Mechanism choices

1. Break a bond
2. Make a bond
3. Add a proton
4. Take away a proton
5. 1,2 shift
Hydrohalogenation
- Double bond attacks hydrogen to attach to the side that forms the most stable
carbocation
- Leaving group then attacks the carbocation

Acid catalyzed hydration

- Draw double bond attacking the H+ to form carbocation (place H using Markovnikov)
- A water molecule (from solution) attacks carbocation to add OH2+
- Arrows from the OH bond to oxonium (OH2) to release H+

Halohydrin formation
- Alkene reaction with Br2, Cl2, etc
- Pi electrons attack halogen molecule and form ‘triangle’ with the 2 attached carbons
- Water attacks more substituted carbon and opens triangle
- Deprotonation where the water removes a proton

Oxymercuration reduction
- Pi electrons attack the electrophilic Hg2+ in Hg(OAc)2 and cyclic mercurinium ion forms
- Water attacks more substituted carbon breaking the triangle (cyclic mercurinium)
- Deprotonation where a base (OAc-) removes a proton to form a hydroxyl group
- NaBH4 is used to replace the Hg(OAc) group with a Hydrogen
- Final product is an alcohol (attached OH)

Hydroboration Oxidation
- BH3
- H2O2, NaOH
- Boron attacks less substituted carbon while Hydrogen adds to more substituted carbon
(syn addition)
- Boron atom is replaced with OH- when H2O2 attacks boron (forms trialkylborate)
- Final product has an alcohol

Catalytic hydrogenation
- Syn addition
- Catalysts: Pd, Pt, Ni, Ru

Oxidation of alkene to glycol

- Oxidizing agent: Osmium tetroxide (OsO4)
- Double bond attacks OsO→ forms cyclic intermediate where Os is bonded to both
Carbons
- Draw the cyclic osmate ester with the 2 O bridging the carbons
- Water attacks the intermediate to form 2 hydroxy groups on adjacent carbons
- Regenerate OsO catalyst
Ozonolysis
- Alkene reacts with O3 to form 5 membered cyclic structure (all 3 oxygens are in the ring)
- Break the intermediate by cleaving C-O and +O-O-
- Use Zn/H2O or PPh3 to reduce the intermediate and form aldehydes or ketones
- Oxidize using H2O2 to replace the terminal aldehydes with carboxylic acids (ketones are
unchanged)

Nucleophilic substitutions
- Only works with primary alkyl halides
- A strong base (like NaNH2) removes an H from the terminal alkyne to form an acetylide
anion
- The anion attacks the alkyl halide to form a new carbon carbon bond

Dehydrohalogenation from internal alkenes

- Strong base removes H from carbon atom adjacent to halogen → forms carbanion
- Halogen leaves and double bond replaces the carbon-halogen bond

Electrophilic addition:
- Similar to alkenes, pi electrons are good nucleophiles

Nucleophilic substitution with base

- Alkyne anions are strong bases and god nucleophiles
- Terminal alkynes have acidic hydrogens

Oxidation- addition of O and/or removal of H from carbon

Reduction- removal of O and/or addition of H from carbon

Acidity of an alkyne
- More s character→ electrons closer to nuclei → more electronegative → more stable
conjugate base → more acidic
Tautomerization
- The interconversion between 2 constitutional isomers in rapid equilibrium
- Keto-enol tautomerism mechanism

- An enol can tautomerize into a ketone or aldehyde

- The keto form is typically more stable than enol

Acid catalyzed hydration (oxymercuration)

- Same steps as oxymercuration of alkenes plus tautomerization to form the ketone from
the enol
- To do that, move H from hydroxyl to adjacent carbon and draw final ketone w/ C=O

Hydrogenation
1. Catalytic Reduction
- H2, Pd (or Pt, Ni) forms full reduction
- Landlords catalyst forms cis alkene
2. Hydroboration
- Syn addition of BH3 to internal alkenes
3. Dissolving metal reduction
- Reduction of alkyne with Na or Li in liquid ammonia (NH3)
- Converts alkyne to alkene with anti stereoselectivity (forms trans alkene)
Alkene Reactions (Chapter 6):

