Chemistry of anthracene-acetylene oligomers. XIV. convenient synthesisof anthrylethynes by double elimination reaction from aldehydes and sulfones

Article abstract of DOI:10.1246/bcsj.82.1287

Three dianthrylethynes and an anthracene-acetylene trimer were conveniently synthesized by doubleelimination reactions starting from anthraldehydes and [(phenylsulfonyl)methyl]anthracenes. In the optimal one-shot process, a THF solution of these substrate

Full text of DOI:10.1246/bcsj.82.1287

© 2009 The Chemical Society of Japan
Bull. Chem. Soc. Jpn. Vol. 82, No. 10, 1287–1291 (2009) 1287
Chemistry of Anthracene-Acetylene Oligomers. XIV.
Convenient Synthesis of Anthrylethynes by Double
Elimination Reaction from Aldehydes and Sulfones1
Shinji Toyota,*1 Rie Azami,1 Tetsuo Iwanaga,1 Daisuke Matsuo,2 Akihiro Orita,2 and Junzo Otera2
1Department of Chemistry, Faculty of Science, Okayama University of Science,
1-1 Ridai-cho, Kita-ku, Okayama 700-0005
2Department of Applied Chemistry, Faculty of Engineering, Okayama University of Science,
1-1 Ridai-cho, Kita-ku, Okayama 700-0005
Received May 29, 2009; E-mail: stoyo@chem.ous.ac.jp
Three dianthrylethynes and an anthracene-acetylene trimer were conveniently synthesized by double elimination
reactions starting from anthraldehydes and [(phenylsulfonyl)methyl]anthracenes. In the optimal one-shot process, a THF
solution of these substrates and diethyl chlorophosphate was treated with LiHMDS at room temperature to give the
desired alkynes in excellent yields without chromatographic purification. The structure of one of the intermediate vinyl
sulfones was determined by X-ray crystallography.
Recently, ³-conjugated compounds with arylethyne repeat-
ing units have been extensively utilized in the chemistry
of molecular machines, organic electronics, and supramole-
cules.2,3 As such compounds, we reported the synthesis of
various anthrylene-ethynylene oligomers to reveal unique
structures, dynamic behavior, and photophysical properties.4
Sonogashira coupling of terminal alkynes and aryl halides has
been routinely used for the construction of arylene-ethynylene
oligomeric structures in most cases.5,6 However, the synthetic
efficiency is not always high because of the limitations of
the coupling reaction: slow conversions, contamination by
undesired homocoupling products, and instability of terminal
alkynes occasionally prepared by desilylation of silylated
alkynes.7 Although several improved conditions and proce-
dures have been reported for the coupling reactions,8 we
needed to adopt other methods for formation of triple bond
moieties toward efficient construction of a wide variety of
oligomeric structures. Double elimination of 1,2-disubstituted
alkanes is another general approach to various alkynes as
exemplified by dehydrohalogenation of 1,2-dihaloalkanes and
Wittig type reaction of carbonyl compounds.3f,9,10 One of the
authors’ groups developed a convenient protocol for the
synthesis of various diarylethynes from aldehydes and sulfones
under mild conditions (Scheme 1).11 The overall conversion
involves aldol type C-C bond formation, trapping of the
addition product with diethyl chlorophosphate (DECP), and
elimination of phosphoric acid and then sulfinic acid. The
series of reactions can be carried out in a simple procedure,
namely addition of a base solution into a solution of the other
reagents at room temperature (one-shot process) rather than
stepwise addition of each reagent (stepwise process).12 There-
fore, we applied this convenient method to the synthesis of
anthracene-substituted acetylenes. We herein report the effec-
tive and convenient synthesis of dianthrylethynes 1-3 and
Stepwise process
1) Base
PhSO2
O−
Ar'
PhSO2
Ar
OPO(OEt)2
ClPO(OEt)2
2) Ar'−CHO
Ar CH2SO2Ph
Ar
C
C
C
C
Ar'
H
H
H
H
Ar
Ar'
H
Base
Base
C
C
Ar
C
C
Ar'
PhSO2
One-shot process
Ar CH2SO2Ph
Base
+
+
Ar' CHO
ClPO(OEt)2
Ar
C
C Ar'
Scheme 1. Synthesis of diarylethynes from aldehydes and sulfones by double elimination.
