Copper nano-catalyst: Sustainable phenyl-selenylation of aryl iodides and vinyl bromides in water under ligand free conditions

Article abstract of DOI:10.1039/b819137a

A simple and efficient procedure for the synthesis of aryl- and vinyl-selenides has been developed by a copper nanoparticle catalysed reaction of aryl iodide/vinyl bromide with diphenyl diselenide in the presence of zinc in water. (E)-Vinyl bromides produce (E)-vinyl selenides stereoselectively, whereas (Z)-vinyl bromides provide mixtures of (E) and (Z) isomers. The catalyst was recycled.

Full text of DOI:10.1039/b819137a

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www.rsc.org/obc | Organic & Biomolecular Chemistry
Copper nano-catalyst: sustainable phenyl-selenylation of aryl iodides and
vinyl bromides in water under ligand free conditions†
Amit Saha, Debasree Saha and Brindaban C. Ranu*
Received 28th October 2008, Accepted 23rd January 2009
First published as an Advance Article on the web 28th February 2009
DOI: 10.1039/b819137a
A simple and efficient procedure for the synthesis of aryl- and vinyl-selenides has been developed by a
copper nanoparticle catalysed reaction of aryl iodide/vinyl bromide with diphenyl diselenide in the
presence of zinc in water. (E)-Vinyl bromides produce (E)-vinyl selenides stereoselectively, whereas
(Z)-vinyl bromides provide mixtures of (E) and (Z) isomers. The catalyst was recycled.
Table 1 Reaction of iodobenzene with diphenyl diselenide using Cu
nanoparticles and Zn in different solvents
Introduction
The aryl–heteroatom bond formation is an important process and
Entry
Solvent
Temp. (◦C)
Yield (%)
requires activation of the aryl moiety. This is usually accomplished
in the presence of a transition metal.1 Organoselenium compounds
in general have been the subject of renewed interest because of their
potential as anticancer and antioxidant agents.2 Vinyl selenides
are very useful precursors in organic synthesis and are often used
as intermediates in the preparation of carbonyl compounds and
functionalized alkenes.3 Thus a number of methods have been
developed for their synthesis.4,5,6 Usually, aryl selenides were pre-
pared by the reaction of halobenzene with phenylselenol (PhSeH)
or benzene selenolate anion (PhSeNa) or diphenyl diselenide (Ph-
SeSePh) in the presence of a transition metal catalyst such as Pd,4
Ni,5 or Cu-salt6 among others.7 However, Cu-catalysed reactions6
using PhSeSePh have been of much interest, possibly because of
the easy availability and low cost of copper derivatives and the
easy handling of the selenium reagent. These catalysts include
CuI/DMSO,6a,6b CuI-bpy in DMSO–H2O,6c CuI/L- proline/Zn
in [bmim]BF4,6d Cu2O-bpy/Mg in DMF,6e CuI/ligand/base in
ionic liquid,6f CuI-bpy/Al in DMF,6g CuI-bpy/Mg in DMF
under microwave irradiation,6h CuI/neocuproine in toluene,6i
and CuI/HMPA.6j In general, all of these methods addressed
either aryl selenides6b,6c,6e,6g,6h,6i or vinyl selenides6a,6d,6f,6j with the
exception of one6b which included two examples of (E)-vinyl
selenides together with aryl selenides. Recently, we reported a one-
pot synthesis of vinyl selenides by an InI promoted cleavage of
diphenyl diselenide and subsequent Pd(0)-catalysed condensation
with vinylic bromides.4a We considered it worthwhile to develop a
general and simpler procedure for both aryl and vinyl selenides
using a copper catalyst and diphenyl diselenide in a benign
reaction media. As part of our continued activities8 towards useful
transformations we report here a copper nanoparticle-catalysed
synthesis of aryl and vinyl selenides by phenyl-selenylation of
aryl iodides and vinyl bromides in H2O without using any ligand
(Scheme 1).The use of metal nanoparticles as efficient catalysts
in organic reactions has attracted considerable interest and has
undergone tremendous growth in recent times.9
1
2
3
4
5
MeOH
EtOH
THF
DMF
H2O
65
78
66
120
100
32
38
41
78
88
Scheme 1 Phenyl-selenylation of aryl iodides and vinyl bromides.
