Synthesis and spectral characteristics of novel bis(tetraarylcyclopentadienones)

Full text of DOI:10.1134/S0012500807010053

ISSN 0012-5008, Doklady Chemistry, 2007, Vol. 412, Part 1, pp. 14–17. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © M.L. Keshtov, N.M. Belomoina, A.S. Peregudov, A.L. Rusanov, A.R. Khokhlov, 2007, published in Doklady Akademii Nauk, 2007, Vol. 412, No. 1,
pp. 204–207.
CHEMISTRY
Synthesis and Spectral Characteristics
of Novel Bis(tetraarylcyclopentadienones)
M. L. Keshtov, N. M. Belomoina, A. S. Peregudov,
A. L. Rusanov, and Academician A. R. Khokhlov
Received September 14, 2006
DOI: 10.1134/S0012500807010053
Bis(tetraarylcyclopentadienones) (BTACPDs) are presence of the above heterocycles in polymer macro-
key monomers used for preparing aromatic polymers molecules determines their electron transport proper-
and, in particular, aryl-substituted polyphenylenes ties [2, 3].
(ASPPs) via the Diels–Alder reaction [1]. ASPPs are
In continuing our studies in the field of novel
unique polymers that combine the aromaticity of mac-
BTACPDs [4] and ASPPs on their basis [5], we carried
romolecules with a high molecular weight and high sol-
out the synthesis and studied the spectral characteristics
ubility in organic solvents. Most ASPPs contain only
of previously unknown BTACPDs containing
carbocyclic fragments, whereas the introduction of het-
thiophene, benzothiophene, dibenzothiophene, and car-
erocycles, such as thiophene, benzothiophene, diben-
bazole rings as core groups or substituents.
zothiophene, and carbazole, would impart a number of
new properties to these polymers, in particular, the pos-
The synthesis of BTACPDs was performed simi-
sibility of their use in light-emitting devices since the larly to [1, 2, 4–6] according to Schemes 1 and 2.
Scheme 1.
[Pd]
Br–Het–Br + 2HC
C
C C Het C C
I‡–Ic
Ph
Ph
O
O
KMnO4
Het
C C Het C C
O O O O
II‡–IIc
O
III‡–IIIc
(a),
(b),
(c)
Het
–Het =
S
N
S
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28,
Moscow, 119991 Russia
14

SYNTHESIS AND SPECTRAL CHARACTERISTICS
15
Scheme 2.
[Pd]
HC C
C CH + 2Br Het
Het C C
C C Het
IVd, IVe
Ph
Ph
Het
O
O
KMnO4
Het C C
O O
C C Het
O O
O
Het
Vd, Ve
VI‡–VIc
Het =
(d),
(e)
S
S
The synthesis involves the following:
with a twofold molar amount of diphenylacetone to
produce BTACPDs IIIa–IIIc [1, 2, 4, 6].
(1) The palladium-catalyzed cross coupling [7–9] of
2,5-dibromothiophene, 2,8-dibromodibenzothiophene,
and 3,6-dibromo(9-ethyl)carbazole with twofold molar
amounts of phenylacetylene; the oxidation of resulting
bis(phenylethynyl)hetarylenes (BPEHAs) Ia–Ic with
KMnO4 to give bis(phenylglyoxalyl)hetarylenes
(BPGHAs) IIa–IIc [11]; and the treatment of BPGHAs
(2) The palladium-catalyzed cross coupling [8] of
1,4-diethynylbenzene with twofold molar amounts of
2-bromothiophene and 3-bromobenzothiophene, the
oxidation of resulting 1,4-bis(hetarylethynyl)phen-
ylenes (BHEPs) IVd and IVe with KMnO4 to yield
Table 1. Selected characteristics of intermediate and final compounds
Elemental analysis,
Elemental analysis,
calculated/found, %
Com-
Com-
calculated/found, %
Yield,
%
Yield,
%
pound Tm, °C
pound Tm, °C
no.
no.
