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Calcium Carbide: A Unique Reagent for Organic Synthesis and

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 DOI: 10.1002/asia.201501323 Focus Review

Synthetic Methods

Calcium Carbide: A Unique Reagent for Organic Synthesis and

Nanotechnology
Konstantin S. Rodygin,[a] Georg Werner,[a] Fedor A. Kucherov,[b] and Valentine P. Ananikov*[a, b]

Chem. Asian J. 2016, 11, 965 – 976 965 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Abstract: Acetylene, HCŽCH, is one of the primary building
blocks in synthetic organic and industrial chemistry. Several
highly valuable processes have been developed based on
this simplest alkyne and the development of acetylene
chemistry has had a paramount impact on chemical science
over the last few decades. However, in spite of numerous
useful possible reactions, the application of gaseous acety-
lene in everyday research practice is rather limited. More-
over, the practical implementation of high-pressure acety-
lene chemistry can be very challenging, owing to the risk of
explosion and the requirement for complex equipment; spe-
1. Introduction
The chemistry of carbon¢carbon triple bonds has been an in-
exhaustible source of fundamentally important processes and
technologies.[1] Acetylene has been the main industrial source
of vinyl chloride, acrylonitrile, vinyl acetate, acetaldehyde, and
several other important compounds for many decades. The ini-
tial interest in acetylene arose when its transformation into
acetaldehyde was first developed in 1916.[1a] The increased in-
dustrial use of acetylene caused the demand for calcium car-
bide. It was not until the late 1950s, after the Wacker process
had been implemented, that the total manufacture of calcium
carbide decreased, because of lowered demand in acetylene.[1k]
Ethylene and propylene turned out to be more-applicable mol-
ecules for industrial use. However, the possibility of making
acetylene an important industrial source worldwide is dis-
cussed again when oil and gas prices change significantly.[2]
It may appear that the rules that govern the storage and
handling of acetylene are well-known and simple.[3] However,
following these rules in a cost-efficient manner can be a chal-
lenging technical task as high-pressure equipment, precautions
for its transportation and storage, and dedicated materials are
required for handling acetylene. Therefore, although acetylene
has industrial applications, it does not follow that it can be
conveniently used in the laboratory, because working with gas-
eous acetylene has several difficulties.[3,4]
Calcium carbide has a number of advantages over gaseous
acetylene. Neither oil nor natural gas is required to synthesize
calcium carbide, its transportation does not have the same
risks as for acetylene, there is no need to use complicated
high-pressure equipment, and working with calcium carbide is
safer and more convenient. Surprisingly, the chemistry of calci-
[a] Dr. K. S. Rodygin, Dr. G. Werner, Prof. Dr. V. P. Ananikov
Institute of Chemistry
Saint Petersburg State University
Universitetsky pr. 26
Stary Petergof 198504 (Russia)
[b] Dr. F. A. Kucherov, Prof. Dr. V. P. Ananikov
Zelinsky Institute of Organic Chemistry
Russian Academy of Sciences
Leninsky pr. 47
Moscow 119991 (Russia)
E-mail: val@ioc.ac.ru
Chem. Asian J. 2016, 11, 965 – 976 www.chemasianj.org
Focus Review
cial safety precautions need to be taken to store and handle
acetylene under high pressure, which limit its routine use in
a standard laboratory setup. Amazingly, recent studies have
revealed that calcium carbide, CaC2, can be used as an easy-
to-handle and efficient source of acetylene for in situ chemi-
cal transformations. Thus, calcium carbide is a stable and in-
expensive acetylene precursor that is available on the ton
scale and it can be handled with standard laboratory equip-
ment. The application of calcium carbide in organic synthe-
sis will bring a new dimension to the powerful acetylene
chemistry.
um carbide, unlike that of acetylene, has been poorly studied
and it is a research area full of opportunities. It is worth men-
tioning that the chemistry of calcium carbide is not confined
to its use as a source of acetylene. The possible applications of
calcium carbide are not limited to the known reactions of acet-
ylene and may eventually lead to the development of new
transformations of the ethynyl moiety. The unique nature of
this small molecule has already started to unfold.
This review provides a concise description of the topic
