High-Pressure Synthesis of Oligoanilines

Article abstract of DOI:10.1055/s-2003-42434

Aniline oligomers can be prepared cleanly and in high yield by the high-pressure promoted SNAr reaction of aromatic amines with fluoronitrobenzenes followed by reduction of the nitro group.

Full text of DOI:10.1055/s-2003-42434

PAPER
2511
High-Pressure Synthesis of Oligoanilines
H
igh-Pressure Sy
h
nthesis of
O
r
ligoanili
ines stopher L. Brown, I. Wayan Muderawan, David J. Young*
School of Science, Griffith University, Queensland 4111, Australia
Fax +61(7)38757656; E-mail: d.young@sct.gu.edu.au
Received 27 March 2003; revised 1 September 2003
Dedicated to Dr Neil S. Isaacs on his retirement.
Abstract: Aniline oligomers can be prepared cleanly and in high
yield by the high-pressure promoted SNAr reaction of aromatic
amines with fluoronitrobenzenes followed by reduction of the nitro
group.
Key words: high-pressure, aromatic nucleophilic substitution,
aniline oligomers
Polyaniline is currently one of the most studied electro-ac-
tive polymers. The interest in this material arises because
of its many potential applications in such diverse areas as
energy storage and transformation materials, chemical ca-
talysis and its applications in sensor and membrane tech-
nologies.1 Unfortunately, these applications are often
hampered by the intractable nature of the polymer and the
inclusion of structural defects that lower its electrical con-
ductivity. More recently aniline oligomers have been in-
vestigated as defect-free models of polyaniline and have
shown promising conductivity profiles.2,3
Scheme 1 Reagents and conditions: (a) Et3N, 1.5 GPa, 30 °C
for 3 days to give the corresponding nitrodiphenylamines
(Scheme 1).
Substituent effects were as expected for an aromatic nu-
cleophilic substitution (SNAr). Excellent yields were ob-
tained with aniline and 4-methoxyaniline (Table 1).
Table 1 Reaction of Substituted Anilines 1 with 4-Fluoronitroben-
zene (2a)
Substituted Aniline (1)
Substituted Diphenlamine (3) Yield
Substituted aniline trimeric species can be prepared by the
oxidation of 4,4 -diaminodiphenylamine or p-phenylene-
diamine in the presence of aniline and electron-rich, sub-
stituted aniline derivatives.4,5 In our hands, however, these
procedures have proved difficult but other researchers
have used the resulting emeraldine trimer to make aniline
oligomers of up to 32 units in size.6
(%)
1a R1 = R2 = R3 = H
3a R1 = R2 = R3 = H
95.8
1b R1 = R2 = H, R3 = OCH3 3b R1 = R2 = H, R3 = OCH3 100
1c R1 = R2 = H, R3 = NO2
1d R1 = R3 = H, R2 = NO2
1e R2 = R3 = H, R1 = NO2
3c R1 = R2 = H, R3 = NO2
3d R1 = R3 = H, R2 = NO2
3e R2 = R3 = H, R1 = NO2
0
32.6
0
Branched oligoarylamines have been prepared by repeti-
tive SNAr reaction of the highly reactive 1-fluoro-2,4-
dinitrobenzene with anilines followed by reduction.7 The
synthesis of linear oligomers requires reaction of 1-fluo-
ro-4-nitrobenzene, but this electrophile is insufficiently
reactive under conventional conditions8 with the displace-
ment of fluoride proceeding in low yield (6–11%) for ar-
omatic amines at pressures of up to 0.9 GPa.9 The effect
of pressure on rate is approximately logarithmic and in
this paper we report that respectable yields can be ob-
tained at 1.5 GPa, providing a general, clean and versatile
route to leucoemeraldine oligoanilines of various lengths.
A nitro substituent at either the 2 or 4 position resulted in
no product and only modest yield was obtained with 3-ni-
troaniline. A self-condensation of 4-fluoro-3-nitroaniline
gave no polymer or other substitution products at this
pressure and temperature.
Linear and bent aniline trimers were prepared by high-
pressure reaction of phenylenediamines 4a–c with fluo-
ronitrobenzene 2 under the same conditions (Scheme 2).
Double substitution reaction products 5a–d were obtained
cleanly and in good yields, (Table 2), with the exception
of 1,2-phenylenediamine (4c) which gave a mixture of
single and double substitution products in a ratio of 79:
21. This low proportion of double substitution is presum-
ably due to steric hindrance of the second NH2. Heating
these reactions at 120 °C and ambient pressure for 3 days
was investigated for comparison with high-pressure medi-
ation and invariably resulted in mixtures of single and
Initial investigations established reaction conditions and
the reactivity associated with the nature and position of ar-
omatic substituents. Anilines 1a–e and 4-fluoronitroben-
zene (2a) were reacted at a pressure of 1.5 GPa and 30 °C
SYNTHESIS 2003, No. 16, pp 2511–2517
x
x.
x
x
.
2
0
0
3
Advanced online publication: 14.10.2003
DOI: 10.1055/s-2003-42434; Art ID: F02603SS.pdf
© Georg Thieme Verlag Stuttgart · New York

2512
C. L. Brown et al.
PAPER
H
R2
+
H2N
N
H
F
n
R1
6
2
a
b
H
H
R2
N
N
R2
n
R1
R1 and/or R2 = NO2
R1
7
Scheme 2 Reagents and conditions: (a) Et3N, 1.5 GPa, 30 °C or 40
°C
H
H
R2
N
N
R2
n
R1
R1
8
double substitution products. Hydrogenation of product
5a over Pd on C (10%) resulted in an amine substituted
aniline trimer suitable for further step-wise elongation.4
R
1 and/or R2 = NH2
Scheme 3 Reagents and conditions: (a) Et3N, 1.5 GPa, 30 °C or 40
°C; (b) H2 Pd/C
Table 2 Reaction of Phenylenediamines 4 with Fluoronitroben-
zenes 2
Table 3 Reaction of Oligoanilines 6 with Fluoronitrobenzenes 2
Phe-
nylenedi- zenes
amines
Fluoronitroben- Reaction
Trimer
Yield
(%)
and Reduction
Conditions
Oligo-
aniline
Fluoro-ni-
trobenzene aniline
Nitrooligo- Yield Aminooligo- Yield
(%)
aniline
(%)
4a 1,4- 2a
1.5 GPa, 30 °C,
3 d
5a 1,4-,
R1 = H,
R2 = NO2
98.0
95.2
90.4
76.3
21.0
R1 = H,
6a n = 2 2a
R1 = H,
R2 = NO2
7a n = 2,
R1 = H,
98.6 8a n = 2,
R1 = H,
68.1
R2 = NO2
R2 = NO2
R2 = NH2
4a 1,4- 2b
1.5 GPa, 40 °C,
3 d
5b 1,4-,
R1 = NO2,
R2 = H
R1 = NO2,
R2 = H
6a n = 2 2b
7b n = 2,
R1 = NO2,
R2 = H
97.5 8b n = 2,
R1 = NH2,
68.0
R1 = NO2,
R2 = H
R2 = H
4b 1,3- 2a
1.5 GPa, 30 °C,
3 d
5c 1,3-,
R1 = H,
R2 = NO2
R1 = H,
2c
7c n = 2,
R1 = NO2,
R2 = NO2
8c n = 2,
6a n = 2
100
67.7
67.5
R1 = NO2,
R2 = NO2
R1 = NH2,
R2 = NH2
R2 = NO2
4b 1,3- 2b
1.5 GPa, 40 °C,
3 d
5d 1,3-,
R1 = NO2,
R2 = H
R1 = NO2,
R2 = H
6b n = 3 2a
R1 = H,
R2 = NO2
7d n = 3,
R1 = H,
92.7 8d n = 3,
R1 = H,
R2 = NO2
R2 = NH2
4c 1,2- 2a
1.5 GPa, 30 °C,
3 d
5e 1,2-,
R1 = H,
R2 = NO2
R1 = H,
6b n = 3 2b
7e n = 3,
R1 = NO2,
R2 = H
84.6 8e n = 3,
R1 = NH2,
65.1
66.7
64.6
65.0
66.4
R1 = NO2,
R2 = H
R2 = NO2
R2 = H
6b n = 3 2c
7f n = 3,
98.1 8f n = 3,
R1 = NH2,
Aniline tetramers, pentamers and hexamers have success-
fully been prepared by successive high-pressure SNAr re-
action (1.5 GPa at 30 °C or 40 °C for 3 d) and subsequent
nitro reduction (Scheme 3, Table 3). The larger aniline
oligomers appeared to be slightly less reactive than the
shorter oligomers. Reduction of the nitro-anilines ob-
tained consistently gave the corresponding aniline oligo-
mers 8a–i in approximately 65% yield.