Results and discussion
To standardise the reaction conditions a series of reactions
were performed in different solvents at varied temperatures as
illustrated in Table 1. It was found that the reaction proceeds
well in water under reflux giving the best yield using 20 mol% of
Cu nanoparticles. With a lesser amount of Cu nanoparticles the
reactions remained incomplete within a reasonable time period.
Thus all reactions were carried out at 100 ◦C in water using
20 mol% of the Cu catalyst.
Cu nanoparticles were prepared from copper sulfate by re-
duction with hydrazine hydrate in ethylene glycol.10 The sizes
(average diameter: 4.3 0.6 nm, polydispersity index (PDI): 13.9%)
of the Cu nanoparticles were determined by a Transmission
Electron Microscope (TEM), (Fig. 1) and their identities were
established by Energy Dispersive X-ray spectroscopy (Fig. 2),
and UV spectroscopy (Fig. 3). The polydispersity index was also
determined by a Dynamic Light Scattering (DLS) experiment
(Fig. 4) as 13.3% and thus is in agreement with the value obtained
by TEM. The increase of the particle size (hydrodynamic radii)
in the DLS experiment was due to the solvation effect in solution
phase.
The experimental procedure was very simple. A mixture of
aryl iodide/vinyl bromide, diphenyl diselenide, Cu nanoparticles
(20 mol%) and Zn dust in water was heated under reflux for
a period of time as required to complete the reaction (Thin
Layer Chromatography, TLC). Standard work-up and purification
provided the product. Several substituted aryl iodides and vinyl
Department of Organic Chemistry, Indian Association for the Cultivation
of Science, Jadavpur, Kolkata – 700 032, India. E-mail: ocbcr@iacs.res.in;
Fax: +91 33 24732805
† Electronic supplementary information (ESI) available: Copies of 1H and
13C NMR spectra of all products in Table 2. See DOI: 10.1039/b819137a
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Fig. 1 TEM image of the Cu nanoparticles.
Fig. 4 Histogram of particle sizes obtained from the DLS experiment.
of the products. The aliphatic vinyl bromide (entry 15, Table 2)
also participated in this reaction.
In general, the reactions are very clean and high yielding.
Several functionalities such as OMe, NO2, CO2H, CO2Me, CF3
and Cl are compatible with this procedure. After extraction of
product, the remaining Cu nanoparticles were recycled for three
more runs with a gradual loss of efficiency (Fig. 5) possibly due
to the agglomerating tendency of the Cu nanoparticles during
exposure in subsequent runs as shown by a TEM image of the Cu
nanoparticles after the first cycle (38–59 nm) (Fig. 6). Usually, the
reactivity and efficiency of nanoparticles decrease with an increase
of size.11
Fig. 2 EDX spectroscopy of the Cu nanoparticles.
Fig. 5 Recyclability chart.
Fig. 3 UV spectrum of the Cu nanoparticles.
bromides underwent phenyl-selenylation to produce the corre-
sponding aryl/vinyl phenyl selenides by this procedure. The results
are summarized in Table 2.
With both electron donating and electron withdrawing sub-
stituents on the aromatic ring of the aryl iodides the reaction
proceeded without any difficulty. 2-Iodobenzoic acid was con-
verted to the corresponding phenyl selenide without any damage
to the carboxylic acid group. The reactions with (E)-styrenyl
bromides (entries 8,10,12,14, Table 2) are highly stereoselective
giving (E)-selenides. However, the (Z)-vinyl bromides (entries
9,11,13, Table 2) produced mixtures of (E)-and (Z)-isomers. A
change of solvent from water to DMF or THF did not improve
the stereoselective distribution of products. The nature of the
substituents on the aromatic ring of the styrenyl bromide did
not have any profound effect in the control of stereoselectivity
Fig. 6 TEM image of the recovered Cu nanoparticles after the first cycle.
