Orgo I - Unit 3 Study Guide

Elimination Reactions
E1 (1st Order Elimination): Stepwise Mechanism
Elimination: Loss of 2 atoms/groups from the substrate, formation of a bond
Slow step: C+ formation
2nd step (fast): base abstracts H+ from C adjacent to C+, C-H bond e- shifted to
bond (fast, Ho < 0)
o Base is usually weak (often the solvent eg. EtOH)
o Adjacent C rehybridizes from sp3 to sp2 as bond forms
Substrate reactivity: 3o < 2o << 1o (1o rarely undergoes E1)
Rate=k [ RX ]

Competition with SN1 results in a mixture of products

Rearrangement is possible
Requires a good polar ionizing solvent eg. H2O, ROH
Zaitsevs Rule: In elimination reactions, the most substituted alkene usually predominates
(Zaitsev product)
Follows order of alkene stability
E2 (2nd Order Elimination): Concerted Mechanism
Strong base abstracts H+ on C next to leaving group, leaving group leaves
o Occurs when a strong base (usu. strong Nuc as well unless it is bulky) is
used w/ a poor SN2 substrate i.e. a 3o or hindered 2o halide
Rate=k [ RX ] [Base ]

Substrate reactivity (follows alkene stability): 3o > 2o > 1o

Follows Zaitsevs Rule
o Hofmann product (less substituted of possible alkenes) may predominate
if base is bulky eg. diisopropylamine, tert-butoxide, triethylamine, 2,6dimethylpyridine
3
Sp of H+ and LG must be either syn or anti coplanar for p orbitals to overlap
o Anti (staggered ) is more stable than syn (eclipsed ) and mechanism is
only syn coplanar if molecule is locked into a syn coplanar conformation
o Stereospecific
No rearrangement
Solvent polarity is unimportant ( spreads out negative charge)
Alkene Structure & Synthesis
Alkenes: Planar, sp2, 120o bond angle
bond is more reactive than bond (lower BDE, weaker)
Elements of unsaturation: X count as H, O ignored, N count as C
Alkane Naming
Terminal & internal alkanes
Cycloalkenes: Only present in cis until rings have 8 C; C=C between C1 and C2

Parent = longest chain containing C=C; number chain so C=C has lowest number
possible
Alkenes as substituents
=CH2 methylene
-CH=CH2 vinyl
-CH2CH=CH2 allyl
Phenyl
Common Alkene Names
CH2=CH2 ethylene
CH2=CH-CH3 propylene
CH2=C(CH3)2 isobutylene
CH2=C(CH3)CH=CH2 isoprene
Styrene/vinylbenzene
Cis/trans, E/Z require two groups on each side of the C=C
Trans is generally more stable (less steric hindrance) but cycloalkenes are
generally cis because it minimizes ring strain
Commercial importance of alkenes: Used as reagents for many syntheses due to reactivity
of C=C
Ethylene, propylene heavily produced as reactive intermediates
Double bonds often used to construct addition polymers eg. PVC, Teflon
Alkene stability (measured w/ Ho of hydrogenation)
More substituted alkenes are more stable
o Alkyl groups donate electron density to C=C
o Bulkier alkyl groups are more stable when further apart
Disubstituted alkene stability: cis<geminal<trans
Bredts Rule: Bridged bicyclic compounds only have a double bond at bridgehead
C if one ring has 8 carbons
Alkene physical properties
Similar to alkanes; low bp and mp
bp increases with number of C due to increasing MW
Nonpolar (only weak van der Waal interactions)
Bond between allyl C and C in C=C is slightly polar
o Alkenes are more polar in cis (bond dipoles add together) than trans
(dipoles cancel out); cis has a higher bp
Alkene Preparation/Synthesis
1. E2 Dehydrohalogenation (-HX): 3o and hindered 2o halides
a. Use strong, bulky bases (weak nucleophiles, Hoffmann product is
dominant) and aprotic solvent
i. Hoffmann product = anti-Zaitsev product (least substituted of
possible alkenes)

