Alkyne

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A 3D model of ethyne (acetylene), the simplest alkyne Acetylene-3D-vdW.png
A 3D model of ethyne (acetylene), the simplest alkyne

In organic chemistry, an alkyne is an unsaturated hydrocarbon containing at least one carbon—carbon triple bond. [1] The simplest acyclic alkynes with only one triple bond and no other functional groups form a homologous series with the general chemical formula CnH2n-2. Alkynes are traditionally known as acetylenes, although the name acetylene also refers specifically to C2H2, known formally as ethyne using IUPAC nomenclature. Like other hydrocarbons, alkynes are generally hydrophobic. [2]

Structure and bonding

In acetylene, the H–C≡C bond angles are 180°. By virtue of this bond angle, alkynes are rod-like. Correspondingly, cyclic alkynes are rare. Benzyne cannot be isolated. The C≡C bond distance of 121 picometers is much shorter than the C=C distance in alkenes (134 pm) or the C–C bond in alkanes (153 pm).

Illustrative alkynes: a, acetylene, b, two depictions of propyne, c, 1-butyne, d, 2-butyne, e, the naturally-occurring 1-phenylhepta-1,3,5-triyne, and f, the strained cycloheptyne. Triple bonds are highlighted blue. Alkyne General Formulae V.2.png
Illustrative alkynes: a, acetylene, b, two depictions of propyne, c, 1-butyne, d, 2-butyne, e, the naturally-occurring 1-phenylhepta-1,3,5-triyne, and f, the strained cycloheptyne. Triple bonds are highlighted blue.

The triple bond is very strong with a bond strength of 839 kJ/mol. The sigma bond contributes 369 kJ/mol, the first pi bond contributes 268 kJ/mol and the second pi-bond of 202 kJ/mol bond strength. Bonding usually discussed in the context of molecular orbital theory, which recognizes the triple bond as arising from overlap of s and p orbitals. In the language of valence bond theory, the carbon atoms in an alkyne bond are sp hybridized: they each have two unhybridized p orbitals and two sp hybrid orbitals. Overlap of an sp orbital from each atom forms one sp–sp sigma bond. Each p orbital on one atom overlaps one on the other atom, forming two pi bonds, giving a total of three bonds. The remaining sp orbital on each atom can form a sigma bond to another atom, for example to hydrogen atoms in the parent acetylene. The two sp orbitals project on opposite sides of the carbon atom.

Terminal and internal alkynes

Internal alkynes feature carbon substituents on each acetylenic carbon. Symmetrical examples include diphenylacetylene and 3-hexyne.

Terminal alkynes have the formula RC2H. An example is methylacetylene (propyne using IUPAC nomenclature). Terminal alkynes, like acetylene itself, are mildly acidic, with pKa values of around 25. They are far more acidic than alkenes and alkanes, which have pKa values of around 40 and 50, respectively. The acidic hydrogen on terminal alkynes can be replaced by a variety of groups resulting in halo-, silyl-, and alkoxoalkynes. The carbanions generated by deprotonation of terminal alkynes are called acetylides. [3]

Naming alkynes

In systematic chemical nomenclature, alkynes are named with the Greek prefix system without any additional letters. Examples include ethyne or octyne. In parent chains with four or more carbons, it is necessary to say where the triple bond is located. For octyne, one can either write 3-octyne or oct-3-yne when the bond starts at the third carbon. The lowest number possible is given to the triple bond. When no superior functional groups are present, the parent chain must include the triple bond even if it is not the longest possible carbon chain in the molecule. Ethyne is commonly called by its trivial name acetylene.

In chemistry, the suffix -yne is used to denote the presence of a triple bond. In organic chemistry, the suffix often follows IUPAC nomenclature. However, inorganic compounds featuring unsaturation in the form of triple bonds may be denoted by substitutive nomenclature with the same methods used with alkynes (i.e. the name of the corresponding saturated compound is modified by replacing the "-ane" ending with "-yne"). "-diyne" is used when there are two triple bonds, and so on. The position of unsaturation is indicated by a numerical locant immediately preceding the "-yne" suffix, or 'locants' in the case of multiple triple bonds. Locants are chosen so that the numbers are low as possible. "-yne" is also used as an infix to name substituent groups that are triply bound to the parent compound.