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Table 2 Synthesis of aryl/vinyl selenides using Cu nanoparticles and Zn
all in the absence of Cu nanoparticles. Thus, a combination of Zn
and Cu nanoparticles is essential for this reaction. Regarding the
mechanism of this reaction it is suggested that Cu(0) nanoparticles,
having a lower redox potential11 than metallic Cu(0), undergo
oxidative addition readily with diphenyl diselenide to form an
intermediate, (PhSe)2Cu(II)6e (Scheme 2). On reduction by Zn
this intermediate leads to the key intermediate, PhSeCu(I) which
reacts with ArI to give the product ArSePh via a transient Cu(III)
intermediate.6e,6g,6k Support for the involvement of PhSeCu(I) in
the reaction cycle was gained when it was found that PhSeCu(I),
prepared separately by a different route,12 reacts with ArI giving
similar results. The CuI, generated in the reaction of PhSeCu(I)
with ArI (Scheme 2), undergoes reduction by Zn to regenerate
Cu(0) nanoparticles which initiate the next cycle. The Zn(SePh)2
formed in the reduction process of Cu(SePh)2 by Zn, reacts with
CuI to give PhSeCu(I). Thus both PhSe moieties of PhSeSePh are
used up in the process.
Yield
Entry R-X
1
Product
Time (h) (%)a Ref.
10
88
72
6e
2
3
12
6e
10
8
87
90
92
75
6e
14
6i
4
5
6
8
8
6i
7
8
9
12
8
83
89
87
4a
4a
Scheme 2 Probable mechanistic pathway.
9
The retention of stereochemistry in the reaction of (E)-vinyl
bromides and the loss of stereochemistry in (Z)-vinyl bromides
may be explained as follows (Scheme 3). The Cu(III) intermediate
A suffers a serious steric interaction between the PhSe and
Ar moieties in the case of (Z)-vinyl bromides, resulting in the
elimination of PhSeH to give a linear Cu(I) vinylidene complex13
as a transient intermediate B. PhSeH then undergoes re-addition
10
11
10
10
87
86
6d
4a
12
13
12
11
88
86
4a
4a
14
15
8
92
82
4a
15
12
a Yields refer to those of the purified products characterized by IR, 1H, 13
NMR spectroscopic data.
C
In the absence of Zn dust the reaction of iodobenzene with
diphenyl diselenide gave only a marginal yield (6%) of the
corresponding product, whereas the reaction did not proceed at
Scheme 3 Stereoselectivity in the phenyl-selenylation of vinyl bromides.
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Table 3 Comparison of the reactions of aryl iodides/vinyl bromides with
diphenyl diselenide in the presence of Cu nanoparticles and metallic copper
powder
for (E)-vinyl selenides, high yields, recyclability of the catalyst to a
certain extent and water as the reaction medium. To the best of our
knowledge, this is the first report of Cu(0) nanoparticle-catalysed
cross couplings of aryl iodides and vinyl bromides with diphenyl
diselenide.
Temp.
(◦C)
Time Yield (%)
Yield (%)
Entry Substrate
1
(h)
Metallic Cu Cu NP
100
10
40
38
88
Experimental
IR spectra were taken as thin films for liquid compounds and
as KBr pellets for solids on a FT-8300 Shimadzu spectrometer.
NMR spectra were recorded on a Bruker DPX 300 instrument at
2
100
8
92
1
300 MHz for H NMR and at 75 MHz for 13C NMR in CDCl3
3
4
100
100
10
12
35
43
87
88
solutions.
Representative experimental procedure for phenyl-selenylation
(entry 1, Table 2)
To a stirred mixture of Cu nanoparticles (13 mg, 0.2 mmol)
and Zn dust (100 mg, 1.5 mmol) in water (2.5 mL) were added
iodobenzene (204 mg, 1 mmol), and diphenyl diselenide (156 mg,
0.5 mmol). The mixture was heated to reflux (oil bath) for 10 h
(TLC). After being cooled the reaction mixture was extracted
with Et2O (3 ¥ 10 mL). The ether extract was washed with water
and brine and dried (Na2SO4). The solvent was evaporated under
reduced pressure to leave a crude product that was purified by
column chromatography over silica gel (hexane) to afford the pure
product, diphenyl selenide (206 mg, 88%) as a colourless oil. IR
Table 4 Comparison of Cu nanoparticle catalysed phenyl-selenylation of
aryl iodides and vinyl bromides with other copper catalysed methods
Cu2O, bpy,
Mg6e
CuI, L-proline,
Zn6d
Copper
nanoparticles, Zn
Solvent
DMF
110
18–36
53–95
[bmim]BF4
110
24
H2O
100
8–12
72–92
Temp. (◦C)
Time (h)
Yield (%)
1
(neat) nmax/cm-1 3055, 2993, 1573, 1475, 1436, 1020. H NMR
68–91
(300 MHz, CDCl3) d: 7.33–7.35 (m, 6H), 7.55–7.58 (m, 4H). 13C
NMR (75 MHz, CDCl3) d: 127.4 (2C), 129.4 (4C), 131.3 (2C),
133.1 (4C). The aqueous part containing the Cu nanoparticles
and zinc residue was recycled in subsequent reactions.
to the Cu(I) vinylidene complex B from both stereogenic faces
leading to two isomeric Cu(III) intermediates C and A which on
reductive elimination provide a mixture of (E)- and (Z)-isomers.