Published on the web October 8, 2009; doi:10.1246/bcsj.82.1287

1288 Bull. Chem. Soc. Jpn. Vol. 82, No. 10 (2009)
Anthrylethynes by Double Elimination
1
2
3
4
Figure 1. Structures of target anthrylethynes.
anthracene-acetylene trimer 4, key structures in the series of
our studies on anthrylene-ethynylene oligomers, by the double
elimination approach (Figure 1).
Table 1. One-Shot Double Elimination Reactions of 5a and
6a for Synthesis of 1a)
CH2SO2Ph
CHO
Results and Discussion
+
ClPO(OEt)2
+
The reaction conditions for double elimination reaction were
optimized for the synthesis of di-9-anthrylethyne (1) from
aldehyde 5a and sulfone 6a. According to conditions reported
previously,12a the reaction was carried out with a small excess
of the sulfone and DECP (1.2 mmol each) relative to the
aldehyde (1.0 mmol) in THF. To a solution of these compounds
in THF was added lithium hexamethyldisilazide (LiHMDS)
or other bases (one-shot process) at 0 °C, and the mixture
was stirred at room temperature. The results are compiled in
Table 1. The above substrates were completely dissolved in
24 mL of THF, and this volume of solvent gave the highest
yield (Entries 1-3). The low concentration as well as the
presence of undissolved materials decreased the yields. The
reaction was almost completed in 18 h (Entries 2 and 4-6), and
the reaction time was set at 24 h. The yield was lowered with a
decrease of amount of base from five equivalents (Entries 2, 7,
and 8) although the overall reaction, in principle, requires three
equivalents of base relative to the starting materials. The
reactions with other typical bases, LDA and t-BuOK, were
unsuccessful for preparative purposes (Entries 9 and 10). The
above findings show that the conditions of Entry 2 gave the
best result among all reactions as far as we have carried out.
The desired product was obtained from the reaction mixture in
a simple manner by taking advantage of its low solubility. The
aqueous work-up was followed by evaporation, and the formed
precipitate was just collected by filtration and washed with
water. This material was found to be practically pure, and
if necessary was further purified by recrystallization from
dichloromethane without chromatography. The yields listed in
Table 1 are isolated yield after recrystallization.
We also synthesized other dianthrylethynes under optimal
conditions (Scheme 2). A minimum amount of solvent was
used for complete dissolution of the starting materials. Di-1-
anthrylethyne (2) was synthesized in 85% yield from the
corresponding aldehyde 5b and sulfone 6b. An unsymmetric
derivative, 1-(1-anthryl)-2-(9-anthryl)ethyne (3), was obtained
either from 5a and 6b or from 5b and 6a in excellent yield.
Dianthrylethynes 1-3 were previously prepared by Wittig type
reaction of phosphonium ylides with acid chlorides and the
subsequent thermal decomposition of betaines at 200-300 °C,
where the concurrently formed triphenylphosphine oxide
should be carefully removed by recrystallization.13,14 There-
fore, the present protocol is much more practical than the
5a
6a
Base
THF, rt
1
Entry THF/mL Base/mmolb)
Time/h Yield/%c)
1
2
3
4
5
6
7
8
9
12
24
48
24
24
24
24
24
12
12
5.0
5.0
5.0
5.0
5.0
5.0
4.0
3.0
24
24
24
18
12
6
24
24
24
24
63
86
78
79
62
47
60
54
39
39
5.0 (LDA in THF)
5.0 (t-BuOK)
10
a) The reaction was carried out with 5a (1.0 mmol), 6a
(1.2 mmol), and DECP (1.2 mmol) in THF at room temperature
(ca. 20 °C). b) Base is LiHMDS (THF solution) unless
otherwise stated. c) Isolated yield based on 5a after
recrystallization from dichloromethane.
classical method in terms of facile conversion under mild
conditions and simple work-up and purification procedures
without chromatography.
