Cyclopentanone -

PROBLEM We'll see in the next chapter that alkynes undergo many of the same reactions that alkenes do. What
8-68 product might you expect from each of the following reactions?
<img class="imgSvg" id = "m6sn3ncic9wywailce6" 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"/>
$\begin{cases}\text { (a) } \xrightarrow{\text { 1 equiv } \mathrm{Br}_{2}} & \text { ? } \\ \text { (b) } \xrightarrow[\text { equiv } \mathrm{H}_{2}, \mathrm{Pd} / \mathrm{C}]{ } & \text { ? } \\ \text { (c) } \xrightarrow{\text { 1 equiv } \mathrm{HBr}} & \text { ? }\end{cases}$
PROBLEM Hydroxylation of cis-2-butene with $\mathrm{OsO}_{4}$ yields a different product than hydroxylation of
8-69 trans-2-butene. Draw the structure, show the stereochemistry of each product, and explain the difference between them.


Cyclopentanone -

PROBLEM Compound $\mathbf{A}, \mathrm{C}_{11} \mathrm{H}_{16} \mathrm{O}$, was found to be an optically active alcohol. Despite its apparent
8-70 unsaturation, no hydrogen was absorbed on catalytic reduction over a palladium catalyst. On treatment of $\mathbf{A}$ with dilute sulfuric acid, dehydration occurred and an optically inactive alkene $\mathbf{B}, \mathrm{C}_{11} \mathrm{H}_{14}$, was the major product. Alkene $\mathbf{B}$, on ozonolysis, gave two products. One product was identified as propanal, $\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CHO}$. Compound $\mathbf{C}$, the other product, was shown to be a ketone, $\mathrm{C}_{8} \mathrm{H}_{8} \mathrm{O}$. How many degrees of unsaturation does $\mathbf{A}$ have? Write the reactions, and identify $\mathbf{A}, \mathbf{B}$, and C.


CHAPTER 9 -


Alkynes: An Introduction to Organic Synthesis -


FIGURE 9.1 Synthesizing organic compounds is like conducting a musical group. When in tune, chemists can create highly complex organic compounds. (credit: modification of work "Jazz great visits Navy" by U.S. Navy, Michael Worner/Wikimedia Commons, Public Domain)


CHAPTER CONTENTS -


CHAPTER CONTENTS - 9.1 Naming Alkynes

9.2 Preparation of Alkynes: Elimination Reactions of Dihalides
9.3 Reactions of Alkynes: Addition of HX and $\mathrm{X}_{2}$
9.4 Hydration of Alkynes
9.5 Reduction of Alkynes
9.6 Oxidative Cleavage of Alkynes
9.7 Alkyne Acidity: Formation of Acetylide Anions
9.8 Alkylation of Acetylide Anions
9.9 An Introduction to Organic Synthesis


CHAPTER CONTENTS - 9.1 Naming Alkynes

WHY THIS CHAPTER? Alkynes are less common than alkenes, both in the laboratory and in living organisms, so we won't cover them in great detail. The real importance of this chapter is that we'll use alkyne chemistry as a vehicle to begin looking at some of the general strategies used in organic synthesis-the construction of complex molecules in the laboratory. Without the ability to design and synthesize new molecules in the laboratory, many of the medicines we take for granted would not exist and few new ones would be made.


CHAPTER CONTENTS - 9.1 Naming Alkynes

An alkyne is a hydrocarbon that contains a carbon-carbon triple bond. Acetylene, $\mathrm{H}-\mathrm{C} \equiv \mathrm{C}-\mathrm{H}$, the simplest alkyne, was once widely used in industry as a starting material for the preparation of acetaldehyde, acetic acid, vinyl chloride, and other high-volume chemicals, but more efficient routes to these substances using ethylene as starting material are now available. Acetylene is still used in the preparation of acrylic polymers, such as


CHAPTER CONTENTS - 9.1 Naming Alkynes

Plexiglas and Lucite, but is probably best known as the gas burned in high-temperature oxy-acetylene welding torches.


CHAPTER CONTENTS - 9.1 Naming Alkynes

In addition to simple alkynes with one triple bond, research is also being carried out on polyynes-linear carbon chains of alternating single and triple bonds. Polyynes with up to eight triple bonds are thought to be present in interstellar space, and evidence has been presented for the existence of carbyne, an allotrope of carbon consisting of alternating single and triple bonds in long chains of indefinite length. The electronic properties of polyynes are being explored for potential use in nanotechnology applications.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0279.jpg?height=44&width=779&top_left_y=542&top_left_x=673)


CHAPTER CONTENTS - 9.1 Naming Alkynes

A polyyne detected in interstellar space


CHAPTER CONTENTS - 9.1 Naming Alkynes

Alkyne nomenclature follows the general rules for hydrocarbons discussed in Section 3.4 and Section 7.3. The suffix -yne is used, and the position of the triple bond is indicated by giving the number of the first alkyne carbon in the chain. Numbering the main chain begins at the end nearer the triple bond so that the triple bond receives as low a number as possible.
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CHAPTER CONTENTS - 9.1 Naming Alkynes

Begin numbering at the end nearer the triple bond.