● Electrophilic Additions:
○ Addition of HX (HCl, HBr, HI) - Markovnikov addition
○ Addition of H2O (acid-catalyzed hydration) - Markovnikov addition
○ Addition of X2 (Br2, Cl2) - anti addition
○ Addition of HOX (HOBr, HOCl) - forms halohydrins
○ Oxymercuration-reduction (HgOAc2/NaBH4) - Markovnikov addition
● Hydroboration-Oxidation:
○ Addition of BH3 followed by H2O2/NaOH - non-Markovnikov addition
● Oxidation Reactions:
○ OsO4 oxidation - forms syn diols
○ Ozone (O3) - cleaves double bond to form carbonyls
● Reduction Reactions:
○ Catalytic hydrogenation (H2/Pt, Pd, or Ni) - forms alkanes
○ Enantioselective reduction using chiral catalysts

Alkyne Reactions (Chapter 7):

● Acid-Base Reactions:
○ Deprotonation with strong base (NaNH2, NaH, LDA) - forms acetylide ions
● Electrophilic Additions:
○ Addition of HX - Markovnikov addition
○ Addition of X2 - forms dihaloalkenes
○ Addition of H2O (HgSO4/H2SO4) - forms ketones/aldehydes
● Reduction Reactions:
○ Complete reduction (H2/Pt, Pd, or Ni) - forms alkanes
○ Partial reduction with Lindlar catalyst - forms cis-alkenes
○ Dissolving metal reduction (Na/NH3) - forms trans-alkenes
○ Hydroboration-protonolysis - forms cis-alkenes
● Carbon-Carbon Bond Formation:
○ Alkylation of acetylide ions with alkyl halides
● Hydroboration Reactions:
○ Addition of BH3 or (sia)2BH followed by:
■ H2O2/NaOH - forms ketones/aldehydes
■ Carboxylic acids - forms cis-alkenes
Electrophilic addition of alkyne
- Acid is a proton donor
- Base is a proton acceptor
- Nucleophile = electron donor
- Electrophile = electron acceptor

- Arrows start at high electron density (acceptor) and point to low electron density (donor)

- Conjugate acid-base pairs differ by a proton

- When acid gives proton to base; acid becomes conjugate base, and base becomes
conjugate acid
- Arrow pushing: breaks the bond where the arrow starts
- Bronsted lowry definitions don't require water as a reactant

- More stable charged species is usually the one that has a more delocalized charge
(resonance explanation)

- Pi electrons can act as a bronsted lowry bases

- Can be found in C-C double or triple bonds
- Strong acid or strong base is completely ionized in water (weak=partial)

- Acid dissociation constant - Ka - tells us strength of acids

- Acid strengths are usually reported as PKa values, which is -log10(Ka)
- Stronger acids = larger Ka = smaller PKa
- COOH group indicates weak acid (carboxylic acid)
- Should always find equilibrium constant

- Ka is the Keq for an acid dissociating

- So Pka = -log(Keq)

- Equilibrium favors reaction of the stronger base with the stronger acid to form a weaker
base and weaker acid
- This means that at equilibrium the major species present are the weaker acid and the
weaker base
-

- A negative PKa value indicates that the majority of molecules of the acid are dissociated
in water, while a positive value indicates that most acid molecules remain undissociated
in water
- Most chemical reactions occur because of collisions
- Reactants must collide with proper orientation/ energy to reach transition state
- Reaction is described by reaction coordinate diagram
- Plots Gibbs free energy vs progress of reaction
- Thermochemistry studies the energy of the entire system at every point in reaction
- Thermodynamics studies relative energies between any two states in ‘wells’
- If products are more stable, thermodynamics favor reaction (exergonic)
- If reactants are more stable, reaction is not favored (endergonic)
- Kinetics studies the rates of chemical reactions
- Gibbs free energy = difference between transition state and starting state
- Lower gibbs free energy = faster rate of reaction
- Enthalpy is the energy contained within chemical bonds and solvation
- If bonds formed are stronger than bonds broken, heat is given off (exothermic)
- If bonds formed are weaker than bonds broken, heat is absorbed (endothermic)
- Entropy measures chaos vs order - chaos is favored