We obtained a moderate amount of vinyl sulfone 7 from the
reaction mixture by chance when 5b and 6a were reacted with a
LiHMDS solution that was not freshly prepared. We carried out
X-ray analysis with a single crystal of this intermediate. An
ORTEP drawing is shown in Figure 2, where the two anthryl
groups lie on the same side of the double bond, namely,
E form. This stereochemistry was also found in a cyclic
intermediate from 2-[(phenylsulfonyl)methyl]benzaldehyde.3g
This isolated sulfone 7 was converted to alkyne 3 upon
treatment with an additional amount of base. This finding
indicates that the second elimination takes place in syn fashion
to give the alkyne.
This protocol was also applied to the synthesis of trimer 4
(Scheme 3): this fundamental 1,8-anthrylene-ethynylene com-

S. Toyota et al.
Bull. Chem. Soc. Jpn. Vol. 82, No. 10 (2009) 1289
CH2SO2Ph
CHO
LiHMDS
+
+
ClPO(OEt)2
2 (85%)
THF, rt, 24 h
5b
6b
LiHMDS
+
+
+
+
6b
6a
ClPO(OEt)2
5a
3 (92%)
3 (89%)
THF, rt, 24 h
LiHMDS
ClPO(OEt)2
5b
THF, rt, 24 h
Scheme 2. Synthesis of dianthrylethynes 2 and 3 by one-shot double elimination.
CH2SO2Ph
CHO
CHO
LiHMDS
+
+
+
ClPO(OEt)2
4 (79%)
THF, rt, 24 h
6b
8
H
I
I
Pd(PPh3)4, CuI
+
4 (21%)
THF, NEt3
reflux, 68 h
10
9
11 (9%)
Scheme 3. Synthesis of anthrylene-ethynylene trimer 4 by one-shot double elimination and Sonogashira coupling.
reaction of 1,8-diiodoanthracene (9) and 1-ethynylanthracene
(10) gave only 21% of the desired product after chromato-
graphic purification to remove homocoupling product 11, other
minor by-products, phosphine, and phosphine oxide.
Conclusion
O
In summary, we developed a practical method for the
synthesis of anthrylethynes by a one-shot process involving
double elimination. The products were readily obtained in a
S
O
pure form by simple work-up and purification procedures. The
SO2Ph
H
double elimination protocol is useful for the synthesis of
symmetric and unsymmetric alkynes if the starting materials
are available, and especially important in the cases where
metal-catalyzed coupling is unsuccessful or the contamination
of a trace amount of transition metals results in significant
problems. Further applications of this method to the synthesis
of complex anthrylethynes are in progress to construct various
anthrylene-ethynylene structures.
7
Figure 2. ORTEP drawing of vinyl sulfone 7. Solvent
molecules are omitted for clarity.
Experimental
Melting points are uncorrected. Elemental analyses were
performed on a Perkin-Elmer 2400 series analyzer. 1H and
13C NMR spectra were measured on a Varian Gemini-300 at 300
and 75 MHz, respectively. High-resolution FAB mass spectra were
measured on a JEOL MStation-700 spectrometer. 9-Anthracene-
carbaldehyde (5a) is commercially available, and the other starting
pound is known to undergo unique photocycloaddition between
the terminal anthracene moieties.15 The reaction of 1,8-
anthracenedicarbaldehyde (8) and sulfone 6b gave the desired
trimer in 79% isolated yield. In contrast, the synthesis of this
trimer by Sonogashira coupling was far from practical. The

1290 Bull. Chem. Soc. Jpn. Vol. 82, No. 10 (2009)
Anthrylethynes by Double Elimination
materials except 1-[(phenylsulfonyl)methyl]anthracene were pre-
pared by known methods.
sulfone was obtained in 20-30% yield. This by-product was
separated by chromatography on silica gel with hexane-dichloro-
methane 5:1 eluent to give yellow crystals. A sample for
microanalysis was obtained by recrystallization from chloroform.