CHAPTER CONTENTS - 9.1 Naming Alkynes

> 6-Methyl-3-octyne
> (New: 6-Methyloct-3-yne)


CHAPTER CONTENTS - 9.1 Naming Alkynes

Compounds with more than one triple bond are called diynes, triynes, and so forth; compounds containing both double and triple bonds are called enynes (not ynenes). Numbering of an enyne chain starts from the end nearer the first multiple bond, whether double or triple. When there is a choice in numbering, double bonds receive lower numbers than triple bonds. For example:
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1-Hepten-6-yne
(New: Hept-1-en-6-yne)
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CHAPTER CONTENTS - 9.1 Naming Alkynes

4-Methyl-7-nonen-1-yne
(New: 4-Methylnon-7-en-1-yne)


CHAPTER CONTENTS - 9.1 Naming Alkynes

As with alkyl and alkenyl substituents derived from alkanes and alkenes, respectively, alkynyl groups are also possible.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0279.jpg?height=191&width=632&top_left_y=1647&top_left_x=584)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0279.jpg?height=61&width=237&top_left_y=1653&top_left_x=1291)


CHAPTER CONTENTS - 9.1 Naming Alkynes


CHAPTER CONTENTS - 9.1 Naming Alkynes

PROBLEM There are seven isomeric alkynes with the formula $\mathrm{C}_{6} \mathrm{H}_{10}$. Draw and name them.
9-2


CHAPTER CONTENTS - 9.2 Preparation of Alkynes: Elimination Reactions of Dihalides

Alkynes can be prepared by the elimination of HX from alkyl halides in a similar manner as alkenes (Section 8.1). Treatment of a 1,2-dihaloalkane (called a vicinal dihalide) with an excess amount of a strong base such as KOH or $\mathrm{NaNH}_{2}$ results in a twofold elimination of HX and formation of an alkyne. As with the elimination of HX to form an alkene, we'll defer a full discussion of this topic and the relevant reaction mechanisms to Chapter 11.


The starting vicinal dihalides are themselves readily available by addition of $\mathrm{Br}_{2}$ or $\mathrm{Cl}_{2}$ to alkenes. Thus, the overall halogenation/dehydrohalogenation sequence makes it possible to go from an alkene to an alkyne. For example, diphenylethylene is converted into diphenylacetylene by reaction with $\mathrm{Br}_{2}$ and subsequent base treatment.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0280.jpg?height=635&width=1270&top_left_y=382&top_left_x=425)


The twofold dehydrohalogenation takes place through a vinylic halide intermediate, which suggests that vinylic halides themselves should give alkynes when treated with strong base. (A vinylic substituent is one that is attached to a double-bond.) This is indeed the case. For example:
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0280.jpg?height=277&width=706&top_left_y=1149&top_left_x=734)


CHAPTER CONTENTS - 9.3 Reactions of Alkynes: Addition of HX and $\mathrm{X}_{2}$

You might recall from Section 1.9 that a carbon-carbon triple bond results from the interaction of two $s p$-hybridized carbon atoms. The two $s p$ hybrid orbitals of carbon lie at an angle of $180^{\circ}$ to each other along an axis perpendicular to the axes of the two unhybridized $2 p_{\mathrm{y}}$ and $2 p_{\mathrm{z}}$ orbitals. When two $s p$-hybridized carbons approach each other, one $s p-s p \sigma$ bond and two $p-p \pi$ bonds are formed. The two remaining $s p$ orbitals form bonds to other atoms at an angle of $180^{\circ}$ from the carbon-carbon bond. Thus, acetylene is a linear molecule with $\mathrm{H}-\mathrm{C} \equiv \mathrm{C}$ bond angles of $180^{\circ}$ (FIGURE 9.2). The length of the $\mathrm{C} \equiv \mathrm{C}$ bond is 120 pm , and its strength is approximately $965 \mathrm{~kJ} / \mathrm{mol}(231 \mathrm{kcal} / \mathrm{mol})$, making it the shortest and strongest known carbon-carbon bond.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0280.jpg?height=437&width=1035&top_left_y=1755&top_left_x=531)

FIGURE 9.2 The structure of acetylene, $\mathbf{H}-\mathbf{C} \equiv \mathbf{C}-\mathbf{H}$. The $\mathbf{H}-\mathbf{C} \equiv \mathbf{C}$ bond angles are $\mathbf{1 8 0}^{\circ}$, and the $\mathbf{C} \equiv \mathbf{C}$ bond length is $\mathbf{1 2 0}$ pm. The electrostatic potential map shows that the $\pi$ bonds create a negative belt around the molecule.


As a general rule, electrophiles undergo addition reactions with alkynes much as they do with alkenes. Take the reaction of alkynes with HX, for instance. The reaction often can be stopped with the addition of 1 equivalent of HX, but reaction with an excess of HX leads to a dihalide product. For example, reaction of 1-hexyne with 2 equivalents of HBr yields 2,2-dibromohexane. As the following examples indicate, the regiochemistry of addition follows Markovnikov's rule, with halogen adding to the more highly substituted side of the alkyne bond
and hydrogen adding to the less highly substituted side. Trans stereochemistry of H and X normally, although not always, occurs in the product.


HBr addition
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0281.jpg?height=155&width=1300&top_left_y=367&top_left_x=456)


1-Hexyne
2-Bromo-1-hexene
2,2-Dibromohexane
HCl addition
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0281.jpg?height=225&width=1232&top_left_y=641&top_left_x=487)


Bromine and chlorine also add to alkynes to give addition products, and trans stereochemistry again results.
$\mathrm{Br}_{2}$ addition
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0281.jpg?height=156&width=919&top_left_y=987&top_left_x=603)

1-Butyne (E)-1,2-Dibromo-1-butene 1,1,2,2-Tetrabromobutane
The mechanism of alkyne addition is similar but not identical to that of alkene addition. When an electrophile such as HBr adds to an alkene, the reaction takes place in two steps and involves an alkyl carbocation intermediate (Section 7.7 and Section 7.8). If HBr were to add by the same mechanism to an alkyne, an analogous vinylic carbocation would be formed as the intermediate.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0281.jpg?height=673&width=831&top_left_y=1406&top_left_x=647)


