CHEM 222 REACTIONS of ALKYNES SPRING 2024

Objective: Students would investigate the reactions of alkynes {WADE: Chapter 9}

Alkynes, like alkenes, undergo electrophilic addition reactions. With a cloud of electrons completely surrounding the σ
bond, an alkyne is an electron-rich molecule, a nucleophile. It will therefore react with an electrophile. The relatively
weak π bond breaks because the π
electrons are attracted to the
electrophilic proton.
The positively charged carbocation
intermediate reacts rapidly with the
negatively charged ion.
The same electrophilic reagents that add to alkenes add to alkynes. Electrophilic addition to a terminal alkyne is
regioselective.
Because the product of electrophilic addition is an alkene, a second electrophilic addition can occur if excess hydrogen
halide is present.

An alkyne is less reactive than an alkene in electrophilic addition reactions!! (see below). Remember that reactivity
depends on the free energy of the transition state, which in turn depends on the stability of the reactant and the
stability of the transition state.

An alkyne is less stable than an alkene

(higher free energy). Likewise, the free
energy of the “alkyne carbocation” is higher
than that of the “alkene cation”.
The carbocation formed when a proton adds to
an alkyne is a vinylic cation, whereas the
carbocation formed when a proton adds to an
alkene is an alkyl cation. A vinylic cation has a
positive charge on a vinylic carbon; it is less
stable than a similarly substituted alkyl cation.

ADDITION of HYDROGEN HALIDES & HALOGENS

If we have a terminal alkyne, the electrophilic addition is regioselective: the electrophile adds to the sp carbon bonded
to the hydrogen because the secondary (20) vinylic cation is more stable than the 10 (primary) vinylic cation formed if the
H+ added to the other sp carbon.
The addition of a hydrogen halide to an alkyne can
be stopped after the addition of one mole of HX
because, although an alkyne is less reactive than an
alkene, the alkyne is more reactive than the halo-
substituted alkene that is the product of the first addition. The halo-substituted alkene is less reactive because
a halogen substituent withdraws electrons inductively (through the σ bond), thereby decreasing the
nucleophilic character of the double bond.
  A second electrophilic addition will take place if excess hydrogen halide is present. The product of the second
addition is a geminal dihalide, a molecule with the two halogens on the same carbon atom.
When the 2nd mole of HX adds to the double bond, H+ (the electrophile) adds to sp2 carbon bonded to the greater
number of hydrogens (Markovnikov’s rule), forming the more stable carbocation.
{So, in the worksheet: 1mol HX gives the alkenyl halide; 2mol (or excess) HX gives the geminal dihalide!!}j {

Many (but not all) alkyne addition reactions are stereoselective. The addition of HCl to but-2-yne forms only (Z)-2-
chlorobut-2-ene, which means that only “anti” (trans-) addition of H and Cl occurs.

 Addition of a hydrogen halide to an unsymmetrical internal alkyne (e.g. pent-2-yne) forms two geminal dihalides
because the initial addition of the proton can occur with equal ease to either of the sp carbons.

 However if the same group is attached to each of the sp carbons of the internal alkyne (a “symmetrical” internal
alkyne- e.g. hex-3-yne), only one geminal dihalide will be formed.

{So in the worksheet: wherever the reaction says “HX (two moles) or “excess HX” the product is a “geminal dihalide”}

 The halogens, Cl2 and Br2 also add to alkynes. In the presence of excess halogen, a second addition reaction
occurs. Typically the solvent is CH2Cl2.

(so “2X2” addition reactions in the worksheet give the tetra-halide).

ADDITION of WATER to ALKYNES  KETONES

 Alkynes also undergo acid-catalyzed addition of water. The initial product of the reaction is an enol, a
compound with a C=C and an OH group bonded to one of the sp2 carbons. The enol immediately rearranges to
a ketone.
  A ketone and an enol differ only in the location of a double bond and a hydrogen. A ketone and its
corresponding enol are called keto-enol tautomers. Tautomers are isomers that are in rapid equilibrium.
Interconversion of the tautomers is called tautomerization. The keto and enol tautomers come to equilibrium
in solution, and the keto tautomer, because it is much more stable than the enol tautomer, predominates.

 The addition of water to a symmetrical internal alkyne forms a single product. However, for a unsymmetric
internal alkynes, two ketones are formed because the initial addition of the proton can occur to either sp carbon
(see below).

 Terminal alkynes are less reactive than internal alkynes toward the addition of water. The addition of water to a
terminal alkyne will occur if mercuric ions (Hg2+) are added to the acidic mixture.

HYDROBORATION-OXIDATION of ALKYNES

 Borane adds to alkynes in the same way it adds to alkenes (B is the electrophile and H- is the nucleophile). One
mole of BH3 reacts with 3 moles of alkyne to form one mole of boron-substituted alkene. When the reaction is
over, aqueous sodium hydroxide and hydrogen peroxide are added to the reaction mixture, resulting in the
replacement of the boron by an OH group. The enol that is formed with an internal alkyne immediately
rearranges to a ketone.