Sometimes a number between hyphens is inserted before it to state which atoms the triple bond is between. This suffix arose as a collapsed form of the end of the word "acetylene". The final "-e" disappears if it is followed by another suffix that starts with a vowel. [4]

Structural isomerism

Alkynes having four or more carbon atoms can form different structural isomers by having the triple bond in different positions or having some of the carbon atoms be substituents rather than part of the parent chain. Other non-alkyne structural isomers are also possible.

Synthesis

Cracking

Commercially, the dominant alkyne is acetylene itself, which is used as a fuel and a precursor to other compounds, e.g., acrylates. Hundreds of millions of kilograms are produced annually by partial oxidation of natural gas: [5]

Propyne, also industrially useful, is also prepared by thermal cracking of hydrocarbons.

Alkynes are prepared from 1,2- and 1,1-alkyl dihalides by double dehydrohalogenation. The reaction provides a means to generate alkynes from alkenes, which are first halogenated and then dehydrohalogenated. For example, phenylacetylene can be generated from styrene by bromination followed by treatment of the resulting of styrene dibromide with sodium amide in ammonia: [6] [7]

Phenylacetylene prepn.png

Via the Fritsch–Buttenberg–Wiechell rearrangement, alkynes are prepared from vinyl bromides. Alkynes can be prepared from aldehydes using the Corey–Fuchs reaction and from aldehydes or ketones by the Seyferth–Gilbert homologation.

Vinyl chlorides are susceptible to dehydrochlorination. Vinyl chlorides are available from aldehydes using the reagent (chloromethylene)triphenylphosphorane.

Reactions, including applications

Featuring a reactive functional group, alkynes participate in many organic reactions. Such use was pioneered by Ralph Raphael, who in 1955 wrote the first book describing their versatility as intermediates in synthesis. [8]

Hydrogenation

Being more unsaturated than alkenes, alkynes characteristically undergo reactions that show that they are "doubly unsaturated". Alkynes are capable of adding two equivalents of H2, whereas an alkene adds only one equivalent. [9] Depending on catalysts and conditions, alkynes add one or two equivalents of hydrogen. Partial hydrogenation, stopping after the addition of only one equivalent to give the alkene, is usually more desirable since alkanes are less useful:

PhC2HH2.png

The largest scale application of this technology is the conversion of acetylene to ethylene in refineries (the steam cracking of alkanes yields a few percent acetylene, which is selectively hydrogenated in the presence of a palladium/silver catalyst). For more complex alkynes, the Lindlar catalyst is widely recommended to avoid formation of the alkane, for example in the conversion of phenylacetylene to styrene. [10] Similarly, halogenation of alkynes gives the alkene dihalides or alkyl tetrahalides:

The addition of one equivalent of H2 to internal alkynes gives cis-alkenes.

Alkynes characteristically are capable of adding two equivalents of halogens and hydrogen halides.

The addition of nonpolar E−H bonds across C≡C is general for silanes, boranes, and related hydrides. The hydroboration of alkynes gives vinylic boranes which oxidize to the corresponding aldehyde or ketone. In the thiol-yne reaction the substrate is a thiol.

Addition of hydrogen halides has long been of interest. In the presence of mercuric chloride as a catalyst, acetylene and hydrogen chloride react to give vinyl chloride. While this method has been abandoned in the West, it remains the main production method in China. [11]

Hydration

The hydration reaction of acetylene gives acetaldehyde. The reaction proceeds by formation of vinyl alcohol, which undergoes tautomerizes to form the aldehyde. This reaction was once a major industrial process but it has been displaced by the Wacker process. This reaction occurs in nature, the catalyst being acetylene hydratase.

