Efficient one-pot preparation of methylthio arylbutadiynes by double elimination protocol

Article abstract of DOI:10.1080/00397911.2012.729280

A novel and efficient method for preparation of methylthio arylbutadiynes (Ar-C≡C-C≡C-SCH₃) was described, and a series of compounds have been expediently obtained by the one-pot protocol starting from methylthiomethyl phenyl sulfone (MP-S) and arylpropargyl aldehydes. The mechanism was discussed on the basis of trapping and characterization of key intermediates. The results from experiments indicated that the reaction involved the initial nucleophilic addition of MP-S to arylpropargyl aldehydes to produce an intermediate carrying two leaving groups and subsequent double elimination reactions. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file.

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Efficient One-Pot Preparation of
Methylthio Arylbutadiynes by Double
Elimination Protocol
Qiong Su a , Hong Yan a , Shi-Chao Gao a , De-Xun Xie a , Qing-Yun Cai
a , Guang Shao b , Zhi-Hong Peng a & De-Lie An a
a State Key Laboratory of Chemo/biosensing and Chemometrics,
College of Chemistry and Chemical Engineering, Hunan University ,
Changsha , China
b College of Chemistry and Chemical Engineering, Sun Yat-Sen
University , Guangzhou , China
Accepted author version posted online: 05 Apr 2013.Published
online: 26 Jun 2013.
To cite this article: Qiong Su , Hong Yan , Shi-Chao Gao , De-Xun Xie , Qing-Yun Cai ,
Guang Shao , Zhi-Hong Peng & De-Lie An (2013) Efficient One-Pot Preparation of Methylthio
Arylbutadiynes by Double Elimination Protocol, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 43:19, 2648-2655, DOI:
10.1080/00397911.2012.729280
To link to this article: http://dx.doi.org/10.1080/00397911.2012.729280
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Synthetic Communications1, 43: 2648–2655, 2013
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2012.729280
EFFICIENT ONE-POT PREPARATION OF METHYLTHIO
ARYLBUTADIYNES BY DOUBLE ELIMINATION
PROTOCOL
Qiong Su,1 Hong Yan,1 Shi-Chao Gao,1 De-Xun Xie,1
Qing-Yun Cai,1 Guang Shao,2 Zhi-Hong Peng,1 and
De-Lie An1
1State Key Laboratory of Chemo=biosensing and Chemometrics, College of
Chemistry and Chemical Engineering, Hunan University, Changsha, China
2College of Chemistry and Chemical Engineering, Sun Yat-Sen University,
Guangzhou, China
GRAPHICAL ABSTRACT
Abstract A novel and efficient method for preparation of methylthio arylbutadiynes
(Ar-CꢀC-CꢀC-SCH3) was described, and a series of compounds have been expediently
obtained by the one-pot protocol starting from methylthiomethyl phenyl sulfone (MP-S)
and arylpropargyl aldehydes. The mechanism was discussed on the basis of trapping and
characterization of key intermediates. The results from experiments indicated that the reac-
tion involved the initial nucleophilic addition of MP-S to arylpropargyl aldehydes to pro-
duce an intermediate carrying two leaving groups and subsequent double elimination
reactions.
Supplemental materials are available for this article. Go to the publisher’s online edition
of Synthetic Communications1 to view the free supplemental file.
Keywords Double elimination; methylthio arylbutadiyne; one-pot preparation
INTRODUCTION
The acetylene family has long been attractive because of its unique structural
features as well as optical and electronic properties.[1] The comparable properties
of arylbutadiynes are also of current interest and new synthetic methodologies are
Received August 9, 2012.
Address correspondence to D.-L. An, Z.-H. Peng, or Q.-Y.Cai, State Key Laboratory of Chemo=
Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University,
Changsha 410082, China. E-mail: deliean@hnu.edu.cn; pzh7251-@hnu.edu.cn; qycai001@yahoo.com.cn
2648

