ALKYNES

GROUP 4 (RAMIREZ, MANUEL, UY)

11.1 Introduction—Structure and Bonding

• Alkynes contain a carbon—carbon triple bond.
• Terminal alkynes have the triple bond at the end of the carbon chain so that
a hydrogen atom is directly bonded to a carbon atom of the triple bond.
• Internal alkynes have a carbon atom bonded to each carbon atom of the
triple bond.
• An alkyne has the general molecular formula CnH2n-2, giving it four fewer
hydrogens than the maximum possible for the number of carbons present.
Thus, the triple bond introduces two degrees of unsaturation.

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• Recall that the triple bond consists of 2 π bonds and 1 σ bond.
• Each carbon is sp hybridized with a linear geometry and bond angles of
0
180 .

• Bond dissociation energies of the C—C bonds in ethylene (one σ and one π
bond) and acetylene (one σ and two π bonds) can be used to estimate the
strength of the second π bond of the triple bond.

4
• Like trans cycloalkenes, cycloalkynes with small rings are unstable. The
carbon chain must be long enough to connect the two ends of the triple
bond without introducing too much strain.
• Cyclooctyne is the smallest isolable cycloalkyne, though it decomposes
upon standing at room temperature after a short time.

11.2 Nomenclature

• Alkynes are named in the same general way that alkenes are named.
• In the IUPAC system, change the –ane ending of the parent alkane
name to the suffix –yne.
• Choose the longest continuous chain that contains both atoms of
the triple bond and number the chain to give the triple bond the
lower number.
• Compounds with two triple bonds are named as diynes, those with
three are named as triynes and so forth.
• Compounds both a double and triple bond are named as enynes.
The chain is numbered to give the first site of unsaturation (either
C=C or C≡C) the lower number.
• The simplest alkyne, H-C≡C-H, named in the IUPAC system as
ethyne, is more often called acetylene, its common name.
• The two-carbon alkyl group derived from acetylene is called an
ethynyl group.

6
Alkynes: Nomenclature

Although some common alkyne names, such as acetylene, are still found in many textbooks, the
International Union of Pure and Applied Chemistry (IUPAC) nomenclature is required for journal
articles. The rules for alkynes in this system are identical with those for alkenes, except for the ending.
The following rules summarize alkyne nomenclature.

1. Identify the longest continuous chain of carbon atoms that contains the carbon‐carbon triple bond.
The parent name of the alkyne comes from the IUPAC name for the alkane of the same number of
carbon atoms, except the ‐ ane ending is changed to ‐ yne to signify the presence of a triple bond. Thus,
if the longest continuous chain of carbon atoms containing a triple bond has five atoms, the compound
is pentyne.

2. Number the carbon atoms of the longest continuous chain, starting at the end closest to the triple
bond. Thus, is numbered from right to left, placing the triple bond between the second and third carbon
atoms of the chain. (Numbering the chain from left to right incorrectly places the triple bond between
the third and fourth carbons of the chain.)

3. The position of the triple bond is indicated by placing the lower of the pair of numbers assigned to
the triple‐bonded carbon atoms in front of the name of the alkyne. Thus the compound shown in rule 2
is 2‐pentyne.

4. The location and name of any substituent atom or group is indicated. For example, the compound is 

5‐chloro‐2‐hexyne.

Alkynes: Physical Properties

The physical properties of alkynes are very similar to those of the alkenes. Alkynes are generally
nonpolar molecules with little solubility in polar solvents, such as water. Solubility in nonpolar
solvents, such as ether and acetone, is extensive. Like the alkanes and alkenes, alkynes of four or fewer
carbon atoms tend to be gases.

Substituted alkynes have small dipole moments due to differences in electronegativity between the
triple‐bonded carbon atoms, which are sp hybridized, and the single‐bonded carbon atoms, which
are sp 3 hybridized. The sp‐hybridized carbon atom, which possesses more s character than the sp 3‐
hybridized carbon atom, is more electronegative in character. The resulting asymmetrical electron
distribution in the bond between such carbon atoms results in the generation of a dipole moment.

Alkynes: Acidity

Alkynes of the general structure 

are referred to as terminal alkynes. These types of alkynes are weakly acidic. Exposure to a strong
base, such as sodium amide, produces an acid‐base reaction.

