Alkynes - Structure, Nomenclature,

Stability, and Reactivity

One C-C s bond and two C-C p bonds
Presence of C-C triple bond prevents bond rotation and stereoisomers
Each carbon sp hybridized, linear geometry

Bond Strengths
- C-C s-bond ~ 100 kcal/mol
- C-C p-bond ~ 50 kcal/mol

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Alkyne Nomenclature
Identify longest chain containing the alkyne (both carbons)
Number carbons in chain so that triple bond carbons have lowest
possible numbers (if same from each direction, number to give first sub
lowest number)
Name, number, and list substituents alphabetically as prefix like alkane
nomenclature
Indicate position of alkyne with number-followed by name of longest
chain with suffix -ane replaced with -yne (if multiple triple bonds use
diyne, triyne etc)
New methodology places number before -yne suffix
If alkene and alkyne present, give first multiple bond lowest possible
number (if same alkene gets lower number) and name as enyne

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Relative Stability & Reactivity of Alkynes
Similar trends as observed for alkene:

Stability: Internal > Terminal

Reactivity: Internal > Terminal

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Alkyne Reactions: HX Addition
With two p-bonds can add electrophile once or twice
May need to consider difference between terminal and internal alkynes

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 Alkyne Reactions: HX Addition

2nd equivalent adds

same direction as first

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Alkyne Reactions: X2 Addition
With two p-bonds can add electrophile once or twice

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Alkyne Reactions: X2 Addition

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Alkyne Reactions: Hydrogenation
Can selectively reduce to alkane, cis-alkene, or trans-alkene
(recall that you cannot use 1 equiv for hydrogenation)

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Alkyne Reactions: Hydrogenation

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Alkyne Reactions: Ozonolysis
Breaks sigma and pi bonds to form carbonyl products
For alkynes, always produces carboxylic acids
Terminal alkynes give CO2

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Alkyne Reactions: Ozonolysis

Where would 1 equiv react?

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Alkyne Reactions: Hydration
Like alkene, terminal alkynes are regioselective

BUT - unlike alkenes we do not get alcohol products!

Vinyl alcohols (enols) unstable and form Carbonyl products

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Alkyne Reactions: Hydration

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Alkyne Reactions: Alkyne Alkylation
Can take advantage of acidity of terminal alkyne to make a nucleophile

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Alkyne Alkylation

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Double Alkyne Alkylation of Acetylene

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Organic Synthesis, Part 1
Propose a sequence of steps to convert the giving starting material (in this case
acetylene) to the indicated product

Key - show your work! Provide the structure of the major

organic product after each reaction step

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Organic Synthesis, Part 2
Can get more complicated when C-C bond formation is followed by alkyne reaction!

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 Organic Synthesis, Part 3
Even more complicated when reactions of alkynes and alkenes are combined:

Two VERY useful clues: (a) if your product contains more C's than SM, need alkyne alkylation
(b) if your product contains fewer C's than SM, need ozonolysis 19
 Alkene Importance
Saturated and Unsaturated Fats

Olive Oil liquid vegetable oil to solid margarine

Oleic Acid 55-88%
Linoleic Acid 3.5-21% at high temp, some cis alkenes
Palmitic Acid 7.5-20% isomerize to trans fats that raise
Stearic Acid 0.5-5% cholesterol levels

margarines no longer produced

this way
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Alkene Importance -intercalates into DNA
-bonds to guanine nucleobases
Benzo[a]pyrene and Carcinogens -distorts double helical DNA
-causes mutations in DNA replication

Benzo[a]pyrene
-burning wood
-chimney soot
-cigarette smoke
-charred BBQ meat
-interstellar space

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Alkene, Alkyne, Aromatic Importance
Enediyne Anticancer Agents

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Alkene Importance
Polymerization

450-470 nm light activates initiator

diene causes cross-linking polymerization

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Alkene Importance
Fullerenes and Nanotubes

Carbon Nanotubes
-extremely strong, rigid, and light
baseball bats, golf clubs, kevlar, bicycle components
car components

-electrical and thermal conductivity

nanotechnology, LCD's and OLED displays
power cables, photovoltaic devices, batteries,
memory devices

Fullerenes
size = one strand of hair
split 10,000 times!

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