PREPARATION OF METHYLTHIO ARYLBUTADIYNES
2649
Scheme 1. Constructing of rigid multidentate sulfur-containing molecules and schematic illustration of
the molecularly mediated assembly of nanoparticles.
being developed.[2] Multidentate sulfur-containing molecules as interparticle linkages
now have generated an increasing interest in the assembly of gold nanoparticles.[3]
Although the fundamental understanding of controlling interparticle spatial proper-
ties remains very limited so far, from the perspective of morphology control,
shape-persistent molecules could serve as an ideal model system for defining inter-
particle structures because of their good spatial orientation properties. However,
compared to extensive studies on the utility of aliphatic derivatives with flexible fra-
meworks, much less attention has been paid to rigid molecular mediators.[4–6]
Recently, we have reported the viability of interparticle linkages via coordination
of some rigid multimethylthio arylethynyls to gold surfaces.[7–9] These interesting
molecules have exhibited some characteristics of controlling sizes of nanoclusters
and reversible behavior of assembly=disassembly.
In our studies on assembly of gold nanoparticles mediated by functional mate-
rials, various well-defined aryl ethynyls in terms of structural rigidity, size, shape,
and number of methylthio group were applied to exploit their unique optical and
electrical properties (Scheme 1).[7–9] To compare further the behavior of different
rigid molecules in the assembly of gold nanoparticles, we need to develop some
efficient methods for the preparation of different terminal building blocks
(Ar-(CꢀC)n-SCH3, n ¼ 0, 1, 2). Otera et al. developed a convenient methodology
for constructing the CꢀC bond by the double elimination of b-substituted sul-
fones,[10] but terminal function groups (-SMe) are not involved in their method.
To our knowledge, there have been known several methods of preparing methylthio
arylethynes (Ar-CꢀC-SCH3),[11] and we also reported a simple and effective method
starting from methylthiomethyl phenyl sulfone (MP-S)[12] and aromatic aldehydes by
the one-pot protocol.[13] However, no effective method for the preparation of
methylthio arylbutadiynes (Ar-CꢀC-CꢀC-SCH3) has been reported so far. Herein,
we describe a double-elimination-based one-pot strategy for the preparation of
methylthio arylbutadiynes 1.
RESULTS AND DISCUSSION
Arylpropargyl aldehydes 2 as starting materials were prepared from the
corresponding substituted iodobenzene and propargyl alcohol by Sonogashira
coupling[14] and then oxidation using MnO2.[15]

2650
Q. SU ET AL.
Scheme 2. One-pot preparation of methylthio arylbutadiynes 1a–1f.
In fact, the one-pot reaction making use of MP-S could give the desired
methylthio arylbutadiynes 1 in good yields (Scheme 2, Table 1). A variety of func-
tionalities, such as methoxy, methyl, chloro, iodo, and nitro groups were well
tolerated under the reaction conditions. Compound 1f is a pivotal building block
for constructing multidentate molecules as shown in Scheme 1. This one-pot reaction
is quite simple and does not require a tedious separation of the respective intermedi-
ates. A typical synthetic procedure was described for compound 1a. To a tetrahydro-
furan (THF) solution of MP-S was added n-BuLi (1.0 eq), arylpropargyl aldehyde 2a
(1.0 eq), ClP(O)(OEt)2 (1.2 eq), and lithium diisopropylamide (LDA) (2.5 eq), in
order. After the usual workup, the crude mixture was subjected to silica-gel chroma-
tography to give product 1a in 88% yield. Similarly, the other methylthio arylbuta-
diynes 1b–1f were prepared from MP-S and the corresponding arylpropargyl
aldehydes 2b–2f.
As a plausible mechanism for the formations of 1, the anion of MP-S reacted
with arylpropargyl aldehyde 2 and then ClP(O)(OEt)2, leading first to alkyne
phosphate 4 carrying two leaving groups, followed by double elimination of 4 with
LDA as a base, to afford methylthio arylbutadiynes 1 (Scheme 3).
To obtain insight into the mechanism of this one-pot reaction, we have tried
the isolation of key intermediates (alkyne phosphate 4 and enynic sulfone 5). Differ-
entiated stepwise procedure was employed to prove the formation of 4 and 5. How-
ever, all attempts to isolate the phosphate 4 [after addition of n-BuLi, 2, and
ClP(O)(OEt)2 and quenching with saturated NH4Cl solution] failed. Although it is
not clear whether 4 is unstable or prone to hydrolysis during column chromato-
graphy, when acetyl chloride instead of ClP(O)(OEt)2 was exploited to trap the pre-
sumptive anion 3, an analogous compound 6 was obtained (e.g., isolated in 66%
yield for 6b), indirectly indicating the occurance of aldol reaction (Scheme 4).
Table 1. One-pot procedure for preparation of compounds 1a–1f
Entry
Ar
Arylpropargyl aldehyde
Product 1 (%)a
1
2
3
4
5
6
Ph
4-NO2C6H4
4-ClC6H4
2a
2b
2c
2d
2e
2f
1a (88)
1b (76)
1c (76)
1d (84)
1e (77)
1f (73)
4-CH3C6H4
4-MeOC6H4
4-IC6H4
aYield of the isolated product.

