Novel fluorine-containing bis(tetraarylcyclopentadienones)

Full text of DOI:10.1134/S0012500809110068

ISSN 0012ꢀ5008, Doklady Chemistry, 2009, Vol. 429, Part 1, pp. 277–282. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © M.L. Keshtov, P.V. Petrovskii, A.S. Stakhanov, V.S. Kochurov, A.R. Khokhlov, 2009, published in Doklady Akademii Nauk, 2009, Vol. 429, No. 2,
pp. 206–211.
CHEMISTRY
Novel FluorineꢀContaining Bis(tetraarylcyclopentadienones)
M. L. Keshtov, P. V. Petrovskii, A. S. Stakhanov, V. S. Kochurov,
and Academician A. R. Khokhlov
Received July 1, 2009
DOI: 10.1134/S0012500809110068
Previously, we prepared new representatives of fluorinated BTACPDs with fluorine in hexafluoroisoꢀ
bis(tetraarylcyclopentadienones) (BTACPDs) [1],
monomers used in the synthesis of phenylꢀsubstituted
polyphenylenes (PSPPs) [2–4] and polyimides
(PSPIs) [5] by the Diels–Alder reaction [6]. PSPPs
and PSPIs are of considerable interest as polymers that
combine high thermal characteristics and low dielecꢀ
tric constants with good processibility and excellent
complexꢀforming properties [7]. Fluorineꢀcontaining
PSPPs and PSPIs are of special interest because the
introduction of fluorine into polymer macromolecules
leads to a further decrease in dielectric constant and
enhancement of polymer solubility [8, 9]. Owing to
these advantages, fluorinated PSPPs attracted considꢀ
erable interest of researchers as interlaminar dielecꢀ
propylidene core fragments or phenyl rings and to
study their spectral characteristics.
BTACPDs containing fluorine in phenyl rings
IIIa, IIIb) were obtained by a general procedure using
(
Pdꢀcatalyzed crossꢀcoupling of dihaloarylenes with
twofold molar amounts of phenylacetylene or 4ꢀfluoꢀ
rophenylacetylene (similarly to [10, 11]). Bis(phenylꢀ
ethynyl)arylenes
and
bis(4ꢀfluorophenylethyꢀ
nyl)arylenes Ia and Ib thus obtained were oxidized
with potassium permanganate to, respectively,
bis(phenylglyoxalyl)arylenes and bis(4ꢀfluoropheꢀ
nylglyoxalyl)arylenes IIa and IIb [9, 10] followed by
their transformation into BTACPDs by the treatment
trics in multiintegrated circuits. Therefore, in this with 1,3ꢀdiphenylacetone or 1,3ꢀbis(4ꢀfluoropheꢀ
work, we attempted to synthesize previously unknown nyl)acetone [1, 12, 13] (Scheme 1).
[
Pd]
+ 2
Br
Br
R
R
R
R'
Ia , Ib
R'
R'
O
R
2
O
O
KMnO
4
R'
R
R
O O
O O
IIa , IIb
R
R'
IIIa , IIIb
'R
Ia (R = H), Ib (R = F); IIa (R = H), IIb (R = F); IIIa (R = H, R' = F), IIIb (R = F, R' = H).
Scheme 1.
Nesmeyanov Institute of Organoelement Compounds,
Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia
277

278
KESHTOV et al.
The synthesis of BTACPD VIa, containing 1,1,1,3,3,3ꢀhexafluoroꢀ2,2ꢀbis(phenylethynyl)proꢀ
hexafluoroisopropylidene core fragment, was carried pane IVa
–
IVc into 1,1,1,3,3,3ꢀhexafluoroꢀ2,2ꢀbis(4ꢀ
out by the reaction of 1,1,1,3,3,3ꢀhexafluoroꢀ2,2ꢀ phenylglyoxalyl)propane Va
–Vc followed by the treatꢀ
bis(4ꢀiodophenyl)propane with a twofold molar ment of the latter with a twofold molar amount of 1,3ꢀ
amount of phenylacetylene, oxidation of resulting diphenylacetone (Scheme 2).