based on selected references. The main focus is placed on ap-
plications in organic chemistry, whilst a brief note is made on
the possible use of CaC2 in the preparation of nanoscale sys-
tems, because this area is now actively developing.
2. Important Processes and Reactions that In-
volve Acetylene
Although acetylene was first described by Davy in 1836,[5] it
was not until the Kucherov reaction was discovered in 1881
that this compound started to be used in chemistry.[6] Owing
to this reaction, acetylene remained the main source for syn-
thesizing various organic compounds until the middle of the
20th century. In this section, we will briefly mention the key
areas of acetylene chemistry to discuss the development of
various synthetic methods. Indeed, acetylene is a simple and
readily available compound that can be used to access
a broad range of valuable products (Scheme 1).[1]
Vinyl chloride,[7] acrylonitrile,[8] and vinyl acetate[9] are key
raw materials in industrial chemistry and can be produced by
the addition of the corresponding acid to acetylene
(Scheme 1). The electrophilic addition of a Brønsted acid re-
quires a suitable catalyst (Hg, Cu, Au) and is hindered by side-
polymerization reactions that “poison” the active surface of the
metal.[10]
Well-known reactions include those of alcohols, thiols, and
amines under basic conditions.[11] These reactions provide easy
access to an important family of compounds, because vinyl
ethers are widely used as co-polymers.[12]
The interaction between the acetylenide anion and carbonyl
compounds through the Favorsky reaction yields propargyl al-
cohols.[13] The use of superbasic media makes it possible to
produce the corresponding alcohols, even with aryl alkyl ke-
966 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Scheme 1. Representative examples of the key reactions of acetylene.
Adapted with permission from Ref. [1a]. Copyright 2014, American Chemical
Society.
tones, which are characterized by lower reactivity
(Scheme 2).[14]
Carbonylation is another method for producing valuable
synthons from acetylene as a starting material (Scheme 3). The
nickel-catalyzed reaction between acetylene and carbon mon-
oxide in the presence of alcohols, thiols, and amines under
high pressure (30 atm) yields the corresponding acrylic acid de-
rivatives.[15]
Scheme 2. Ethynylation of ketones by acetylene.
Scheme 3. Carbonylation reactions involving alcohols, amines, and thiols.
The catalytic chemistry of acetylene, developed by Reppe,
uses a catalyst to perform selective conversions at relatively
low temperatures and pressures (Scheme 4).[16] By varying the
catalyst and the solvent, it is possible to direct the reaction to-
wards tetrameric or trimeric products. The nature of the sub-
stituent at the triple bond also plays an important role in the
outcome of the reaction. These processes are used to produce
Chem. Asian J. 2016, 11, 965 – 976 www.chemasianj.org
Focus Review
various cyclic aromatic compounds, including pyridine deriva-
tives.[17] Several catalytic methods for the synthesis of polyacet-
ylene have also been described (Scheme 4).[18]
Konstantin Rodygin received his doctoral
degree in Organic Chemistry from the Institute
of Chemistry, Syktyvkar, in 2010. After two
years as a Postdoctoral Researcher at St. Pe-
tersburg State University, he joined the group
of Prof. Ananikov as a Research Associate. His
scientific interests include the chemistry of
calcium carbide and vinylation reactions.
Georg Werner received his doctoral degree
from Hannover University, Germany, in 2011.
Currently, he is a Postdoctoral Researcher in
the group of Prof. Ananikov at St. Petersburg
State University, Russia. His scientific interests
include the chemistry of alkynes.
Fedor Kucherov received his doctoral degree
from Zelinsky Institute of Organic Chemistry,
Moscow, in 2004. In 2006, he joined the
Chemical Diversity Institute as a Senior Re-
searcher in the medicinal chemistry laborato-
ry. In 2015, he moved back to his alma mater
to continue his research work. His scientific in-
terests include organic chemistry and the
design and synthesis of conjugates for selec-
tive drug delivery.
Valentine Ananikov received his PhD in 1999,
his Habilitation in 2003, and, in 2005, he
became a Professor and Laboratory Head at
the Zelinsky Institute of Organic Chemistry,
Russian Academy of Sciences. In 2008, he was
elected as a Member of the Russian Academy
of Sciences. He has been a recipient of the
Russian State Prize for Outstanding Achieve-
