Alkynes are known to be compounds that have triple bonds within the molecule. While many compounds have the structure of alkanes and alkenes, there are also compounds that have triple bonds within the molecule.

Unlike single and double bonds, triple bonds have special properties. For example, due to their high acidity, they can be synthesized differently from other compounds.

It is also possible to synthesize double bonds from alkynes. Through addition reactions, alkenes can be made freely. Of course, it is also possible to synthesize new alkyne compounds.

How does a compound with a triple bond react chemically? The addition reaction of alkynes, acidity and acetylide synthesis will be explained here.

Alkynes Produce Alkenes by Electrophilic Addition Reaction

If a compound has a triple bond, it can be made into a double bond through a chemical reaction. When synthesizing alkenes from alkynes, electrophilic addition reactions are widely used.

Alkynes have π bonds (π-electrons). Among the covalent bonds, the pi bond is the one with a relatively weak force bond. Due to the presence of π-electrons, alkynes are electron-rich. Therefore, an addition reaction occurs when an alkyne reacts with an electrophilic reagent.

In electrophilic addition reactions, HX (hydrogen halide) is frequently used as an example. For example, the following compounds are produced by the addition reaction of hydrogen bromide to alkynes.

The reaction mechanism is the same as that of the addition reaction to alkenes. The carbocation is generated as an intermediate, and the addition reaction is completed by the subsequent attack of the bromo ion.

Stability and Hyperconjugation of Vinyl Carbocation

Note that when alkynes undergo the addition reaction, a vinyl carbocation is formed in the intermediate. The stability of the vinyl carbocation is lower than that of the common carbocation.

The order of stability of the carbocation is as follows.

Compared to alkenes, the addition reaction of alkynes is slower than that of alkenes. This is because the vinyl carbocation is less stable and is less likely to produce intermediates.

-Regioselectivity by Hyperconjugation

But what is important is where the substituents will bound in the addition reaction. With the compound we just mentioned, you may get the following two types of compounds.

What is the best way to think about this point? The key point is the hyperconjugation.

The stability of the carbocation is explained by the hyperconjugation. Carbocations are unstable intermediates, but they share electrons weakly when there is a C-H bond next to them.

The p-orbital of the carbocation and the C-H bond are parallel to each other. As a result, the molecule becomes stable as the electrons are dispersed in various locations.

In the case of vinyl carbocation, the effect of hyperconjugation is as follows.

When the addition reaction of alkynes occurs, the methyl group is next to the alkynes, so hyperconjugation by the C-H bond occurs. The p-orbital of the carbocation and the C-H bond are parallel to each other.

In contrast, the other carbocation has no hyperconjugation. The neighboring carbon atom is anchored by a double bond and the C-H bond cannot be parallel to the p-orbital of the carbocation. As a result, one compound can be obtained.

Alkynes and Other sp-Hybrid Orbitals Are Highly s-Character and High Acidity

Why are vinyl-type carbocations more unstable than common carbocations? That is because the molecules with sp hybrid orbitals, such as alkynes and vinyl-type carbocations, have high s-character.

In sp hybrid orbitals, there is one s-orbital and one p-orbital. In other words, the s-character is 50%. On the other hand, in the case of sp2 hybrid orbitals, there is one s-orbital and two p-orbitals. Therefore, the s-character is 33%. The sp3 hybrid orbitals have one s-orbital and three p-orbitals, so the s-character is 25%.

The s-orbitals are smaller than the p-orbitals. Therefore, the higher the s-character, the closer the electron is to the nucleus. Alkynes are known to be highly acidic because electrons with a negative charge and protons with a positive charge attract each other.

The order of acidity is as follows

  • HC ≡ CH (acetylene: pKa25)
  • H2C=CH2 (ethylene: pKa44)
  • CH3CH3 (ethane: pKa50)

In other words, compared to alkanes and alkenes, alkynes are more likely to release H+ and become ions (HC≡C and H+). This high acidity is due to their high s-character. Even if they produce a negative charge, they are closer to the proton (positive charge) and easier to stabilize.