R''
CF
3
I
I + 2
R'
CF3
R''
R''
R''
R''
R''
CF3
CF3
[Pd]
R'
R'
IVa–IVc
R''
R''
R
R''
R''
CF3
CF3
KMnO4
IVa–IVc
R'
R'
O O
O O
Va–Vc
R
R
R''
R'
R''
2
O
CF3
CF3
O
R
R
Va–Vc
O
R''
R'
R''
R
VIa–VIe
IVa (R' = R'' = H), IVb (R'' = H, R' = F), IVc (R'' = CF3, R' = H);
Va (R' = R'' = H), Vb (R'' = H, R' = F), Vc (R'' = CF3, R' = H);
VIa (R = R' = R'' = H), VIb (R = R'' = H, R' = F),
VIc (R'' = H, R' = R = F), VIe (R'' = CF3, R' = R = F).
Scheme 2.
And finally, BTACPDs VIb
rine both in the core fragment and in the phenyl rings formed in the synthesis of BTACPDs (Schemes 1, 2),
were obtained by the reaction of 1,1,1,3,3,3ꢀhexafluꢀ namely, diethynylenes ( IV) and bis( ꢀdiketones (II
oroꢀ2,2ꢀbis(4ꢀiodophenyl)propane with a twofold ), are of real interest as monomers for the synthesis of
molar amount of appropriate fluorineꢀcontaining aryꢀ different polymers. Thus, compounds Ia Ib, and IVa
lacetylene followed by oxidation of resulting diethyꢀ IVc can be used for the preparation of phenylꢀsubstiꢀ
nylenes (IVb IVc) to bis( ꢀdiketones) (Vb Vc) and tuted polyphenylenes under conditions of the Diels–
treatment of the latter with 1,3ꢀdiphenylacetone or Alder reaction and for the preparation of crosslinked
1,3ꢀbis(4ꢀfluorophenyl)acetone (Scheme 2). polyphenylenes; compounds IIa IIb, and Va Vc can
–VIe, containing fluoꢀ
It is worth noting that the intermediate compounds
I,
α
,
V
,
–
,
α
,
,
–
DOKLADY CHEMISTRY Vol. 429
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NOVEL FLUORINEꢀCONTAINING BIS(TETRAARYLCYCLOPENTADIENONES)
279
Table 1. Certain characteristics of intermediate and final compounds
Elemental analysis (calculated/found), %
Molecular forꢀ
Compound no.
Tm, °C
Yield, %
mula
C
H
F
93.94
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
5.07
ꢀꢀꢀꢀꢀꢀꢀ
Ia
184–186
191–192
125–127
223–225
312–314
325–327
90–91.5
176–178
115–117
155–158
111–113
115–117
236–238
178–180
220–222
229–231
145–147
C22H14
–
81
78
68
67
87
83
89
92
81
95
88
81
87
82
91
95
95
94.67
4.98
84.06
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
3.85
ꢀꢀꢀꢀꢀꢀꢀ
12.09
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
Ib
C22H12F2
83.92
3.69
11.91
77.18
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
4.12
ꢀꢀꢀꢀꢀꢀꢀ
IIa
IIb
IIIa
IIIb
IVa
IVb
IVc
Va
C22H14O4
–
77.11
4.22
69.84
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
3.20
ꢀꢀꢀꢀꢀꢀꢀ
10.09
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
C22H12F2O4
C52H30F4O2
C52H32F2O2
C31H18F6
69.43
3.11
9.65
81.88
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
3.96
ꢀꢀꢀꢀꢀꢀꢀ
9.96
ꢀꢀꢀꢀꢀꢀꢀ
82.13
3.73
9.71
85.95
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
4.43
ꢀꢀꢀꢀꢀꢀꢀ
5.23
ꢀꢀꢀꢀꢀꢀꢀ
85.67
4.26
5.00
73.81
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
3.60
ꢀꢀꢀꢀꢀꢀꢀ
22.60
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
73.66
3.58
22.34
68.89
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
2.98
ꢀꢀꢀꢀꢀꢀꢀ
28.14
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
C31H16F8
68.59
2.87
28.00
54.14
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
1.80
ꢀꢀꢀꢀꢀꢀꢀ
44.04
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
C35H14F18
54.09
1.75
39.65
65.50
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
3.19
ꢀꢀꢀꢀꢀꢀꢀ
20.05
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
C31H18F6O4
C31H16F8O4
C35H14F18O4
C61H38F6O2
C61H36F8O2
C61H34F10O2
C61H32F12O2
C65H34F18O2
65.32
3.15
19.61
61.59
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
2.66
ꢀꢀꢀꢀꢀꢀꢀ
25.14
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
Vb
61.33
2.42
24.69
50.02
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
1.68
ꢀꢀꢀꢀꢀꢀꢀ
40.69
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
Vc
49.87
1.61
40.31
79.89
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
4.17
ꢀꢀꢀꢀꢀꢀꢀ
12.43
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
VIa
VIb
VIc
VId
VIe
79.58
4.19
12.21
76.88
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
3.80
ꢀꢀꢀꢀꢀꢀꢀ
15.95
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
76.70
3.94
15.71
74.09
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
3.70
ꢀꢀꢀꢀꢀꢀꢀ
19.21
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
73.91
3.46
18.94
71.49
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
3.15
ꢀꢀꢀꢀꢀꢀꢀ
22.24
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
71.09
3.21
21.73
65.66
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
2.88
ꢀꢀꢀꢀꢀꢀꢀ
28.76
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
65.20
2.93
28.41
be used in the synthesis of polyquinoxalines, in high yields and elemental analysis data agree well
poly(asymꢀtriazines), and poly(aryl ether ketones).