A vinylic carbocation has an $s p$-hybridized carbon and generally forms less readily than an alkyl carbocation (FIGURE 9.3). As a rule, a secondary vinylic carbocation forms about as readily as a primary alkyl carbocation, but a primary vinylic carbocation is so difficult to form that there is no clear evidence it even exists. Thus, many alkyne additions occur through more complex mechanistic pathways.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0282.jpg?height=402&width=445&top_left_y=181&top_left_x=241)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0282.jpg?height=293&width=564&top_left_y=271&top_left_x=775)


A $2^{\circ}$ vinylic carbocation
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0282.jpg?height=245&width=470&top_left_y=319&top_left_x=1413)

A $\mathbf{2}^{\circ}$ alkyl carbocation


FIGURE 9.3 The structure of a secondary vinylic carbocation. The cationic carbon atom is sp-hybridized and has a vacant $p$ orbital perpendicular to the plane of the $\pi$ bond orbitals. Only one R group is attached to the positively charged carbon rather than two, as in a secondary alkyl carbocation. The electrostatic potential map shows that the most positive regions coincide with lobes of the vacant $p$ orbital and are perpendicular to the most negative regions associated with the $\pi$ bond.


PROBLEM What products would you expect from the following reactions?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0282.jpg?height=212&width=1335&top_left_y=821&top_left_x=346)


CHAPTER CONTENTS - 9.4 Hydration of Alkynes

Like alkenes (Section 8.4 and Section 8.5), alkynes can be hydrated by either of two methods. Direct addition of water catalyzed by mercury(II) ion yields the Markovnikov product, and indirect addition of water by a hydroboration-oxidation sequence yields the non-Markovnikov product.


Mercury (II)-Catalyzed Hydration of Alkynes -

Alkynes don't react directly with aqueous acid but will undergo hydration readily in the presence of mercury(II) sulfate as a Lewis acid catalyst. The reaction occurs with Markovnikov regiochemistry, so the - OH group adds to the more highly substituted carbon and the -H attaches to the less highly substituted one.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0282.jpg?height=191&width=1405&top_left_y=1487&top_left_x=357)


1-Hexyne -


An enol -

2-Hexanone (78\%)
Interestingly, the actual product isolated from alkyne hydration is not a vinylic alcohol, or enol (ene $+o l$ ), but is instead a ketone. Although the enol is an intermediate in the reaction, it immediately rearranges into a ketone by a process called keto-enol tautomerism. The individual keto and enol forms are said to be tautomers, a word used to describe two isomers that undergo spontaneous interconversion accompanied by the change in position of a hydrogen. With few exceptions, the keto-enol tautomeric equilibrium lies on the side of the ketone; enols are almost never isolated. We'll look more closely at this equilibrium in Section 22.1.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0282.jpg?height=299&width=557&top_left_y=2016&top_left_x=784)


An enol -

As shown in FIGURE 9.4, the mechanism of the mercury(II)-catalyzed alkyne hydration reaction is analogous to the oxymercuration reaction of alkenes (Section 8.4). Electrophilic addition of mercury(II) ion to the alkyne gives a vinylic cation, which reacts with water and loses a proton to yield a mercury-containing enol intermediate. In contrast with alkene oxymercuration, however, no treatment with $\mathrm{NaBH}_{4}$ is necessary to remove the mercury. The acidic reaction conditions alone are sufficient to effect replacement of mercury by
hydrogen. Tautomerization then gives the ketone.
FIGURE 9.4 MECHANISM
Mechanism of the mercury(II)-catalyzed hydration of an alkyne to yield a
ketone. The reaction occurs through initial formation of an intermediate enol, which tautomerizes to the ketone.
(1) The alkyne uses a pair of electrons to attack the electrophilic mercury(II) ion, yielding a mercury-containing
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0283.jpg?height=143&width=384&top_left_y=533&top_left_x=1215)
vinylic carbocation intermediate.
(2) Nucleophilic attack of water on the carbocation forms a $\mathrm{C}-\mathrm{O}$ bond and yields a protonated mercurycontaining enol.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0283.jpg?height=172&width=392&top_left_y=711&top_left_x=1059)
$\bigcirc$
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0283.jpg?height=228&width=297&top_left_y=1019&top_left_x=1147)
-
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0283.jpg?height=131&width=481&top_left_y=1385&top_left_x=1147)
(4) Replacement of $\mathrm{Hg}^{2+}$ by $\mathrm{H}^{+}$ occurs to give a neutral enol.


An enol -

$$
\text { (4) } \mathrm{H}_{3} \mathrm{O}^{+}
$$


An enol -


An enol -

A mixture of both possible ketones results when an unsymmetrically substituted internal alkyne ( $\mathrm{RC} \equiv \mathrm{CR}^{\prime}$ ) is hydrated. The reaction is therefore most useful when applied to a terminal alkyne ( $\mathrm{RC} \equiv \mathrm{CH}$ ) because only a methyl ketone is formed.


An internal alkyne -


A terminal alkyne -


A terminal alkyne -

A methyl ketone
PROBLEM What products would you obtain by mercury-catalyzed hydration of the following alkynes?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0284.jpg?height=134&width=982&top_left_y=779&top_left_x=344)


Hydroboration-Oxidation of Alkynes -

Borane adds rapidly to an alkyne just as it does to an alkene, and the resulting vinylic borane can be oxidized by $\mathrm{H}_{2} \mathrm{O}_{2}$ to give an enol, which tautomerizes to either a ketone or an aldehyde, depending on the alkyne. Hydroboration-oxidation of an internal alkyne such as 3-hexyne is straightforward and gives a ketone, but hydroboration-oxidation of a terminal alkyne is more complex because two molecules of borane often add to the triple bond, complicating the situation. To prevent this double addition, a bulky, sterically encumbered borane such as bis(1,2-dimethylpropyl)borane, known commonly as disiamylborane is used in place of $\mathrm{BH}_{3}$. When a terminal alkyne such as 1-butene reacts with disiamylborane, addition to the triple bond occurs normally, but a second addition is hindered by the bulk of the dialkylborane. Oxidation with $\mathrm{H}_{2} \mathrm{O}_{2}$ then gives an enol, which tautomerizes to the aldehyde.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0284.jpg?height=784&width=903&top_left_y=1603&top_left_x=611)