R1 = NO2,
R2 = NO2
R1 = NO2,
R2 = NO2
R2 = NH2
6c n = 4 2a
7g n = 4,
R1 = H,
90.7 8g n = 4,
R1 = H,
R1 = H,
R2 = NO2
R2 = NO2
R2 = NH2
6c n = 4 2b
7h n = 4,
R1 = NO2,
R2 = H
85.9 8h n = 4,
R1 = NH2,
R1 = NO2,
R2 = H
R2 = H
N,N -Bis(4 -aminophenyl)-1,4-quinonenediimine
(9),
prepared using the Wei method,4,5 also reacted with fluo-
ronitrobenzenes 2a–c at elevated pressures to give disub-
stitution products (10a–c) in partially oxidized form
which could be reduced with hydrazine to give the previ-
ously made pentamers 7d–f, (Scheme 4, Table 4). Once
again, hydrogenation of the nitro groups using Pd on C as
catalyst afforded pentamers 8d–f.
6c n = 4 2c
7i n = 4,
93.2 8i n = 4,
R1 = NH2,
R1 = NO2,
R2 = NO2
R1 = NO2,
R2 = NO2
R2 = NH2
Synthesis 2003, No. 16, 2511–2517 © Thieme Stuttgart · New York

PAPER
High-Pressure Synthesis of Oligoanilines
4 -Methoxy-4-nitrodiphenylamine (3b)
The reaction of 4-methoxyaniline (1b) (3.695 g, 0.03 mol) with 1-
fluoro-4-nitrobenzene (2a) (4.656 g, 0.033 mol) in the presence of
Et3N (3.036 g, 0.03 mol) at 1.5 Gpa and 30 °C for 3 d gave a yellow
solid (7.424 g, 100%); mp 151–152 °C (Lit.11 149–150 °C).
2513
F
R2
H2N
N
N
NH2
+
R1
9
2
1H NMR (200 MHz, DMSO-d6): = 6.88 (d, J = 9.6 Hz, 2 H, =CH),
6.98 (d, J = 9.8 Hz, 2 H, =CH), 7.18 (d, J = 8.8 Hz, 2 H, =CH), 8.05
(d, J = 8.8 Hz, 2 H, =CH), 9.12 (s, 1 H, NH).
a
13C NMR (50 MHz, DMSO-d6): = 56.0, 113.0, 115.5, 124.7,
126.9, 133.2, 137.8, 152.8, 156.8.
H
N
H
N
R2
R2
N
N
R1
R1
10
4,3 -Dinitrodiphenylamine (3d)
The reaction of 3-nitroaniline (1d) (4.144 g, 0.03 mol) with 1-fluo-
ro-4-nitrobenzene (2a) (4.656 g, 0.033 mol) in the presence of Et3N
(3.036 g, 0.03 mol) at 1.5 Gpa and 30 °C for 3 d gave a pale-yellow
solid (2.530 g, 32.6%);mp 248–249 °C (Lit.12 247–248 °C).
b
H
N
H
N
H
N
H
N
1H NMR (200 MHz, DMSO-d6): = 6.78 (d, J = 8.0 Hz, 1 H, =CH),
7.20 (d, J = 8.0 Hz, 2 H, =CH), 7.74 (dd, J = 8.0 Hz, 7.8 Hz, 1 H,
=CH), 8.02 (d, J = 8.0 Hz, 1 H, =CH), 8.18 (d, J = 8.0 Hz, 2 H,
=CH), 8.20 (s, 1 H, =CH), 9.65 (s, 1 H, NH).
R2
R2
R1
R1
7
13C NMR (50 MHz, DMSO-d6): = 107.7, 110.4, 115.5, 120.6,
124.0, 126.4, 126.7, 130.6, 149.4, 150.8.
Scheme 4 Reagents and conditions: (a) Et3N, 1.5 GPa, 30 °C or 40
°C; (b) H2NNH2
N,N -Bis(4 -nitrophenyl)-1,4-benzenediamine (5a)
Table 4 Reaction of ‘Wei Trimer’ 9 with Fluoronitrobenzenes 2 and
Reduction
The reaction of 1,4-phenylenediamine (4a) (2.704 g, 0.025 mol)
with 1-fluoro-4-nitrobenzene (2a) (7.055 g, 0.055 mol) in the pres-
ence of Et3N (5.060 g, 0.05 mol) at 1.5 Gpa and 30 °C for 3 d gave
a brown solid (8.572 g, 98.0%); mp 273–274 °C.
Fluoro-
nitrobenzene
Partially oxi- Yield
dized pentamer (%)
Reduced
pentamer
Yield
(%)
IR (KBr): 3372, 3304, 3106, 1595, 1521, 1495, 1475, 1400, 1305,
1183, 1111, 832, 748, 486 cm–1.
1H NMR (200 MHz, DMSO-d6): = 7.04 (d, J = 9.4 Hz, 4 H, =CH),
7.28 (s, 4 H, =CH), 8.10 (d, 4 H, J = 8.8 Hz, =CH), 9.31 (s, 2 H,
NH).
13C NMR (50 Hz, DMSO-d6): = 113.8, 123.1, 126.9, 136.4, 138.4,
151.75.
2a
10a
58.7
54.6
99.8
7d
83.2
83.8
84.6
R1 = H,
R2 = NO2
R1 = H,
R2 = NO2
R1 = H,
R2 = NO2
2b
10b
7e
R1 = NO2,
R2 = H
R1 = NO2,
R2 = H
R1 = NO2,
R2 = H
UV/Vis (EtOH): max = 203.2, 264.0, 404.8 nm.
2c
10c
7f
R1 = NO2,
R2 = NO2
R1 = NO2,
R2 = NO2
R1 = NO2,
R2 = NO2
Anal. Calcd for C18H14N4O4: C, 61.71; H, 4.03; N, 16.00; O, 18.27.