with calculated values. The synthetic route to target
compounds III and VI was monitored by Raman and
FTIR spectroscopy (Table 2). In particular, the
The composition and structure of intermediate
compounds I, II, IV, and V and target compounds III
Raman spectra of compounds
absorption bands in the region of 2210–2221 cm–1
typical for acetylene bonds ( ) and weak bands in
I and IV show strong
and VI were confirmed by the data of elemental analꢀ
ysis (Table 1) and IR and Raman spectroscopy
(Table 2). According to the data given in Table 1, all
C C
≡
the intermediate and target compounds were obtained the region of 1668–1681 cm–1 related to the stretching
DOKLADY CHEMISTRY Vol. 429
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280
KESHTOV et al.
Table 2. Spectral characteristics of intermediate and final compounds
NMR spectra, δ, ppm
Raman
spectra,
ν, cm–1
1H
13C
19F
Ia
2215 7.46–7.52 (m, 4H),
7.19–7.24 (m, 6H)
134.68, 131.66, 128.22, 123.48, 114.77, 89.96 (C
≡
C),
–
89.43 (C
163.79, 161.30, 133.47, 131.40, 115.73, 115.51, 90.10 (C
88.65 (C C)
1671 8.10 (s, 4H), 7.96 (d, 4H) 193.32 (C=O), 193.17 (CO), 137.04 (ч), 135.17, 132.48 (h),
CO 7.68 (t, 2H), 7.52 (t, 4H) 130.16, 129.88, 129.06
1668 8.15 (s, 4H), 8.09 (t, 8H), 192.44 (C=O), 192.10 (CO), 167.13, 161.56, 134.24, 132.51, –101.21
≡
C)
Ib
2219 7.44–7.54 (m, 8H),
≡
C), –110.44
C
≡
C
7.05 (t, 4H)
≡
IIa
IIb
–
CO
7.47 (t, 8H)
115.99, 115.78
IIIa 1709 6.60–8.10 (m, 30H)
CO
200.31, 165.05, 162.41, 151.93, 151.55, 137.58, 137.26, 132.45, –112.37,
132.31, 130.65, 127.10, 126.74, 125.33, 116.57, 116.32
–113.05
IIIb 1711 7.30–7.72 (m, 22H)
CO
199.21 (C=O), 164.53, 161.95, 159.33, 152.29, 137.33, 135.08, –113.15
133.58, 132.86, 132.74, 132.68, 126.95, 126.15, 125.61, 125.31,
115.37, 115.09
IVa
2212 7.20–7.56 (m, 18H)
C≡
136.19 (C), 134.32, 131.27 (C), 130.18 (C), 129.63, 129.15, –63.11
128.83, 128.31, 127.11, 123.61, 121.55, 116.12, 82.17 (C≡C),
93.95 (C≡C), 65.88, 65.56, 65.31, 65.06, 64.81, 64.56, 64.31
C
IVb 2221 7.50–7.54 (m, 8H),
7.37 (d, 4H),
7.05 (t, 4H)
163.85, 161.35, 133.48, 133.17, 132.87, 131.24, 130.07, 128.14, –109.85,
125.27, 124.14, 122.43, 119.58, 118.78, 115.53, 115.07, 98.89 –63.32
(C C), 87.73 (C C), 65.10, 64.85, 64.60, 64.35, 64.09, 63.59
C C
≡
≡
≡
IVc
2210 7.96 (s, 4H), 7.84 (s, 2H), 133.78, 132.49, 132.15, 131.81, 131.51, 131.45, 130.23, 125.01, –63.11 (12CF3)
7.57 (d, 4H), 7.42 (d, 4H) 124.15, 123.02, 121.86, 121.43, 87.8 (C C), 91.20 (C C), 65.78, –63.54 (6CF3)
61.16, 65.16, 62.19, 64.49, 62.67, 63.87
C
≡
C
≡
≡
Va
1681 7.55 (t, 8H); 7.67 (t, 2H), 193.95 (C=O), 193.58 (C=O), 138.17 (C), 135.74, 133.07 (C), –63.55 (CF3)