ments in Science and Technology (2004), an
Award of the Science Support Foundation
(2005), a Medal of Russian Academy of Scien-
ces (2000), the Liebig Lectureship by the
German Chemical Society (2010), the Balandin
Prize for outstanding achievements in cataly-
sis (2010), and the Thomson Reuters Highly Cited Researcher—Russia (2015).
His scientific interests are focused on molecular complexity and synthetic trans-
formations.
967 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Scheme 4. Oligomerization reactions of acetylene[16–18] (the maximum acety-
lene concentration for safe operation is shown[16]).
The reactions described above have been well-studied and
many industrial processes involve these transformations. How-
ever, numerous synthetic applications of acetylene are not lim-
ited to these possibilities and include several other fundamen-
tal transformations.[1] The recent development of alkynes
chemistry has led to the emergence of cross-coupling reac-
tions,[19] click chemistry,[20] transition-metal-catalyzed atom-eco-
nomical transformations,[21] alkyne cyclization,[22] triple-bond
metathesis,[23] organocatalytic transformations,[1d] and materials
science[24] as attractive directions in acetylene chemistry.
When searching for new methods for acetylene conversion,
one needs to consider the processes that take place in living
organisms. Five anaerobic bacteria[25] and the obligate anae-
robe Pelobacter acetylenicus,[26] which use acetylene in its free
state as a source of energy and carbon, have been described.
The key transformation of acetylene into acetaldehyde in
P. acetylenicus is catalyzed by the acetylene hydratase enzyme
(Figure 1 A),[27] whose structure contains a cubic iron¢sulfur
cluster [4Fe:4S] and a tungsten atom (Figure 1 B).[28]
Acetylene biodegradation takes place under strictly anaero-
bic conditions through a non-redox mechanism,[29] which is
not typical of tungsten-based enzymes.[30] The unique structure
of acetylene provides two of the most-important factors for
living cells, that is, a carbon source and an energy source.
Thus, acetylene was considered as a plausible component in
the evolution of microbial ecosystems.[31]
In this section, we have given a brief overview of the key
processes involving acetylene that are commonly used in
modern organic chemistry. Many other fascinating reactions
that involve alkynes have been described in details in numer-
ous review articles.[1]
Figure 1. A) Structure of acetylene hydratase from P. acetylenicus; B) struc-
ture of the active site of acetylene hydratase. Reproduced with permission
from Ref. [28b]. Copyright 2007, National Academy of Sciences.
Chem. Asian J. 2016, 11, 965 – 976 www.chemasianj.org
Focus Review
3. Calcium Carbide in Organic Synthesis
Calcium carbide has been used in conventional organic synthe-
sis to irreversibly remove water from reaction mixtures (e.g.,
during aldol condensation and esterification reactions).[32] How-
ever, the use of water-containing solvents to generate acety-
lene in situ opens up new prospects for alkyne chemistry.
A pioneering article on the synthesis of diphenylacetylene
chlorides from benzene, calcium carbide, and chlorine was
published in 1918.[33] During the early development of calcium
carbide chemistry, a number of polyconjugated polymers were
synthesized from the reactions of powdered calcium carbide
with a,b-dibromoethylbenzene, methyl 2,3-dibromopropa-
noate, and 2,3-dibromopropanenitrile at 150–300 8C in a pres-
sure-vessel.[34] The reaction of calcium carbide with chlorodi-
methylsilane in eutectic mixture LiCl/KCl (46 mol % KCl) result-
ed in the formation of a twelve-membered cyclic product in
a low yield (Scheme 5).[35]
Scheme 5. Reaction of calcium carbide with chlorodimethylsilane.
Deuterated bisvinyl sulfide was obtained from calcium car-
bide, sodium sulfide, and D2O in polar aprotic solvent
(Scheme 6) and d10-2,5-dimethyl-4-methylene-1,3-oxythiolane
was formed as a byproduct.[36]
Scheme 6. Synthesis of deuterated bisvinyl sulfide from calcium carbide.
When the reaction was performed in a steel autoclave with-
out any solvent (Scheme 7 A), some vinyl ethers were obtained
from the alcohols and calcium carbide.[37] The direct use of
CaC2 was also possible: 2,5-dimethylhex-3-yne-2,5-diol was syn-
thesized from calcium carbide and acetone under basic condi-
tions followed by acid hydrolysis (Scheme 7 B).[38]
Scheme 7. Reaction of calcium carbide with alcohols (A) and acetone (B).
968 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