PREPARATION OF METHYLTHIO ARYLBUTADIYNES
2651
Scheme 3. Plausible reaction mechanism.
Scheme 4. Trapping of the anion 3b.
Subsequently, when LDA as base was replaced with t-BuONa, a controllable
elimination process occurred to give the enynic sulfone intermediates 5 (Scheme 5).
As expected, all intermediates 5a–5f were isolated. It is worth noting that only one
type of geometric isomer for all enynic sulfone intermediates 5a–5f were obtained
after the reaction. These isomers were speculated to be E-configuration, owing to
=
the strong stereohindrance of the substituted groups on both sides of C C bond.
As an evidence, the structure of 5e was unambiguously determined by x-ray analysis
=
(Fig. 1). The bond lengths of C(1)–C(2) and C(3)–C(4) show characteristics of C C
and CꢀC bonds, respectively. (See the Supplementary Data, available online). Two
bulky priority groups (PhSO2- and 4-MeOC6H4CꢀC-) lie on the opposite sides of
=
C C bond, indicating clearly E-configuration of 5e.
Furthermore, we have investigated the elimination of enynic sulfone inter-
mediates 5, which, upon treatment with LDA, occurred smoothly to provide
methylthio arylbutadiynes 1 in good yields (Scheme 5, Table 2). Therefore, we
can conclude that the formation of 1 involves the double elimination reactions
of intermediate 4.
Scheme 5. Formation of intermediates 5 and preparation of compounds 1 via 5.

2652
Q. SU ET AL.
Figure 1. X-ray crystal structure of enynic sulfone intermediate 5e. (Figure is provided in color online.)
Table 2. Stepwise procedures for preparation of compounds 1a–1f
Entry
Arylpropargyl aldehyde
Intermediate 5 (%a)
Product 1 (%)a,b
1
2
3
4
5
6
2a
2b
2c
2d
2e
2f
5a (72)
5b (73)
5c (76)
5d (85)
5e (78)
5f (82)
1a (88)
1b (82)
1c (91)
1d (88)
1e (93)
1f (89)
aYield of the isolated product.
bYield based on intermediate 5.
CONCLUSION
In summary, we have developed a convenient one-pot synthetic method of
methylthio arylbutadiynes using arylpropargyl aldehydes and MP-S, by which six
compounds 1a–1f were obtained in good yields. The mechanism for the formation
of 1 was discussed on the basis of trapping and characterization of some important
intermediates. Experimental results have indicated that the reaction process involves
the initial nucleophilic addition of MP-S to arylpropargyl aldehyde to produce an
intermediate 4 carrying two leaving groups, followed by double eliminations using
LDA as base to form 1.
EXPERIMENTAL
All reactions were carried out under an atmosphere of nitrogen with freshly
distilled solvents, unless otherwise noted. THF was distilled from sodium=benzophe-
none. LDA was prepared from diisopropylamine and BuLi before use. Silica gel
(ZCX-II or SG1115) was used for column chromatography. All melting points were
determined with a Taike XT-4 micro-melting-point apparatus and were uncorrected.
NMR spectra were recorded on a Varian Inova-400 instrument using tetramethylsi-
lane (TMS) as an internal standard. Mass spectra were measured on Shimazu
GC-17A QP-5000 and ThermoFinnigan MAT95XP spectrometers. (IR) spectra
were recorded on a Nicolet 6700 Fourier transform (FT)–IR spectrometer. Ultra-
violet–visible UV-vis spectra were obtained with a LabTech UV2100 spectrometer.
The crystal used for x-ray diffraction was grown in a solution of chloroform
and petroleum ether. X-ray analysis on a single crystal was carried out at 293(2)