C=O 7.99 (t, 8H) 132.08 (C), 130.89, 130.14, 129.89, 129.54, 128.01, 124.91,
122.05, 118.02, 66.88, 64.06, 66.18, 63.16, 65.47, 62.66, 64.77
Vb
1683 7.20 (t, 4H), 7.52 (d, 4H), 192.43 (C=O), 191.64 (C=O), 168.13, 165.56, 116.53, 116.31, –62.94 (2CF3)
C=O 7.96–8.05 (m, 8H)
132.81, 132.72, 127.68, 133.19, 129.48, 130.73, 139.04,
127.68, 124.83, 121.96, 119.10, 66.88, 64.06, 66.18, 63.16,
65.47, 62.66, 64.77
–100.14 (2F)
Vc
1661 7.58 (d, 4H), 8.07 (d, 4H), 190.32 (C=O), 189.30 (C=O), 139.62 (C), 134.20 (s), 133.07 –63.01 (CF3),
–63.18 (CF3)
C=O 8.17 (s, 2H), 8.46 (s, 4H) (C), 132.72 (s), 130.94, 130.05, 129.90, 129.77, 126.61,
123.87, 121.16, 118.45, 58.38
VIa 1710 7.31–7.13 (m, 22H),
C=O 7.18–7.14 (m, 8H),
6.99–6.91 (d, 4H),
199.11 (C=O), 154.01 (C), 152.87 (C), 134.67 (C), 132.97 (C), –63.45 (CF3)
132.60 (C), 130.36 (C), 130.16 (C), 129.97, 129.59, 129.12,
128.97, 128.61, 127.99, 127.86, 127.69, 127.51, 125.75 (C),
6.85 (d.4H)
125.05 (C), 123.74 (CF3), 64.22 (t, JCF = 25.4)
VIb 1714 7.59–6.80 (m, 36H)
C=O
199.77, 164.41, 161.09, 153.03, 152.61, 134.31, 133.22, 131.36, –63.75 (CF3),
131.26, 130.35, 130.09, 129.86, 129.76, 129.32, 129.15, 128.74, –111.23 (F)
128.63, 128.23, 128.16, 127.93, 127.81, 127.25, 127.09, 126.09,
125.43, 115.45, 115.16, 64.89
VIc 1710 6.90–7.05 (m, 17H)
C=O 7.20–7.33 (m, 17H)
199.92 (C=O), 164.04, 163.95, 160.75, 160.65, 154.03, 152.84, –63.64 (CF3),
134.11, 133.28, 132.50, 131.90, 131.79, 129.86, 129.17, 129.05, –112.69 (F),
128.04, 128.15, 126.44, 126.39, 126.27, 126.22, 124.87, 124.19, –113.04
115.49, 115.45, 115.20, 115.17, 65.07, 64.70, 64.38, 64.38, 64.05
VId 1716 6.80–7.10 (m, 20H),
C=O 7.26–7.40 (m, 12H),
199.65, 164.48, 164.02, 161.15, 160.78, 152.91, 152.44, 134.12, –63.64 (CF3),
133.36, 132.55, 132.41, 131.88, 131.78, 131.28, 131.17, 130.71, –110.7 (F),
130.00, 129.59, 129.05, 128.46, 126.26, 126.11, 125.05, 124.37, –112.40 (F),
115.90, 115.59, 115.50, 115.30, 115.21, 114.90, 64.11, 63.74
–112.73
VIe 1714 8.2–7.29 (m, 34H)
C=O
199.28, 158.32, 156.77, 140.56, 139.14, 138.14, 135.11, 128.21, –63.18(CF3),
128.01, 127.77, 126.65, 126.14, 125.81, 125.32, 120.73, 120.57, –63.58 (CF3)
120.32, 117.45, 114.61, 111.75, 64.73, 64.45, 64.18, 63.89,
63.61, 63.33, 63.06
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NOVEL FLUORINEꢀCONTAINING BIS(TETRAARYLCYCLOPENTADIENONES)
281
vibrations of CO groups in the αꢀdiketone fragments pounds IIa, IIb, Va , and Vc show strong signals related
of compounds II and V. The absence of signals of ethyꢀ to different kinds of carbon atoms, which agree well
nyl group in the region of 2210–2221 cm–1 confirms
with the suggested structures.