The hydration of phenylacetylene gives acetophenone, [12] and the (Ph3P)AuCH3- catalyzed hydration of 1,8-nonadiyne to 2,8-nonanedione: [13]

Tautomerism

Terminal alkyl alkynes exhibit tautomerism. Propyne exists in equilibrium with allene:

Cycloadditions and oxidation

Alkynes undergo diverse cycloaddition reactions. The Diels–Alder reaction with 1,3-dienes give 1,4-cyclohexadienes. This general reaction has been extensively developed. Electrophilic alkynes are especially effective dienophiles. The "cycloadduct" derived from the addition of alkynes to 2-pyrone eliminates carbon dioxide to give the aromatic compound. Other specialized cycloadditions include multicomponent reactions such as alkyne trimerisation to give aromatic compounds and the [2+2+1]-cycloaddition of an alkyne, alkene and carbon monoxide in the Pauson–Khand reaction. Non-carbon reagents also undergo cyclization, e.g. Azide alkyne Huisgen cycloaddition to give triazoles. Cycloaddition processes involving alkynes are often catalyzed by metals, e.g. enyne metathesis and alkyne metathesis, which allows the scrambling of carbyne (RC) centers:

Oxidative cleavage of alkynes proceeds via cycloaddition to metal oxides. Most famously, potassium permanganate converts alkynes to a pair of carboxylic acids.

Reactions specific for terminal alkynes

Terminal alkynes are readily converted to many derivatives, e.g. by coupling reactions and condensations. Via the condensation with formaldehyde and acetylene is produced butynediol: [5] [14]

In the Sonogashira reaction, terminal alkynes are coupled with aryl or vinyl halides:

Sonogashira reaction scheme ACS.png

This reactivity exploits the fact that terminal alkynes are weak acids, whose typical pKa values around 25 place them between that of ammonia (35) and ethanol (16):

where MX = NaNH2, LiBu, or RMgX.

The reactions of alkynes with certain metal cations, e.g. Ag+ and Cu+ also gives acetylides. Thus, few drops of diamminesilver(I) hydroxide (Ag(NH3)2OH) reacts with terminal alkynes signaled by formation of a white precipitate of the silver acetylide. This reactivity is the basis of alkyne coupling reactions, including the Cadiot–Chodkiewicz coupling, Glaser coupling, and the Eglinton coupling: [15]

In the Favorskii reaction and in alkynylations in general, terminal alkynes add to carbonyl compounds to give the hydroxyalkyne.

Metal complexes

Alkynes form complexes with transition metals. Such complexes occur also in metal catalyzed reactions of alkynes such as alkyne trimerization. Terminal alkynes, including acetylene itself, react with water to give aldehydes. The transformation typically requires metal catalysts to give this anti-Markovnikov addition result. [16]

Alkynes in nature and medicine

According to Ferdinand Bohlmann, the first naturally occurring acetylenic compound, dehydromatricaria ester, was isolated from an Artemisia species in 1826. In the nearly two centuries that have followed, well over a thousand naturally occurring acetylenes have been discovered and reported. Polyynes, a subset of this class of natural products, have been isolated from a wide variety of plant species, cultures of higher fungi, bacteria, marine sponges, and corals. [17] Some acids like tariric acid contain an alkyne group. Diynes and triynes, species with the linkage RC≡C–C≡CR′ and RC≡C–C≡C–C≡CR′ respectively, occur in certain plants ( Ichthyothere , Chrysanthemum , Cicuta , Oenanthe and other members of the Asteraceae and Apiaceae families). Some examples are cicutoxin, oenanthotoxin, and falcarinol . These compounds are highly bioactive, e.g. as nematocides. [18] 1-Phenylhepta-1,3,5-triyne is illustrative of a naturally occurring triyne.