PREPARATION OF METHYLTHIO ARYLBUTADIYNES
2653
K on a Bruker Smart CCD area detector using graphite-monochromated Mo ka
˚
radiation (k ¼ 0.71073 A). An empirical absorption correction was carried out using
SADABS. Stucture solutions and full-matrix least-squares refinements based on F2
were performed with SHELXS-97 and SHELXL-97 programs, respectively. The
nonhydrogen atoms were refined anisotropically, and the hydrogen atoms were
placed in geometrical positions and constrained to ride on their parent atoms. Ana-
lytical expressions of neutral atom scattering factors were employed, and anomalous
dispersion corrections were incorporated.[16] (See the Supplementary data.)
Synthesis of Methylthio (4-Phenyl)butadiyne (1a)
BuLi (2.5 M in hexane, 0.8 mL, 2.0 mmol) was added dropwise to a solution of
methylthiomethyl phenyl sulfone (405 mg, 2.0 mmol) in THF (25 mL) at ꢁ78 ꢂC, and
the mixture was stirred for 10 min. Phenylpropargyl aldehyde 2a (260 mg, 2.0 mmol)
in THF (3 mL) was added dropwise at this temperature. After an additional 10 min,
ClP(O)(OEt)2 (414 mg, 2.4 mmol) was added at ꢁ78 ꢂC, and the cooler was then
removed. The resulting mixture was allowed to warm up to room temperature and
stirred for 30 min. The solution was then cooled to ꢁ78 ꢂC, and LDA (5.0 mmol)
was added. After stirring for 30 min, the reaction was quenched with aqueous NH4Cl
solution and extracted with ethyl acetate (30 mL ꢃ 3). The organic layer was washed
with brine, dried over MgSO4, and filtered. The solvent was evaporated in vacuo,
and the residue was subjected to chromatography (SiO2, hexane) to give 1a
(301 mg, 88%) as orange oil; 1H NMR (400 MHz, CDCl3): d ¼ 2.45 (s, 3H),
7.29–7.35 (m, 3H), 7.47 (dd, J ¼ 8.0 Hz, J ¼ 1.6 Hz, 2H); 13C NMR (100 MHz,
CDCl3): d ¼ 18.93, 74.25, 75.47, 77.79, 79.07, 121.60, 128.33, 129.05, 132.44; MS
(EI) m=z (%): 172 (Mþ, 82). HRMS (EI) m=z: calcd. for C11H8S 172.0341; found
172.0347; IR (KBr): t ¼ 3060, 2927, 2853, 2197, 2105, 1595, 1488, 1441, 1312,
1069, 1023, 976, 754, 688 cmꢁ1
;
UV-vis (EtOH, 1.0 ꢃ 10ꢁ4 mol=L): kmax
(emax) ¼ 248 nm (1.8 ꢃ 104), 266 nm (9.6 ꢃ 103), 280 nm (7.9 ꢃ 103), 297 nm
(5.6 ꢃ 103), 317 nm (4.2 ꢃ 103).
Synthesis of (E)-1-Methylthio-1-phenylsulphonyl-4-phenyl-1-butene-
3-yne (5a)
BuLi (2.5 M in hexane, 0.8 mL, 2.0 mmol) was added dropwise to a solution of
methylthiomethyl phenyl sulfone (405 mg, 2.0 mmol) in THF (25 mL) at ꢁ78 ꢂC, and
the mixture was stirred for 10 min. Phenylpropargyl aldehyde 2a (260 mg, 2.0 mmol)
in THF (3 mL) was added dropwise. After an additional 10 min, ClP(O)(OEt)2
(414 mg, 2.4 mmol) was added at ꢁ78 ꢂC, and the cooler was then removed. The
resulting mixture was then allowed to warm up to room temperature and stirred
for 30 min. The solution was cooled to ꢁ78 ꢂC, and t-BuONa (384 mg, 4.0 mmol)
was added. After stirring for 30 min, the reaction was quenched with aqueous NH4Cl
solution and extracted with ethyl acetate (30 mL ꢃ 3). The organic layer was washed
with brine, dried over MgSO4, and filtered. The solvent was evaporated in vacuo,
and the residue was subjected to chromatography (SiO2, hexane–AcOEt ¼ 10:1)
1
to give 5a (452 mg, 72%) as pale yellow solid; mp 78–79 ꢂC; H NMR (400 MHz,
CDCl3): d ¼ 2.41 (s, 3H), 7.34–7.43 (m, 3H), 7.48 (s, 1H), 7.51 (d, J ¼ 7.2 Hz, 2H),