- Reactions that result from KE being put into a reaction vessel due to temperature are
called thermal reactions
- During collisions between molecules, KE becomes potential energy
- During a collision that yields a reaction, a structure (called transition state) forms
- Transition state is also called the activated complex
- The activated complex has so much strain that it transitions to new structures that are
less strained

where T is temperature in Kelvins (K)

- Fundamental principle of nature: all systems will spontaneously move to a lower energy
state if a pathway is available
- delta(G) = G(products) - G(reactants)

- H = Enthalpy = energy contained in bonds

- Enthalpy of products - reactants = heat of reaction (Hrxn)(deltaH)
- Structures with stronger bonds (or are better solvated) are more stable and thus have
lower enthalpy

- Entropy (S) = randomness/ disorder/ chaos

- Chaos is favored because of the second law of thermodynamics (everything decays over
time)
- Positive value S means more entropy (favored)
- Negative value for S means less entropy (not favored)

- High temps often lead to negative delta(G) - which means spontaneous bond breaking
- Acidity of an acid is determined by the stability of its conjugate base
- Stronger/ more acidic acids form more stable anions upon deprotonation
- Things that affect the stability of an anion:
- Electronegativity of the atom with the negative charge (more electronegative
atoms = more stable anions)
- Size of atom with the negative charge (larger atom can handle more electrons
since spread out over larger area)
- Delocalization of charge in the anion (requires looking at resonance structures)
(greater delocalization = more stable)
- The inductive effect (?) (because adjacent electronegative atoms like Halogens
will attract the negative charge and delocalize it)
- Hybridization of the atom with the negative charge (since greater percentage of s
character in the hybrid orbital = more stable anion)

- all Brønsted-Lowry acids are protic acids; Lewis acids may be protic acids or aprotic
acids.
- Unsaturated hydrocarbon: a hydrocarbon that has 1+ C-C double or triple bonds
- 3 classes of unsaturated hydrocarbons: alkenes, alkynes, arenes
- Unsaturated = fewer hydrogens bonded to C than in an alkane
- Alkenes
- Carbon carbon double bond
- Alkynes
- Carbon carbon triple bond

- Alkene = unsaturated hydrocarbon that has at least one C-C double bond
- Double bond consists of 1 sigma bond (formed by overlap of sp^2 hybrid orbitals)
and 1 pi bond (formed by overlap of parallel 2p orbitals)
- Index of Hydrogen Deficiency (IHD):
- For each ring and pi bond, an atom has two fewer hydrogens
- IHD is the sum of rings/ pi bonds in a molecule
- Compares the number of hydrogens of the molecule in question to the number of
hydrogens in the reference molecule with same number of carbons, which would
only have single bonds (reference alkane)
- Index of Hydrogen deficiency (DoU) = (Hreference - Hmolecule) / 2

- Rotation is restricted around a pi bond, whereas rotation about a single C-C bond is free
- Because of this restricted rotation, any molecule with a C=C double bond and 2 different
group bound to the ends has a cis form and a trans form (cis, trans, isomerism)
- Cis Isomer
- The two groups are on the same side of the double bond
- Z nomenclature
- Trans Isomer
- The two groups are on opposite sides of the double bond
- E Nomenclature
- Cis and trans isomers cannot be converted into each other at room temp because of the
restricted rotation about the double bond
- This means they are different molecules w/ different physical/chemical properties
- Diastereomers

- Cis alkenes are less stable than trans alkenes because of the steric strain between
substituents on the same side of the bond
- Steric strain: increase in potential energy (strain) of a molecule because of the
repulsion of electrons that are not bonded to each other
 - IUPAC naming changes when there is a double bond from -an to -en
- For two or more double bonds, infix changes to -adien or -atrien etc.