A number of propargyl alcohols were synthesized from the
interaction between acetylene and aliphatic aldehydes and ke-
tones.[39] It should be mentioned that only the a-branched
compounds participated in the reaction; no interaction at all
was observed for benzaldehyde (Scheme 8 A, C). A seminal
recent discovery of Schreiner and co-workers revealed a crucial
role of fluoride ions in the reaction between acetylene and ke-
tones (Scheme 8 B).[40] It is possible that fluoride from
Scheme 8. Reactions between CaC2 and aliphatic carbonyl compounds.
TBAF = Tetra-n-butylammonium fluoride.
TBAF·3 H2O activates ethynylcalcium hydroxide, which is
formed from the reaction of water with solid calcium carbide.
The corresponding “ate” complex attacks the carbonyl compo-
nent to give the propargylic alcohols.
The three-component reaction between acetylene and alde-
hydes (AAA coupling) or haloalkanes[41] (AHA coupling) in the
presence of a secondary amine gave rise to a broad variety of
aminopropynes (Scheme 9).[42] In the case of coupling reactions
with benzaldehydes and bulky secondary amines, the reaction
predominantly proceeded through enaminone formation.[43]
Propargylamine was only observed among the reaction prod-
ucts in a few cases of a typical AAA reaction.
The Sonogashira reaction is one of the key cross-coupling
reactions in organic chemistry. A number of methods for ob-
taining tolane derivatives through the interaction of aryl hal-
ides with gaseous acetylene have been described.[44] It is im-
portant to mention examples in which calcium carbide was di-
Scheme 9. Reactions of CaC2 with aldehyde/amine and aldehyde/dichloro-
methane systems.
Chem. Asian J. 2016, 11, 965 – 976 www.chemasianj.org
Focus Review
Scheme 10. Cross-coupling of aryl- and heteroaryl halides with acetylene.
TEA = triethylamine, DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene.
rectly used as an acetylene source to synthesize symmetric
diaryl ethynes (Scheme 10 A, B).[45] As expected, the involve-
ment of para-diiodobenzenes in a similar reaction
(Scheme 10 C) gave rise to polymerization products.[46]
Bis-trialkyl- or bis-triarylstannylacetylenes are also promising
synthons that can be produced from the ultrasound-promoted
reaction of calcium carbide and an appropriate bis-trialkyl- or
bis-triarylstannyl halide.[47]
The synthesis of mononuclear triazoles is another important
field of acetylene chemistry, because only a limited number of
methods for the preparation of these structures are known.[48]
Thus, the copper-catalyzed click reaction[49] of acetylene with
alkyl- and aryl azides[50] gives rise to unsubstituted aryl triazoles
in high yields (Scheme 11 A).[51] Notably, the two-stage one-pot
synthesis, in which the initial azide for the click reaction is syn-
thesized from sodium azide and the corresponding aryl boron-
ic acid, is also possible (Scheme 11 B).[52]
Scheme 11. Synthesis of 1-phenyl-1H-1,2,3-triazoles from CaC2.
The extremely low solubility of CaC2 in organic solvents[53]
requires special procedures for its application in chemical pro-
cesses.[54] One important factor that needs to be tuned for the
optimal generation of acetylene is the reaction between CaC2
and water. To tackle this issue, a useful multiphase procedure
was proposed for conducting the reactions.[55] In this one-pot
system, the bottom layer, which contained calcium carbide,
was separated from the water phase by a fluorous solvent
(Galden HT135), which acted like a liquid membrane and facili-
tated water and heat transport in a controllable manner
(Figure 2). Gaseous acetylene passed through the fluorous sol-
vent and was applied in situ to the top organic layer to under-
go the Sonogashira coupling reaction, Cu-catalyzed azide¢
alkyne cycloaddition, or three-component aldehyde/alkyne/
amine coupling reaction in high yields.
969 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 2. Multiphase system for Sonogashira coupling reactions, “click” reac-
tions, and AAA condensation reactions of calcium carbide. Reproduced with
permission from Ref. [55]. Copyright 2015, American Chemical Society.
CuAAC = copper(I)-catalyzed azide–alkyne cycloaddition.
Vinyl thioethers, important compounds in materials science,
can be easily synthesized by the addition of thiols to CaC2
(Scheme 12).[56] This method can also be used with selenium
compounds for the preparation of vinyl selenides. The reaction