its complete transformation into
α
ꢀdiketone fragꢀ
19
The F NMR spectra of compounds Ib and IIb
ment. The IR spectra of target compounds III and VI
show bands in the region of 1709–1716 cm–1 typical of
the stretching vibrations of the carbonyl group of the
tetraphenylcyclopentadienone fragment and the lack
show signals at –110.44 and –101.21 ppm typical of
fluorine atoms in the para position to the acetylene
and bis(
of compounds IV and
63.35, –109.85, and –100.14 ppm corresponding to
α
ꢀdiketone) fragments. The 19F NMR spectra
V
exhibit signals at –62.94 to
of bands at 1668–1681 cm– related to the
groups.
α
ꢀdiketone
⎯
CF3 and Ar–F groups.
The structure of intermediate compounds
, and target compounds III and VI was also conꢀ
firmed by 1H, 13C, and 19F NMR. The 1H NMR specꢀ
tra of compounds Ia and Ib show two multiplets at
I
,
II IV,
,
1
The H NMR spectra of bis(cyclones) III and VI
V
are rather complex and display downfield multiplets in
the range 6.90–7.77 ppm. The C NMR spectra are
more informative. The specific feature of the spectra
of compounds III and VI is the presence of downfield
signals in the range of 200.31–199.11 ppm typical of
the carbonyl group of the cyclopentadienone fragꢀ
13
δ
7.46–7.52 (m, 4H), 7.19–7.24 (m, 6H) and 7.44–7.54
(m, 8H), 7.05 ppm (t, 4H), respectively. The 1H NMR
spectra of bis( ꢀdiketones) IIa and IIb show signals in
α
the ranges 8.10–7.52 and 8.15–7.47 ppm, which are
shifted downfield relative to the signals of diethynyl
13
ment. All C NMR spectra of bis(cyclones) VI conꢀ
taining hexafluoroisopropylidene fragments show a
signal at –63.75 to –63.18 ppm split into septet due to
CF3 groups. Along with the above signals, the specꢀ
trum of compound VIb show a doublet signal of aroꢀ
matic moiety at 164.41–161.09 ppm typical of the carꢀ
bon atom directly bound to fluorine atom. The spectra
of compounds VIc and VId exhibit two and four douꢀ
blets at 164.04–163.95 and 160.75–160.67 and
164.48–164.38, 164.02–163.93, 161.15–161.06, and
160.78–160.68 ppm related to carbon atoms directly
bound to two and four nonequivalent fluorine atoms.
intermediates
electronꢀwithdrawing CO–CO groups. The distincꢀ
tive feature of the H NMR spectra of compounds
I on account of the inductive effect of
1
I
and II is the presence of strong singlets related to the
core benzene fragment. The 1H NMR spectra of comꢀ
pounds IVb and Vb show in aromatic region two douꢀ
blets at 7.57, 7.53 and 7.99, 7.52 ppm and two multipꢀ
lets at 7.51, 7.05 and 8.03, 7.21 ppm which agree well
with the supposed structures. The 1H NMR spectra of
compounds IVc and Vc are well resolved and show two
couples of singlets at 7.96, 7.83 and 8.46, 8.10 ppm and
two doublets at 7.57, 7.41 and 8.07, 7.59 ppm, respecꢀ
tively.
ACKNOWLEDGMENTS
1
Signal assignment in the H NMR spectra was
This work was supported by the Russian Academy
of Sciences, Division of Chemistry and Materials Sciꢀ
ence (project no. OKhꢀ2, “Design of New Metallic,
made on the basis of the integrated intensity ratio and
the values of spin–spin coupling constants. The
13C NMR spectra of all bis(ethynyl) compounds
I
and Ceramic, Glass, Polymeric, and Composite Mateꢀ
= 80–90 ppm show two intense rials”).
signals related to the acetylene fragments. In the case
of compounds IVa IVc, the spectra of aliphatic moiety
IV in the region of
δ
–
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DOKLADY CHEMISTRY Vol. 429
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2009