Alkynes occur in some pharmaceuticals, including the contraceptive noretynodrel. A carbon–carbon triple bond is also present in marketed drugs such as the antiretroviral Efavirenz and the antifungal Terbinafine. Molecules called ene-diynes feature a ring containing an alkene ("ene") between two alkyne groups ("diyne"). These compounds, e.g. calicheamicin, are some of the most aggressive antitumor drugs known, so much so that the ene-diyne subunit is sometimes referred to as a "warhead". Ene-diynes undergo rearrangement via the Bergman cyclization, generating highly reactive radical intermediates that attack DNA within the tumor. [19]

See also

Related Research Articles

<span class="mw-page-title-main">Acetylene</span> Hydrocarbon compound (HC≡CH)

Acetylene is the chemical compound with the formula C2H2 and structure H−C≡C−H. It is a hydrocarbon and the simplest alkyne. This colorless gas is widely used as a fuel and a chemical building block. It is unstable in its pure form and thus is usually handled as a solution. Pure acetylene is odorless, but commercial grades usually have a marked odor due to impurities such as divinyl sulfide and phosphine.

<span class="mw-page-title-main">Alkene</span> Hydrocarbon compound containing one or more C=C bonds

In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond.

<span class="mw-page-title-main">Diacetylene</span> Organic compound (HCCCCH)

Diacetylene (also known as butadiyne) is the organic compound with the formula C4H2. It is the simplest compound containing two triple bonds. It is first in the series of polyynes, which are of theoretical but not of practical interest.

In chemistry, a hydration reaction is a chemical reaction in which a substance combines with water. In organic chemistry, water is added to an unsaturated substrate, which is usually an alkene or an alkyne. This type of reaction is employed industrially to produce ethanol, isopropanol, and butan-2-ol.

In chemistry, an electrophile is a chemical species that forms bonds with nucleophiles by accepting an electron pair. Because electrophiles accept electrons, they are Lewis acids. Most electrophiles are positively charged, have an atom that carries a partial positive charge, or have an atom that does not have an octet of electrons.

<span class="mw-page-title-main">Triple bond</span> Chemical bond involving six bonding electrons; one sigma plus two pi bonds

A triple bond in chemistry is a chemical bond between two atoms involving six bonding electrons instead of the usual two in a covalent single bond. Triple bonds are stronger than the equivalent single bonds or double bonds, with a bond order of three. The most common triple bond, that between two carbon atoms, can be found in alkynes. Other functional groups containing a triple bond are cyanides and isocyanides. Some diatomic molecules, such as dinitrogen and carbon monoxide, are also triple bonded. In skeletal formulae the triple bond is drawn as three parallel lines (≡) between the two connected atoms.

<span class="mw-page-title-main">Unsaturated hydrocarbon</span>

Unsaturated hydrocarbons are hydrocarbons that have double or triple covalent bonds between adjacent carbon atoms. The term "unsaturated" means more hydrogen atoms may be added to the hydrocarbon to make it saturated. The configuration of an unsaturated carbons include straight chain, such as alkenes and alkynes, as well as branched chains and aromatic compounds.

In chemistry, halogenation is a chemical reaction that entails the introduction of one or more halogens into a compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens (F2, Cl2, Br2, I2). Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

<span class="mw-page-title-main">Propyne</span> Hydrocarbon compound (HC≡C–CH3)

Propyne (methylacetylene) is an alkyne with the chemical formula CH3C≡CH. It is a component of MAPD gas—along with its isomer propadiene (allene), which was commonly used in gas welding. Unlike acetylene, propyne can be safely condensed.

Cyclopropene is an organic compound with the formula C3H4. It is the simplest cycloalkene. Because the ring is highly strained, cyclopropene is difficult to prepare and highly reactive. This colorless gas has been the subject for many fundamental studies of bonding and reactivity. It does not occur naturally, but derivatives are known in some fatty acids. Derivatives of cyclopropene are used commercially to control ripening of some fruit.