successfully occurred in a simple and environmentally benign
procedure under mild conditions by using a standard laborato-
ry setup. The reaction could also be scaled up to synthesize
vinyl sulfides on the gram scale.
Scheme 12. Synthesis of vinyl seleno- and thioethers.
Extension of the scope to the nucleophilic addition of di-
thiols to the triple bond has recently been reported
(Scheme 13 A).[57] This procedure provides a convenient path-
way for the synthesis of divinyl thioethers, which are promising
monomers for the construction of branched polymers. The
same procedure, with DMSO instead of DMF, gave rise to vinyl
ethers of heterocyclic thiols (Scheme 13 B).
Scheme 13. Synthesis of divinyl thioethers and thiovinyl ethers that contain
a heterocyclic moiety.
A new procedure for the synthesis of arylpyrrols was elabo-
rated based on acetylene that was generated from calcium car-
bide (Scheme 14).[58] Vinylation products were formed in some
cases; however, the yield of these adducts was less than 5 %.
Chem. Asian J. 2016, 11, 965 – 976 www.chemasianj.org
Focus Review
Scheme 14. Synthesis of arylpyrrols from oximes and calcium carbide.
To summarize, the development of calcium carbide chemis-
try has led to the discovery of an impressive number of syn-
thetic reactions that involve the acetylenic CŽC unit; a brief
summary of these transformations is shown in Scheme 15.
Indeed, using calcium carbide with the addition of a controlled
amount of water opens up a new dimension for acetylene
chemistry, that is, the in-flask release of reactive gaseous mole-
cule from an easy-to-handle solid precursor.
Scheme 15. Various families of organic compounds that can be synthesized
from calcium carbide.
4. Methods for the Preparation of Calcium Car-
bide
In this section and the next section, a brief overview of the
methods for the synthesis of calcium carbide and its properties
will be discussed to give the necessary background for its syn-
thetic applications. Wçhler first synthesized calcium carbide in
1862 by heating an alloy of zinc and calcium in the presence
of coke.[59] Since then, several methods for the preparation of
CaC2 have been introduced, almost all of which are based on
the high-temperature fusion of a calcium-containing com-
pound (lime, calcium oxide, or metallic calcium) and a source
of carbon (coal, coke, biomass, lignin, or graphite). There is
also significant interest in the mechanism of the reaction,
which is, in fact, rather complicated.
The first industrial method for the synthesis of calcium car-
bide was proposed over a century ago. Calcium oxide and
coke granules (diameter: 5–30 mm) were fused in an electric
furnace and carbon monoxide was released as a side prod-
uct.[60] The reaction required heating at about 2200 8C for 1–
2 hours, owing to poor contact between the solid reagents.[61]
Pure calcium carbide can be synthesized from the corre-
sponding elemental compounds (Scheme 16 A) or calcium cy-
970 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Scheme 16. Thermal synthesis of calcium carbide.
anamide (Scheme 16 B);[62] however, both processes are not
suitable for the practical production of CaC2.
The production of calcium carbide by the carbothermal re-
duction of calcium oxide was first described in 1984.[63] The
standard process was modified by using rotating furnaces,
which provided partial heating by fuel combustion in a flow of
oxygen.[64] The reactor could also be completely heated, owing
to the combustion of fuel in oxygen.[65] The use of a direct-cur-
rent plasma-fluidized bed reactor allowed the temperature and
reaction time for the carbide synthesis to be decreased.[66] Al-
ternative methods for industrial-scale synthesis that have been
elaborated over the past decades have used pit-type electric
furnaces fitted with plasma burners (plasmotrons).[61, 66, 67] Tech-
nical-grade calcium carbide consists of about 80–85 % CaC2. A
mechanochemical approach for obtaining calcium carbide in
high yields (up to 98 %) from the corresponding elements was
recently proposed.[68] Owing to the high purity of the resulting
product, the authors suggested that 11C- and 13C-enriched al-
kynes could be prepared by using this method. The solid-
phase synthesis of calcium carbide by the reaction between
calcium oxide and carbon was also studied.[69]
In the synthesis of calcium carbide, coke can be replaced
with biocoal that is produced by the pyrolysis of lignin-con-
