl3) δ 145.8, 141.4, 134.4, 130.8, 129.2, 128.8, 127.6, 120.9, 1482, 1381, 1299, 1245, 1220, 1164, 1118, 1039, 1009, 904,
117.3, 116.8; HRMS-ESI: Calcd. for C18H16N2O2S [M+Na]+ 812, 757, 699, 645, 559, 493 cm-1; 1H NMR (400 MHz, CDCl3) δ
m/z:347.0830; Found 347.0790.
10.00 (s, 1H), 8.87 (s, 1H), 7.95 (d, J = 7.7 Hz, 1H), 7.86 (d, J =
8.2 Hz, 2H), 7.61 (d, J = 8.1 Hz, 2H), 7.55 (d, J = 8.2 Hz, 2H), 7.49
3-(diphenylamino)benzofuran-2-carboxamide (4i): Yellow (d, J = 8.2 Hz, 2H), 7.32 (t, J = 7.8 Hz, 3H), 7.26 – 7.21 (m, 1H),
powder: 88 mg, 96% yield; Rf (30% EtOAc-Hexane): 0.42; FTIR 7.18 – 7.12 (m, 2H), 7.06 (d, J = 8.3 Hz, 1H), 6.95 (t, J = 7.5 Hz,
(KBr) λmax: 3177, 3100, 2992, 2947, 1635, 1596, 1556, 1477, 1H), 6.26 (d, J = 4.1 Hz, 1H); 13C NMR (CDCl3/TMS, 100 MHz): δ
1397, 1345, 1262, 1158, 1026, 932, 820, 754, 701, 676, 594 72.3, 118.6, 119.6, 121.0, 122.8, 124.7, 125.3, 127.5,127.6,
1
cm-1; H NMR (400 MHz, CDCl3) δ 7.86 – 7.82 (m, 2H), 7.76 (s, 128.2, 128.5, 129.0, 129.6, 130.2, 133.6, 135.3, 137.8, 139.6,
1H), 7.36 – 7.30 (m, 7H), 7.16 – 7.11 (m, 3H), 6.90 – 6.87 (m, 141.0, 144.8, 145.5,146.2, 164.5, 191.8; HRMS-ESI: Calcd. for
2H), 6.62 (dd, J = 7.3, 0.8 Hz, 1H), 6.43 (dd, J = 7.9, 0.8 Hz, 1H), C27H20N2O2 [M+H]+ m/z:405.1295; Found 405.1291.
5.83 (s, 1H); 13C NMR (CDCl3/TMS, 100 MHz): δ 112.9, 117.8,
118.6, 121.7, 123.0, 123.4, 124.6, 125.7, 126.7, 128.5, 128.6,
2,2'-([1,1'-biphenyl]-4,4'-diyl)bis(1-phenyl-2,3-dihydro
128.8, 129.0, 129.4, 129.6, 135.3, 137.2, 149.9, 166.3, 166.9, quinazolin-4(1H)-one) (5b): Colourless powder: 60 mg, 43%
168.9; HRMS-ESI: Calcd. for C21H16N2O2 [M+H]+ m/z: 329.1012; yield; Rf (30% EtOAc-Hexane): 0.45; FTIR (KBr) λmax: 3643,
Found 329.1054.
3201, 3059, 3035, 2922, 2853, 2361, 2340, 1929, 1667, 1606,
1495, 1452, 1375, 1304, 1252, 1233, 1183, 1156, 1111, 1003,
2-(diphenylamino)nicotinamide (4j): Red powder: 95 mg, 956, 907, 862, 823, 798, 752, 696, 646, 618, 592, 555, 521,
1
98% yield; Rf (30% EtOAc-Hexane): 0.46; FTIR (KBr) λmax: 3379, 456, 418 cm-1; H NMR (400 MHz, CDCl3) δ 9.82 (d, J = 4.4 Hz,
3112, 3050, 2906, 1952, 1643, 1605, 1590, 1509, 1439, 1363, 1H), 9.12 (d, J = 4.0 Hz, 1H), 7.91 (d, J = 7.8 Hz, 2H), 7.43 (d, J =
1265, 1186, 1139, 1109, 1025, 952, 827, 755, 690, 643, 556, 8.1 Hz, 4H), 7.37 (d, J = 7.8 Hz, 1H), 7.29 (m, 9H), 7.18 (d, J =
512 cm-1; 1H NMR (400 MHz, CDCl3) δ 8.97 (dd, J = 7.3, 1.9 Hz, 8.1 Hz, 4H), 7.13 – 7.09 (m, 4H), 6.91 (t, J = 7.5 Hz, 2H), 6.23
1H), 8.31 (dd, J = 8.1, 1.5 Hz, 1H), 8.00 (dd, J = 6.4, 1.9 Hz, 1H), (dd, J = 16.2, 4.2 Hz, 2H); 13C NMR (CDCl3/TMS, 100 MHz): δ
7.52 (ddd, J = 5.7, 3.4, 1.8 Hz, 5H), 7.46 (dd, J = 3.7, 1.8 Hz, 2H), 72.0, 72.2, 118.9, 119.8, 120.9, 121.0,122.3,122.8, 124.3,
7.42 – 7.37 (m, 1H), 7.20 – 7.16 (m, 2H), 6.81 – 6.76 (m, 1H); 124.6, 127.0, 127.2, 128.4, 128.5, 129.6,133.6, 133.7, 139.9,
13C NMR (CDCl3/TMS, 100 MHz): δ 108.1, 122.5, 122.6, 124.1, 140.2, 144.5, 145.5, 145.8, 165.0, 165.2; HRMS-ESI: Calcd. for