(E)-2-(1-Anthryl)-1-(9-anthryl)-1-(phenylsulfonyl)ethene (7): mp
1-[(Phenylsulfonyl)methyl]anthracene (6b). To a solution
of 1-(bromomethyl)anthracene16 (631 mg, 2.32 mmol) in DMF
(5 mL) was added sodium benzenesulfinate dihydrate (571 mg,
3.48 mmol). The mixture was heated at 80 °C for 10 min, then
poured into water and stirred for 30 min. The precipitate was
filtered, washed with water, and dried. The crude product was
purified by recrystallization from hexane-dichloromethane to give
the desired compound as light yellow crystals. Yield 761 mg
1
121-124 °C; H NMR (CDCl3): ¤ 6.71 (1H, t, J = 8.7 Hz), 6.83
(1H, d, J = 7.2 Hz), 7.10-7.17 (4H, m), 7.29-7.36 (4H, m), 7.41
(2H, d, J = 8.6 Hz), 7.55 (1H, t, J = 7.2 Hz), 7.64 (1H, t, J = 7.8
Hz), 7.73 (2H, d, J = 8.7 Hz), 7.93 (2H, d, J = 8.7 Hz), 7.98 (1H,
d, J = 8.7 Hz), 8.25 (1H, d, J = 7.8 Hz), 8.34 (1H, s), 8.48 (1H, s),
8.96 (1H, s), 9.52 (1H, s); 13C NMR (CDCl3): ¤ 121.90, 124.13,
124.35, 125.20, 125.70, 125.97, 126.14, 126.20, 126.30, 127.40,
127.88, 128.41, 128.60, 128.63, 128.88, 129.01, 129.22, 129.90,
130.74, 131.01, 131.07, 131.35, 131.52, 132.06, 133.21, 137.90,
138.66, 140.36; HRMS (FAB) calcd for C36H24O2S m/z 520.1497,
found m/z 520.1469 [M+]; Anal. calcd for C36H24O2S¢CHCl3: C,
69.43; H, 3.94%. Found: C, 69.79; H, 3.83%.
1
(99%); mp 122-144 °C (dec); H NMR (CDCl3): ¤ 4.96 (2H, s),
7.19 (1H, d, J = 7.1 Hz), 7.25-7.34 (3H, m), 7.39-7.49 (3H, m),
7.63 (2H, d, J = 7.9 Hz), 7.88 (1H, t, J = 7.6 Hz), 7.92-8.01 (2H,
m), 8.32 (1H, s), 8.37 (1H, s); 13C NMR (CDCl3): ¤ 60.32, 122.62,
124.22, 125.72, 125.84, 127.10, 127.70, 128.52, 128.63, 128.74,
128.79, 129.79, 130.09, 130.33, 131.33, 131.58, 131.70, 133.68,
137.95; HRMS (FAB) calcd for C21H16O2S m/z 332.0871, found
m/z 332.0857 [M+]; Anal. calcd for C21H16O2S: C, 75.88; H,
4.85%. Found: C, 75.95; H, 5.06%.
1,8-Bis(1-anthrylethynyl)anthracene (4).
This compound
was similarly prepared from 1,8-anthracenedicarbaldehyde (8)18
(81 mg, 0.35 mmol), 6b (276 mg, 0.83 mmol), DECP (0.12 mL,
0.83 mmol), and a LiHMDS solution (3.46 mL, 3.46 mmol) in dry
THF (5 mL). The crude product was recrystallized from chloro-
form to give the pure product as yellow crystals. Yield 158 mg
(79%); mp 300-303 °C; 1H NMR (CDCl3): ¤ 6.74 (2H, t, J =
8.4 Hz), 7.19-7.26 (2H, m), 7.54-7.60 (8H, m), 7.63-7.72 (2H, m),
7.85-7.89 (2H, m), 7.98 (2H, d, J = 8.6 Hz), 7.99 (2H, s), 8.14
(2H, d, J = 8.7 Hz), 8.62 (1H, s), 8.89 (2H, s), 10.22 (1H, s);
HRMS (FAB) calcd for C46H26 m/z 578.2035, found m/z
578.2013 [M+]; Anal. calcd for C46H26: C, 95.47; H, 4.53%.