The acidity of a terminal alkyne is due to the high level of s character in the sp hybrid orbital, which
bonds with the s orbital of the hydrogen atom to form a single covalent bond. The high level
of s character in an sp‐hybridized carbon causes the overlap region of the σ bond to shift much closer
to the carbon atom. This polarizes the bond, causing the hydrogen atom to become slightly positive.
This slight positive charge makes the hydrogen atom a weak proton, which can be removed by a strong
base.

In the case of alkanes and alkenes, the s character in the hybridized carbon bonds is less, resulting in
fewer electronegative carbon atoms and a corresponding lesser shift toward those atoms in the overlap
region of the σ bond. The location of the overlap region makes the corresponding hydrogen atoms less
electron deficient and thus less acidic. In reality, the hydrogen atoms bonded to alkanes and alkenes
can be removed as protons, but much stronger nonaqueous bases are necessary.

The reaction that forms the acetylide ion is reversible. Thus, the base may not form an acid of greater
strength than the starting alkyne by acceptance of the proton, or the newly formed conjugate acid will
reprotonate the acetylide ion. The fact that stronger acids are capable of reprotonating the acetylide ion
can be seen in its reaction with water.

Alkynes: Preparations

The preparations of alkynes are very similar to those of the alkenes. The main preparative reactions
involve the elimination of groups or ions from molecules, resulting in the formation of π bonds.

Dehydrohalogenation. The loss of a hydrogen atom and a halogen atom from adjacent alkane carbon
atoms leads to the formation of an alkene. The loss of additional hydrogen and halogen atoms from the
double‐bonded carbon atoms leads to alkyne formation. The halogen atoms may be located on the
same carbon (a geminal dihalide) or on adjacent carbons (a vicinal dihalide).

During the second dehydrohalogenation step, certain conditions are necessary, namely high
temperatures and an extremely strong basic solution.
Dehalogenation. Vicinal tetrahaloalkanes can be dehalogenated with zinc metal in an organometallic
reaction to form alkynes.

Substitution. Larger alkynes can be generated by reacting an alkyl halide with an acetylide ion, which
is generated from a shorter alkyne.

Because acetylide ions are bases, elimination reactions can occur, leading to the formation of an alkene
from the alkyl halide. Because substitution and elimination reactions proceed through the formation of
a common intermediate, these two types of reactions always occur simultaneously.

Ethyne (acetylene) preparation. Ethyne, which is commonly called acetylene, is the simplest

alkyne. Historically, it was prepared by reacting calcium carbide with water.

Today, ethyne is normally prepared by the pyrolysis of methane. In this procedure, a stream of
methane gas is briefly heated to 1500°C in an airless chamber. Air must be excluded from the reaction
or oxidation (combustion) will occur.

Alkynes: Addition Reactions

The principal reaction of the alkynes is addition across the triple bond to form alkanes. These addition
reactions are analogous to those of the alkenes.
Hydrogenation. Alkynes undergo catalytic hydrogenation with the same catalysts used in alkene
hydrogenation: platinum, palladium, nickel, and rhodium. Hydrogenation proceeds in a stepwise
fashion, forming an alkene first, which undergoes further hydrogenation to an alkane.

This reaction proceeds so smoothly that it is difficult, if not impossible, to stop the reaction at the
alkene stage, although by using palladium or nickel for the catalyst, the reaction can be used to isolate
some alkenes. Greater yields of alkenes are possible with the use of poisoned catalysts. One such
catalyst, the Lindlar catalyst, is composed of finely divided palladium coated with quinoline and
absorbed on calcium carbonate. This treatment makes the palladium less receptive to hydrogen, so
fewer hydrogen atoms are available to react. When a catalyst is deactivated in such a manner, it is
referred to as being poisoned.

The mechanism of alkyne hydrogenation is identical to that of the alkenes. Because the hydrogen is
absorbed on the catalyst surface, it is supplied to the triple bond in a syn manner.

Alkynes can also be hydrogenated with sodium in liquid ammonia at low temperatures. This reaction is
a chemical reduction rather than a catalytic reaction, so the hydrogen atoms are not attached to a
surface, and they may approach an alkene from different directions, leading to the formation
of trans alkenes.

Halogenation. The addition of halogens to an alkyne proceeds in the same manner as halogen addition
to alkenes. The halogen atoms add to an alkyne molecule in a stepwise fashion, leading to the
formation of the corresponding alkene, which undergoes further reaction to a tetrahaloalkane.