- Methylene: double bonded =CH2

- Vinyl: bonded -CH=CH2
- Allyl: bonded -CH2CH=CH2

IUPAC Naming:

Common Names:
For Cycloalkenes:

- The ends of the double bond are numbered 1 and 2 and the rest proceeds in the order
that would give the first encountered bonded group the smallest number
Just in case it comes up:
- For an alkene with any number N of C=C double bonds, each of which can have
cis,trans isomerism, a total of 2𝑁𝑁 stereoisomers are possible to have
- Alkenes are essentially nonpolar, and the only attractive forces between their molecules
are dispersion forces
- This means the physical properties of alkenes are similar to alkanes
- Dispersion forces are nonpolar

- 2,3, and 4 carbon alkenes are gaseous at room temperature

- The larger ones are colorless liquids less dense than water
- Alkenes are insoluble in water but soluble in other alkenes, in other nonpolar organic
liquids, and in ethanol (C2H6O)

- Terpene: compound with a carbon skeleton that can be split into 2 or more units that are
identical to isoprene
- Isoprene is naturally occurring, and so are terpenes
- Isoprene: 2-methyl-1,3-butadiene (CH₂=C−CH=CH₂ )
- 1st carbon of isoprene is the head, 4th carbon is the tail
- Isoprene rule: terpenes are formed by bonding the tail of one isoprene to the tail
of another
- Cross linking between isoprenes in a terpene can give cyclic structures
- Most common alkene reaction is an addition reaction
- Addition reaction: breaks pi bond, produces 2 new sigma bonds
- Reactive intermediate: energy minimum between two transition states
- Rate determining step: the step that crosses the highest energy barrier (slowest step)
- Common reactive intermediates:
- Carbocations (+ charge on C with 6 valence electrons)
- Carbon radicals (1 unpaired electron, so only 7 valence electrons on a C)
- Carbanions (3 bonds and 1 lone pair on a C)
- Bond dissociation enthalpy: the amount of energy required to break bond into 2 radicals
- Used to determine if a reaction will be favorable (exothermic) or unfavorable
(endothermic)
- Change in enthalpy (𝛥𝛥𝛥𝛥) = Hproducts - Hreactants
- Exothermic if the bonds made in products are stronger than the ones broken in
reactants

- The peaks on the surface are called transition states

- Transitions have basically no lifetime while intermediates have very short lifetimes

BDE = bond dissociation enthalpy

- Negative delta H means exothermic (change in enthalpy)
- Exergonic = change in gibbs energy, (exergonic = release)
- Electron rich molecule: nucleophile (seeking positive charge)
- Electron deficient molecule: electrophile (seeking negative charge)
- Empty orbitals and positive charges are electrophilic
- weak bonds are also electrophilic
Electrophilic addition reactions
- Occur when electrophiles add to a pi bond
- Rate determining step is the first time a new pi/ double bond forms between the alkene
and the electrophile

- Carbocation is made when the electrophile is a BL acid and a proton is added

- Carbocation: carbon with only 6 valence electrons and a positive charge
- Stability of carbocations: 3∘ , 2∘ , 1∘
- Carbocations are stabilized by the inductive effect (nearby alkyl/ R groups) and
by hyperconjugation (overlap of pi bonding e-density with empty 2p orbitals)
- Carbocations can rearrange
- Driving force for rearrangement is if you can switch it to a more stable
degree
- Rearranging happens via 1,2 shift where an atom moves to an adjacent
or more electron deficient region

- Regioselective reaction: a reaction that always happens in a way that favors one
direction of bond breaking or forming
- Markovnikov's rule: the addition of HX or H2O to a non-symmetrical alkene
should add the X or OH to the more substituted carbon
- H goes to the carbon that already has the most H
- Molecule that follows the rule (takes X or OH to most substituted side) is called
Markovnikov, and if it doesn’t follow the rule it is called anti-Markovnikov
- Markovnikov molecule is the more stable of the two carbocations that can form
from adding an electrophile to an asymmetric alkene