taining biomass. Because biocoal is a renewable resource, it is
an attractive raw material for large-scale syntheses.[70]
In 1975, the null-dimension model for the formation of calci-
um carbide into solid pellets was proposed.[71] It was assumed
that heat energy was transferred through a layer of the prod-
uct and controlled the propagation rate of the reaction over
the entire pellet.
A series of studies have been focused on the properties and
reactions of calcium oxide and the diffusion of carbon in incan-
descent lime.[72] As a result, an integrated assessment of the re-
actions between calcium oxide and carbon in the solid and
liquid phases was performed.
The available data on the mechanism of formation of calci-
um carbide are rather contradictory. However, an examination
of these data showed that the stages of the process not only
depended on the reaction conditions, but also on the ratio of
the components.[73] The first stage in the synthesis was the
direct interaction between coke and calcium oxide
(Scheme 17 A), starting at 1460 8C. The second stage was the
reaction between CaC2 and CaO (Scheme 17 B), which began at
1520 8C, only once no more coke was left. The third stage
(Scheme 17 C) involved decomposition of the resulting calcium
carbide to metallic calcium and carbon, and its rate depended
on the speed of calcium evaporation from the surface.
The underlying principles in synthesis of calcium carbide
have remained unchanged for over a century. However, numer-
Chem. Asian J. 2016, 11, 965 – 976 www.chemasianj.org
Focus Review
Scheme 17. Possible transformations during the synthesis of calcium car-
bide.
ous modifications and new approaches are being proposed as
researchers seek to make this rather energy-consuming pro-
cess less expensive, which also reflects the level of interest in
this unique compound. Mechanistic studies have shown the
complexity of the processes and the enormous untapped po-
tential of this field.
5. Structure and Properties of Calcium Carbide
Structural studies of calcium carbide were stimulated by re-
search endeavors in search for new superconductors and appli-
cations of CaC2 in nanoscience. Early structural studies of calci-
um carbide demonstrated that this compound has a body-cen-
tered tetragonal lattice structure,[74] a distorted version of the
NaCl lattice in which the dumbbells of the two carbon atoms
are oriented along the tetragonal c axis. These findings were
later supported by powder neutron diffraction and single-crys-
tal X-ray diffraction studies.[75] The first data on the polymorph-
ism of calcium carbide were inferred from the phase dia-
gram.[76] The following modifications were observed, in addi-
tion to the tetragonal structure that is stable at room tempera-
ture (I): a cubic high-temperature modification with a NaCl-
type structure[77] (IV), a low-temperature modification (II), and
presumably a metastable modification (III). Calcium ions
occupy the lattice sites (like Na ions), whilst the disordered
carbon atoms occupy the Cl sites. Single-crystal X-ray diffrac-
tion analysis of other polymorphic modifications have also
been reported.[77b, 78] Interesting findings were observed in the
solid-state magic angle spinning (MAS) NMR data,[79] based on
analysis of the chemical shifts: 1) carbon atoms in calcium car-
bide have an asymmetric environment along the axes; and
2) the “acetylide ion” is not analogous to an alkyne CŽC triple
bond.
Analysis of the electronic structure of calcium carbide by
using theoretical calculations demonstrated that it is an ionic
compound and that a disordered structure in which two
carbon atoms lie along the c axis is the most-stable structure
(Figure 3).[80] These calculations supported the available data
on the stable modification of CaC2. Based on these findings, it
was proposed that rotation around the carbon atoms would
be almost impossible at low temperatures.[80]
Phase diagrams (Figure 4) within the temperature range 10–
823 K confirmed that calcium carbide has four polymorphic
modifications and demonstrated the effect of particle size,
sample purity, and heating rate on the final structure.[81]
It should be mentioned that pure calcium carbide, which
can be synthesized from the corresponding elements, was
used in the aforementioned study. Compared to technical-
971 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Focus Review