Found: C, 61.35; H, 4.09; N, 15.70.
N,N -Bis(2 -nitrophenyl)-1,4-benzenediamine (5b)
The reaction of 1,4-phenylenediamine (4a) (2.704 g, 0.025 mol)
with 1-fluoro-2-nitrobenzene (2b) (7.055 g, 0.05 mol) in the pres-
ence of Et3N (5.06 g, 0.05 mol) at 1.5 Gpa and 40 °C for 3 d gave a
red solid (8.339 g, 95.2%); mp 238–239 °C.
High Pressure Reactions; General Procedure
Aromatic amine, fluoronitrobenzene (1.1 or 2.2 equiv) and Et3N
(1.0 or 2.0 equiv) in anhyd DMF (1.0–5.0 mL) were mixed together
in a teflon reaction vessel. This vessel was placed in the reaction
chamber of a PSIKA dual piston cylinder 2.0 GPa reactor filled with
castor oil–MeOH (85:15) and subjected to 1.5 GPa of pressure at 30
°C or 40 °C for 3 d. The reaction mixture was then poured into water
(50 mL) and the precipitate filtered under vacuum, washed with wa-
ter and dried (vacuum).
IR (KBr): 3448, 3328, 3235, 1611, 1575, 1510, 1494, 1429, 1399,
1346, 1326, 1260, 1221, 1147, 741, 518 cm–1.
1H NMR (200 MHz, DMSO-d6): = 6.90 (t, J = 7.4 Hz, 2 H, =CH),
7.25 (d, J = 9.4 Hz, 2 H, =CH), 7.39 (s, 4 H, =CH), 7.55 (t, J = 8.2
Hz, 2 H, =CH), 8.14 (d, J = 8.8 Hz, 2 H, =CH), 9.42 (s, 2 H, NH).
13C NMR (50 MHz, DMSO-d6): = 117.6, 118.8, 125.5, 125.6,
125.9, 126.9, 136.7, 142.8.
4-Nitrodiphenylamine (3a)
The reaction of aniline (1a) (4.657 g, 0.05 mol) with 1-fluoro-4-ni-
trobenzene (2a) (7.761 g, 0.055 mol) in the presence of Et3N (5.060
g, 0.05 mol) at 1.5 Gpa and 30 °C for 3 d gave a yellow solid (10.256
g, 95.8%).; mp 133–134 °C (Lit.10 134 °C).
UV/Vis (EtOH): max = 205.1, 220.5, 247.4, 285.8, 436.8 nm.
Anal. Calcd for C18H14N4O4: C, 61.71; H, 4.03; N, 16.00; O, 18.27.
Found: C, 61.57; H, 4.02; N, 15.89.
1H NMR (200 MHz, DMSO-d6): = 7.06 (d, J = 8.8 Hz, 2 H, =CH),
7.10 (t, J = 7.4 Hz, 1 H, =CH), 7.24 (d, J = 7.2 Hz, 2 H, =CH), 7.39
(t, J = 8.2 Hz, 2 H, =CH), 8.09 (d, J = 9.4 Hz, 2 H, =CH), 9.31 (s, 1
H, NH).
N,N -Bis(4 -nitrophenyl)-1,3-benzenediamine (5c)
The reaction of 1,3-phenylenediamine (4b) (2.163 g, 0.02 mol) with
1-fluoro-4-nitrobenzene (2a) (5.930 g, 0.042 mol) in the presence of
Et3N (4.048 g, 0.04 mol) at 1.5 Gpa and 30 °C for 3 d gave a brown
solid (6.330 g, 90.4%); mp 228–230 °C.
13C NMR (50 MHz, DMSO-d6): = 114.1, 121.5, 124.1, 126.8,
130.1, 138.6, 140.7, 151.5.
IR (KBr): 3359, 3150, 1584, 1541, 1500, 1400, 1303, 1181, 1165,
1112, 830, 749, 483 cm–1.
Synthesis 2003, No. 16, 2511–2517 © Thieme Stuttgart · New York

2514
C. L. Brown et al.
PAPER
N,N -Bis(2 -nitrophenyl)-4,4 -diaminodiphenylamine (7b)
The reaction of 4,4 -diaminodiphenylamine (6a) (3.985 g, 0.020
mol) with 1-fluoro-2-nitrobenzene (2b) (6.208 g, 0.044 mol) in the
presence of Et3N (4.250 g, 0.042 mol) at 1.5 Gpa and 40 °C for 3 d
gave a brown solid (8.610 g, 97.5%); mp 208–210 °C.
1H NMR (200 MHz, DMSO-d6): = 6.97 (d, J = 8.0 Hz, 2 H, =CH),
7.09 (s, 1 H, =CH), 7.13 (d, J = 8.8 Hz, 4 H, =CH), 7.37 (t, J = 8.0
Hz, 1 H, =CH), 8.13 (d, J = 9.6 Hz, 4 H, =CH), 9.36 (s, 2 H, NH).
13C NMR (50 Hz, DMSO-d6): = 112.6, 114.6, 115.7, 126.8, 131.2,
138.9, 142.0, 151.0.
IR (KBr): 3405, 3361, 3345, 3111, 1614, 1570, 1507, 1437, 1412,
1350, 1322, 1262, 1239, 1211, 1147, 1036, 744, 512 cm–1.
1H NMR (200 MHz, DMSO-d6): = 6.80 (d, J = 8.8 Hz, 2 H, =CH),
7.06 (d, J = 8.8 Hz, 2 H, =CH), 7.19 (dd, J = 8.8 Hz, 8 H, 5.8 Hz,
=CH), 7.47(t, J = 8.8 Hz, 2 H, =CH), 8.11 (d, J = 8.8 Hz, 2 H, =CH),
8.39 (s, 1 H, NH), 9.39 (s, 2 H, NH).
UV/Vis (EtOH): max = 200.6, 253.1, 396.5 nm.
Anal. Calcd for C18H14N4O4: C, 61.71; H, 4.03; N, 16.00; O, 18.27.
Found: C, 62.08; H, 4.07; N, 16.29.
N,N -Bis(2 -nitrophenyl)-1,3-benzenediamine (5d)
The reaction of 1,3-phenylenediamine (4b) (2.704 g, 0.025 mol)
with 1-fluoro-2-nitrobenzene (2b) (7.055 g, 0.05 mol) in the pres-
ence of Et3N (5.06 g, 0.05 mol) at 1.5 Gpa and 40 °C for 3 d gave a
brown solid (6.686 g, 72.3%); mp 156–157 °C.
13C NMR (50 MHz, DMSO-d6): = 116.8, 117.6, 118.3, 126.8,
127.1, 131.3, 132.9, 136.8, 142.0, 144.4.
UV/Vis (EtOH): max = 206.4, 303.7, 438.1 nm.
IR (KBr): 3455, 3356, 3230, 1598, 1573, 1522, 1493, 1348, 1265,
1149, 740, 518 cm–1.
1H NMR (200 MHz, DMSO-d6): = 6.92 (t, J = 8.0 Hz, 2 H, =CH),
7.13 (d, J = 8.2 Hz, 2 H, =CH), 7.27 (s, 1 H, =CH), 7.39 (m, 3 H,
=CH), 7.55 (t, J = 7.4 Hz, 2 H, =CH), 8.12 (d, J = 8.0 Hz, 2 H, =CH),
9.35 (s, 2 H, NH).