- Stereoselective region: a region in which one stereoisomer is formed over all other ones
- Can be enantioselective or diastereoselective (depends on products)
- Anti addition: addition of 2 groups from opposite sides of a double bond
- Often occur with anti stereoselectivity
- In cyclic systems, anti addition = trans coplanar addition
- Syn addition: addition of atoms/ groups to the same side of a double bond

- For electrophilic addition reactions, pay attention to:

- Intermediates (carbocation, halonium ion, etc.)
- How intermediates predict regioselectivity (Markovnikov, anti-M)
- How intermediates predict stereochemistry (anti or syn)

- Molecular halogens (𝑋𝑋2 ) have relatively weak bonds and can be considered electrophilic
- Reactions with molecular halogens usually release more stable halogen anions
- Hydrogen halides: HCl, HBr, HI add to alkenes to give haloalkanes
- Can add in pure reagents (neat) or in a polar solvent (acetic acid)(CH3COOH)

- 2 step reactions:
- Step 1 (slow, rate-determining step): add a proton

- Step 2: make new bond between electrophile and nucleophile

- pi/ double bond is relatively electron rich

- In an electrophilic addition reaction, energy is released
 - Inductive effect: nearby groups delocalize the positive charge of a cation
- Hyperconjugation: partial overlap of sigma bonding region with a nearby empty 2p orbital

Addition of water: acid- catalyzed hydration:

- Water+acid catalyst converts alkene to an alcohol

Carbocation Rearrangements:
- Typically, either an alkyl group or a hydrogen migrates to an adjacent electron deficient
C
- In acid catalyzed hydration of alkenes, the group that shifts can also be a 𝐻𝐻 −
Addition of Bromine and Chlorine

This is stereoselective in terms of allowing anti-addition only (because the cyclic intermediate
forces the second Br to attack from the back side)
The products are all trans-isomers, since one Br always goes into the page and the other
always comes out of the page

- Racemic mixture: equal amounts of 2 mirror-image products are formed

- Stereospecific: different starting geometries (E vs Z) yield different products

Addition of HOCl and HOBr

- Halohydrins: molecule containing a halogen and a hydroxyl group on adjacent carbons
- Bromohydrin: contains Br and OH
- Chlorohydrin: contains Cl and OH
- 𝐶𝐶𝐶𝐶2 or 𝐵𝐵𝐵𝐵2 in the presence of H2O converts alkenes to halohydrins
- Alkene’s double bond attacks the 𝑋𝑋2 bond and yields a bridged halonium ion
intermediate (cation)
- H2O attacks the intermediate from the back side to give intermediate #2
- Intermediate #2 loses a proton to form the final halohydrin
- No rearrangements occur
- Reaction exhibits anti addition stereoselectivity (because of halonium intermediate)
- Reaction has Markovnikov regioselectivity
- Reaction is stereospecific because Z-alkenes give different products than E-alkenes

- 3 step mechanism to form halohydrin:

 1. Make a new bond (from double bond to electrophile)

2. Make new bond from nucleophile (H2O) to electrophile (more substituted C)

3. Take a proton away (proton transfer to water completes reaction)

Oxymercuration Reduction
- Converts alkenes to alcohols
- Reacts alkene pi bond with 𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻 + to give bridged mercurinium cation intermediate
- Backside of intermediate cation is attacked by H2O to give a new intermediate
- NaBH4 is added as a reducing agent to replace the Hg with an H
- New intermediate loses a proton
- Whole process is scrambles syn and anti addition
- Displays Markovnikov regioselectivity since OH ends up bound to more substituted C
- No rearrangements