Found: C, 95.14; H, 4.51%.
Typical Procedure for the One-Shot Process. To a solution
of 5a (206 mg, 1.00 mmol), 9-[(phenylsulfonyl)methyl]anthracene
(6a)17 (399 mg, 1.20 mmol), and DECP (0.173 mL, 1.20 mmol) in
¹1
dry THF (24 mL) was added a 1.0 mol L THF solution of
LiHMDS (5.0 mL, 5.0 mmol) at 0 °C under Ar. The solution was
stirred at 0 °C for 10 min then at room temperature for 24 h. After
the addition of aq NH4Cl (1 mL), the solvent was mostly removed
by evaporation. The precipitate was filtered, washed with water,
and dried in vacuo. The crude product was recrystallized from
dichloromethane to give the pure product as orange crystals. Di-9-
anthrylethyne (1): yield 326 mg (86%); mp 309-313 °C (dec) [ref.
310 °C (dec)];13 1H NMR (CDCl3): ¤ 7.56 (4H, t, J = 8.2 Hz), 7.66
(4H, t, J = 7.9 Hz), 8.08 (4H, d, J = 8.6 Hz), 8.52 (2H, s), 8.91
(4H, d, J = 8.6 Hz); HRMS (FAB) calcd for C30H18 m/z 378.1409,
found m/z 378.1428 [M+]. The reactions under various conditions
were similarly carried out.
This compound was also synthesized by Sonogashira coupling.
To a degassed solution of 1-ethynylanthracene (10)19 (100 mg,
0.50 mmol) and 1,8-diiodoanthracene (9)20 (71 mg, 0.17 mmol) in a
mixture of THF (15 mL) and NEt3 (15 mL) were added Pd(PPh3)4
(19.1 mg, 17 ¯mol) and CuI (4.7 mg, 25 ¯mol). The reaction
mixture was refluxed for 68 h under Ar atmosphere. The solvent
was evaporated, and the residue was subjected to chromatography
on silica gel with hexane-chloroform 2:1 eluent. The desired
compound was obtained as a yellow solid (20 mg) in 21% yield. A
small amount of di-1-anthrylbutadiyne19 was also isolated as a
yellow solid. Di-1-anthrylbutadiyne (11): yield 9 mg (9%); mp
296-297 °C (dec) [ref. 289-291 °C (dec)];19 1H NMR (CDCl3):
¤ 7.47 (2H, dd, J = 6.3, 7.8 Hz), 7.52-7.56 (4H, m), 7.91 (2H,
d, J = 7.2 Hz), 8.03-8.09 (4H, m), 8.18 (2H, d, J = 9.3 Hz), 8.49
(2H, s), 9.02 (2H, s); HRMS (FAB) calcd for C32H18 m/z
402.1409, found m/z 402.1443 [M+].
Di-1-anthrylethyne (2).
This compound was similarly
prepared from 1-anthracenecarbaldehyde (5b)16 (71 mg, 0.35
mmol), 6b (138 mg, 0.42 mmol), DECP (0.060 mL, 0.42 mmol),
and a LiHMDS solution (1.73 mL, 1.73 mmol) in dry THF (3 mL).
The crude product was recrystallized from diethyl ether to give the
pure product as yellow crystals. Yield 112 mg (85%); mp 272-
275 °C (ref. 267-270 °C);13 1H NMR (CDCl3): ¤ 7.51-7.55 (6H,
m), 7.96 (2H, d, J = 7.2 Hz), 8.06-8.15 (6H, m), 8.51 (2H, s), 9.23
(2H, s); HRMS (FAB) calcd for C30H18 m/z 378.1409, found m/z
378.1450 [M+].
1-(1-Anthryl)-2-(9-anthryl)ethyne (3).
