An efficient metal-free pathway to vinyl thioesters with calcium carbide as the acetylene source

Article abstract of DOI:10.1039/c5gc01552a

Chemical reactions involving high-pressure acetylene are not easily performed in a standard laboratory setup. The risk of explosion and technical difficulties drastically complicate the equipment and greatly increase the cost. In this study, we propose th

Full text of DOI:10.1039/c5gc01552a

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Efficient Metal-Free Pathway to Vinyl Thioesters with Calcium
Carbide as the Acetylene Source
Konstantin S. Rodygin,a and Valentine P. Ananikov*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
Chemical reactions involving high-pressure acetylene are not easily performed in a standard laboratory setup. The risk of
explosion and technical difficulties drastically complicate the equipment and greatly increase the cost. In this study, we
propose the replacement of acetylene with calcium carbide, which was successfully utilized to synthesize practically useful
vinyl thioesters in accordance with a simple and environmentally benign procedure. The reaction proceeded under mild
conditions using a standard laboratory setup. The optimized reaction conditions allowed the selective synthesis of the
vinyl thioesters in high yields, and the reaction conditions can be scaled up to synthesize grams of sulfides from
inexpensive starting materials.
DOI: 10.1039/x0xx00000x
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sulfur functional groups via well-developed polymerization routes
(Scheme 1). Sulfur-containig functional groups are in demand for
increasing refractive index in polymers.[3] The polymers with high
refractive index attract attention due to their potential applications
in advanced optoelectronic materials. Post-modified copolymers
allow incorporation of optoelectronic groups,[4] and preparation of
core-shell nanoparticles with thermoresponsive ability and cross-
linked optoelectronic cores.[5] Several other applications of S-
containing polymers were recently reviewed.[6]
In addition to material science, chemical applications of vinyl
thioesters involve cycloaddition[7] and palladium catalyzed Heck-like
reactions with aryl halides.[8] The preparation of vinyllithium is a
step toward producing substituted vinyl sulfides,[9] which yield the
corresponding ketones under hydrolytic conditions with aqueous
Brønsted or Lewis acids[10]. Vinyl sulfides may also be utilized as
sensitive substrates to examine novel hydrosilylation,[11] diimide
reduction,[12] and asymmetric oxidation to the corresponding
sulfoxides.[13]
Introduction
Atom-economic organic reactions have shown great potential for
developing cost-efficient and environmentally benign synthetic
procedures.[1] A variety of techniques aimed toward constructing
new C–C, C–Hal, C–O, C–P, and C–S bonds via addition processes
were successfully employed in the search for new materials,
pharmacological substances, and synthetic building blocks.[2]
The simplest alkyne – acetylene – has the potential to be the
primary unsaturated core for performing sequential addition
reactions and for accessing a variety of building blocks. Through a
sequence of addition reactions, different products can be prepared
under simple conditions without any byproducts (the addition
reaction is atom-economic and does not produce waste).
Nowadays, vinyl thioesters can be synthesized from acetylene
and thiols using hydrothiolation (i.e., the thiol-yne reaction). Vinyl
sulfides can be synthesized using high-pressure acetylene
equipment (14 atm) under highly basic conditions (Scheme 2,
route a).[14] Similar protocols have also been utilized for several
other addition reactions involving acetylene. This approach is very
attractive; however, the number of practical applications in
everyday laboratory practice is limited. High-pressure acetylene
equipment is a specialized and expensive hardware designed to
avoid the risk of explosion and to control inert gas dilution to obtain
a desired pressure.
Scheme 1 Representative example of the synthesis of sulphur-functionalized polymers
via co-polymerization with styrene.
An important task is the preparation of vinyl thioesters, which
are crucial building blocks in material science for incorporating
a.Saint Petersburg State University, Universitetsky pr. 26, Stary Petergof 198504,
Russia.
b.Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky pr.
47, Moscow 119991, Russia. E-mail: val@ioc.ac.ru
†
Electronic Supplementary Information (ESI) available: General procedures,
experimental details, details of the mechanistic studies, and NMR-spectra. See
DOI: 10.1039/x0xx00000x
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temperatures and reagent ratios. The key points of the optimization
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procedure are provided in Table 1, uDsOinIg: 10t.1h0e39/aCd5dGitCio01n552oAf
benzenethiol as a model reaction. Complete details on the reaction
optimization are provided in the Supporting Information.