Anal. Calcd for C24H19N5O4: C, 65.30; H, 4.34; N, 15.87; O, 14.50.
Found: C, 65.22; H, 4.31; N, 15.85.
N,N -Bis(2 ,4 -dinitrophenyl)-4,4 -diaminodiphenylamine (7c)
The reaction of 4,4 -diaminodiphenylamine (6a) (3.985 g, 0.02 mol)
with 1-fluoro-2,4-dinitrobenzene (2c) (7.816 g, 0.055 mol) in the
presence of Et3N (4.086 g, 0.04 mol) at 1.5 Gpa and 30 °C for 3 d
gave a brown solid (10.63 g, 100%); mp 249–250 °C.
13C NMR (50 MHz, DMSO-d6): = 117.8, 118.2, 119.2, 119.6,
126.9, 131.1, 134.9, 136.5, 141.4, 141.9.
IR (KBr): 3407, 3327, 3107, 1616, 1511, 1417, 1314, 1224, 1143,
1126, 1061, 929, 830, 742, 621, 508 cm–1.
1H NMR (200 MHz, DMSO-d6): = 7.07 (d, J = 9.4 Hz, 2 H, =CH),
7.26 (s, 8 H, =CH), 8.22 (dd, J = 9.4 Hz, 2.2 Hz, 2 H, =CH), 8.63 (s,
1 H, NH), 8.89 (d, J = 2.1 Hz, 2 H, =CH), 10.11 (s, 2 H, NH).
13C NMR (50 MHz, DMSO-d6): = 117.5, 118.3, 124.2, 128.0,
130.0, 130.4, 131.3, 136.6, 142.8, 148.1.
UV/Vis (EtOH): max = 206.4, 229.4, 255.0, 424.0 nm.
Anal. Calcd for C18H14N4O4: C, 61.71; H, 4.03; N, 16.00; O, 18.27.
Found: C, 61.71; H, 3.96; N, 15.79.
N,N -Bis(4 -nitrophenyl)-1,2-benzenediamine (5e)
The reaction of 1,2-phenylenediamine (4c) (2.163 g, 0.02 mol) with
1-fluoro-4-nitrobenzene (2a) (5.930 g, 0.042 mol) in the presence of
Et3N (4.048 g, 0.04 mol) at 1.5 GPa and 30 °C for 3 d gave an or-
ange solid (1.5 g, 21.4%); mp 295–296 °C.
UV/Vis: max = 203.5, 373.8 nm.
Anal. Calcd for C24H17N7O8: C, 54.24; H, 3.22; N, 18.45; O, 24.09.
Found: C, 53.68; H, 3.20%; N, 18.15.
IR (KBr): 3443, 3332, 3194, 3104, 3079, 1604, 1584, 1528, 1497,
1486, 1461, 1343, 1308, 1298, 1184, 1113, 838, 750, 454 cm–1.
1H NMR (200 MHz, DMSO-d6): = 6.89 (d, J = 8.6 Hz, 4 H, =CH),
7.27 (d, J = 3.6 Hz, 2 H, =CH), 7.44 (t, J = 3.6 Hz, 2 H, =CH), 8.03
(d, J = 9.4 Hz, 4 H, =CH), 8.91 (s, 2 H, NH).
13C NMR (50 Hz, DMSO-d6): = 114.1, 125.2, 126.1, 126.5, 134.3,
138.4, 152.0.
N ,N -Bis(4 -nitrophenyl)-N,N -bis(4 -aminophenyl)-1,4-ben-
zenediamine (7d)
The reaction of N,N -bis(4 -aminophenyl)-1,4-benzenediamine (6b)
(2.90 g, 10.0 mmol) with 1-fluoro-4-nitrobenzene (2a) (3.10 g, 22
mmol) in the presence of Et3N (2.13 g, 21 mmol) at 1.5 Gpa and 40
°C for 3 d gave a brown solid (4.93 g, 92.7%); mp 215–217 °C.
UV/Vis (EtOH): max = 243.2, 386.6 nm.
IR (KBr): 3356, 3128, 1596, 1506, 1471, 1400, 1297, 1182, 1112,
824, 512 cm–1.
1H NMR (200 MHz, DMSO-d6): = 6.88 (d, J = 8.8 Hz, 4 H, =CH),
7.05 (m, 12 H, =CH), 7.97 (s, 2 H, NH), 8.04 (d, J = 9.4 Hz, 4 H,
=CH), 9.09 (s, 2 H, NH).
13C NMR (50 MHz, DMSO-d6): = 112.9, 116.8, 120.4, 124.7,
130.0, 131.2, 137.3, 137.5, 142.6, 153.1.
Anal. Calcd for C18H14N4O4: C, 61.71; H, 4.03; N, 16.00; O, 18.27.
Found: C, 61.63; H, 4.08; N, 16.22.
N,N -Bis(4 -nitrophenyl)-4,4 -diaminodiphenylamine (7a)
The reaction of 4,4 -diaminodiphenylamine (6a) (4.981 g, 0.025
mol) with 1-fluoro-4-nitrobenzene (2a) (7.765 g, 0.055 mol) in the
presence of Et3N (5.060 g, 0.05 mol) at 1.5 Gpa and 40 °C for 3 d
gave a brown solid (10.88 g, 98.6%); mp 191.5–192.5 °C.
UV/Vis (EtOH): max = 207.2, 310.6, 405.4 nm.
IR (KBr): 3386, 3310, 3105, 1595, 1499, 1474, 1400, 1293, 1184,
1112, 827, 749, 512, 489 cm–1.
1H NMR (200 MHz, DMSO-d6): = 6.91 (d, J = 8.8 Hz, 4 H, =CH),
7.13 (s, 8 H, =CH), 8.05 (d, J = 8.8 Hz, 4 H, =CH), 8.23 (s, 1 H,
NH), 9.13 (s, 2 H, NH).
Anal. Calcd for C30H24N6O4: C, 67.68; H, 4.54; N, 15.79; O, 12.02.
Found: C, 67.74; H, 4.46; N, 15.67.
N ,N -Bis(2 -nitrophenyl)-N,N -bis(4 -aminophenyl)-1,4-ben-
zenediamine (7e)
The reaction of N,N -bis(4 -aminophenyl)-1,4-benzenediamine (6b)
(0.435 g, 1.5 mmol) with 1-fluoro-2-nitrobenzene (2b) (0.466 g, 3.3
mmol) in the presence of Et3N (0.319 g, 3.15 mmol) at 1.5 Gpa and
40 °C for 3 d gave a black solid (0.675 g, 84.6%); mp 198–200 °C.
13C NMR (50 MHz, DMSO-d6): = 113.0, 118.3, 124.3, 126.9,
132.4, 137.7, 141.0, 152.7.
UV/Vis (EtOH): max = 203.2, 299.2, 404.8 nm.
Anal. Calcd for C24H19N5O4: C, 65.30; H, 4.34; N, 15.87; O, 14.50.
Found: C, 65.44; H, 4.36; N, 15.52.
IR (KBr): 3398, 3111, 1617, 1571, 1528, 1497, 1430, 1351, 1318,
1253, 1146, 1037, 797, 735, 508 cm–1.