The hydroboration-oxidation sequence is complementary to the direct, mercury(II)-catalyzed hydration reaction of a terminal alkyne because different products result. Direct hydration with aqueous acid and mercury(II) sulfate leads to a methyl ketone, whereas hydroboration-oxidation of the same terminal alkyne
leads to an aldehyde.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0285.jpg?height=500&width=675&top_left_y=254&top_left_x=725)


Hydroboration-Oxidation of Alkynes -


Hydroboration-Oxidation of Alkynes -

PROBLEM How would you prepare the following carbonyl compounds starting from an alkyne (reddish brown
9-7 = Br)?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0285.jpg?height=475&width=1204&top_left_y=1156&top_left_x=401)


Hydroboration-Oxidation of Alkynes - 9.5 Reduction of Alkynes

Alkynes are reduced to alkanes by addition of $\mathrm{H}_{2}$ over a metal catalyst. The reaction occurs in two steps through an alkene intermediate, and measurements show that the first step in the reaction is more exothermic than the second.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0285.jpg?height=199&width=1085&top_left_y=1863&top_left_x=517)


Complete reduction to the alkane occurs when palladium on carbon ( $\mathrm{Pd} / \mathrm{C}$ ) is used as catalyst, but hydrogenation can be stopped at the alkene stage if the less active Lindlar catalyst is used. The Lindlar catalyst is a finely divided palladium metal that has been precipitated onto a calcium carbonate support and then deactivated by treatment with lead acetate and quinoline, an aromatic amine. The hydrogenation occurs with syn stereochemistry (Section 8.5), giving a cis alkene product.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0286.jpg?height=212&width=1261&top_left_y=187&top_left_x=432)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0286.jpg?height=220&width=248&top_left_y=432&top_left_x=933)


The alkyne hydrogenation reaction has been explored extensively by the Hoffmann-LaRoche pharmaceutical company, where it is used in the commercial synthesis of vitamin A. The cis isomer of vitamin A produced initially on hydrogenation is converted to the trans isomer by heating.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0286.jpg?height=475&width=1266&top_left_y=798&top_left_x=424)


7-cis-Retinol
(7-cis-vitamin A; vitamin A has
a trans double bond at C7)
An alternative method for the conversion of an alkyne to an alkene uses sodium or lithium metal as the reducing agent in liquid ammonia as solvent. This method is complementary to the Lindlar reduction because it produces trans rather than cis alkenes. For example, 5-decyne gives trans-5-decene on treatment with lithium in liquid ammonia. The mechanism is explained below.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0286.jpg?height=156&width=1126&top_left_y=1597&top_left_x=497)


5-Decyne -

trans-5-Decene (78\%)
Alkali metals dissolve in liquid ammonia at $-33^{\circ} \mathrm{C}$ to produce a deep blue solution containing the metal cation and ammonia-solvated electrons. When an alkyne is then added to the solution, reduction occurs by the mechanism shown in FIGURE 9.5. An electron first adds to the triple bond to yield an intermediate anion radical-a species that is both an anion (has a negative charge) and a radical (has an odd number of electrons). This anion radical is a strong base, able to remove $\mathrm{H}^{+}$from ammonia to give a vinylic radical. Addition of a second electron to the vinylic radical gives a vinylic anion, which abstracts a second $\mathrm{H}^{+}$from ammonia to give trans alkene product.


5-Decyne -

FIGURE 9.5 MECHANISM
Mechanism of the lithium/ammonia reduction of an alkyne to produce a trans alkene.
(1) Lithium metal donates an electron to the alkyne to give an anion radical . . .
2. . . which abstracts a proton from ammonia solvent to yield a vinylic radical.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0287.jpg?height=616&width=397&top_left_y=429&top_left_x=1192)

The vinylic radical accepts another electron from a second lithium atom to produce a vinylic anion . . .
4. . . which abstracts another proton from ammonia solvent to yield the final trans alkene product.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0287.jpg?height=310&width=389&top_left_y=1070&top_left_x=1193)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0287.jpg?height=134&width=340&top_left_y=1405&top_left_x=1237)


5-Decyne -

A trans alkene


5-Decyne -

Trans stereochemistry of the alkene product is established during the second reduction step (3) when the less-hindered trans vinylic anion is formed from the vinylic radical. Vinylic radicals undergo rapid cis-trans equilibration, but vinylic anions equilibrate much less rapidly. Thus, the more stable trans vinylic anion is formed rather than the less stable cis anion and is then protonated without equilibration.


5-Decyne -

PROBLEM Using any alkyne needed, how would you prepare the following alkenes?
9-8 (a) trans-2-Octene
(b) cis-3-Heptene
(c) 3-Methyl-1-pentene


5-Decyne - 9.6 Oxidative Cleavage of Alkynes

Alkynes, like alkenes, can be cleaved by reaction with powerful oxidizing agents such as ozone or $\mathrm{KMnO}_{4}$, although the reaction is of little value and it is mentioned only for completeness. A triple bond is generally less reactive than a double bond, and yields of cleavage products can be low. The products obtained from cleavage of an internal alkyne are carboxylic acids; from a terminal alkyne, $\mathrm{CO}_{2}$ is formed as one product.