Unlike most hydrogenation reactions, it is possible to stop this reaction at the alkene stage by running
it at temperatures slightly below 0°C.

Hydrohalogenation. Hydrogen halides react with alkynes in the same manner as they do with alkenes.
Both steps in the above addition follow the Markovnikov rule. Thus, the addition of hydrogen bromide
to 1‐butyne gives 2‐bromo‐1‐butene as the major product of the first step.

The reaction of 2‐bromo‐1‐butene in the second step gives 2,2‐dibromobutane as the major product.

Hydration. The addition of the elements of water across the triple bond of an alkyne leads to the
formation of aldehydes and ketones. Water addition to terminal alkynes leads to the generation
of aldehydes, while nonterminal alkynes and water generate ketones.

These products are produced by rearrangement of an unstable enol (vinyl alcohol) intermediate. The
term “enol” comes from the en in “alkene” and ol in “alcohol,” reflecting that one of the carbon atoms
in vinyl alcohol has both a double bond (alkene) and an OH group (alcohol) attached to it. A vinyl
group is 

and a vinyl alcohol is

Water adds across the triple bond of an alkyne via a carbocation mechanism. Dilute mineral acid and
mercury(II) ions are needed for the reaction to occur.
The first step of the mechanism is an acid‐base reaction between the mercury(II) ion (Hg 2+) and the π
system of the alkyne to form a π complex.

The π complex is converted into a single bond between one or the other of the carbons of the triple
bond and the mercury (II) ion, with the resulting generation of a carbocation.

A molecule of water is attracted to the carbocation to form an oxonium ion.

The oxonium ion loses a proton to stabilize itself.

The vinyl alcohol precursor that results is converted into vinyl alcohol (enol) by reaction with a
hydronium ion (H 3O +).

Vinyl alcohols (enols) are unstable intermediates, and they undergo rapid isomerization to form
ketones. Such isomerization is called keto‐enol tautomerism.
In a similar fashion, the less‐stable intermediate generates an aldehyde.

Oxidation. Alkynes are oxidized by the same reagents that oxidize alkenes. Disubstituted alkynes react
with potassium permanganate to yield vicinal diketones (Vic‐diketones or 1,2‐diketones) or, under
more vigorous conditions, carboxylic acids.

Ozonolysis of an alkyne also leads to carboxylic acid formation.

Polymerization. Alkynes can be polymerized by both cationic and free‐radical methods. The reactions
and mechanisms are identical with those of the alkenes.

Alkynes: Molecular and Structural Formulas

The alkynes comprise a series of carbon‐ and hydrogen‐based compounds that contain at least one
triple bond. This group of compounds is a homologous series with the general molecular formula of
C n H 2 n‐‐2 , where n equals any integer greater than one.

The simplest alkyne, ethyne (also known as acetylene), has two carbon atoms and the molecular
formula of C 2H 2. The structural formula for ethyne is
In longer alkyne chains, the additional carbon atoms are attached to each other by single covalent
bonds. Each carbon atom is also attached to sufficient hydrogen atoms to produce a total of four single
covalent bonds about itself. In alkynes of four or more carbon atoms, the triple bond can be located in
different positions along the chain, leading to the formation of structural isomers. For example, the
alkyne of molecular formula C 4H 6 has two isomers,

Although alkynes possess restricted rotation due to the triple bond, they do not have stereoisomers like
the alkenes because the bonding in a carbon‐carbon triple bond is sp hybridized. In sp hybridization,
the maximum separation between the hybridized orbitals is 180°, so the molecule is linear. Thus, the
substituents on triple‐bonded carbons are positioned in a straight line, and stereoisomers are
impossible.

Alkynes: Unsaturation

The alkyne triple bond is composed of one σ and two π covalent bonds. The π bonds are the structures
that preclude any rotation around the σ‐bond axis. As with the alkenes, any rotation on the σ‐bond axis
would require disruption of the π‐bond system. Breaking the π‐bond system requires energy and thus
would lead to a molecule with a less stable, higher energy state.