- Hydration of alkene can be done using mercuric acetate and water, followed by
reduction of the resulting organomercury intermediate using NaBH4
 - Oxymercuration Overall Steps
1. Oxymercuration: adds HgOAc and OH across the double bond
- Similar to hydration, but forms organomercury compound intermediate
- Follows Markovnikov
2. Reduction:
- Uses NaBH4
- Reduces C-Hg bond to C-H bond
- Specifically a reduction step

- Final product/ net results looks like a hydration of an alkene

Ex.
Hydroboration Oxidation
- Leads to non-Markovnikov hydration of an alkene
- Involves a 4-membered transition state using syn-addition (no carbocation intermediate)

- Net reaction is the hydration of a carbon carbon double bond

- But, since H is added to the more substituted and OH to the less substituted
carbon, this is considered anti-Markovnikov

- Overall ex.
- Hydroboration: addition of borane (BH3) to an alkene to form trialkyl-borane
- Reaction occurs in 3 steps
1. BH3 reacts with one molecule of alkene and forms an alkylborane
2. Then that reacts with a second molecule of alkene to form dialkylborane
3. Same dialkylborane reacts with a 3rd alkene and forms final trialkylborane

- Borane can’t be isolated/ can’t exist by itself because it reacts with itself to form
diborane, a toxic gas that ignites spontaneously in air
- Technically means hydroboration oxidation uses B2H6, but it reacts as if it was
BH3 so we just use that (or BH3 and THF)

- All trivalent compounds of boron are electrophiles (because of its empty 2p orbital)
- Adding borane to alkenes is regioselective (anti Markovnikov) and stereoselective (syn)
- Trialkylboranes are rarely isolated

- Usually convert directly into other atoms (H,O,N,C, halogen) that substitute boron
- Very important reaction of trialkylborane is with hydrogen peroxide (H2O2) in aq. Sodium
hydroxide (NaOH)
- H2O2 acts as oxidizing agent
- Oxidizes trialkylborane into alcohol + sodium borate (Na3BO3)
- This is stereoselective because configuration of alkyl group is retained (OH is
subbed into exactly the same position as the boron it replaces.
- Net product of hydroboration-oxidation is the syn stereoselective addition of H and OH to
a C=C double bond, combines with non-Markovnikov regioselectivity

- Trialkylboranes are rarely isolated

Oxidation (of Carbon):
- Loss of electrons
- Addition of O and/or removal of H
-

Reduction (of Carbon):

- Gaining of electrons
- Removal of O and/or addition of H
-

Depending on environment, a molecule can be either oxidized or reduced

Oxidation of an alkene to Glycol

One way to tell if a reaction includes oxidation or reduction is to use balanced half-reactions

How to write a balanced half reaction:

- If electrons are on the right side of the balanced half reaction, it is oxidation
- If electrons are on the left side, the reaction gains electrons and is reduced
- If no electrons are in the half reactions, the transformation involves neither

Example: propene (CH3CH=CH2) to propane (CH3CH2CH3)

 Ozone- cleavage of a C=C double bond (ozonolysis)

- Ozone (O3) with dimethylsulfide ((𝐶𝐶𝐶𝐶3 )2 𝑆𝑆) breaks an alkene’s double bond and gives
two carbonyl groups (C=O) in its place
- O3 is very electrophilic
- First forms molozonide intermediate, which rearranges into ozonide intermediate
- Dimethyl sulfide reduces the intermediate into the carbonyl products

- This is one of the few organic reactions that breaks C-C bonds

- Trans alkene is more stable than a cis alkene

Reduction with H2; catalytic reduction/ catalytic hydrogenation

- If a transition metal is present as a catalyst, H2 reduces alkenes to alkanes
- This reduction happens with syn stereoselectivity and no rearrangement
 - Reaction is stereospecific because Z vs E alkenes form different products
- Reaction is exothermic but extremely slow without a catalyst
- Breaks double bond by adsorption into the surface of the transition metal
- Then, as the alkane desorbs, it forms two C-H bonds

★ Even though H2 addition is syn stereoselective, this reaction can form trans isomers
Heats of Hydrogenation (HoH) and relative stabilities of alkenes:
- Reduction of alkene to alkane is exothermic
- HoH depends on the degree of substitution of a C=C double bond
- Greater degree of substitution = lower HoH
- Lower HoH = more stable
- HoH of a trans alkene is lower than that of a cis alkene

6.8 (not in syllabus and hurt my brain so skipped)

(what is optically active????)