The 1,3-dipolar cycloaddition is a chemical reaction between a 1,3-dipole and a dipolarophile to form a five-membered ring. The earliest 1,3-dipolar cycloadditions were described in the late 19th century to the early 20th century, following the discovery of 1,3-dipoles. Mechanistic investigation and synthetic application were established in the 1960s, primarily through the work of Rolf Huisgen. Hence, the reaction is sometimes referred to as the Huisgen cycloaddition. 1,3-dipolar cycloaddition is an important route to the regio- and stereoselective synthesis of five-membered heterocycles and their ring-opened acyclic derivatives. The dipolarophile is typically an alkene or alkyne, but can be other pi systems. When the dipolarophile is an alkyne, aromatic rings are generally produced.

In organic chemistry, an alkyne trimerisation is a [2+2+2] cycloaddition reaction in which three alkyne units react to form a benzene ring. The reaction requires a metal catalyst. The process is of historic interest as well as being applicable to organic synthesis. Being a cycloaddition reaction, it has high atom economy. Many variations have been developed, including cyclisation of mixtures of alkynes and alkenes as well as alkynes and nitriles.

The azide-alkyne Huisgen cycloaddition is a 1,3-dipolar cycloaddition between an azide and a terminal or internal alkyne to give a 1,2,3-triazole. Rolf Huisgen was the first to understand the scope of this organic reaction. American chemist Karl Barry Sharpless has referred to this cycloaddition as "the cream of the crop" of click chemistry and "the premier example of a click reaction".

<span class="mw-page-title-main">Organoaluminium chemistry</span>

Organoaluminium chemistry is the study of compounds containing bonds between carbon and aluminium. It is one of the major themes within organometallic chemistry. Illustrative organoaluminium compounds are the dimer trimethylaluminium, the monomer triisobutylaluminium, and the titanium-aluminium compound called Tebbe's reagent. The behavior of organoaluminium compounds can be understood in terms of the polarity of the C−Al bond and the high Lewis acidity of the three-coordinated species. Industrially, these compounds are mainly used for the production of polyolefins.

<span class="mw-page-title-main">Organonickel chemistry</span>

Organonickel chemistry is a branch of organometallic chemistry that deals with organic compounds featuring nickel-carbon bonds. They are used as a catalyst, as a building block in organic chemistry and in chemical vapor deposition. Organonickel compounds are also short-lived intermediates in organic reactions. The first organonickel compound was nickel tetracarbonyl Ni(CO)4, reported in 1890 and quickly applied in the Mond process for nickel purification. Organonickel complexes are prominent in numerous industrial processes including carbonylations, hydrocyanation, and the Shell higher olefin process.

Carbonylation refers to reactions that introduce carbon monoxide into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbonylation also refers to oxidation of protein side chains.

<span class="mw-page-title-main">Vinyl cation</span>

The vinyl cation is a carbocation with the positive charge on an alkene carbon. Its empirical formula is C
2
H+
3
. More generally, a vinylic cation is any disubstituted, trivalent carbon, where the carbon bearing the positive charge is part of a double bond and is sp hybridized. In the chemical literature, substituted vinylic cations are often referred to as vinyl cations, and understood to refer to the broad class rather than the C
2
H+
3
variant alone. The vinyl cation is one of the main types of reactive intermediates involving a non-tetrahedrally coordinated carbon atom, and is necessary to explain a wide variety of observed reactivity trends. Vinyl cations are observed as reactive intermediates in solvolysis reactions, as well during electrophilic addition to alkynes, for example, through protonation of an alkyne by a strong acid. As expected from its sp hybridization, the vinyl cation prefers a linear geometry. Compounds related to the vinyl cation include allylic carbocations and benzylic carbocations, as well as aryl carbocations.

In organic chemistry, the term ethynyl designates a functional group with a double bond with 2 carbon atoms both with sp hybridisation and a triple bond(1 sigma and 2 pi bond). It is a species similar to acetylene with a less H atom thus joined to root chain.

In organic chemistry, alkynylation is an addition reaction in which a terminal alkyne is added to a carbonyl group to form an α-alkynyl alcohol.

In organic chemistry, methylenation is a chemical reaction that inserts a methylene group into a chemical compound:

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