On the other hand, direct reductive elimination from intermediate
A may lead to (Z)-vinyl selenides.
A comparative study of the reaction of aryl iodides and vinyl
bromides with diphenyl diselenide using freshly prepared Cu
powder and Cu(0) nanoparticles (Table 3) under identical con-
ditions established the higher efficiency of the Cu(0) nanoparticles
compared to Cu powder.
This procedure was followed for all the reactions listed in
Table 2. All of these products except one (entry 7, Table 2)
are known and have been identified by comparison of their
1
spectroscopic data (IR, H NMR and 13C NMR) with those re-
ported (references in Table 2). The compounds were characterised
properly by their spectroscopic data as follows:
1-Methoxy-4-phenylselanylbenzene (entry 2, Table 2)
Yield 72%, (colourless oil). IR (neat) nmax/cm-1 3056, 2935, 1680,
1592, 1490, 1462, 1438, 1385, 1248, 1102, 1032, 1006, 735. H
NMR (CDCl3, 300 MHz) d 3.82 (s, 3H), 6.87 (d, J = 8.6 Hz, 2H),
7.20–7.24 (m, 3H), 7.33–7.35 (m, 2H), 7.52 (d, J = 8.6 Hz, 2H).
13C NMR (CDCl3, 75 MHz) d 55.4, 115.2 (2C), 120.0, 126.6, 129.3
(2C), 131.0 (2C), 133.3, 136.7 (2C), 159.9.
Furthermore, a comparison of the results of our procedure with
those of two other related procedures using Cu2O/bpy/Mg6e and
CuI/L-proline/Zn6d also showed a better performance by Cu(0)
nanoparticles (Table 4). Interestingly, although reactions of (E)-
vinyl bromides were addressed in a few procedures,6a,6d,6j those
of (Z)-vinyl bromides6f were reported only in one paper (two
examples).
1
1-Nitro-4-phenylselanylbenzene (entry 3, Table 2)
Yield 87% (pale yellow oil). IR (neat) nmax/cm-1 2922, 2360, 1655,
1575, 1472, 1438, 1109, 1062, 850, 772, 737, 690. 1H NMR (CDCl3,
300 MHz) d 7.33–7.45 (m, 5H), 7.61–7.64 (m, 2H), 8.02 (d, J =
8.8 Hz, 2H). 13C NMR (CDCl3, 75 MHz) d 124.0 (2C), 127.2,
129.4, 129.7 (2C), 130.1 (2C), 135.9 (2C), 144.0, 146.2.
Conclusion
In conclusion, we have developed a procedure for the efficient
synthesis of unsymmetrical aryl and vinyl selenides by copper(0)
nanoparticle-catalysed phenyl-selenylation of aryl iodides and
vinyl bromides in the presence of Zn in water and in the absence of
any ligand. The significant advantages of this procedure are sim-
plicity in operation, neutral reaction conditions and compatibility
with a variety of functional groups, general applicability to the
synthesis of both aryl and vinyl selenides, excellent stereoselectivity
2-Phenylselanyl-benzoic acid (entry 4, Table 2)
Yield 90% (white solid). IR (KBr) nmax/cm-1 2972, 2871, 2827,
2659, 2563, 1670, 1583, 1556, 1460, 1415, 1313, 1282, 1259, 1151,
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1
1031, 1020, 750, 734, 682. H NMR (CDCl3, 300 MHz) d 6.92–
Mixture of (E)- and (Z)-1-methyl-4-(2-phenylselanylvinyl)-
6.95 (m, 1H), 7.20–7.25 (m, 2H), 7.43–7.46 (m, 3H), 7.71–7.73
(m, 2H), 8.18–8.21 (m, 1H). 13C NMR (CDCl3, 75 MHz) d 125.0,
126.2, 128.8, 129.2, 129.4, 130.0 (2C), 132.6, 133.6, 137.7 (2C),
141.7, 172.3.
benzene (entry 11, Table 2)
Yield 86% (pale yellow oil). IR (neat) nmax/cm-1 3015, 1634, 1640.