-Carbocation Becomes Unstable in High s-Character

But the high acidity means that they are more likely to stabilize negative charges, which means they are more unstable with positive charges.

The vinyl carbocation is a sp hybrid orbital and has 50% s-character. Like acetylene, it has a high s-character. The vinyl carbocation is more unstable than other carbocations because the carbon atom is positively charged and has a sp hybridization.

More than 2 Equivalents of Hydrogen Halide Make Alkane

So far, we have explained how alkynes cause addition reactions when hydrogen halides such as HCl (hydrogen chloride) and HBr (hydrogen bromide) are used.

However, the addition reaction occurs not only in the triple bond but also in the double bond. Therefore, the addition of two or more equivalents of hydrogen halide (HX) produces a single-bonded alkane instead of a double-bonded alkene.

We have already described the synthesized alkenes and how they become regioselective. However, when an alkene is synthesized from an alkene, we again have to take into account the positional selectivity. For example, which of the following compounds will be synthesized?

As for which compound is given preference, consider the stability of the intermediate in the same way. When alkanes (single bonds) are synthesized from alkenes (double bonds), the carbocation with the bromo bonded next to it can write a resonance structure.

The more you can write resonance structures, the more stable the molecule will be. Therefore, when alkanes are synthesized from alkenes, only certain intermediates are produced and the synthetic reaction proceeds.

In this case, we can get a compound with two bromine atoms bonded to the same carbon atom.

For what compounds you will get, check the stability of the intermediates. Then you can predict the main product.

In general, consider the Markovnikov’s rule for alkene addition reactions. You can predict which compound will be formed by the stability of the carbocation, such as tertiary or secondary. However, in this case, both carbocation are secondary carbocation.

Therefore, even if we use the Markovnikov’s rule, we cannot identify which of the two compounds is the main product. Then, we need to take into account the other factor of resonance structure.

-Trans Compounds Can Be Obtained by Halogen Addition

Although we have been considering the addition reaction of hydrogen halide, the reaction mechanism is simple if the reaction is an addition reaction of a halogen (such as Cl2 or Br2). This is because the same halogen atom, such as a chlorine atom or a bromine atom, is added. There are fewer situations where you have to consider the position selectivity of which substituent to bond to.

If the halogen does the addition reaction, the anti-addition yields a trans alkene. If more than two equivalents of the halogen are present, the reaction can proceed further to give an alkane.

This is how the synthesis reaction proceeds.

Synthesis of Ketones by Hydration: Keto-Enol Tautomerism

In a typical addition reaction, as described above, alkenes (double bonds) are synthesized from alkynes (triple bonds). If the amount of reagent is large, the product will be an alkane (single bond). On the other hand, in the hydration reaction, ketones are synthesized.

In the hydration reaction, an acid catalyst such as sulfuric acid is used. These acid catalysts (sulfuric acid) give rise to carbocation in alkynes. After the formation of the carbocation, the water molecules attack it to obtain the alcohol. The reaction mechanism is as follows.

It is common that alkenes are synthesized by hydration reactions. Also, although positional selectivity must be taken into account for some molecules, if you understand what has been explained so far, you will be able to predict where the substituents will be bound.

-Keto-Enol Tautomerism to Ketone

But in the hydration reaction of alkynes, the compound you get is not an alcohol, but a ketone. Why ketones and not alcohols? This involves the keto–enol tautomerism.

When an alcohol is attached to a double bond, it is called the enol form. However, the enol form is unstable and is usually in the keto form. In the keto form, it is a ketone. Therefore, in the hydration reaction of alkynes, the enol form is converted to the keto form. They are as follows.

Normally, after alkenes are synthesized by addition to alkynes, if there is an excess of reagent, the reaction proceeds further to give alkanes (single bonds). However, in the hydration reaction of alkynes, ketones can be obtained by keto-enol tautomerization in this way.

Hydroboration to Alkynes to Obtain Aldehyde

In addition reactions to alkynes, keto-enol tautomerism must be taken into account. In such cases, a popular synthesis for addition reactions is hydroboration.