Low solubility of calcium carbide in organic solvents and its
rapid reaction with water is the first factor to be considered. In our
case, this issue was resolved by adding a controlled amount of
water. Excess of water led to the rapid release of the acetylene
fraction that was unable to react with the thiol. In contrast, a
deficiency of water led to the incomplete utilization of calcium
carbide. A trace amount of product and a low yield were found in
the cases of MeOH and PrOH (Table 1, entries 1-2), whereas a good
yield was observed in the case of BuOH (82%, entry 3). The yields
noticeably increased with the elongation of the aliphatic chain,
most likely due to the lower acidity of the alcohols. Markedly better
results were achieved in the aprotic solvents DMSO (90%, entry 4)
and DMF (93%, entry 5) in which the hydrolysis of calcium carbide
was fully controlled by external water additives. Under these
conditions, CaC2 was slowly converted to acetylene, which was
reacted with benzenethiol in situ. The process was completed at the
optimal temperature of 100 °C (Table 1, entries 5, 9). It should be
emphasized that the mild optimized reaction conditions were
employed compared with those used for the thiovinylation of
gaseous acetylene (120 °C, 5 h, 14 atm).[14] Attention should be
given to the reaction time because the product was observed to
degrade at longer reaction times, accompanied by a color change of
the reaction mixture from colorless to black.
Scheme 2 Available preparation routes to access vinyl sulfides.
Although it is potentially simple and attractive, the addition of
thiols to acetylene (route a)[14,15] is rarely used compared with other
synthetic protocols (Scheme 2). Other synthetic routes to vinyl
sulfides involve (b) elimination from trimethylsilyl sulfides;[16] (c)
sulfoxide reduction;[17] (d) dehydrohalogenation;[18] (e) free
radical-,[19] base-,[20] or metal-[21] mediated hydrothiolation of
alkynes; (f) addition-elimination;[22] and (g) free radical
chain-substitution.[23] We should also mention the plethora of
transformations,[24] including the protocols developed for the
construction of tetrasubstituted vinyl sulfides.[25] In overall, the
available protocols (Scheme 2) were not optimized for
environmental concerns; many of the transformations are eco-
dangerous and produce toxic waste. Some of the protocols involve
relatively expensive starting materials (i.e., more expensive than
the expected cost of the product).
Despite the great potential of the acetylene molecular core and
the addition methodology, the corresponding practical
implementations are challenging. Currently, the cost of simple
phenyl vinyl sulfide – the primary building block of thioesters – is
more than 20 € per gram.[26]
In the present study, we found that calcium carbide is an
excellent starting material for constructing vinyl units within the
framework of addition reactions. No special equipment was
required, and the reactions were performed with a standard
laboratory setup. Calcium carbide is inexpensive and nontoxic, and
it is convenient to store, weigh and handle.
Table 1 Optimization of reaction conditions in the synthesis of vinyl thioesters.[a]
Yield
(%)[b]
Entry
Solvent[c]
Conditions
Base[c]
1
2
MeOH
PrOH
BuOH
DMSO
DMF
DMF
DMF
DMF
DMF
DMF
DMF
100 °C, 3 h
100 °C, 3 h
100 °C, 3 h
100 °C, 3 h
100 °C, 3 h
50 °C, 3 h
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
Cs2CO3
Et3N
Trace
18
3
82
4
90
5
93
6
12
7
120 °C, 3 h
100 °C, 2 h
100 °C, 5 h
100 °C, 3 h
100 °C, 3 h
89
The developed approach has important practical and
environmental advantages, as follows: (1) it is metal-free; (2) it has
high selectivity with a minimal amount of byproducts; (3) it is an
easily scalable procedure suitable for the preparation of varying
amounts of product; and (4) it constitutes one-pot synthesis under
mild reaction conditions.
8
71
9
92
10
11
59
41
[a]
Experimental conditions: powdered CaC2 (2 mmol); benzenethiol (1 mmol);
[b]
[c]
Results and Discussion
Our efforts to maximize selectivity and achieve high yields
involved optimization of the reaction conditions, including the use
of different solvents and bases as well as varying reaction times,
dried DMF; H2O (3 mmol).