2654
Q. SU ET AL.
7.56 (t, J ¼ 7.6 Hz, 2H), 7.65 (t, J ¼ 7.4 Hz, 1H), 7.98 (d, J ¼ 7.6 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d ¼ 18.53, 84.13, 106.50, 121.74, 126.40, 128.57, 128.72, 129.03,
129.94, 132.02, 133.71, 138.48, 147.79; MS (EI) m=z (%): 314 (Mþ, 10); HRMS (EI)
m=z: calcd. for C17H14O2S2 314.0430; found 314.0426. IR (KBr): t ¼ 3078, 3016,
2920, 2870, 2193, 1553, 1445, 1316, 1151, 1087, 912, 759, 717, 688 cmꢁ1
.
General Procedure for Synthesis of Compounds 1a–1f from
Intermediates 5a–5f
LDA (1.1 mmol) was added dropwise to a solution of 5 (1.0 mmol) in THF
(15 mL) at ꢁ78 ꢂC. When 5 disappeared (monitored by thin-layer chromatography,
TLC), the reaction was quenched with aqueous NH4Cl solution and extracted with
ethyl acetate (30 mL ꢃ 3). The organic layer was washed with brine, dried over
MgSO4, and filtered. The solvent was evaporated in vacuo, and the residue was
subjected to chromatography (SiO2, hexane) to give 1 (Table 2).
Synthesis of (1-(4-Nitro)phenyl)-3-acetyloxyl-4-methylthio-
4-phenylsulphonyl Butyne (6b)
BuLi (2.5 M in hexane, 0.8 mL, 2.0 mmol) was added dropwise to a solution of
methylthiomethyl phenyl sulfone (405 mg, 2.0 mmol) in THF (25 mL) at ꢁ78 ꢂC, and
the mixture was stirred for 10min. (4-Nitrophenyl)propargyl aldehyde 2b (350mg,
2.0 mmol) in THF (3mL) was added dropwise at this temperature. After an additional
10min, acetyl chloride (188mg, 2.4 mmol) was added dropwise at ꢁ78ꢂC, and the
cooler was then removed. The resulting mixture was allowed to warm up to room
temperature and stirred for 30min. The mixture was then poured into water and
extracted with ethyl acetate. The organic layer was washed with brine, dried over
MgSO4, and filtered. The solvent was evaporated in vacuo, and the residue was
subjected to chromatography (SiO2, hexane–AcOEt ¼ 10:1) to give 6b (553mg, 66%)
1
as pale yellow solid; mp 121–122 ꢂC; H NMR (400MHz, CDCl3): d ¼ 2.10 (s, 3H),
2.42 (s, 3H), 4.23 (d, J ¼ 4.0 Hz, 1H), 6.23 (d, J ¼ 4.0 Hz, 1H), 7.43 (d, J ¼ 8.8 Hz,
2H), 7.55 (t, J ¼ 7.4 Hz, 2H), 7.63 (t, J ¼ 7.2 Hz, 1H), 8.05 (d, J ¼ 7.2 Hz, 2H), 8.14
(d, J ¼ 8.8 Hz, 2H); 13C NMR (100MHz, CDCl3): d ¼ 17.26, 20.68, 62.69, 73.23,
86.42, 86.77, 123.36, 127.91, 128.84, 130.09, 132.75, 134.36, 136.56, 147.60, 168.94;
MS (EI) m=z (%): 419 (Mþ, 57). HRMS (EI) m=z: calcd. for C19H17NO6S2 419.0485;
found 419.0475. IR (KBr): t ¼ 3105, 3066, 2928, 2857, 2230, 1743, 1595, 1518, 1447,
1341, 1224, 1152, 1081, 1022, 856, 778, 750, 688 cmꢁ1
.
Supplementary Data
Crystallographic data for the structural analysis has been deposited with
the Cambridge Crystallographic Data Center. CCDC 691648 contains the x-ray data
in CIF format for this article. These data can be obtained, free of charge, via http://
www.ccdc.cam.ac.uk/products/csd/request/(or from the Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK; fax: þ44 1223
1
336033; or e-mail: deposit@ccdc.cam.ac.uk). Full experimental details, H and 13C

PREPARATION OF METHYLTHIO ARYLBUTADIYNES
2655
NMR spectra, and X-ray crystallography data for 5e can be found via the
Supplementary Content section of this article’s WebPage.
ACKNOWLEDGMENTS
We are grateful for the financial support from the National Natural Science
Foundation of China (No. 21072052), the National Basic Research Program
of China (No. 2009CB421601), and Hunan Provincial Science and Technology
Department Program (Nos. 2011WK4007, 06FJ4115).
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