C
H
S
N
–
C
H
S
–
N
89.19 5.10
------------ ---------
89.31 5.01
1.73
---------
1.87
84.47 4.25 11.17
------------ --------- ------------
84.52 4.28 11.41
IIIc
IVd
IVe
Vd
275–277
187–189
197–199
171–173
238–240
343–345
271–273
91
95
95
90
89
70
72
Ia
88
90
94
95
93
88
96
72
82
87.47 4.20
------------ ---------
87.52 4.23
8.00
---------
8.23
74.45 3.47 22.10
------------ --------- ------------
74.28 3.46 22.20
Ib
171–172
159–160
95–97
–
–
–
–
–
–
–
91.11 5.35
------------ ---------
91.11 5.51
3.54
---------
3.56
79.97 3.61 16.42
------------ --------- ------------
80.01 3.66 16.81
Ic
–
68.95 3.47
------------ ---------
69.03 3.41
9.20
---------
9.39
61.00 2.84 18.09
------------ --------- ------------
60.97 2.84 17.79
IIa
IIb
IIc
–
–
75.00 3.57
------------ ---------
75.03 3.70
7.14
---------
7.20
68.71 3.10 14.11
------------ --------- ------------
68.71 3.24 13.83
238–240
219–220
Ve
78.41 4.61
------------ ---------
78.32 5.31
3.05
---------
3.03
82.02 4.30
------------ ---------
81.91 4.38
9.12
---------
9.24
–
VId
VIe
86.18 4.63
------------ ---------
87.31 4.51
4.60
---------
4.27
83.76 4.27
------------ ---------
83.78 4.27
7.99
---------
7.93
IIIa 230–232
IIIb 220–222
–
–
87.41 4.55
------------ ---------
87.31 4.52
4.02
---------
4.58
DOKLADY CHEMISTRY Vol. 412 Part 1 2007

16
KESHTOV et al.
Table 2. Spectral characteristics of intermediate and final compounds
Com-
pound spectra,
no.
ν, cm–1
Raman
1H NMR spectra,
13C NMR spectra,
δ, ppm
δ, ppm
Ia
2202 (C≡C) 7.20 (s, 2H), 7.38 (m, 6H), 7.56 (m, 4H) 82.17 (C≡C), 93.95 (C≡C), 122.42 (C), 124.48 (C),
128.27 (CH), 128.53 (CH), 131.34 (CH), 131.71 (CH)
Ib
Ic
2202 (C≡C) 7.43 (m, 6H), 7.58 (m, 4H), 7.65 (d, 2H), 89.79 (C≡C), 119.21 (C), 122.61 (C), 123.76 (CH), 125.62 (CH),
8.03 (d, 2H), 8.63 (s, 2H)
129.10 (CH), 130.36 (CH), 131.63 (CH), 134.95 (C), 139.67 (C)
2210 (C≡C) 7.38 (m, 8H), 7.62 (d, 4H), 7.68 (d, 2H), 87.5 (C≡C), 90.9 (C≡C), 108.4 (CH), 113.6 (C), 122.3 (C),
8.31 (s, 2H, ), 4.33 (m, 2H, CH2),
1.45 (t, 3H, CH3)
123.5 (CH), 123.9 (CH), 127.6 (CH), 128.1 (CH), 129.4 (CH),
131.2 (CH), 139.6 (C), 37.5 (CH2), 13.5 (CH3)
IIa 1681 (C=O) 7.54 (t, 4H ), 7.69 (t, 2H), 7.84 (s, 2H), 128.94 (CH), 130.25 (CH), 131.93 (C), 135.18 (CH),
8.05 (d, 4H)
135.76 (CH), 146.11 (C), 184.97 (C=O), 190.57 (C=O)
IIb 1675 (C=O) 7.63 (t, 4H),7.76 (t, 2H), 7.98 (d, 4H),
126.40 (CH), 125.61 (CH), 126.70 (C), 129.020 (CH),
8.04 (d, 2H), 8.29 (d, 2H), 9.05 (s, 2H) 129.89 (CH), 130.71 (CH), 132.36 (C), 134.29 (CH),
148.04 (C), 148.38 (C), 194.27 (CO), 194.57 (CO)
IIc 1661 (C=O) 7.53 (t, 6H), 7.67 (t, 2H), 8.04 (d, 4H), 109.4 (CH), 122.9 (C), 124.1 (CH), 125.5 (C), 128.1 (CH),