A terminal alkyne - 9.7 Alkyne Acidity: Formation of Acetylide Anions

The most striking difference between alkenes and alkynes is that terminal alkynes are relatively acidic. When a terminal alkyne is treated with a strong base, such as sodium amide, $\mathrm{Na}^{+}{ }^{-} \mathrm{NH}_{2}$, the terminal hydrogen is removed and the corresponding acetylide anion is formed.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0288.jpg?height=90&width=861&top_left_y=898&top_left_x=632)


Acetylide anion -

According to the Brønsted-Lowry definition (Section 2.7), an acid is a substance that donates $\mathrm{H}^{+}$. Although we usually think of oxyacids $\left(\mathrm{H}_{2} \mathrm{SO}_{4}, \mathrm{HNO}_{3}\right)$ or halogen acids $(\mathrm{HCl}, \mathrm{HBr})$ in this context, any compound containing a hydrogen atom can be an acid under the right circumstances. By measuring dissociation constants of different acids and expressing the results as $\mathrm{p} K_{\mathrm{a}}$ values, an acidity order can be established. Recall from Section 2.8 that a lower $\mathrm{p} K_{\mathrm{a}}$ corresponds to a stronger acid and a higher $\mathrm{p} K_{\mathrm{a}}$ corresponds to a weaker one.


Acetylide anion -

Where do hydrocarbons lie on the acidity scale? As the data in TABLE 9.1 show, both methane ( $\mathrm{p} K_{\mathrm{a}} \approx 60$ ) and ethylene $\left(\mathrm{p} K_{\mathrm{a}}=44\right)$ are very weak acids and thus do not react with any of the common bases. Acetylene, however, has $\mathrm{p} K_{\mathrm{a}}=25$ and can be deprotonated by the conjugate base of any acid whose $\mathrm{p} K_{\mathrm{a}}$ is greater than 25 . Amide ion $\left(\mathrm{NH}_{2}{ }^{-}\right.$), for example, the conjugate base of ammonia ( $\mathrm{p} K_{\mathrm{a}}=35$ ), is often used to deprotonate terminal alkynes.


Acetylide anion -

TABLE 9.1 Acidity of Simple Hydrocarbons


Acetylide anion -

| Family | Example | $K_{\mathrm{a}}$ |  | $\mathrm{p} K_{\mathrm{a}}$ |
| :--- | :--- | :--- | :--- | :---: |
| Alkyne | $\mathrm{HC} \equiv \mathrm{CH}$ | $10^{-25}$ | 25 | Stronger
 acid |
| Alkene | $\mathrm{H}_{2} \mathrm{C}=\mathrm{CH}_{2}$ | $10^{-44}$ | 44 |  |
| Alkane | $\mathrm{CH}_{4}$ | $10^{-60}$ | 60 | Weaker
 acid |


Acetylide anion -

Why are terminal alkynes more acidic than alkenes or alkanes? In other words, why are acetylide anions more stable than vinylic or alkyl anions? The simplest explanation involves the hybridization of the negatively charged carbon atom. An acetylide anion has an sp-hybridized carbon, so the negative charge resides in an orbital that has $50 \%$ " $s$ character." A vinylic anion has a $s p^{2}$-hybridized carbon with $33 \% s$ character, and an alkyl anion $\left(s p^{3}\right)$ has only $25 \% s$ character. Because $s$ orbitals are nearer the positive nucleus and lower in energy than $p$ orbitals, the negative charge is stabilized to a greater extent in an orbital with higher $s$ character (FIGURE 9.6).
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0289.jpg?height=771&width=1079&top_left_y=189&top_left_x=520)

FIGURE 9.6 A comparison of alkyl, vinylic, and acetylide anions. The acetylide anion, with $s p$ hybridization, has more $s$ character and is more stable. Electrostatic potential maps show that placing the negative charge closer to the carbon nucleus makes carbon appear less negative (red).


Acetylide anion -

PROBLEM The $\mathrm{p} K_{\mathrm{a}}$ of acetone, $\mathrm{CH}_{3} \mathrm{COCH}_{3}$, is 19.3. Which of the following bases is strong enough to 9-9 deprotonate acetone?
(a) $\mathrm{KOH}\left(\mathrm{p} K_{\mathrm{a}}\right.$ of $\left.\mathrm{H}_{2} \mathrm{O}=15.7\right)$
(b) $\mathrm{Na}^{+-} \mathrm{C} \equiv \mathrm{CH}\left(\mathrm{p} K_{\mathrm{a}}\right.$ of $\left.\mathrm{C}_{2} \mathrm{H}_{2}=25\right)$
(c) $\mathrm{NaHCO}_{3}\left(\mathrm{p} K_{\mathrm{a}}\right.$ of $\left.\mathrm{H}_{2} \mathrm{CO}_{3}=6.4\right)$
(d) $\mathrm{NaOCH}_{3}\left(\mathrm{p} K_{\mathrm{a}}\right.$ of $\left.\mathrm{CH}_{3} \mathrm{OH}=15.6\right)$


Acetylide anion - 9.8 Alkylation of Acetylide Anions

The negative charge and unshared electron pair on carbon make an acetylide anion strongly nucleophilic. As a result, an acetylide anion can react with electrophiles, such as alkyl halides, in a process that replaces the halide and yields a new alkyne product.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0289.jpg?height=204&width=998&top_left_y=1530&top_left_x=569)


We won't study the details of this substitution reaction until Chapter 11, but for now you can picture it as happening by the pathway shown in FIGURE 9.7. The nucleophilic acetylide ion uses an electron pair to form a bond to the positively polarized, electrophilic carbon atom of bromomethane. As the new $\mathrm{C}-\mathrm{C}$ bond forms, $\mathrm{Br}^{-}$ departs, taking with it the electron pair from the former $\mathrm{C}-\mathrm{Br}$ bond and yielding propyne as product. We call such a reaction an alkylation because a new alkyl group has become attached to the starting alkyne.