the formation of polyanionic carbide at a relatively high pres-

sure (ca. 20 GPa).[87] Polyanionic carbides have semi metallic or
metallic character and are promising superconductors.
The phase transitions that were induced by changes in pres-
sure were also described.[88] USPEX calculations demonstrated
that calcium carbide acted as a superconductor under ex-
tremely high pressures. Studies at various pressures made it
possible to detect several additional stable forms, two of
which were successfully synthesized for the first time. The re-
sulting compounds were identical to previous theoretical cal-
culations. Figure 5 shows that the properties and composition
of calcium carbide significantly depended on the pressure; this
fact could allow the discovery of new compounds with promis-
ing properties by using computational modeling.

Figure 3. Crystal structure of tetragonal calcium carbide. Reproduced with

permission from Ref. [80]. Copyright 1995, American Chemical Society.

Figure 4. Phase diagram of calcium carbide.[81]

grade or commercial-grade calcium carbide, it was possible to

draw a conclusion about the effect of impurities on the phase
diagrams. These findings also supported the hypothesis about
the metastability of the CaC2 modification, first put forward in
1942.[76c] In 2000, this modification was isolated and character-
ized in a pure form.[82] After milling, the CaC2 III modification
was converted back into CaC2 II. Heating the metastable modi-
fication at 460 8C caused a reversible phase-transformation into
the cubic modification, CaC2 IV.
According to density functional theory analysis, the total
energy minimum was attained in the T-shaped singlet state
with a very large dipole moment, whilst the transient form was
characterized by the linear isomer.[83] Surprisingly, the small cal-
cium carbide clusters, CamCn (m ‹ 8, n ‹ 12), which have been Figure 5. Top) Stability of new calcium carbides. Solid lines denote thermo-
dynamically stable phases; dashed lines denote metastable phases; metallic
studied by using theoretical methods, can be used to store hy-
and semiconductor properties are shown in red and blue, respectively. Bot-
drogen owing to the weak interactions between calcium tom) Variation in the composition of the carbide depending on the carbon
atoms (as compared to those in transition metals).[84] content. Only thermodynamically stable phases are shown. Reproduced with
Theoretical calculations predicted that there could be addi- permission from Ref. [88c]. Copyright 2015, Nature Publishing Group.
tional metastable structures of calcium carbide at high pres-
sures. At a transition pressure of 30 GPa, the six-coordinate
NaCl-type structure of CaC2 became an eight-coordinate CsCl- The interaction of calcium carbide with transition metal
type structure.[85] Experimental studies, which focused on the complexes remains an underexplored field. The reaction be-
behavior of calcium carbide in a high-pressure diamond anvil tween a carbide anion (C22¢) and a ruthenium carbonyl cluster
cell, also showed that calcium carbide existed in several poly- was proposed to involve an unusual Ca[Ru10(C)2(CO)24]
morphic modifications.[86] Ab initio theoretical calculations and complex, which was subsequently converted into
the USPEX algorithm were used to predict the possibility of [ppn]2[Ru10(C)2(CO)24] (Figure 6).[89]

Chem. Asian J. 2016, 11, 965 – 976 www.chemasianj.org 972 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 6. Molecular structure of the anionic part of [ppn]2[Ru10(C)2(CO)24];
ppn = hexaphenyldiphosphazene. Reproduced with permission from
Ref. [89]. Copyright 2002, Royal Society of Chemistry.
6. Preparation of Carbon Nanostructures from
Calcium Carbide
Nanotechnology is one of the key advancement areas of the
21st century, and it continues to develop tremendously quickly.
The properties of nanoparticles are mainly caused by their fa-
vorable morphology and the ratio of their surface area to
volume. Calcium carbide can be used as a source of carbon in
this highly promising field.
One of the most commonly used methods for preparing
nanomaterials from calcium carbide involves heating CaC2 to
100–600 8C in the presence of water-containing compounds,
such as the crystal hydrates of inorganic salts. Water is released
during heating and interacted with calcium carbide to produce
acetylene. Acetylene undergoes polymerization and pyrolysis
at high temperatures and pressure, thus giving rise to carbon
nanoparticles. The size, shape, and properties of the final mate-
rial not only depend on the conditions of the process, but also
on the water source and the catalyst that were used (Figure 7).
To facilitate the formation of shallow nanospheres (diameter:
30 nm), calcium carbide was heated at 500 8C in the presence
of AlCl3·6 H2O for 5 hours.[90] Carbon nanoflakes (diameter:
30 nm) were produced in a similar fashion by heating calcium
carbide in the presence of CuCl2·2 H2O.[91] Because the reaction
that gave rise to acetylene required an acidic proton, com-
pounds such as acids or chloroform (which release HCl when
heated) could also be used for this purpose.[92] Organic acids
can also act as a source of water molecules: for example,
oxalic acid forms calcium oxalate, thus contributing to acety-
lene release. This approach has been used to produce nano-
spheres.[93]
Another method for producing nanoparticles involves heat-
ing calcium carbide in the presence of chlorides of other
metals (e.g., Na or Mg) to about 400–900 8C. An anion-ex-
change reaction takes place under these conditions to afford
Chem. Asian J. 2016, 11, 965 – 976 www.chemasianj.org
Focus Review
Figure 7. Electron microscopy images: A–C) shallow nanospheres that were
prepared by using the AlCl3·6 H2O/CaC2 system; D–F) Carbon nano-onions
that were prepared by using the CuCl2·2 H2O/CaC2 system; G–I) nanospheres
that were prepared by using the oxalic acid/CaC2 system. Reproduced with
permission from Refs. [90, 91, 93]. Copyright 2002, Elsevier; 2011, American
Chemical Society; and 2010, Elsevier, respectively.
calcium chloride and the carbide of the corresponding metal,
the pyrolysis of which leads to the formation of carbon nano-
particles.[94] The reaction is performed at a lower temperature
(250 8C) if titanium chloride (TiCl4) is used.[95] Hollow carbon
spheres are manufactured by using the CaC2/CCl4 system in
the presence of an FeCl3 catalyst.[96]
7. Other Applications of Calcium Carbide
The unique properties of calcium carbide, considered in the
previous section, also govern its application as a denitrifying
agent.[97] Soil denitrification is the rapid conversion of ammoni-
um nitrogen found in fertilizers into nitrate. This process is
possible owing to bacteria in the soil. The resulting nitrates are
toxic, but they are rapidly washed out of the soil. When ap-
plied together with fertilizers, encapsulated calcium carbide
lowers the activity of soil bacteria, thus enhancing the fixation
of ammonium nitrogen by plants and increasing the crop.
Wax-like materials are usually used as encapsulating agents.
Encapsulation slows down the hydrolysis of calcium carbide to
several days, even in wet soil. Calcium carbide has higher activ-
ity in certain soil types compared to the standard denitrifica-
tion inhibitors (4-amino-1,2,4-triazole and dicyandiamide). Fur-
thermore, calcium carbide and the products of its hydrolysis
are non-toxic to the environment. All of these facts demon-
strate that calcium carbide is a promising agent for the inhibi-
tion of denitrification.
Acetylene released from calcium carbide also inhibits the ac-
tivity of methane-producing bacteria.[98] This property may be
973 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