 Hydroboration-oxidation of a terminal alkyne produces an aldehyde (the carbonyl group is on the terminal
carbon), whereas the mercuric-ion-catalyzed addition produces a ketone (the carbonyl group is not on the
terminal carbon) {see the difference in the example below}.

*Note that both oxidation reactions (H2O/H+; hydroboration-oxidation) involve an enol intermediate*.

ADDITION of HYDROGEN to ALKYNES

  Alkynes undergo catalytic hydrogenation – with metal catalysts being used {Ni, Pt, Pd} forming cis- alkenes.
The reaction is prevented from going all the way to the alkane by using a “poisoned” (partially deactivated)
metal catalyst.
 The most common poisoned
catalyst is “Lindlar catalyst”- (a
“poisoned” palladium (Pd)
catalyst, referred to as “Lindlar Pd”). Both hydrogens are delivered to the same side of the triple bond (syn-
addition) and the cis-isomer is formed. So, in the pent-2-yne example below, cis- pent-2-ene is formed

 Internal alkynes can be converted to trans- alkenes using sodium (or lithium) in liquid ammonia, (e.g. the but-
2-yne to trans- but-2-ene example below). The reaction stops at the alkene stage because the alkali metal
reacts more rapidly with triple bonds than
with double bonds.

The trans- isomer would be more stable than the cis- isomer.

ACIDITY of ALKYNES & ALKYLATION

 The hybridization of an atom affects the acidity of a hydrogen bonded to it because the electronegativity of an
atom depends on its hybridization. An sp carbon is more electronegative than an sp2 carbon, which is more
electronegative than an sp3 carbon.
 Because the most acidic compound is the one with its hydrogen attached to
the most electronegative atom, ethyne is a stronger acid than ethene,
which is a stronger acid than ethane.
Recall from General Chemistry that in order to remove a proton from an acid, the
base must be stronger than the (conjugate) base that is generated as a result of removing that proton. Because NH3 is
a weaker acid (pKa = 36) than a terminal alkyne (pKa = 25), the conjugate base of NH3 (-NH2) is a stronger base than the
carbanion –called the acetylide ion – that is formed when a hydrogen is removed from the sp carbon of a terminal
alkyne. Therefore, an amide ion (-NH2) can be used to prepare an acetylide ion.

 Consequently, a hydrogen bonded to a sp carbon is an “acidic hydrogen”; terminal alkynes are the most acidic
hydrocarbons, and this acidic property is one way their reactivity differs from that of alkenes.

 Reactions that form C – C bonds are important in the synthesis of organic compounds. An acetylide ion can
react with an alkyl halide to form a C – C bond in synthesis reactions.
  The above reaction is an alkylation reaction. In this reaction, an alkyl group is attached to an alkyne to
lengthen the alkyne molecule.

Alkylation reactions are used to convert terminal alkynes to internal alkynes and other compounds such as alkenes,
ketones, and alkyl halides (see section below).

ALKYNE SYNTHESIS

We can convert terminal alkynes to internal alkynes of any desired chain lengths simply by choosing an alkyl halide of
the appropriate structure; e.g. in converting pent-1-yne to hept-3-yne we need to add an alkyl halide with 2 carbon
atoms through alkylation.

{Remember these are sequential reactions; the second reagent is not added until reaction with the first reagent is
completed}

 The alkylation reaction opens up a whole new area of organic synthesis reactions.

 We will look at how ethyne can be converted to 2-

bromopentane as an example.
 Pent-1-yne can be prepared from ethyne and an
alkyl halide with 3 carbons. Pent-1-ene can be prepared from pent-1-yne, then 2-bromopentane can be
prepared from pent-1-ene.

 So, we need to know what reagents we need to (i) convert ethyne to pent-1-yne (ii) pent-1-yne to pent-1-ene
and (iii) pent-1-ene to 2-bromopentane, and write the synthetic scheme:

 Starting with but-1-yne, how would you make the ketone shown below?
The reactions we have studied to form a ketone from an alkyne
are the acid-catalyzed addition of water to an alkyne and the
hydroboration-oxidation of an alkyne. The acid-catalyzed
reaction is easier so we should use it. If the alkyne used has
identical substituents on both sp carbons, only one ketone would be obtained. So, hex-3-yne should be the alkyne
to synthesize the desired ketone.

Hex- 3-yne can be obtained from

but-1-yne by forming the acetylide ion and
alkylation with an appropriate alkyl halide. To
obtain the 6-C alkyne, a two-carbon alkyl halide
has to be used. The synthetic scheme can now be written by following the steps and including the reagents required
for each step.
Richard Jacques/March 2024