FIGURE 9.7 MECHANISM -


A mechanism for the alkylation reaction of acetylide anion with bromomethane to give propyne. -

(1) The nucleophilic acetylide anion uses its electron lone pair to form a bond to the positively polarized, electrophilic carbon atom of bromomethane. As the new $C-C$ bond begins to form, the $\mathrm{C}-\mathrm{Br}$ bond begins to break in the transition state.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0290.jpg?height=137&width=443&top_left_y=430&top_left_x=1161)
(1)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0290.jpg?height=177&width=475&top_left_y=692&top_left_x=1150)


Transition state
(2) The new $\mathrm{C}-\mathrm{C}$ bond is fully formed and the old $\mathrm{C}-\mathrm{Br}$ bond is fully broken at the end of the reaction.
(2)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0290.jpg?height=144&width=391&top_left_y=1061&top_left_x=1184)


Alkyne alkylation is not limited to acetylene itself. Any terminal alkyne can be converted into its corresponding anion and then allowed to react with an alkyl halide to give an internal alkyne product. Hex-1-yne, for instance, gives dec-5-yne when treated first with $\mathrm{NaNH}_{2}$ and then with 1-bromobutane.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0290.jpg?height=128&width=1129&top_left_y=1427&top_left_x=498)

Because of its generality, acetylide alkylation is a good method for preparing substituted alkynes from simpler precursors. A terminal alkyne can be prepared by alkylation of acetylene itself, and an internal alkyne can be prepared by further alkylation of a terminal alkyne.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0290.jpg?height=71&width=1036&top_left_y=1699&top_left_x=547)


Acetylene
A terminal alkyne
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0290.jpg?height=69&width=1042&top_left_y=1863&top_left_x=555)


A terminal alkyne -

An internal alkyne
The only limit to the alkylation reaction is that it can only use primary alkyl bromides and alkyl iodides because acetylide ions are sufficiently strong bases to cause elimination instead of substitution when they react with secondary and tertiary alkyl halides. For example, reaction of bromocyclohexane with propyne anion yields the elimination product cyclohexene rather than the substitution product 1-propynylcyclohexane.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0291.jpg?height=538&width=1348&top_left_y=192&top_left_x=410)


A terminal alkyne -

PROBLEM Show the terminal alkyne and alkyl halide from which the following products can be obtained. If 9-10 two routes look feasible, list both.
(a)
$\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{C} \equiv \mathrm{CCH}_{3}$
(b)
$\left(\mathrm{CH}_{3}\right)_{2} \mathrm{CHC} \equiv \mathrm{CCH}_{2} \mathrm{CH}_{3}$
(c)
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A terminal alkyne -

PROBLEM How would you prepare cis-2-butene starting from propyne, an alkyl halide, and any other reagents
9-11 needed? This problem can't be worked in a single step. You'll have to carry out more than one reaction.


A terminal alkyne - 9.9 An Introduction to Organic Synthesis

As mentioned in the introduction, one of the purposes of this chapter is to use alkyne chemistry as a vehicle to begin looking at some of the general strategies used in organic synthesis-the construction of complex molecules in the laboratory. There are many reasons for carrying out the laboratory synthesis of an organic compound. In the pharmaceutical industry, new molecules are designed and synthesized in the hope that some might be useful new drugs. In the chemical industry, syntheses are done to devise more economical routes to known compounds. In academic laboratories, the synthesis of extremely complex molecules is sometimes done just for the intellectual challenge involved in mastering so difficult a subject. The successful synthesis route is a highly creative work that is sometimes described by such subjective terms as elegant or beautiful.


In this book, too, we will often devise syntheses of molecules from simpler precursors, but the purpose here is to learn. The ability to plan a successful multistep synthetic sequence requires a working knowledge of the uses and limitations of many different organic reactions. Furthermore, it requires the practical ability to piece together the steps in a sequence such that each reaction does only what is desired without causing changes elsewhere in the molecule. Planning a synthesis makes you approach a chemical problem in a logical way, draw on your knowledge of chemical reactions, and organize that knowledge into a workable plan-it helps you learn organic chemistry.

There's no secret to planning an organic synthesis: all it takes is a knowledge of the different reactions and some practice. The only real trick is to work backward in what is often called a retrosynthetic direction. Don't look at a potential starting material and ask yourself what reactions it might undergo. Instead, look at the final product and ask, "What was the immediate precursor of that product?" For example, if the final product is an alkyl halide, the immediate precursor might be an alkene, to which you could add HX. If the final product is a cis alkene, the immediate precursor might be an alkyne, which you could hydrogenate using the Lindlar catalyst. Having found an immediate precursor, work backward again, one step at a time, until you get back to the starting material. You have to keep the starting material in mind, of course, so that you can work back to it, but you don't want that starting material to be your main focus.


Let's work several examples of increasing complexity.


WORKED EXAMPLE 9.1 -


Devising a Synthesis Route -

How would you synthesize cis-2-hexene from 1-pentyne and an alkyl halide? More than one step is needed.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0292.jpg?height=201&width=825&top_left_y=428&top_left_x=647)


Strategy -

When undertaking any synthesis problem, you should look at the product, identify the functional groups it contains, and then ask yourself how those functional groups can be prepared. Always work retrosynthetically, one step at a time.