126.2, 127.0, 127.7, 129.4, 133.8, 141.4, 143.7, 144.6, 150.6, C40H30N4O2 [M]+ m/z:598.1909; Found 598.1906.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2018, 00, 1-3 | 7
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New Journal of Chemistry
Page 8 of 10
ARTICLE
5-(dibenzo[b,d]furan-4-yl)-2-(phenylamino)benzamide
Journal Name
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145.4, 145.2, 144.1, 140.3, 140.1, 139.3, 134.0, 129.7, 129.6,
View Article Online
DOI: 10.1039/C8NJ05823G
(6a): Colourless powder: 52 mg, 93% yield; Rf (30% EtOAc- 129.0, 128.3, 127.3, 127.1, 126.3, 124.8, 124.6, 124.1, 123.2,
Hexane): 0.45; FTIR (KBr) λmax: 3639, 3392, 3354, 3184, 3051, 122.7, 120.6, 119.5, 119.3, 118.7, 114.0, 111.8, 72.2; HRMS-
2923, 2856, 1833, 1708, 1636, 1590, 1526, 1457, 1392, 1320, ESI: Calcd. for C64H42N2O4 [M-H]+ m/z:929.2346; Found
1250, 1186, 1113, 909, 879, 828, 795, 740, 700, 657, 601, 560, 929.2357.
1
497 cm-1; H NMR (400 MHz, CDCl3) δ 9.66 (s, 1H), 8.07 (d, J =
2.0 Hz, 1H), 7.99 (d, J = 7.4 Hz, 1H), 7.90 (dd, J = 7.6, 1.0 Hz, Conflicts of interest
1H), 7.85 (dd, J = 8.8, 1.9 Hz, 1H), 7.60 (d, J = 8.2 Hz, 1H), 7.55
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(dd, J = 7.6, 1.0 Hz, 1H), 7.48 (d, J = 8.7 Hz, 2H), 7.42 (d, J = 7.6 There are no conflicts to declare
Hz, 1H), 7.39 – 7.34 (m, 3H), 7.30 (d, J = 7.4 Hz, 2H), 7.08 (t, J =
1
7.2 Hz, 1H), 6.01 (s, 2H); 13C NMR (CDCl3/TMS, 100 MHz): δ Supporting Information: Copies of H NMR, 13C NMR, DEPT-
111.8, 114.0, 115.3, 115.8, 119.1, 120.7, 121.8, 122.9, 123.2, 135, and HRMS of all the compound and absorption and
123.3, 124.2, 125.8, 127.2, 128.6, 129.3, 133.2, 140.9, 146.1, emission spectra for selected compounds are provided.
153.1, 156.1, 171.9; HRMS-ESI: Calcd. for C25H18N2O2Na
[M+Na]+ m/z:401.1266; Found 401.1212.
ACKNOWLEDGMENTS
P.S. thanks the Director, CSIR-CLRI for providing infrastructure
2-(phenylamino)-5-(pyren-1-yl)benzamide (6b): Brown facilities. RSM thanks DST (New Delhi) for the award of DST-
powder: 70 mg, 90 % yield; Rf (20% EtOAc-Hexane): 0.45; FTIR INSPIRE fellowship. Financial supports from the DST (New
(KBr) λmax: 3532, 3493, 3355, 3285, 3152, 2924, 2857, 1789, Delhi) vide Grant No. SB/EMEQ-044/2014 is acknowledged.
1659, 1576, 1566, 1448, 1383, 1314, 1267, 1168, 919, 879,
834, 783, 742, 645, 607, 510, cm-1; 1H NMR (400 MHz, CDCl3) δ Key Words
9.68 (s, 1H), 8.20 – 8.13 (m, 4H), 8.07 (s, 2H), 8.04 – 7.97 (m,
2H), 7.93 (d, J = 7.8 Hz, 1H), 7.69 (s, 1H), 7.53 (dd, J = 22.1, 9.2 Triarylamine / Diarylamine / N-arylation / Benzyne / hetaryne /
Hz, 2H), 7.39 – 7.30 (m, 4H), 7.08 (t, J = 7.0 Hz, 1H), 5.97 (s, amino amide / Fluorescence
2H); 13C NMR (100 MHz, CDCl3/TMS) δ 171.9, 145.8, 141.1,
136.6, 135.1, 131.5, 130.9, 130.5, 130.2, 129.4, 128.6, 127.6, References and notes
127.4, 126.1, 125.2, 125.0, 124.9, 124.8, 124.7, 123.2, 121.8,
115.7, 115.22; HRMS-ESI: Calcd. for C29H20N2O [M+H]+ m/z:
413.1276; Found 413.1260.