Normally, the electrophilic addition reaction proceeds according to the Markovnikov rule. However, the hydroboration is an anti-Markovnikov addition reaction that does not follow the Markovnikov rule. Although Markovnikov’s rule is important in both alkenes and alkynes, the addition reaction proceeds in the opposite position in the case of the hydroboration.

In hydroboration, borane (BH3) is used as a reagent. Due to steric hindrance, the boron atom of borane, whether alkene or alkyne, reacts chemically with the lesser substituent atom.

Synthesis with terminal alkynes is particularly important in the hydroboration of alkynes. When an alkyne is present at the end of the molecule, the borane reacts as follows.

According to Markovnikov’s rule, as already explained, the stability of the carbocation is important. Therefore, a hydrogen atom (proton) is added to a carbon atom with few substituents, taking into account the effects of hyperconjugation, etc.

However, no intermediates of the carbocation are formed in hydroboration. Hydroboration is an addition reaction by syn-addition (addition reaction from the same direction). At this time, due to a steric hindrance, a boron atom is attached to the carbon atom at the end of the substituent with few substituents.

Afterwards, alcohol is synthesized through a separate oxidation reaction with hydrogen peroxide (H2O2) or other substances.

However, since it is an alkyne addition reaction, the compound synthesized is an enol type alcohol. Therefore, the form of the compound changes depending on the keto–enol tautomerism. When a synthetic reaction of hydroboration and oxidation is performed on a molecule with a terminal alkyne, the final compound is an aldehyde.

If the alkynes are in the middle of the molecule, ketones can be obtained by keto-enol tautomerization. If, on the other hand, the terminal alkyne is hydroborated, an aldehyde is obtained.

Acetylide Is Produced by Strong Base

So far, we have explained the electrophilic addition reactions to alkynes. However, addition reactions are not the only important part of alkynes. It is also important in the synthesis of triple bonds using acetylides.

Although the addition reaction is useful, the triple bond is always lost. In other words, a compound with a double bond or a single bond can be obtained. So what can be done to synthesize compounds with triple bonds? In this case, acetylides are especially important.

As mentioned above, terminal alkynes have a higher degree of acidity than alkanes (single bond) and alkenes (double bond). It is known that the high acidity is due to the fact that the H+ (proton) is easily pulled out to form ions.

Therefore, a compound with terminal alkynes is reacted with a strong base such as sodium amide (NaNH2). As a result, the hydrogen atoms of the terminal alkynes are pulled out to form acetylides.

As for acetylide, sodium acetylide is sometimes sold as a reagent, which can be used. However, metal acetylides can be explosive and should be handled with care.

Nucleophilic Substitution Reactions to Synthesize Alkyl Chains with Triple Bonds

Thus, after obtaining acetylide by strong base, alkyne compounds can be obtained through nucleophilic substitution reactions.

The acetylide anion is a strong base and has strong nucleophilic properties. Therefore, they can be alkylated by undergoing nucleophilic substitution reactions. As a result, an alkylated compound with a triple bond can be synthesized.

There are two types of nucleophilic substitution reactions: the SN1 and SN2 reactions. In particular, the SN2 reaction is frequently used and enables alkylation with acetylide anions by the following nucleophilic substitution reactions.

When you want to synthesize compounds with triple bonds, one method is the nucleophilic substitution reaction using acetylides. Since terminal alkynes such as acetylene are highly acidic, this property can be used to synthesize alkyne compounds.

Understanding the Synthesis of Compounds with Triple Bonds

In organic chemistry, the main focus is on synthetic reactions of compounds with single and double bonds. Therefore, most reaction mechanisms focus on the movement of electrons in single and double bonds.

However, some compounds have triple bonds. The two most important reactions in these alkynes are following.

  • Electrophilic addition reactions
  • Alkylation with acetylides

In addition reactions of alkynes, the final product depends on the type of synthetic reaction. It is also important to know where the substituents will be bound. The stability of the intermediates should be taken into account so that you can predict what kind of compound you will be able to synthesize.

If you want to synthesize a compound with a triple bond, you can utilize acetylide anions. Nucleophilic substitution reactions can yield alkyne compounds. Understanding these reaction mechanisms will help you to think about how to proceed with the synthesis of alkynes.