Strategy -

The product in this case is a cis-disubstituted alkene, so the first question is, "What is an immediate precursor of a cis-disubstituted alkene?" We know that an alkene can be prepared from an alkyne by reduction and that the right choice of experimental conditions will allow us to prepare either a trans-disubstituted alkene (using lithium in liquid ammonia) or a cis-disubstituted alkene (using catalytic hydrogenation over the Lindlar catalyst). Thus, reduction of 2 -hexyne by catalytic hydrogenation using the Lindlar catalyst should yield cis-2-hexene.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0292.jpg?height=150&width=833&top_left_y=1118&top_left_x=646)


cis-2-Hexene -

Next ask, "What is an immediate precursor of 2-hexyne?" We've seen that an internal alkyne can be prepared by alkylation of a terminal alkyne anion. In the present instance, we're told to start with 1-pentyne and an alkyl halide. Thus, alkylation of the anion of 1-pentyne with iodomethane should yield 2-hexyne.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0292.jpg?height=324&width=962&top_left_y=1467&top_left_x=579)


Solution -

cis-2-Hexene can be synthesized from the given starting materials in three steps.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0292.jpg?height=165&width=1353&top_left_y=1899&top_left_x=386)
cis-2-Hexene


WORKED EXAMPLE 9.2 -


Devising a Synthesis Route -

How would you synthesize 2-bromopentane from acetylene and an alkyl halide? More than one step is needed.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0293.jpg?height=202&width=692&top_left_y=189&top_left_x=711)


Strategy -

Identify the functional group in the product (an alkyl bromide) and work the problem retrosynthetically. What is an immediate precursor of an alkyl bromide? Perhaps an alkene plus HBr. Of the two possibilities, Markovnikov addition of HBr to 1-pentene looks like a better choice than addition to 2 -pentene because the latter reaction would give a mixture of isomers.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0293.jpg?height=158&width=711&top_left_y=645&top_left_x=704)


Strategy -

What is an immediate precursor of an alkene? Perhaps an alkyne, which could be reduced.


Strategy -

$$
\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{C} \equiv \mathrm{CH} \xrightarrow[\text { Lindlar catalyst }]{\mathrm{H}_{2}} \mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{CH}=\mathrm{CH}_{2}
$$


Strategy -

What is an immediate precursor of a terminal alkyne? Perhaps sodium acetylide and an alkyl halide.


Strategy -

$$
\mathrm{Na}^{+}: \overline{\mathrm{C}} \equiv \mathrm{CH}+\mathrm{BrCH}_{2} \mathrm{CH}_{2} \mathrm{CH}_{3} \longrightarrow \mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{CH}_{2} \mathrm{C} \equiv \mathrm{CH}
$$


Solution -

The desired product can be synthesized in four steps from acetylene and 1-bromopropane.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0293.jpg?height=129&width=1210&top_left_y=1215&top_left_x=455)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0293.jpg?height=201&width=277&top_left_y=1355&top_left_x=1382)


WORKED EXAMPLE 9.3 -


Devising a Synthesis Route -

How would you synthesize 5-methyl-1-hexanol (5-methyl-1-hydroxyhexane) from acetylene and an alkyl halide?
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0293.jpg?height=104&width=769&top_left_y=1951&top_left_x=678)


Devising a Synthesis Route -

Acetylene Alkyl 5-Methyl-1-hexanol halide


Strategy -

What is an immediate precursor of a primary alcohol? Perhaps a terminal alkene, which could be hydrated with non-Markovnikov regiochemistry by reaction with borane followed by oxidation with $\mathrm{H}_{2} \mathrm{O}_{2}$.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0293.jpg?height=129&width=939&top_left_y=2299&top_left_x=590)


Strategy -

What is an immediate precursor of a terminal alkene? Perhaps a terminal alkyne, which could be reduced.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0294.jpg?height=131&width=909&top_left_y=189&top_left_x=605)


Strategy -

What is an immediate precursor of 5-methyl-1-hexyne? Perhaps acetylene and 1-bromo-3-methylbutane.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0294.jpg?height=128&width=1075&top_left_y=367&top_left_x=525)


Solution -

The synthesis can be completed in four steps from acetylene and 1-bromo-3-methylbutane:
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0294.jpg?height=421&width=1275&top_left_y=603&top_left_x=422)


Solution -


Solution -

PROBLEM Beginning with 4-octyne as your only source of carbon, and using any inorganic reagents necessary,
9-12 how would you synthesize the following compounds?
(a) cis-4-Octene
(b) Butanal (c) 4-Bromooctane
(d) 4-Octanol
(e) 4,5-Dichlorooctane
(f) Butanoic acid

PROBLEM Beginning with acetylene and any alkyl halide needed, how would you synthesize the following 9-13 compounds?
(a) Decane
(b) 2,2-Dimethylhexane
(c) Hexanal
(d) 2-Heptanone


CRO CHEMISTRY MATTERS -

The Art of Organic Synthesis
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0295.jpg?height=622&width=830&top_left_y=437&top_left_x=645)


CRO CHEMISTRY MATTERS -

FIGURE 9.8 Vitamin $B_{12}$ has been synthesized from scratch in the laboratory, but the bacteria growing on sludge from municipal sewage plants do a much better job. (credit: "Aeration and sludge-wasting" by U.S. Department of Agriculture/Flickr, Public Domain)


CRO CHEMISTRY MATTERS -

If you think some of the synthesis problems at the end of this chapter are difficult, try devising a synthesis of vitamin $\mathrm{B}_{12}$ starting only from simple substances you can buy in a chemical catalog. This extraordinary achievement was reported in 1973 as the culmination of a collaborative effort headed by Robert B. Woodward of Harvard University and Albert Eschenmoser of the Swiss Federal Institute of Technology in Zürich. More than 100 graduate students and postdoctoral associates contributed to the work, which took more than a decade to complete.
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0295.jpg?height=633&width=868&top_left_y=1429&top_left_x=626)