Method 1: The
reaction was similarly carried out with 5a (71 mg, 0.35 mmol),
6b (138 mg, 0.42 mmol), DECP (0.060 mL, 0.42 mmol), and a
LiHMDS solution (1.73 mL, 1.73 mmol) in dry THF (7 mL). The
crude product was recrystallized from diethyl ether to give the pure
product as yellow crystals (120 mg) in 92% yield. Method 2: The
reaction was similarly carried out with 5b (71 mg, 0.35 mmol),
6a (138 mg, 0.42 mmol), DECP (0.060 mL, 0.42 mmol), and the
LiHMDS solution (1.73 mL, 1.73 mmol) in dry THF (7 mL). The
crude product was recrystallized from diethyl ether to give the pure
product as yellow crystals (116 mg) in 89% yield. Mp 284-286 °C
(ref. 286-288 °C);13 1H NMR (CDCl3): ¤ 7.51-7.59 (5H, m), 7.67
(2H, t, J = 8.7 Hz), 8.01-8.09 (6H, m), 8.51 (1H, s), 8.52 (1H, s),
8.88 (2H, d, J = 7.8 Hz), 9.27 (1H, s); HRMS (FAB) calcd for
C30H18 m/z 378.1409, found m/z 378.1440 [M+].
X-ray Analysis.
A single crystal of 7 was obtained by
crystallization from a chloroform solution. The diffraction data
were collected on a Rigaku RAXIS-IV imaging plate diffractom-
eter with Mo K¡ radiation (- = 0.71070 ¡) to a maximum 2ª
value of 55.0° at ¹150 °C. The reflection data were corrected for
Lorentz-polarization effects and secondary extinction. The struc-
ture was solved by direct method (SHELXS-97)21 and refined by a
full-matrix least-squares method. The non-hydrogen atoms were
refined anisotropically, and hydrogen atoms were refined isotropi-
cally. Formula C36H24O2S¢CHCl3, FW 639.98, crystal size 0.60 ©
0.45 © 0.18 mm3, monoclinic, space group P21/c (No. 14), a =
12.9479(9), b = 10.0875(4), c = 23.4865(18) ¡, ¢ = 97.8576(9)°,
V = 3038.8(3) ¡3, Z = 4,
Dcalcd = 1.399 g cm , ®(Mo K¡) =
¹3
0.404 mm¹1, No. of data 6576, R1 = 0.0511 [I > 2.00·(I)],
wR2 = 0.1205, GOF = 1.094. Crystallographic data have been
deposited with the Cambridge Crystallographic Data Centre as
When the reaction of Method 2 was carried out with a LiHMDS
solution that was not freshly prepared, the intermediate vinyl

S. Toyota et al.
Bull. Chem. Soc. Jpn. Vol. 82, No. 10 (2009) 1291
coupling product of the former substrate. See, Ref. 4b.
deposition number CCDC 726901. Copies of the data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/conts/
retrieving.html (or from the Cambridge Crystallographic Data
Centre, 12, Union Road, Cambridge, CB2 1EZ, U.K.; Fax: +44
1223 336033; e-mail: deposit@ccdc.cam.ac.uk).
8
a) K. Nakamura, H. Okubo, M. Yamaguchi, Synlett 1999,
549. b) T. Hundertmark, A. F. Littke, S. L. Buchwald, G. C. Fu,
Org. Lett. 2000, 2, 1729. c) A. Soheili, J. Albaneze-Walker, J. A.
Murry, P. G. Dormer, D. L. Hughes, Org. Lett. 2003, 5, 4191. d) A.
Elangovan, Y.-H. Wang, T.-I. Ho, Org. Lett. 2003, 5, 1841. e) Y.
Nishihara, E. Inoue, Y. Okada, K. Takagi, Synlett 2008, 3041. f) Z.
Novák, P. Nemes, A. Kotschy, Org. Lett. 2004, 6, 4917.
This work was partly supported by a Grant-in-Aid for
Scientific Research on Priority Areas “Advanced Molecular
Transformations of Carbon Resources” (No. 19020069) from
MEXT (Ministry of Education, Culture, Sports, Science and
Technology) and by a “High-Tech Research Center” Project for
Private Universities: matching fund subsidy from MEXT. The
authors thank Mr. M. Kuga and Ms. A. Takatsu for technical
assistance.
9
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10 A. Orita, J. Otera, Chem. Rev. 2006, 106, 5387.
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