Like alkenes, alkynes are unsaturated because they are capable of reacting with hydrogen in the
presence of a catalyst to form a corresponding fully saturated alkane. Each π bond signals that two
hydrogen atoms have been lost from the molecular formula of the alkane with the same number of
carbon atoms. Because alkynes possess two π bonds per molecule, they are said to contain
two elements of unsaturation
 Figure 11.1 Examples of alkyne nomenclature

11.3 Physical Properties

• The physical properties of alkynes resemble those of hydrocarbons

of similar shape and molecular weight.
• Alkynes have low melting points and boiling points.
• Melting point and boiling point increase as the number of carbons
increases.
• Alkynes are soluble in organic solvents and insoluble in water.

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Chemical Properties of Alkynes

Acidic nature

Coming to the chemical properties of alkynes, we begin with their slightly acidic nature. Now Alkynes are
slightly electronegative in nature. The triply bonded carbon atoms in alkynes are sp hybridized, Whereas
like in alkanes the single bond atoms are sp3 hybridized, causing the difference in the electronegativity.
This makes it easier for them to attract the shared electron pair of the C-H bond.

So when we react a strong base like NaNH2 with ethyne, we will get sodium acetylide and
liberated hydrogen (H2) gas. But such reactions will not happen in alkanes and alkenes. The conclusion
being that the hydrogen atoms attached to the carbon-carbon triple bond in alkynes are slightly acidic in
nature. It is to be noted the other hydrogen atoms baring these ones are not acidic.

HC ≡ CH + Na → HC ≡ C– Na+ + 1/2H2

Addition Reactions

Under suitable conditions (temperature and pressure) alkynes will undergo hydration reactions quite
easily. Alkynes will react with halogens, hydrogen and other such elements to give a saturated compound
as a product. Since they have a triple bond, two atoms of H2 or halides or halogens can be added to
its structure.

1] Addition of Dihydrogen

The reaction occurs in presence of a catalyst such as Nickel or Platinum or Palladium. Here the addition of
hydrogen to the alkyne gives us an alkene.

C3H4(g) + 2H2(g)   C3H8(g)

2] Addition of Halogens

When alkynes and halogens like Bromine react, halogen will add itself to the structure of the alkynes and
result in halogen substituted alkenes. The resulting product will be tetrabromopropane.
3] Addition of Water

Just like other hydrocarbons (alkanes and alkenes) alkynes also do not react with a water molecule. This is
called immiscibility. But if alkynes is bubbled through dilute sulphuric acid (about 40%) in presence of
the catalyst mercuric Sulphate, then a reaction occurs. The products will be carbonyl compounds, and such
a reaction can be called a hydration reaction.

(Source: chemistryassignment)

4] Polymerization

Alkynes can undergo linear and cyclic polymerization under suitable conditions. They polymerize to give
compounds that have a higher molecular weight than the original alkyne. Like for example, ethyne will
polymerize to give polyacetylene or polyethene (of higher molecular weight), This is an example of linear
polymerization.

For cyclic polymerization, high temperatures and the presence of a catalyst is required. Like passing
ethyne through a red-hot iron tube at a minimum of 877K which gives benzene.

Reactions of Alkynes - Addition of HX and X₂

Addition by Electrophilic Reagents

Since the most common chemical transformation of a carbon-carbon double bond is an addition
reaction, we might expect the same to be true for carbon-carbon triple bonds. Indeed, most of
the alkene addition reactions also take place with alkynes with similar regio- and stereoselectivity.

When the addition reactions of electrophilic reagents, such as strong Brønsted acids and halogens, to
alkynes are studied we find a curious paradox. The reactions are even more exothermic than the
additions to alkenes, and yet the rate of addition to alkynes is slower by a factor of 100 to 1000 than
addition to equivalently substituted alkenes. The reaction of one equivalent of bromine with 1-penten-
4-yne, for example, gave 4,5-dibromo-1-pentyne as the chief product.

HC≡C-CH2-CH=CH2 + Br2 → HC≡C-CH2-CHBrCH2Br

Although these electrophilic additions to alkynes are sluggish, they do take place and generally display
Markovnikov Rule regioselectivity and anti-stereoselectivity. One problem, of course, is that the
products of these additions are themselves substituted alkenes and can therefore undergo further
addition. Because of their high electronegativity, halogen substituents on a double bond act to reduce
its nucleophilicity, and thereby decrease the rate of electrophilic addition reactions. Consequently,
there is a delicate balance as to whether the product of an initial addition to an alkyne will suffer
further addition to a saturated product. Although the initial alkene products can often be isolated and
 identified, they are commonly present in mixtures of products and may not be obtained in high yield.
The following reactions illustrate many of these features. In the last example, 1,2-diodoethene does not
suffer further addition inasmuch as vicinal-diiodoalkanes are relatively unstable.