Vitamin $B_{12}$
Why put such extraordinary effort into the laboratory synthesis of a molecule so easily obtained from natural sources? There are many reasons. On a basic human level, a chemist might be motivated primarily by the challenge, much as a climber might be challenged by the ascent of a difficult peak. Beyond the pure challenge, the completion of a difficult synthesis is also valuable in that it establishes new standards and raises the field to a new level. If vitamin $B_{12}$ can be made, then why can't any molecule found in nature be made? Indeed, the decades that have passed since the work of Woodward and Eschenmoser have seen the laboratory synthesis of many enormously complex and valuable substances. Sometimes these substances-for instance, the anticancer compound paclitaxel, trade named Taxol-are not easily available in nature, so laboratory synthesis is the only
method for obtaining larger quantities.
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CRO CHEMISTRY MATTERS -

But perhaps the most important reason for undertaking a complex synthesis is that, in so doing, new reactions and new chemistry are discovered. It invariably happens in a complex synthesis that a point is reached at which the planned route fails. At such a time, the only alternatives are either to quit or to devise a way around the difficulty. New reactions and new principles come from such situations, and it is in this way that the science of organic chemistry grows richer. In the synthesis of vitamin $B_{12}$, for example, unexpected findings emerged that led to the understanding of an entire new class of reactions-the pericyclic reactions that are the subject of Chapter 30 in this book. From synthesizing vitamin $\mathrm{B}_{12}$ to understanding pericyclic reactions-no one could have possibly predicted such a link at the beginning of the synthesis, but that is the way of science.


Key Terms -

- acetylide anion - Lindlar Catalyst
- alkylation - retrosynthetic
- alkyne
- tautomer
- enol


Key Terms -


Summary -

Alkynes are less common than alkenes, both in the laboratory and in living organisms, so we haven't covered them in great detail. The real importance of this chapter is that alkyne chemistry is a useful vehicle for looking at the general strategies used in organic synthesis-the construction of complex molecules in the laboratory.


Summary -

An alkyne is a hydrocarbon that contains a carbon-carbon triple bond. Alkyne carbon atoms are $s p$-hybridized, and the triple bond consists of one $s p-s p \sigma$ bond and two $p-p \pi$ bonds. There are relatively few general methods of alkyne synthesis. Two favorable ones are the alkylation of an acetylide anion with a primary alkyl halide and the twofold elimination of HX from a vicinal dihalide.


Summary -

The chemistry of alkynes is dominated by electrophilic addition reactions, similar to those of alkenes. Alkynes react with HBr and HCl to yield vinylic halides and with $\mathrm{Br}_{2}$ and $\mathrm{Cl}_{2}$ to yield 1,2-dihalides (vicinal dihalides). Alkynes can be hydrated by reaction with aqueous sulfuric acid in the presence of mercury(II) catalyst. The reaction leads to an intermediate enol that immediately tautomerizes to yield a ketone. Because the addition reaction occurs with Markovnikov regiochemistry, a methyl ketone is produced from a terminal alkyne. Alternatively, hydroboration-oxidation of a terminal alkyne yields an aldehyde.


Summary -

Alkynes can be reduced to yield alkenes and alkanes. Complete reduction of the triple bond over a palladium hydrogenation catalyst yields an alkane; partial reduction by catalytic hydrogenation over a Lindlar catalyst yields a cis alkene. Reduction of the alkyne with lithium in ammonia yields a trans alkene.


Summary -

Terminal alkynes are weakly acidic. The alkyne hydrogen can be removed by a strong base such as $\mathrm{Na}^{+-} \mathrm{NH}_{2}$ to yield an acetylide anion. An acetylide anion acts as a nucleophile and can displace a halide ion from a primary alkyl halide in an alkylation reaction. Acetylide anions are more stable than either alkyl anions or vinylic anions because their negative charge is in a hybrid orbital with $50 \% s$ character, allowing the charge to be closer to the nucleus.


Summary of Reactions -

No stereochemistry is implied unless specifically indicated with wedged, solid, and dashed lines.


Summary of Reactions -

1. Preparation of alkynes
a. Dehydrohalogenation of vicinal dihalides (Section 9.2)
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b. Alkylation of acetylide anions (Section 9.8)
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2. Reactions of alkynes
a. Addition of HCl and HBr (Section 9.3)
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b. Addition of $\mathrm{Cl}_{2}$ and $\mathrm{Br}_{2}$ (Section 9.3)
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c. Hydration (Section 9.4)
(1) Mercuric sulfate catalyzed
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Summary of Reactions -

An enol
A methyl ketone
(2) Hydroboration-oxidation
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d. Reduction (Section 9.5)
(1) Catalytic hydrogenation
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(2) Lithium in liquid ammonia
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Summary of Reactions -

A trans alkene
e. Conversion into acetylide anions (Section 9.7)


Summary of Reactions -

$$
\mathrm{R}-\mathrm{C} \equiv \mathrm{C}-\mathrm{H} \xrightarrow[\mathrm{NH}_{3}]{\mathrm{NaNH}_{2}} \mathrm{R}-\mathrm{C} \equiv \mathrm{C}:-\mathrm{Na}^{+}+\mathrm{NH}_{3}
$$


Additional Problems -


Visualizing Chemistry -

PROBLEM Name the following alkynes, and predict the products of their reaction with (1) $\mathrm{H}_{2}$ in the presence
9-14 of a Lindlar catalyst and (2) $\mathrm{H}_{3} \mathrm{O}^{+}$in the presence of $\mathrm{HgSO}_{4}$ :
(a)
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(b)
![](https://cdn.mathpix.com/cropped/2025_02_06_5556f7656cbdcaa0f9a7g-0298.jpg?height=411&width=657&top_left_y=1307&top_left_x=1016)


Visualizing Chemistry -

PROBLEM From what alkyne might each of the following substances have been made? (Green = Cl.)


Visualizing Chemistry -


Visualizing Chemistry -

PROBLEM How would you prepare the following substances, starting from any compounds having four
9-16 carbons or fewer?
(a)
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(b)
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Visualizing Chemistry -

PROBLEM The following cycloalkyne is too unstable to exist. Explain.
9-17
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