8.21 (d, 2H), 8.66 (s, 2H), 4.44 (m, 2H, 129.01 (CH), 129.7 (CH), 132.9 (C), 134.5 (CH), 144.1 (C),
CH2), 1.48 (m, 3H CH3)
193.6 (C), 194.7 (Cé), 38.1 (CH2), 13.5 (CH3)
IIIa 1711 (C=O) 7.25–7.38 (m, 20H), 7.43 (s, 2H),
200.14 (CO), 164.05 (C), 157.04 (C), 145.27 (C), 139.12 (C),
137.07 (C), 134.84 (C), 133.14 (C), 122.26 (C), 132.48 (CH),
131.93 (CH), 127.57 (CH), 126.78 (CH), 126.38 (CH),
126.13 (CH), 126.08 (CH), 125.85 (CH), 124.85 (CH)
7.58–7.77 (m, 8H)
IIIb 1711 (C=O) 6.90 (d, 6H), 7.05 (d, 4H), 7.13 (d, 8H), 200.16 (CO), 154.34 (C), 153.75 (C), 139.74 (C), 134.84 (C),
7.15–7.30 (m, 16H), 7.60 (d, 2H)
132.98 (C), 130.51 (C), 129.61 (C), 125.29 (C), 125.21 (C),
130.02 (CH), 129.97 (CH), 129.09 (CH), 128.42 (CH), 127.99
(CH), 127.53 (CH), 127.42 (CH), 122.34 (CH), 122.11 (CH)
IIIc 1710 (C=O) 6.9–7.26 (m, 36H, Ar), 1.45 (m, 3H, CH3), 200.29 (CO), 155.07 (C), 154.34 (C), 140.08 (C), 133.31 (C),
4.25 (m, 2H, CH2)
131.20 (C), 130.79 (C), 125.52 (C), 124.21 (C), 123.77 (C),
122.21 (C), 130.07 (CH), 129.27 (CH), 128.29 (CH), 127.87
(CH), 127.76 (CH), 127.26 (CH), 127.11 (CH), 121.70
(CH), 108.03 (CH), 37.76 (CH2), 13.81 (CH3)
IVd 2191 (C≡C) 7.16 (m, 2H), 7.46 (m, 2H), 7.61 (s, 4H), 85.42 (C≡C), 93.10 (C≡C), 122.76 (C), 123.41 (C), 128.57 (CH),
7.72 (m, 2H) 129.87 (CH), 132.27 (CH), 133.81 (CH)
IVe 2191 (C≡C) 7.50 (t, 2H), 7.58 (t, 2H), 7.68 (s, 4H), 85.07 (C≡C), 91.62 (C≡C), 118.18 (C), 122.69 (C), 123.07 (C),
7.78 (s, 2H), 7.95 (d, 2H), 8.13 (d, 2H) 123.11 (CH), 124.83 (CH), 125.18 (CH), 130.21 (CH),
131.67 (CH), 131.73 (CH), 138.88 (CH), 139.09 (CH)
Vd 1681 (CO) 7.39 (m, 2H), 8.06 (m, 2H), 8.25 (s, 4H), 131.29 (CH), 137.67 (C), 139.00 (CH), 139.59 (CH),
8.38 (m, 2H)
139.72, 185.69 (CO), 192.27 (CO)
Ve 1680 (C=O) 7.65 (t, 2H), 7.72 (t, 2H), 8.28 (d, 2H), 124.54 (C), 124.70 (C), 128.32 (C), 129.65 (C), 129.87 (C),
8.36 (s, 4H), 8.82 (d, 2H), 9.14 (s, 2H) 130.08 (C), 132.69 (CH), 135.12 (CH), 135.69 (C),
146.59 (CH), 194.46 (CO), 194.54 (CO)
VId 1709 (C=O) 7.10–7.70 (m, 26H), 7.72 (s, 4H)
122.26 (C), 124.86 (CH), 125.70 (CH), 125.85 (CH), 126.13
(CH), 126.25 (CH), 126.38 (CH), 129.17 (CH), 131.80
(CH), 131.93 (CH), 132.48 (CH), 133.50 (C), 134.84 (C),
137.06 (C), 139.11 (C), 143.84 (C), 155.30 (C), 156.86 (C),
200.14 (CO)
VIe 1709 (C=O) 6.73 (s, 4H), 7.00–7.29 (m, 28H, Ar),
199.98 (CO), 153.39 (C), 148.03 (C), 139.63 (C), 136.32 (C),
133.35 (C), 130.66 (C), 130.22 (C), 128.93 (C), 126.03 (C),
125.28 (C), 129.93 (CH), 129.30 (CH), 128.70 (CH), 127.99
(CH), 127.93 (CH), 127.63 (CH), 127.39 (CH), 124.45