1H NMR (200 MHz, DMSO-d6): = 6.77 (dd, J = 8.2, 7.2 Hz, 2 H,
=CH), 7.09 (m, 12 H, =CH), 7.15 (d, J = 8.8 Hz, 2 H, =CH), 7.46
Synthesis 2003, No. 16, 2511–2517 © Thieme Stuttgart · New York

PAPER
High-Pressure Synthesis of Oligoanilines
2515
(dd, J = 7.4, 7.2 Hz, 2 H, =CH), 8.07 (s, 2 H, NH), 8.09 (d, J = 9.6
Hz, 2 H, =CH), 9.38 (s, 2 H, NH).
Anal. Calcd for C36H29N7O4: C, 69.33; H, 4.69; N, 15.72; O, 10.26.
Found: C, 69.23; H, 4.67; N, 15.57.
13C NMR (50 MHz, DMSO-d6): = 116.5, 116.8, 117.4, 120.5,
126.8, 127.4, 129.8, 132.6, 136.8, 137.2, 143.7, 144.7.
N ,N -Bis(2 ,4 -dinitrophenyl)-N,N -bis(4 -aminophenyl)-
4,4 -diaminodiphenylamine (7i)
UV/Vis (EtOH): max = 202.2, 313.6, 439.0 nm.
The reaction of N,N -bis(4 -aminophenyl)-4,4 -diaminodipheny-
lamine (6c) (1.00 g, 0.0026 mol) with 1-fluoro-2,4-dinitrobenzene
(2c) (1.024 g, 0.0055 mol) in the presence of Et3N (0.53 g, 0.0052
mol) at 1.5 GPa and 30 °C for 3 d gave a brown solid (1.743 g,
93.2%); mp 196–200 °C.
Anal. Calcd for C30H24N6O4: C, 67.68; H, 4.54; N, 15.79; O, 12.02.
Found: C, 67.33; H, 4.51; N, 15.66.
N ,N -Bis(2 ,4 -nitrophenyl)-N,N -bis(4 -amino-phenyl)-1,4-
benzenediamine (7f)
The reaction of N,N -bis(4 -aminophenyl)-1,4-benzenediamine (6b)
(2.50 g, 8.6 mmol) with 1-fluoro-2,4-dinitrobenzene (2c) (3.37 g, 18
mmol) in the presence of Et3N (1.83 g, 18 mmol) at 1.5 GPa, 30 °C
for 3 d gave a brown solid (5.26 g, 98.1%); mp 241–242 °C.
IR (KBr): 3384, 3333, 3101, 1615, 1502, 1420, 1330, 1127, 1060,
928, 820, 742, 508 cm–1.
1H NMR (200 MHz, DMSO-d6): = 7.04 (s, 16 H, =CH), 7.16 (d,
J = 8.0 Hz, 2 H, =CH), 7.82 (s, 1 H, NH), 8.08 (s, 2 H, NH), 8.20 (d,
J = 7.2 Hz, 2 H, =CH), 8.88 (s, 2 H, =CH), 10.07 (s, 2 H, NH).
13C NMR (50 MHz, DMSO-d6): = 115.7, 117.5, 118.5, 121.8,
124.2, 127.9, 130.3, 131.0, 135.2, 136.3, 139.4, 145.5, 148.3.
IR (KBr): 3373, 3110, 1616, 1508, 1425, 1307, 1128, 1059, 925,
806, 743, 503 cm–1.
1H NMR (200 MHz, DMSO-d6): = 7.04 (d, J = 8.8 Hz, 2 H, =CH),
7.11 (s, 10 H, =CH), 7.19 (d, J = 8.8 Hz, 2 H, =CH), 8.20 (d, J = 6.6
Hz, 2 H, =CH), 8.22 (s, 2 H, NH), 8.90 (s, 2 H, =CH), 10.09 (s, 2 H,
NH).
UV/Vis (EtOH): max = 204.8, 252.2, 336.6 nm.
Anal. Calcd for C36H27N9O8: C, 60.62; H, 3.82; N, 17.68; O, 17.95.
Found: C, 60.00; H, 4.02; N, 17.64.
13C NMR (50 MHz, DMSO-d6): = 116.2, 117.5, 120.9, 124.2,
128.0, 128.4, 130.4, 131.1, 136.4, 147.0, 144.8, 148.3.
N ,N -Bis(4 -nitrophenyl)-N,N -bis(4 -amino-phenyl)-1,4-
quinonediimine (10a)
The reaction of N,N -bis(4 -aminophenyl)-1,4-quinonediimine (9)
(1.442 g, 0.005 mol) with 1-fluoro-4-nitrobenzene (2a) (1.482 g,
0.0105 mol) in the presence of Et3N (1.012 g, 0.01 mol) at 1.5 Gpa
and 40 °C for 3 d gave a black solid (1.557 g, 58.7%); mp > 375 °C.
UV/Vis (EtOH): max = 204.8, 334.1 nm.
Anal. Calcd for C30H22N8O8: C, 57.87; H, 3.56; N, 18.00; O, 20.56.
Found: C, 57.72; H, 3.47; N, 17.77.
N ,N -Bis(4 -nitrophenyl)-N,N -bis(4 -amino-phenyl)-4,4 -di-
aminodiphenylamine (7g)
IR (KBr): max = 3355, 3050, 1593, 1500, 1400, 1297, 1180, 1110,
827, 750, 509 cm–1.
The reaction of N,N -bis(4 -aminophenyl)-4,4 -diaminodipheny-
lamine (6c) (2.0 g, 5.24 mmol) with 1-fluoro-4-nitrobenzene (2a)
(1.627 g, 11.50 mmol) in the presence of Et3N (1.114 g, 11.01 mol)
at 1.5 Gpa and 40 °C for 3 d gave a black solid (2.965 g, 90.7%); mp
151–153 °C.
1H NMR (200 MHz, DMSO-d6): = 6.88 (d, J = 8.8 Hz, 4 H, =CH),
7.05 (m, 12 H, =CH), 7.99 (d, J = 9.8 Hz, 2 H), 8.04 (d, J = 8.8 Hz,
2 H, =CH), 9.08 (s, 2 H, NH).
13C NMR (50 MHz, DMSO-d6): = 112.9, 116.8, 120.2, 124.7,
127.0, 131.2, 137.3, 137.5, 142.6, 153.0.
IR (KBr): 3373, 3197, 3130, 1596, 1506, 1294, 1182, 1111, 825,
509 cm–1.
UV/Vis (EtOH): max = 201.9, 309.4, 401.6 nm.
1H NMR (200 MHz, DMSO-d6): = 6.87 (d, J = 8.0 Hz, 4 H, =CH),
7.00 (m, 16 H, =CH), 7.71 (s, 1 H, NH), 7.88 (s, 2 H, NH), 8.04 (d,
J = 8.0 Hz, 4 H, =CH), 9.08 (s, 2 H, NH).
Anal. Calcd for C30H22N6O4: C, 67.91; H, 4.18; N, 15.84; O, 12.06.
Found: C, 67.83; H, 4.21; N, 15.80.