Molecules containing chiral centers as reactants or products:

- When the reaction makes chiral centers in the products using achiral reagents and
environment, the products will always be racemic
- All stereospecific reactions are stereoselective, but not all stereoselective reactions are
stereospecific
Alkynes: contain one or more carbon carbon triple bond (1 sigma bond, 2 pi bonds)
- Most common alkyne is C2H2, also called acetylene (linear molecule)
- Shortest to longest: triple bonds, double bonds, single bonds
- Bond dissociation enthalpy of triple bond is the greatest, then double, then single
- Indicated that the pi bond in an alkyne is weaker than the pi bond in an alkene

Alkynes Nomenclature:
- Infix yn is used to show presence of triple bond
- Name the main chain containing the triple bond so that the end carbons have lowest #s
- Common names are derived by adding a prefix for the substituent to the word acetylene

- If there is only one possible location for a triple bond in each molecule, no need to
include the number of the chain where the triple bond starts
- If a hydrocarbon chain contains more than one triple bond, use infixes adiyn, atriyn, etc.

- If both double and triple bonds are present, location of the double bond goes first
- If the triple bond in an alkyne is between carbons 1 and 2, it is called a terminal alkyne
(as opposed to in the middle of a molecule = internal alkyne)

Physical properties of alkynes:

- Similar to alkanes and alkenes with analogous carbon skeletons
- Lower molecular weight alkynes are gaseous at room temperature
- The ones that are liquid at room temp have densities less than 1g/mL
Acidity of 1-Alkynes:
- pKa values of terminal alkynes are ~25
- Less acidic than water and alcohols
- More acidic than alkanes, alkenes, and ammonia

- The H atom triple bonded to a C-C triple bond is decently acidic

- Can be removed by a strong base
- most commonly sodium amide (NaNH2), sodium hydride (NaH), or LDA
- This removal via base yields an acetylide salt

- Because water is more acidic than acetylene, OH is not a strong enough base to convert
a terminal alkyne to an alkyne anion

Preparation of alkynes:
- Alkynes can be prepared via alkylation of acetylene ions with methyl or primary halides
- This reaction creates a C-C bond
- Using 2 sequential deprotonation-alkylation reactions, non-symmetrical alkynes
can be made
- Alkynes can be made from alkenes
- 2 step sequence: halogenation with 𝑋𝑋2 and then double
dehydrohalogenation
- Hallenes (compound with 2 adjacent C=C double bonds) are sometimes made as
byproduct of the double dehydrohalogenation

Alkylation with methyl and 1∘ haloalkanes

- Acetylide anions are nucleophiles and strong bases (will displace halide ion from methyl
and 1∘ haloalkanes)

- In nucleophilic substitution reaction: acetylide ion donates its electron pair and replaces
a halogen atom

- Because alkyl group is added to the molecule, this is also called alkylation reaction
Alkynes from alkenes:
- Treating alkene with Br2 or Cl2 gives dihaloalkane
 - Treating this dihaloalkane with a strong base (NaNH2) causes two
dehydrohalogenations and makes an alkyne

- Meso compounds: a molecule with 2 or more stereocenter, but is optically inactive and
superimposable on its mirror image
- Meso compounds are achiral, even though they contain stereocenters
- Have an internal plane of symmetry that divides the molecule in half, and the two
halves reflect each other

- With weaker bases, it is possible to stop the reaction after the first dehydrohalogenation
and to isolate the haloalkene
- Much more common to use a strong base and go straight to the alkyne