(CH), 123.95 (CH), 123.77 (CH), 122.45 (CH)
7.83 (d, 2H)
1,4-bis(hetarylglyoxalyl)phenylenes (BHGPs) Vd and
It is worth noting that the intermediate compounds
Ve, and the treatment of BHGPs with a twofold molar formed in the course of the synthesis of BTACPDs
amount of 1,3-diphenylacetone to give BTACPDs VId (Schemes 1, 2), namely, BPEHAs Ia–Ic, BPGHAs IIa–
and VIe [1, 2, 4, 6].
IIc, BHEPs IVd and IVe, and BHGPs Vd and Ve, are
DOKLADY CHEMISTRY Vol. 412 Part 1 2007

SYNTHESIS AND SPECTRAL CHARACTERISTICS
17
of intrinsic interest as monomers for the synthesis of ence of upfield signals at δ = 80–90 ppm from the acet-
different polymers. Thus, BPEHAs Ia–Ic and BHEPs ylene moieties and downfield signals at 190–200 ppm
IVd and IVe can be used for preparing cross-linked from the two different carbonyl groups of the α-dike-
1
polyphenylenes and as the comonomers of BTACPDs
in the synthesis ofASPPs containing an increased num-
ber of aryl substituents [9], while BPGHAs IIa–IIc and
BHGPs Vd and Ve can be used in the synthesis of
polyquinoxalines and poly(asym-triazines) containing
phenyl and hetaryl substituents.
tone moiety. The H NMR spectra of bis-cyclones III
and VI are rather complex. The aromatic protons
appear as downfield multiplets at 7.25–7.77 and 6.80–
7.50 ppm, respectively. The spectrum of compound
IIIc shows two upfield multiplets at δ = 1.45 ppm and
δ = 4.25 ppm from the CH3 and CH2 groups, respec-
All syntheses of BPEHAs Ia–Ic and BHEPs IVd tively, and the ratio of the integrated intensities of the
and IVe were carried out in triethylamine using aliphatic and aromatic portions agrees well with the
proposed structure. The 13ë NMR spectra are more
PdCl2(PPh3)2, PPh3, and CuI as catalysts and promot-
ers. The reaction mixtures were boiled under reflux
for 10 h.
The oxidation of BPEHAs Ia–Ic to BPGHAs IIa–
IIc and the oxidation of BHEPs IVd and IVe to BHGPs
Vd and Ve were accomplished using KMnO4 in acetone
with glacial CH3COOH under reflux for 2–3 h until the
crimson color disappeared.
BTACPDs IIIa–IIIc, VId, and VIe were synthe-
sized in boiling absolute ethanol during 1 h using a
KOH solution in ethanol.
All the intermediate and target compounds were
obtained in high yields, and elemental analysis data
agree well with calculated values (Table 1).
13
informative. The ë NMR spectra of compounds III
and VI show a signal at ~200 ppm due to the CO group
of the cyclopentadienone moiety, whereas the signals
between 110 and 160 ppm belong to the quaternary car-
bon atoms.
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DOKLADY CHEMISTRY Vol. 412 Part 1 2007