N ,N -Bis(2 -nitrophenyl)-N,N -bis(4 -amino-phenyl)-1,4-
quinonediimine (10b)
The reaction of N,N -bis(4 -aminophenyl)-1,4-quinonediimine (9)
(0.432 g, 1.5 mmol) with 1-fluoro-2-nitrobenzene (2b) (0.466 g, 3.3
mmol) in the presence of Et3N (0.319 g, 3.15 mmol) at 1.5 Gpa and
40 °C for 3 d gave a black solid (0.434 g, 54.6%); mp > 375 °C.
13C NMR (50 MHz, DMSO-d6): = 112.8, 116.3, 118.5, 120.8,
124.8, 127.0, 130.9, 136.0, 137.4, 139.1, 143.1, 153.1.
UV/Vis (EtOH): max = 204.5, 318.8, 404.2 nm.
Anal. Calcd for C36H29N7O4: C, 69.33; H, 4.69; N, 15.72; O, 10.26.
Found: C, 69.28; H, 4.68; N, 15.70.
IR (KBr): 3383, 3294, 3050, 1614, 1572, 1504, 1401, 1299, 1260,
1146, 825, 509 cm–1.
1H NMR (200 MHz, DMSO-d6): = 6.79 (t, J = 8.2 Hz, 2 H, =CH),
7.07 (m, 12 H, =CH), 7.17 (d, J = 8.8 Hz, 2 H, =CH), 7.47 (t, J = 8.0
Hz, 2 H, =CH), 8.11 (d, J = 8.8 Hz, 2 H, =CH), 9.39 (s, 2 H, NH).
13C NMR (50 MHz, DMSO-d6): = 115.6, 116.6, 116.8, 117.4,
120.5, 126.8, 127.4, 129.8, 132.6, 136.8, 137.2, 143.8, 144.8.
N ,N -Bis(2 -nitrophenyl)-N,N -bis(4 -amino-phenyl)-4,4 -di-
aminodiphenylamine (7h)
The reaction of N,N -bis(4 -aminophenyl)-4,4 -diaminodiphen-
ylamine (6c) (1.144 g, 3 mmol) with 1-fluoro-2-nitrobenzene (2b)
(0.931 g, 6.6 mmol) in the presence of Et3N (0.637 g, 6.3 mol) at 1.5
Gpa and 40 °C for 3 d gave a black solid (1.607 g, 85.9%); mp 276–
278 °C.
IR (KBr): 3355, 3133, 1615, 1572, 1402, 1347, 1259, 1145, 1075,
1037, 820, 740, 510 cm–1.
1H NMR (200 MHz, DMSO-d6): = 6.77 (t, J = 7.2 Hz, 2 H, =CH),
7.02 (s, 16 H, =CH), 7.12 (d, J = 8.0 Hz, 2 H, = CH), 7.46 (t, J = 8.0
Hz, 2 H, =CH), 7.76 (s, 1 H, NH), 7.97 (s, 2 H, NH), 8.10 (d, J = 8.0
Hz, 2 H, =CH), 9.38 (s, 2 H, NH).
UV/Vis (EtOH): max = 206.4, 313.9, 434.1 nm.
Anal. Calcd for C30H22N6O4: C, 67.91; H, 4.18; N, 15.84; O, 12.06.
Found: C, 67.78; H, 4.35; N, 15.76.
N ,N -Bis(2 ,4 ,-dinitrophenyl)-N,N -bis(4 -amino-phenyl)-
1,4-quinonediimine (10c)
The reaction of N,N -bis(4 -aminophenyl)-1,4-quinonediimine (9)
(1.442 g, 0.005 mol) with 1-fluoro-2,4-dinitrobenzene (2c) (1.954
g, 0.0105 mol) in the presence of Et3N (1.012 g, 0.01 mol) at 1.5
Gpa and 30 °C for 3 d gave a brown solid (3.095 g, 99.8%); mp 243–
245 °C.
13C NMR (50 MHz, DMSO-d6): = 116.7, 117.3, 126.8, 129.9,
132.5, 136.8, 144.8.
UV/Vis (EtOH): max = 203.5, 321.3, 435.2 nm.
Synthesis 2003, No. 16, 2511–2517 © Thieme Stuttgart · New York

2516
C. L. Brown et al.
PAPER
IR (KBr): 3418, 3104, 1617, 1587, 1511, 1400, 1334, 1143, 832,
742, 505 cm–1.
1H NMR (200 MHz, DMSO-d6): = 6.92–7.26 (m, 12 H, =CH),
7.44 (d, 2 H, =CH), 8.23 (d, 2 H, =CH), 8.90 (s, 2 H, =CH), 10.18
(s, 2 H, NH).
1H NMR (200 MHz, DMSO-d6): = 4.60 (s, 4 H, NH2), 6.49 (d,
J = 8.8 Hz, 4 H, =CH), 6.76 (s, 12 H, =CH), 7.08 (s, 2 H, NH), 7.21
(s, 1 H, NH).
13C NMR (50 MHz, DMSO-d6): = 115.6, 117.3, 118.8, 120.7,
134.7, 137.4, 139.5, 143.0.
13C NMR (50 MHz, DMSO-d6): = 117.8, 122.7, 124.1, 127.0,
UV/Vis (EtOH) : max = 206.4, 311.4, 598.4 nm.
130.4, 132.0, 135.5, 137.1, 147.3, 148.9, 158.8.
Anal. Calcd for C24H23N5: C, 75.61; H, 6.08; N, 18.38. Found: C,
75.56; H, 6.01; N, 18.29.
UV/Vis (EtOH): max = 204.8, 344.3 nm.
Anal. Calcd. for C30H20N8O8: C, 58.06; H, 3.25; N, 18.06; O, 20.63.
Found: C, 57.99; H, 3.35; N, 17.78.
N,N -Bis(2 -aminophenyl)-4,4 -diaminodiphenylamine (8b)
Reduction of N,N -bis(2 -nitrophenyl)-4,4 -diaminodiphenylamine
(7b) (0.442 g, 1.0 mmol) gave a black tetramer product (0.260 g,
68.0%); mp 162 °C.
N ,N -Bis(4 -nitrophenyl)-N,N -bis(4 -amino-phenyl)-1,4-ben-
zenediamine (7d)
N ,N -Bis(4 -nitrophenyl)-N,N -bis(4 -aminophenyl)-1,4-qui-
nonediimine (10a) (0.2 g, 0.377 mmol) was refluxed in 10 mL of
35% aq hydrazine for 4 h. The mixture was then cooled to r.t. and
filtered. The solid was washed with plenty of deionized water and
dried under vacuum to give 7d (0.167g, 83.2%).
IR (KBr): 3373, 3050, 1600, 1513, 1400, 1307, 1261, 1220, 817,
512 cm–1.
1H NMR (200 MHz, DMSO-d6): = 4.72 (b s, 4 H, NH2), 6.53 (br
s, 2 H, NH), 6.72 (br s, 10 H, =CH), 6.87 (br s, 6 H, =CH), 7.23 (s,
1 H, NH).
13C NMR (50 MHz, DMSO-d6): = 115.7, 117.3, 118.6, 120.2,
122.7, 127.1, 130.9, 138.0, 138.4, 141.0.