As a rule, electrophilic addition reactions to alkenes and alkynes proceed by initial formation of a pi-
complex, in which the electrophile accepts electrons from and becomes weakly bonded to the multiple
bond. Such complexes are formed reversibly and may then reorganize to a reactive intermediate in a
slower, rate-determining step. Reactions with alkynes are more sensitive to solvent changes and
catalytic influences than are equivalent alkenes.

Why are the reactions of alkynes with electrophilic reagents more sluggish than the corresponding
reactions of alkenes? After all, addition reactions to alkynes are generally more exothermic than
additions to alkenes, and there would seem to be a higher π-electron density about the triple bond ( two
π-bonds versus one ). Two factors are significant in explaining this apparent paradox. First, although
there are more π-electrons associated with the triple bond, the sp-hybridized carbons exert a strong
attraction for these π-electrons, which are consequently bound more tightly to the functional group than
are the π-electrons of a double bond. This is seen in the ionization potentials of ethylene and acetylene.

Acetylene HC≡CH + Energy → [HC≡CH •(+) + e(–)

Ethylene H2C=CH2 + Energy → [H2C=CH2] •(+) + e(–)
Ethane H3C–CH3 + Energy → [H3C–CH3] •(+) + e(–)

As defined by the preceding equations, an ionization potential is the minimum energy required to
remove an electron from a molecule of a compound. Since pi-electrons are less tightly held than sigma-
electrons, we expect the ionization potentials of ethylene and acetylene to be lower than that of ethane,
as is the case. Gas-phase proton affinities show the same order, with ethylene being more basic than
acetylene, and ethane being less basic than either. Since the initial interaction between an electrophile
and an alkene or alkyne is the formation of a pi-complex, in which the electrophile accepts electrons
from and becomes weakly bonded to the multiple bond, the relatively slower reactions of alkynes
becomes understandable.

A second factor is presumed to be the stability of the carbocation intermediate generated by sigma-
bonding of a proton or other electrophile to one of the triple bond carbon atoms. This intermediate has
its positive charge localized on an unsaturated carbon, and such vinyl cations are less stable than their
saturated analogs. Indeed, we can modify our earlier ordering of carbocation stability to include these
vinyl cations in the manner shown below. It is possible that vinyl cations stabilized by conjugation
with an aryl substituent are intermediates in HX addition to alkynes of the type Ar-C≡C-R, but such
intermediates are not formed in all alkyne addition reactions.
≈ RCH=CH(+) < RCH2(+) ≈ RCH=CR(+) < R2CH(+) ≈ CH2=CH-CH2(+)
1°-Vinyl 1° 2°-Vinyl 2° 1°-Allyl

Application of the Hammond postulate indicates that the activation energy for the generation of a vinyl
cation intermediate would be higher than that for a lower energy intermediate. This is illustrated for
alkenes versus alkynes by the following energy diagrams.

Despite these differences, electrophilic additions to alkynes have emerged as exceptionally useful
synthetic transforms.

Addition of Hydrogen Halide to an Alkyne

Summary: Reactivity order of hydrogen halides: HI > HB r> HCl > HF.

Follows Markovnikov’s rule:

 Hydrogen adds to the carbon with the greatest number of hydrogens, the halogen adds to the
carbon with fewest hydrogens.
 Protination occurs on the more stable carbocation. With the addition of HX, haloalkenes form.
 With the addition of excess HX, you get anti addition forming a geminal dihaloalkane.

Addition of a HX to an Internal Alkyne

As shown in Figure 2 below, the ππ electrons react with the hydrogen of the HBr and because the
alkyne carbons are equivalent it does not matter which carbon adds the hydrogen. Once the hydrogen is
covalently bonded to one of the carbons, the bromide will react with the carbocation intermediate to
form a vinyl halide as shown in the example of forming 2-bromobutene from 2-butyne reacting with
HBr. The reaction below assumes a 1:1 mole ratio of the alkyne and HBr.

Now, what happens if there is excess HBr?