Isolated yields. For more details concerning
solvents and bases optimization see the Supporting Information.
Several bases were evaluated, and the reaction proceeded with
KOH, Cs2CO3 and Et3N (entries 5, 10, 11; Table 1). The best
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performance was observed with KOH, which was also confirmed for observed with a good yield. As we expected, gaseousVaiecwetAyrtlieclneeOnclainne
the other studied thiols.
react under the studied reaction conditionsDtOoI:p1r0o.d10u3c9e/Cth5GeCd0e1s5i5re2dA
The treatment of calcium carbide (grinding) was the key vinyl thioester.
parameter for achieving high yields of the vinyl ester. In the case of
Table
2 Substrate scope of the thiovinylation reaction involving calcium
large particles of calcium carbide, the reaction proceeded on the
surface and stopped in a short time after the carbide particles
become covered with insoluble calcium hydroxide. Freshly
powdered calcium carbide demonstrated the best reactivity for the
studied transformation. A simple mechanical grinding was suitable
for obtaining powdered calcium carbide in the laboratory (see
Supporting Information). Characterization by the field-emission
scanning electron microscopy (FE-SEM) technique indicated particle
sizes in the range of 50 - 1000 µm and a layered morphology of
calcium carbide (see Supporting Information).
carbide.[a]
Entry
Substrate
Product
Yield (%)[b]
1
93 (91) [91][c]
2
91 (90)
The substrate scope for the thiovinylation reaction involving
calcium carbide was then investigated employing the optimized
reaction conditions (Table 2). A number of thiols, including those
bearing aliphatic, cyclic aliphatic, aromatic and heteroaromatic
groups, reacted efficiently with calcium carbide to selectively
produce the desired vinyl sulfides in excellent isolated yields of 87–
96% (entries 1-15; Table 2). The atom-economic advantage of the
addition reaction avoided formation of wastes and gradually
simplified isolation and purification procedure. Thus, a simple
procedure was utilized to separate the products, and the measured
difference between the gas chromatograph (GC)/isolated yields was
rather small. Even in the challenging case of thioester 16 (Table 2;
entry 16), a yield as high as 88% was observed (the product is
difficult to purify due to its high volatility during isolation). A slight
decrease in the yield was observed for heteroaromatic vinyl sulfide
17 (69%; entry 17) and for product 18, containing an electron-
withdrawing fluorine atom (88%; entry 18). Amazingly, the addition
of benzeneselenol was also possible using the developed protocol
and resulted in the target phenyl vinyl selenide in a good yield
(62%; entry 19, Table 2).
It was of interest to assess the reactivity of O-nucleophiles in
the studied reaction. A variety of different alcohols (MeOH; EtOH;
PrOH; BuOH; i-BuOH; phenol; α-naphtol; o-, m- and p-cresol;
propylene glycol and glycerol) were evaluated under the same
experimental conditions. Small aliphatic alcohols (MeOH, EtOH and
PrOH) reacted with calcium carbide is a similar way as water and
resulted in the release of acetylene. Larger alcohols did not lead to
the release of noticeable amounts of acetylene. In all the studied
cases formation of O-vinylated products was not observed. In
contrast to thiols, addition of alcohols to acetylene did not take
place under studied conditions.
3
4
93 (91)
94 (93)
5
6
91 (90)
94 (92)
7
8
9
95 (92)
97 (95)
94 (92)
10
11
94 (92)
95 (93)
12
13
14
94 (92)
98 (95)
98 (96)
Next, we studied the possibility of scaling of the developed
process for the addition of thiols. Important to note, that the same
yield and selectivity were obtained in the 1 mmol- and 4 mol-scale
reactions. Phenyl vinyl sulfide was isolated in an amount of 5 g with
a 91% yield utilizing the developed protocol (entry 1, Table 2).