1H NMR (CDCl3, 300 MHz) d 2.22 (s, 3H), 2.26 (s, 3H), 6.62 (d,
J = 10.3 Hz, 1H), 6.77 (d, J = 15.7 Hz, 1H), 6.85 (d, J = 10.3 Hz,
1H), 6.99–7.23 (m, 15H), 7.42–7.49 (m, 4H). 13C NMR (CDCl3,
75 MHz) d 21.3, 21.4, 117.8, 122.8 (2C), 126.1 (2C), 127.3, 127.6
(2C), 128.3 (2C), 129.1 (2C), 129.3 (4C), 129.4, 130.1, 130.5, 131.8,
132.3, 132.7 (2C), 134.3, 134.5, 137.2 (2C), 137.7.
2-Phenylselanylbenzoic acid methyl ester (entry 5, Table 2)
Yield 92% (colourless oil). IR (neat) nmax/cm-1 3055, 3014, 2997,
2949, 1708, 1583, 1560, 1303, 1273, 1253, 1141, 1101, 738, 692. 1H
NMR (CDCl3, 300 MHz) d 3.96 (s, 3H), 6.89–6.92 (m, 1H), 7.14–
7.19 (m, 2H), 7.40–7.45 (m, 3H), 7.69–7.71 (m, 2H), 8.02–8.05
(m, 1H). 13C NMR (CDCl3, 75 MHz) d 52.7, 125.2, 127.5, 129.3,
129.4, 129.6, 130.2 (2C), 131.7, 133.0, 138.0 (2C), 140.9, 167.7.
(E)-1-Chloro-4-(2-phenylselanylvinyl)-benzene (entry 12, Table 2)
Yield 88% (pale yellow oil). IR (neat) nmax/cm-1 3028, 1575, 1488,
1
1436. H NMR (CDCl3, 300 MHz) d 6.89 (d, J = 15.7 Hz, 1H),
7.26–7.47 (m, 8H), 7.66–7.69 (m, 2H). 13C NMR (CDCl3, 75 MHz)
d 120.8, 127.3 (2C), 127.8, 128.9 (2C), 129.5 (3C), 129.8, 132.9 (2C),
133.3, 135.6.
1-(4-Phenylselanylphenyl) ethanone (entry 6, Table 2)
Yield 75% (pale yellow solid). IR (KBr) nmax/cm-1 3054, 2995,
1678, 1581, 1468, 1432, 1393, 1268, 1057, 1002, 956, 819, 747, 690.
1H NMR (CDCl3, 300 MHz) d 2.53 (s, 3H), 7.33–7.37 (m, 5H),
7.56–7.59 (m, 2H), 7.77 (d, J = 8.4 Hz, 2H). 13C NMR (CDCl3,
75 MHz) d 26.5, 128.4, 128.6 (2C), 128.9 (2C), 129.7 (2C), 130.3
(2C), 135.1 (2C), 140.3, 197.3.
Mixture of (E)- and (Z)-1-chloro-4-(2-phenylselanylvinyl)-benzene
(entry 13, Table 2)
Yield 86% (pale yellow oil). IR (neat) nmax/cm-1 3028, 1488, 734.
1H NMR (CDCl3, 300 MHz) d 6.60–6.69 (m, 2H), 6.77 (d, J =
10.4 Hz, 1H), 7.00–7.21 (m, 15H), 7.40–7.49 (m, 4H). 13C NMR
(CDCl3, 75 MHz) d 120.7, 125.0, 127.2 (2C), 127.7, 127.8, 128.6
(2C), 128.8 (4C), 129.4 (2C), 129.4 (2C), 129.5, 129.7, 130.9, 131.3,
132.8 (2C), 132.9 (2C), 133.1, 133.2, 135.5, 135.7.