Addition due to excess HX yields a geminal dihaloalkane

Here, the electrophilic addition proceeds with the same steps used to achieve the product in Addition of
a HX to an Internal Alkyne. The ππ electrons react with the hydrogen (shown in blue) adding it to the
carbon on the left because the lone pair electrons of the bromine can help stabilize the carbocation
intermediate that reacts with the bromide ions to form a geminal dihalide.

Addition of HX to Terminal Alkyne

For terminal alkynes, the carbon atoms sharing the triple bond are not equivalent. The addition of HX
to terminal alkynes occurs in a Markovnikov-manner in which the halide attaches to the most
substituted carbon. The pi electrons react with the hydrogen and it bonds to the terminal carbon. The
bromide reacts with the resulting carbocation intermediate to form the vinyl halide. The overall
reaction and mechanism are shown below.

Addition due to excess HBr present

Similar to the addition of excess HBr to internal alkynes, both halides will add to the same carbon to
form a geminal dihalide.
HBr Addition With Radical Mechanism

Most hydrogen halide reactions with terminal alkynes occur in a Markovnikov-manner in which the
halide attaches to the most substituted carbon since it is the most positively polarized. However, there
are two specific reactions among alkynes where anti-Markovnikov reactions take place: the radical
addition of HBr and Hydroboration Oxidation reactions. For alkynes, an anti-Markovnikov addition
takes place for terminal alkynes.

The Br of the Hydrogen Bromide (H-Br) attaches to the less substituted 1-carbon of the terminal
alkyne shown below in an anti-Markovnikov manner while the Hydrogen proton attaches to the second
carbon. As mentioned above, the first carbon is the less substituted carbon since it has fewer bonds
attached to carbons and other substituents. The H-Br reagent must also be reacted with heat or some
other radicial initiator such as a peroxide in order for this reaction to proceed in this manner. This
presence of the radical or heat leads to the anti-Markovnikov addition since it produces the most stable
reaction.

The product of a terminal alkyne that is reacted with a peroxide (or light) and H-Br is a 1-bromoalkene.

Regioselectivity: The Bromine can attach in a syn  or anti  manner which means the resulting alkene
can be both cis and trans. Syn addition is when both Hydrogens attach to the same face or side of the
double bond (i.e. cis) while the anti addition is when they attach on opposite sides of the bond (trans).

Halogenation of Alkynes
The additon of X2 to alkynes is analogous to the addition of X2 to alkenes. The halogen molecule
becomes polarized by the approach of the nucleophilic alkyne. The pi electrons of the alkyne react with
the bromine to form a carbon-bromine bond and cyclic halonium ion with halide as the leaving group.
The formation of the cyclic halonium ion requires anti-addition of the nucleophilic halide to produce a
vicinal dihalide alkene as shown in the reaction below.

Figure 6 below shown the reaction of bromine with 2-buttyne to form (E)-2,3-ibromo-2-butene along
with the mechanism.

HBr Addition With Radical Yields 1-bromoalkene

The product of a terminal alkyne that is reacted with a peroxide (or light) and H-Br is a 1-
bromoalkene. Regioselectivity: The Bromine can attach in a syn or anti manner which means the
resulting alkene can be both cis and trans

Reaction of Alkynes with HBr (radical)

Reaction type: Radical Addition

Summary

 When treated with 1 equivalent of HBr in the presence of oxygen or peroxides or uv light, an
alkyne forms a vinyl bromide.
 However, under these conditions which promote the radical addition, the regioselectivity is
anti Markovnikov


Peroxides (or uv light) facilitate the formation of a bromine radical e.g. RO.+ HBr -> ROH +
Br .

Reaction proceeds via the more stable radical intermediate.

In the presence of excess HBr, a second addition can occur to the product alkene giving a
vicinal or 1,2-dibromide (see above).

The major product from the reaction of excess HBr in the presence of peroxides to terminal
alkynes are the 1,2-dibromoalkanes.

Note the difference in regiochemistry between this radical mechanism (see above) and
the heterolytic pathway (see below).

Reaction with halogens

The addition of halogens to an alkyne proceeds in the same manner as halogen addition to alkenes.

The halogen atoms add to an alkyne molecule in a stepwise fashion, leading to the formation of the
corresponding alkene, which undergoes further reaction to a tetrahaloalkane.