b. Stereospecific: H and X should be anti coplanar unless molecule is

sterically locked into syn coplanar
c. Cycloalkenes: H and X must be trans diaxial to be anti coplanar
d. Vicinal dibromides (anti coplanar): 1 Br removed by NaI in acetone/ ZnI
in acetic acid, other Br leaves, bond e- forms bond
2. E1 Dehydrohalogenation: 3o or 2o halides
a. Use weak bases, protic solvent
b. Possible rearrangements
c. Completition with SN1, not used often in synthesis
3. Alcohol dehydration (E1)
a. Acid (conc. H2SO4/H3PO4) catalyzed
b. Reaction is reversible
i. Acid removes alkene as it forms
c. 1st step: -OH protonated by acid so it can act as a LG
i. Rest of the reaction follows E1
4. Industrial Synthesis
, alkene+ shorter alkane
a. Catalytic cracking: Long alkane catalyst

b. Hydrogenation: Alkane , catalyst alkane

i. Endothermic, but entropically favored (So > 0)

c. Neither are suitable for lab synthesis with respect to reaction conditions
Addition Reactions of Alkenes
Reactivity of C=C: Electrons in bond are loosely held; attract electrophiles (E+), form a
carbocation intermediate, nucleophile adds to carbocation
E+ and Nuc can be added to same (syn) or opposite (anti) side(s) of the double
bond
Alkene Hydrohalogenation
Alkene + HX alkyl halide
Follows Markovnikovs Rule (proton/acidic species adds to the least substituted
carbon, nucleophile/basic species adds to the most substituted carbon)
Free-Radical Addition of HBr to an Alkene
Requires peroxides (R-O-O-R) ie. peroxide effect
A lkene+ HBr ROOR Alkyl halide ; RO2R as radical initiator

Produces anti-Markovnikov product (H+ adds to most substituted carbon because

Br radical adds first)
Only HBr has the right bond energy (HCl is too strong, HI breaks heterolytically)
Alkene Hydration (reverse of alcohol dehydration)
Alkene+ H 2 O dilute H 2 SO 4 /H 3 PO 4 Alcohol

Markovnikov product
Oxymercuration-Demercuration

OAc 2 , H 2 O ( 2 ) NaB H 4 , OH Alcohol

(1) Hg
Alkene
Markovnikov product (H2O adds to more substituted carbon), anti addition (H2O
adds to most substituted carbon)
Product is an ether if the nucleophile is an alcohol instead of H2O
Hydroboration-Oxidation
( 1 ) BH 3 THF ( 2 ) H 2 O2 , OH alcohol

Alkene
Anti-Markovnikov product, syn addition
o BH3 prefers less substituted carbon due to steric hindrance and charge
distribution
BH3 exists as dimer (B2H6), is able to reduce three alkenes -> trialkylborane
Alkene Halogenation (X = Cl, Br)
Alkene + X 2 vicinal dihalide

Anti addition, Markovnikovs Rule does not apply (E+ and Nuc are both X)
Add Br2 in CCl4 to an alkene in the presence of light; color disappears as Br adds
to double bond (decolorizing bromine test)
Halohydrin Formation
Alkene + X 2 H 2 O halohydrin

H2O = Nuc
Markovnikov product (Nuc attacks most highly substituted carbon), anti addition
Catalytic Hydrogenation
Pb , Pt ,

H 2 , metal
Alkene
Alkene attaches to catalyst (catalyst attached to H2 from charcoal)
H adds to double bond (syn addition)
Alkane detaches
Less substituted C react faster (less crowded so it is easier for H to attach)
Carbene Addition Possible through three different reactions
Because of its lone pair and empty octet, a carbene can act as both an electro- and
nucleophile
N 2 C H 2 N 2+:CH 2 ; alkene+:CH 2 alkane with cyclopropane ring
1.
a. N2CH2 is toxic and explosive
2. Simmons-Smith reagent:
Alkene CH 2 I 2+ Zn+CuCl alkene with cyclopropane ring