1
For reviews: (a) H.-J. Yen and G.-S. Liou, Polym. Chem., 2018, 9,
3001-3018; (b) P. Agarwala and D. J. Kabra, Mater. Chem. A,
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4'-(6-(dibenzo[b,d]furan-4-yl)-4-oxo-1-phenyl-1,2,3,4-
tetrahydroquinazolin-2-yl)-[1,1'-biphenyl]-4-carbaldehyde
(7a): Colourless powder: 26 mg, 35% yield; Rf (40% EtOAc-
Hexane): 0.42; FTIR (KBr) λmax: 3988, 3193, 3055, 2923, 2856,
2733, 2367, 1930, 1666, 1603, 1496, 1456, 1370, 1254, 1184,
1
1009, 910, 825, 752, 703, 643, 557, 500 cm-1; H NMR (400
2
3
M. Wan, G. Sang, Y. Zou, S. Tan and Y. Li, J. Appl. Polym. Sci.,
2009, 113, 1415-1421.
MHz, CDCl3) δ 9.99 (s, 1H), 8.51 (s, 1H), 8.33 (bs, 1H), 8.06 –
8.02 (m, 1H), 7.96 (d, J = 7.6 Hz, 1H), 7.86 (t, J = 7.7 Hz, 3H),
7.64 – 7.58 (m, 5H), 7.54 (t, J = 6.4 Hz, 3H), 7.43 (s, 1H), 7.39 –
7.33 (m, 4H), 7.25 (t, J = 4.7 Hz, 2H), 7.16 (t, J = 8 Hz, 2H), 6.28
(d, J = 3.5 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 191.8, 156.0,
146.1, 144.9, 144.7, 140.7, 139.9, 139.2, 135.3, 134.2, 130.2,
129.8, 129.0, 128.4, 127.6, 127.2, 126.3, 125.2, 124.9, 124.4,
124.1, 123.6, 123.4, 123.2, 122.8, 120.6, 119.5, 118.3, 115.9,
114.0, 111.8, 72.7; HRMS-ESI: Calcd. for C39H26N2O3 [M-H]+
m/z:569.1343; Found 569.1370.
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2,2'-([1,1'-biphenyl]-4,4'-diyl)bis(6-(dibenzo[b,d]furan-4-
yl)-1-phenyl-2,3-dihydroquinazolin-4(1H)-one) (7b): Colourless
powder: 57 mg, 47% yield; Rf (55% EtOAc-Hexane): 0.40; FTIR
(KBr) λmax: 3427, 2923, 2855, 2360, 2254, 1663, 1607, 1498,
1455, 1370, 1290, 1257, 1186, 999, 906, 827, 756, 700, 639,
562, 509 cm-1; 1H NMR (400 MHz, CDCl3) δ 9.63 (s, 1H), 9.15 (s,
1H), 8.47 (d, J = 9.9 Hz, 2H), 7.98 (t, J = 9.3 Hz, 2H), 7.93 (d, J =
7.5 Hz, 2H), 7.84 (d, J = 7.6 Hz, 2H), 7.57 – 7.46 (m, 10H), 7.38 –
7.30 (m, 12H), 7.25 (s, 6H), 7.16 – 7.12 (m, 2H), 6.29 (d, J = 3.8
Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 165.0, 156.0, 153.1,
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DOI: 10.1039/C8NJ05823G
Graphical abstract
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Chemoselective synthesis of amide substituted triaryl amine and diaryl amine derivatives by N-mono and
N, N-diarylation of aryl/hetaryl amino amides using benzyne/arynes has been acheived. Selected
triarylamine derivative showed blue-red emission with high quantum yield. Synthesized products were
synthetically transformed to highly functionalized biphenyl bridged heterocycles.
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O
O
O
X
O
N
NH2
MW 200 W
MK-10 catalyst
NH
Suzuki Coupling
NH2
NH
NH
O
N
NH
N
O
X= I
N= C
4,4' Biphenyl
biscarboxaldehyde
O
O
KF, 18-crown-6
ACN
+
N
O
O
NH2
+
+
O
N
HN
20 examples
CHO
N
NH2
NH2
N
O
O
N
NH2
NH2
N
N
N= C
Red emission
Blue emission; Quantum yield = 0.81
This journal is © The Royal Society of Chemistry 20xx
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