N ,N -Bis(2 -nitrophenyl)-N,N -bis(4 -amino-phenyl)-1,4-ben-
zenediamine (7e)
N ,N -Bis(2 -nitrophenyl)-N,N -bis(4 -aminophenyl)-1,4-qui-
nonediimine (10b) (0.2 g, 0.377 mmol) was refluxed in 10 mL of
35% aq hydrazine for 4 h. The mixture was then cooled to r.t. and
filtered. The solid was washed with plenty of deionized water and
dried under vacuum to give 7e (0.168 g, 83.8%).
UV/Vis (EtOH): max = 203.7, 313.8, 615.8 nm.
Anal. Calcd for C24H23N5: C, 75.61; H, 6.08; N, 18.38. Found: C,
75.45; H, 6.01; N, 18.10%.
N,N -Bis(2 ,4 -diaminophenyl)-4,4 -diaminodiphenylamine
(8c)
Reduction of N,N -bis(2 ,4 -dinitrophenyl)-4,4 -diaminodiphenyl-
amine (7c) (0.531 g, 1.0 mmol) gave a black product (0.279 g,
67.7%); mp > 375 °C.
N ,N -Bis(2 ,4 -nitrophenyl)-N,N -bis(4 -aminophenyl)-1,4-
benzenediamine (7f)
N ,N -Bis(2 ,4 -nitrophenyl)-N,N -bis(4 -aminophenyl)-1,4-qui-
nonediimine (10c) (0.5 g, 0.806 mmol) was refluxed in 15 mL of
35% aq hydrazine for 4 h. The mixture was then cooled to r.t. and
filtered. The solid was washed with plenty of deionized water and
dried under vacuum to give 7f (0.425g, 84.6%).
IR (KBr): 3333, 3190, 1615, 1500, 1250, 820 cm–1.
1H NMR (200 MHz, DMSO-d6): = 4.49 (br s, 6 H, NH2), 5.85 (s,
2 H, NH2), 6.01 (s, 2 H, NH), 6.30 (s, 1 H, NH), 6.47–6.94 (m, 14
H, =CH).
13C NMR (50 MHz, DMSO-d6): = 101.5, 104.3, 114.6, 115.1,
118.9, 127.4, 128.0, 145.2, 145.5, 146.8.
General Procedure for Hydrogenation
In a 250 mL pressure bottle was placed the nitrophenyl compound,
MeOH (100–200 mL) and 10% by weight of 10% Pd on carbon.
The bottle was attached to a Parr Pressure Reaction Apparatus and
flushed 3 times with H2. The reaction vessel was pressurized with
H2 gas to approximately 40 psi and the mixture was hydrogenated
until the pressure remained constant. After reduction was complete
(about 2–3 d), the solution was filtered and the solvent was evapo-
rated to give black solid.
UV/Vis (EtOH): max = 209.0, 301.1, 489.3, 674.9 nm.
MS (ESI): m/z (%) = 411.21 (9.33) [MH+], calcd 412.51.
Anal. Calcd for C24H25N7: C, 70.05; H, 6.12; N, 23.84. Found: C,
66.30; H, 5.60; N, 21.53.
N ,N -Bis(4 -aminophenyl)-N,N -bis(4 -aminophenyl)-1,4-
benzenediamine (8d)
Reduction of N ,N -bis(4 -nitrophenyl)-N,N -bis(4 -aminophe-
nyl)-1,4-benzenediamine (7d) (0.15 g, 0.28 mmol) gave a black
product (0.090 g, 67.5%); mp 192–195 °C.
N,N -Bis(4 -aminophenyl)-1,4-benzenediamine (6b)
Reduction of N,N -bis(4-nitrophenyl)-1,4-benzenediamine (5a) (1.0
g, 2.85 mmol) gave a black product (0.712 g, 85.9%); mp 197–198
°C (Lit.4 198 °C).
IR (KBr): 3391, 3174, 1600, 1506, 1400, 1300, 1154, 820, 511
cm–1.
IR (KBr): 3363, 3198, 1600, 1517, 1399, 1288, 1262, 1229, 1167,
821, 563, 506 cm–1.
1H NMR (200 MHz, DMSO-d6): = 4.79 (br s, 4 H, NH2), 6.52 (br
s, 4 H, NH), 6.87 (br s, 20 H, =CH).
1H NMR (200 MHz, DMSO-d6): = 4.58 (s, 4 H, NH2), 6.48 (d,
J = 8.0 Hz, 4 H, =CH), 6.71 (s, 8 H, =CH), 7.00 (s, 2 H, NH).
13C NMR (50 MHz, DMSO-d6): = 112.8, 115.6, 116.8, 117.2,
120.3, 121.1, 124.6, 1127.0, 133.5, 137.3.
13C NMR (50 MHz, DMSO-d6): = 115.6, 117.7, 120.2, 135.0,
138.6, 142.7.
UV/Vis (EtOH): max = 207.7, 311.4, 600.0 nm.
UV/Vis (EtOH): max = 203.7, 304.8, 568.5 nm.
Anal. Calcd for C30H28N6: C, 76.30; H, 5.98; N, 17.80. Found: C,
76.06; H, 5.90; N, 17.78.
N,N -Bis(4 -aminophenyl)-4,4 -diaminodiphenylamine (8a)
Reduction of N,N -bis(4 -nitrophenyl)-4,4 -diaminodiphenylamine
(7a) (2.0 g, 4.5 mmol) gave a black product (1.221 g, 68.1%); mp
206–207 °C.
N ,N -Bis(2 -aminophenyl)-N,N -bis(4 -aminophenyl)-1,4-
benzenediamine (8e)
Reduction of N ,N -bis(2 -nitrophenyl)-N,N -bis(4 -aminophe-
nyl)-1,4-benzenediamine (7e, 0.15 g, 0.28 mmol) gave a black
product (0.087 g, 65.1%); mp 201–203 °C.
IR (KBr): 3373, 3050, 1600, 1513, 1400, 1307, 1261, 1220, 817,
512 cm–1.
Synthesis 2003, No. 16, 2511–2517 © Thieme Stuttgart · New York

PAPER
High-Pressure Synthesis of Oligoanilines
2517
IR (KBr): 3388, 3332, 3102, 1618, 1508, 1400, 1253, 815, 619, 509,
455 cm–1.
13C NMR (50 MHz, DMSO-d6): = 115.7, 117.3, 118.6, 118.8,
120.3, 122.8, 130.8, 137.8, 138.0, 138.1, 138.5, 141.0.
1H NMR (200 MHz, DMSO-d6): = 4.40 (br s, 4 H, NH2), 4.56 (br
s, 4 H, NH2), 5.80 (d, J = 8.0 Hz, 2 H, =CH), 5.97 (s, 2 H, NH), 6.07
(s, 2 H, NH), 6.38 (s, 2 H, =CH), 6.48–6.58 (m, 4 H, =CH), 6.63–
6.82 (m, 6 H, =CH), 7.09 (d, 2 H, J = 8.2 Hz, =CH).
UV/Vis (EtOH): max = 202.6, 273.0, 307.5, 445.8 nm.
MS (ESI): m/z (%) = 564.29 (75.44) [MH+], calcd 564.69.
Anal. Calcd for C36H33N7: C, 76.70; H, 5.90; N, 17.40. Found: C,
75.37; H, 5.58; N, 16.18.
13C NMR (50 MHz, DMSO-d6): = 101.6, 104.3, 113.9, 115.6,
117.1, 120.83, 126.6, 127.9, 140.3, 144.8, 146.4.