- If there is at least one hydrogen atom on each adjacent carbon, a side reaction usually
occurs (and forms and allene)

- Most allenes are less stable than their isomeric alkynes

- This means allenes are normally the minor product instead of the major
Alkyne reaction mechanism:
- Always start the arrow at the electron source and point it at the electron sink
- Electron source: bond or lone pair
- Electron sink: an atom or molecule that can accept a new bond or electrons

- Alkynes add Br2 to to give dibromoalkenes (via anti addition stereochemistry)

- 2nd mole of Br2 can be added to give tetrabromoalkane
- Addition of Cl2 occurs with less stereoselectivity than the addition of Br2
- For terminal alkynes, Makovnikov’s rule is followed and the H is added to the
terminal carbon

Addition of Br2 and Cl2

- Anti stereoselective
- Anti addition of halogen to an alkyne yields an E-dihaloalkene

Adding another Br ex.

Addition of Hydrogen Halides:
- Addition of HX is regioselective
- Addition of 2 HX gives a geminal dihaloalkane
- Reaction by way of vinylic carbocation intermediate follows Markovnikov rule

2 step mechanism for each addition:

1. Proton transfer:
- H-Br breaks into H⁺ (proton) and Br⁻
- The H⁺ (proton) adds to the alkyne's π bond
- This creates the vinylic carbocation
- The Br⁻ hasn't reacted yet at this point

2. New bond:
- Br⁻ uses its electron pair to form a new bond
- Attacks the carbocation
- Forms 2-bromopropene (final product)
Hydration of alkynes to aldehydes and ketones:
- Alkynes reacted with borane (BH3) and then basic peroxide (H2O2) to produce ketones
and aldehydes
- In equilibrium between keto and enol form, keto usually dominates

- Hydroboration of an internal alkyne is syn stereoselective

- Oxidation of the resulting trialkenylborane by H2O2/ NaOH gives an enol that is in
equilibrium, through keto-enol tautomerism, with a ketone.

- Hydroboration of a terminal alkyne using a hindered dialkylborane followed by oxidation

of the resulting trialkenylborane with H2O2/ NaOH and then keto-enol tautomerism gives
an aldehyde
- Enol: a compound containing a hydroxyl group bonded to a carbon of a C=C
- Alkene + alcohol = enol
- Keto: refers to a molecule where the functional group is a carbonyl group (C=O)
- Tautomers: constitutional isomers that are in equilibrium with each other and the only
difference is the location of a Hydrogen atom and a double bond
Acid-Catalyzed Hydration:

- In the presence of concentrated sulfuric acid () and an Hg salt as a catalyst, alkynes

undergo the addition of water similar to oxymercuration of alkenes
- Common Hg salts are: HgO, HgSO4, or Hg(OAc)2
- For terminal alkynes, addition of water follows Markovnikov’s rule
- Resulting enol is in equilibrium with the more stable keto form
- This means the product isolated is a ketone
Ex
Reduction of Alkynes:
- Alkynes react with 2 moles of H2 in the presence of a transition metal catalyst to give
alkanes (reaction does not usually stop at alkene stage)

Catalytic reduction:
- Most common transition metal catalysts: palladium (Pd), platinum (Pt), nickel (Ni)
- Not possible to stop the reaction at alkene stage unless the catalyst is specifically
chosen for that
- This would be the lindlar catalyst (finely powdered palladium metal deposited on
solid calcium carbonate that has been specially modified with lead salts)

Hydroboration-Protonolysis:
- Hydroboration of an alkyne followed by protonolysis converts an alkyne to a cis-alkene
- This is because treating the trialkylborane with a carboxylic acid (like acetic acid) results
in stereoselective replacement of boron by hydrogen
Dissolving Metal Reduction:

- Alkali metal reduction is stereoselective (anti addition of hydrogens to an internal alkyne

gives a trans-alkene)
- Mechanism involves a radical mechanism and 2 sequential single-electron transfers
(from Na or Li metal), each followed by deprotonation of the amine solvent