applied to partially mitigate the problem of the “greenhouse
effect”. The use of a small amount of calcium carbide that is
encapsulated in wax or paraffin in industrial solid-waste land-
fills significantly decreases methanogenesis. By varying the car-
bide/encapsulating-agent ratio or capsule material, an accu-
rately dosed acetylene flow can be obtained that can be re-
leased over several days or months.
An interesting application concerns the use of encapsulated
calcium carbide as an autonomous fuel-free power source.[99]
The in-situ-generated acetylene made the carbide-containing
capsule move by a distance of up to 37 cm within 16 s at an
average speed of 2.3 cm s¢1. Figure 8 shows an image of the
capsule and its path.
Figure 8. Left) A capsule with calcium carbide. The white arrow denotes the
initial position. Right) The red curve shows the path of the capsule; the
black bar denotes the scale (1 cm). Reproduced with permission from
Ref. [99]. Copyright 2014, Royal Society of Chemistry.
8. Conclusion
Calcium carbide is readily available, easy to handle, and safe
for laboratory use, and it has been utilized as a convenient
source of in-situ-generated acetylene. In particular, calcium car-
bide has been successfully applied to various transformations,
including Sonogashira reactions, “click” reactions, three-com-
ponent coupling reactions in alkylamine/aldehyde systems, the
production of vinyl thioethers, and the synthesis of heterocy-
clic substrates. The replacement of gaseous acetylene with an
easy-to-handle solid reagent has been of significant benefit to
all of these processes. Calcium carbide may also have applica-
tions in cutting-edge areas of research, such as the preparation
of nanostructures. As representative examples, CaC2 has been
used to synthesize a number of nanocarbon structures, that is,
nanospheres, nano-onions, and nanoflakes.
Calcium carbide has outstanding potential in organic
chemistry, because CaC2 can be probed instead of acetylene in
many cases. We anticipate that many studies in the near future
will explore this fascinating opportunity. The renaissance of cal-
cium carbide chemistry and its corresponding synthetic appli-
cations promote the concept of “new life of old molecules”.[100]
Demanding synthetic challenges and the requirements of
“green” and sustainable development will further stimulate
this trend to reconsider the potential of well-known small mol-
ecules.
Chem. Asian J. 2016, 11, 965 – 976 www.chemasianj.org
Focus Review
Acknowledgements
This work is supported by the RFBR (grant Nos 15-33-20536
and 14-03-01005). G.W. acknowledges Saint Petersburg State
University for a postdoctoral fellowship (No. 0.50.1186.2014).
Mechanistic studies on the calcium carbide project at Zelinsky
Institute were supported by the Russian Science Foundation
(RSF; No. 14-50-00126).
Keywords: acetylene · calcium carbide · industrial chemistry ·
nanotechnology · synthetic methods
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Final Article published: February 22, 2016

Chem. Asian J. 2016, 11, 965 – 976 www.chemasianj.org 976 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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