1-Phenylselanyl-3-trifluoromethyl-benzene (entry 7, Table 2)
Yield 83% (Pale yellow oil). IR (neat) nmax/cm-1 3060, 2927, 1577,
1477, 1421, 1321, 1166, 1128. 1H NMR (CDCl3, 300 MHz) d: 7.26–
7.40 (m, 4H), 7.47–7.68 (m, 5H). 13C NMR (CDCl3, 75 MHz) d:
135.18, 134.0 (2C), 133.1, 129.6 (2C), 129.5, 129.4, 128.5, 128.2,
125.5, 123.7, 121.9. HRMS Calc. for C13H9F3SeNH3+ (M++NH3):
319.0087, Found: 318.8902.
(E)-1-Methoxy-4-(2-phenylselanylvinyl)-benzene (entry 14,
Table 2)
Yield 92% (colourless oil). IR (neat) nmax/cm-1 3029, 1432, 732. 1H
NMR (CDCl3, 300 MHz) d 3.72 (s, 3H), 6.76–6.82 (m, 3H), 6.94
(d, J = 15.6 Hz, 1H), 7.19–7.24 (m, 5H), 7.43–7.46 (m, 2H). 13C
NMR (CDCl3, 75 MHz) d 55.4, 114.2 (2C), 116.0, 127.2, 127.5
(2C), 129.4 (2C), 130.0, 130.9, 132.1 (2C), 136.0, 159.5.
(E)-2-Phenylselanyl-vinyl benzene (entry 8, Table 2)
Yield 89% (colourless oil). IR (neat) nmax/cm-1 3050, 1585, 1476.
1H NMR (CDCl3, 300 MHz) d 6.88 (d, J = 15.7 Hz, 1H), 7.16–
7.33 (m, 9H), 7.54–7.57 (m, 2H). 13C NMR (CDCl3, 75 MHz) d
119.5, 126.2 (2C), 127.6, 127.8 (2C), 128.8 (2C), 129.5 (2C), 130.3,
132.7, 135.3, 137.1.
Mixture of (E)- and (Z)-Undec-1-enylselanylbenzene (entry 15,
Table 2)
Yield 82% (pale yellow oil). IR (neat) nmax/cm-1 2954, 2923, 2852,
1577, 1477, 1436, 734. 1H NMR (CDCl3, 300 MHz) d 0.90 (t, J =
6.7 Hz, 6H), 1.29–1.45 (m, 28H), 2.13–2.23 (m, 4H), 6.03–6.15 (m,
Mixture of (E)- and (Z)-2-phenylselanyl-vinyl benzene (entry 9,
Table 2)
2H), 6.37–6.46 (m, 2H), 7.26–7.30 (m, 6H), 7.45–7.50 (m, 4H). 13
C
Yield 87% (colourless oil). IR (neat) nmax/cm-1 3050, 1579, 1477.
1H NMR (CDCl3, 300 MHz) d 6.80 (d, J = 10.3 Hz, 1H), 6.89 (d,
J = 15.7 Hz, 1H), 6.99 (d, J = 10.3 Hz, 1H), 7.17–7.42 (m, 17H),
7.55–7.59 (m, 4H). 13C NMR (CDCl3, 75 MHz) d 119.5, 124.1,
126.1 (2C), 127.3, 127.5, 127.7 (4C), 128.4 (2C), 128.5 (2C), 128.7
(2C), 129.3 (4C), 130.2 (2C), 131.7, 132.6, 132.8, 135.2, 137.1,
137.3.
NMR (CDCl3, 75 MHz) d 13.2 (2C), 21.8 (2C), 28.0 (2C), 28.2,
28.3, 28.4, 28.6 (2C), 28.7 (2C), 30.3 (2C), 31.0 (2C), 33.4, 115.0,
119.1, 125.7, 125.8 (2C), 128.2 (4C), 130.4 (2C), 130.8 (2C), 134.6
(2C), 139.9.
Acknowledgements
We are pleased to acknowledge the financial support from DST
[Grant No. SR/S5/GC-02/2006] for this investigation. A.S. and
D.S. thank CSIR, New Delhi for their fellowship.
(E)-1-Methyl-4-(2-phenylselanylvinyl)-benzene (entry 10, Table 2)
Yield 87% (colourless oil). IR (neat) nmax/cm-1 3049, 3020, 1575,
1
1508, 1475, 1435. H NMR (CDCl3, 300 MHz) d 2.37 (s, 3H),
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126.1 (2C), 127.3, 129.4 (2C), 129.5 (2C), 130.6, 132.4 (2C), 134.4,
135.8, 137.7.
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