N ,N -Bis(2 ,4 -diaminophenyl)-N,N -bis(4 -aminophenyl)-
4,4 -diaminodiphenylamine (8i)
UV/Vis (EtOH): max = 208.8, 301.0, 654.2 nm.
Reduction of N ,N -bis(2 ,4 -dinitrophenyl)-N,N -bis(4 -ami-
nophenyl)-4,4 -diaminodiphenylamine (7i, 0.250 g, 0.35 mmol)
gave a black product (0.138 g, 66.4%); mp 202–204 °C.
Anal. Calcd for C30H28N6: C, 76.30; H, 5.98; N, 17.80. Found: C,
75.86; H, 6.03; N, 17.68.
N ,N -Bis(2 ,4 -diaminophenyl)-N,N -bis(4 -aminophenyl)-
1,4-benzenediamine (8f)
Reduction of N ,N -bis(2 ,4 -nitrophenyl)-N,N -bis(4 -aminophe-
nyl)-1,4-benzenediamine (7f) (0.250 g, 0.4 mmol) gave a black
product (0.135 g, 66.7%); mp > 375 °C.
IR (KBr): 3378, 3173, 1599, 1500, 1400, 1287, 817 cm–1.
1H NMR (200 MHz, DMSO-d6): = 4.47 (br s, 4 H, NH2), 5.36 (br
s, 2 H, NH2), 5.88 (br s, 2 H, NH2), 6.00 (s, 1 H, NH), 6.48–7.03 (m,
22 H, =CH), 7.42–7.65 (m, 4 H, NH).
13C NMR (50 MHz, DMSO-d6): = 101.4, 105.2, 109.0, 110.7,
115.5, 116.6, 120.7, 124.8, 130.2, 136.5, 138.9, 140.8, 148.2.
IR (KBr): 3333, 3147, 1597, 1507, 1286, 814 cm–1.
1H NMR (200 MHz, DMSO-d6): = 4.45 (br s, 4 H, NH2), 4.61 (br
s, 4 H, NH2), 5.85 (s, 2 H, NH), 5.99 (s, 2 H, NH), 6.35–6.62 (m, 8
H, =CH), 6.73–7.09 (m, 10 H, =CH).
UV/Vis (EtOH): max = 206.4, 313.9, 434.2, 665.9 nm.
MS (ESI): m/z (%) = 594.33 (5.05) [MH+], calcd 594.73.
13C NMR (50 MHz, DMSO-d6): = 101.5, 104.3, 109.0, 114.7,
115.6, 117.0, 122.4, 127.9, 136.6, 140.5, 145.4, 147.1.
Anal. Calcd for C36H35N9: C, 72.82; H, 5.94; N, 21.24. Found: C,
67.34; H, 5.54; N, 18.81.
UV/Vis (EtOH): max = 203.8, 310.1, 482.9, 678.7 nm.
MS (ESI): m/z (%) = 502.23 (4.01) [MH+], calcd 503.62.
Acknowledgment
Anal. Calcd for C30H30N8: C, 71.68; H, 6.02; N, 22.30. Found: C,
66.10; H, 5.76; N, 18.38.
We gratefully acknowledge the Australian Research Council for fi-
nancial support.
N ,N -Bis(4 -aminophenyl)-N,N -bis(4 -aminophenyl)-4,4 -
diaminodiphenylamine (8g)
References
Reduction of N ,N -bis(4 -nitrophenyl)-N,N -bis(4 -aminophe-
nyl)-4,4 -diaminodiphenylamine (7g) (0.15 g, 0.24 mmol) gave a
dark green product (0.087 g, 64.6%); mp > 375 °C.
(1) (a) Gospodinova, N.; Terlemezyan, L. Prog. Polym. Sci.
1998, 23, 1443; and references therein. (b) Lu, W.; Meng,
X. S.; Wang, Z. Y. J. Polym. Sci., Part A: Polym. Chem.
1999, 37, 4295.
(2) Wienk, M. M.; Janssen, A. J. J. Am. Chem. Soc. 1996, 118,
10626.
(3) MacDiarmid, A. G.; Zhou, Y.; Feng, J. Synth. Met. 1999,
100, 131.
(4) Wei, Y.; Yang, C.; Ding, T. Tetrahedron Lett. 1996, 37, 731.
(5) Wang, Z. Y.; Yang, C.; Gao, J. P.; Lin, J.; Meng, X. S.
Macromolecules 1998, 31, 2702.
IR (KBr): 3384, 3179, 1598, 1505, 1400, 1298, 1154, 1112, 820,
510 cm–1.
1H NMR (200 MHz, DMSO-d6): = 4.76 (br s, 4 H, NH2), 6.56 (br
s, 5 H, NH), 6.88 (br s, 24 H, =CH).
13C NMR (50 MHz, DMSO-d6): = 112.9, 116.5, 118.6, 121.2,
124.8, 127.0, 131.07, 134.3, 135.0, 135.8, 136.0, 137.5.
UV/Vis (EtOH): max = 206.4, 311.4, 605.8 nm.
(6) Zhang, W. J.; Feng, J.; MacDiarmid, A. G.; Epstein, A. J.
Synth. Met. 1997, 84, 119.
MS (ESI): m/z (%) = 564.28 (5.11) [MH+], calcd 564.69.
Anal. Calcd for C36H33N7: C, 76.70; H, 5.90; N, 17.40. Found: C,
75.72; H, 5.84; N, 16.20.
(7) Hall, H. K.; Polis, D. W. Polym. Bull. 1987, 17, 409.
(8) Bunnett, J. F.; Zahler, R. E. Chem. Rev. 1951, 49, 273.
(9) (a) Ibata, T.; Isogami, Y.; Toyoda, J. Bull. Chem. Soc. Jpn.
1991, 64, 42. (b) Kotsuki, H.; Kobayashi, S.; Matsumoto,
K.; Suenaga, H.; Nishizawa, H. Synthesis 1990, 1147.
(10) Buckingham, J. Dictionary of Organic Compounds, Vol. 4,
5th ed.; Chapman and Hall: New York, 1982, 4244.
(11) Modena, G. Boll. Sci. Foc. Ind. Bologna 1959, 17, 45; Chem.
Abstr. 1969, 54, 12773.
N ,N -Bis(2 -aminophenyl)-N,N -bis(4 -aminophenyl)-4,4 -
diaminodiphenylamine (8h)
Reduction of N ,N -bis(2 -nitrophenyl)-N,N -bis(4 -aminophe-
nyl)-4,4 -diaminodiphenylamine (7h, 0.312 g, 0.5 mmol) gave a
black product (0.183 g, 65.0%); mp 181–183 °C.
IR (KBr): 3385, 3174, 2925, 1613, 1505, 1457, 1400, 1293, 1231,
1155, 817, 746, 511 cm–1.
1H NMR (200 MHz, DMSO-d6): = 4.73 (br s, 4 H, NH2), 6.54 (br
(12) Buckingham, J. Dictionary of Organic Compounds, Vol. 2;
Chapman and Hall: New York, 1982, 5th ed., 2264.
s, 3 H, NH), 6.72–7.04 (m, 24 H, =CH), 7.41 (s, 2 H, NH).
Synthesis 2003, No. 16, 2511–2517 © Thieme Stuttgart · New York