Mechanistic considerations suggest the involvement of
acetylene (formed in situ) in the addition reaction (Scheme 3;
pathway A). To elaborate this pathway, an aliquot of DMSO-d6 was
saturated with gaseous acetylene. The solution was stable, and the
NMR spectra showed the good solubility of acetylene in DMSO at
room temperature. Then, benzenethiol and base were added to the
solution and heated at 100 °C. The formation of vinyl sulfide 1 was
15
90 (87)
16
17
98 (88)
72 (69)
18
90 (88)
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the mixture was heated to 100 °C with vigorous stirring for 3 h.
Then, the mixture was diluted with aqueous alkaline solution (10
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DOI: 10.1039/C5GC01552A
19
65 (62)
[a]
mL), and the aqueous layer was extracted with diethyl ether (2 × 10
mL), dried over Na2SO4, and concentrated under vacuum to yield a
crude product. The temperature during solvent evaporation should
be controlled to avoid product loss due to volatility of some vinyl
sulfides. The crude product was further purified by column
chromatography on silica gel (hexane or ether/hexane) to afford
the corresponding product. For further purification, if required, the
products can be distilled in vacuum.
Materials and methods, experimental procedures for the
mechanistic studies, calcium carbide preparation, compounds
preparation and characterization are described in Supporting
Information.
Conditions: powdered CaC2 (2 mmol), thiol (1 mmol), H2O (3 mmol), and KOH (1.5
[b]
mmol) in dry DMF at 100 °C for 3 h; see experimental section for details.
The GC
yields and isolated yields (in parenthesis) are indicated. [c] Experimental conditions for a
larger scale: powdered CaC2 (8 mol); thiophenol (4 mol); H2O (12 mol), dried DMF.
An important mechanistic question is the possibility of a direct
reaction of calcium carbide with thiols in the absence of water. For
the mechanistic study, we performed the reaction in a dry solvent
in the presence of molecular sieves. The reaction gave
1,2-bis(phenylthio)-ethene in 45 % yield (GCMS), while a noticeable
production of phenyl vinyl sulfide was not observed. A plausible
pathway in this case (Scheme 3; pathway B) would involve the
reaction of calcium carbide with the thiol, leading to the formation
of thiophenylacetylene, followed by hydrothiolation with the
second molecule of the thiol, which is a known step.[27] Note that
formation of phenyl vinyl sulfide was not observed in the absence
of water in accordance with the proposed reaction mechanism.
Acknowledgements
K. S. Rodygin gratefully acknowledges Saint Petersburg State
University for a postdoctoral fellowship (№ 12.50.1560.2013). The
authors also express their gratitude to the Centre for Magnetic
Resonance and the Centre for Chemical Analysis and Materials
Research (Saint Petersburg State University) for physicochemical
measurements. This work was supported by Russian Foundation of
Basic Research (grants 14-03-01005 and 15-33-20536). Electron
microscopy characterization was performed at the Department of
Structural Studies of Zelinsky Institute of Organic Chemistry,
Moscow and supported by the grant of Russian Science Foundation
(RSF grant 14-50-00126).
Notes and references
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Scheme 3 Plausible mechanistic pathways in the studied system.
Conclusions
In summary, we developed an alternative efficient protocol for
the preparation of vinyl thioesters via the reaction of calcium
carbide with thiols. This cost-efficient procedure can be easily
employed for the preparation of important sulfur building blocks
using standard laboratory equipment. Mechanistic studies
demonstrated that the thiovinylation involves the initial in situ
formation of acetylene, confirming the potential of calcium carbide
as an acetylene replacement in organic synthesis.
Using calcium carbide as an acetylene equivalent presents a
straightforward advantage that can strongly influence the
development of this field. We anticipate that a number of processes
involving acetylene will be explored and adapted to these
substantially more convenient reaction conditions in the future.
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Experimental Section
General procedure for the thiovinylation reaction was as
follows: KOH (1.5 mmol, 84 mg), thiol (1 mmol), and water (3 mmol,
54 µL) were added to a reaction tube (10 mL) with 1 mL of dry DMF
under inert atmosphere. After stirring at room temperature for 30
min, powdered calcium carbide (2 mmol, 128 mg) was added, and
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Green Chemistry
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DOI: 10.1039/C5GC01552A
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Acetylene was replaced with calcium carbide and utilized for the synthesis of practically useful vinyl
thioesters in a simple and environmentally benign procedure.