3. Alpha elimination (H and X come from same carbon): cis/trans retention

CH X 3 , OH . H O alkane with cyclopropane ring ; 2 X at ' ape x ' of ring
2

Alkene
Epoxidation
Requires a peroxyacid ie. RCO3H; common acid = mCPBA
Alkene peroxyacid epoxide+carboxylic acid ; epoxide can be isolated if

solution is not too acidic

H +, H O

trans-glycol (acid-catalyzed); backside attack by H2O

Epoxide
To get trans-glycol without stopping at epoxide: treat alkene with CH3CO3H or
HCO3H (very strong peroxyacids); stereospecific
Syn Dihydroxylation of Alkenes two possible reactions to yield cis-1,2-glycols
, H O
KMnO 4 ( cold , dilute ) , OH

1.
cis-glycol
Alkene
a. KMnO4 is deep purple, loses color as it reacts with the double bond
Alkene
Os O4, H 2 O 2 , H 2 O cis-glycol
2.
2

a. OsO4 produces a better yield than KMnO4, but is much more expensive
3. Both mechanisms involve syn addition of O/oxidation to OH
Oxidative Cleavage
Cleavage with warm, concentrated KMnO4 yields ketones and carboxylic acids
o Terminal CH2 -> CO2
Cleavage with O3 and Zn, H2O or (CH3)2S (ozonolysis, ozonide intermediate)
yields ketones and aldehydes and Zn(OH)2 or DMSO
Alkene Polymerization
Yields addition polymers
Ethylene derivatives (CH2=CHZ) used as monomers; polymer has Z on every
other C
1. Cationic polymerization (C+ intermediate, E+ adds to least sub. C)
2RO)
2. Radical polymerization (FR initiator eg. ROOR
3. Anionic polymerization (requires strong e- withdrawer bonded to C in double
bond)
Olefin metathesis
Break molecules at double bond, reassemble them
Alkene = 2 alkyldienes (=CHR); metathesis trades/interchanging =CHR using
Schrock or Grubbs catalysts
Alkynes & Alkyne Reactions
Alkenes: 2 elements of unsaturation (CnH2n-2)
Naming
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1. Find longest chain containing CC; change ane to yne

2. Number chain starting at end closest to triple bond
a. Position of triple bond designated by lowest-numbered C
3. Additional functional groups besides ethers and halides have higher priority than
alkenes/-ynes
4. Common names: Many alkynes can be described as acetylene (CHCH)
derivatives eg. CH3CH2CHCHCH3 = Ethylmethylacetylene
Physical properties
Nonpolar
bp similar to alkanes of similar size
Less dense than H2O
Gaseous with 4 or less C, liquid with 5 or more
Commercial importance
Acetylene used in welding torches
OH 2
C2H2 synthesis: 3 C+CaO CaC + CO ; CaC +2 H O C H +Ca
2
2
2
2
2

Electronic structure
sp hybridized; linear geometry, 180o bond angle
Acidity
Alkynes have a high amount of s character; conjugate base holds e- tighter than
those of alkenes or alkanes therefore alkynes are stronger acids (terminal alkynes
are the most acidic HCs)
o Can be deprotonated by strong bases eg. H- or NH21
+ H 2(evolves out)
+ N H 3
2

RC C
+ N H 2

+ N H 2
F e 3 +catalyst Na

RC CH + Na
NH 3 + Na

Acetylide ions are very strong bases and good nucleophiles; can undergo SN2 to
yield substituted acetylene (fastest with methyl and primary halides)
o Can also remove H+ from hindered secondary and tertiary halides (E2)
Addition of Acetylide to Carbonyl Groups
C=O bond is polarized; C is electrophilic
Addition of H2O/dilute acid alcohol (alkoxide intermediate is protonated)
Adding to formaldehyde yields a primary alcohol w/ one more C than the
acetylide
Adding to an aldehyde yields a secondary alcohol (R1 from acetylide, R2 from
aldehyde)
Adding to a ketone yields a tertiary alcohol

Alkyne Synthesis by Elimination

2 eliminations required to yield an alkyne; also requires higher T and a stronger
base than elimination to an alkene
2 eliminations needed to remove 2 mol HX from a vicinal/geminal dihalide
Molten or alcoholic KOH yields an internal alkyne, NaNH2 followed by H2O @
150oC yields a terminal alkyne
Addition Reactions of Alkynes
bonds 2 bonds; may see double addition to triple bond
1. Catalytic Hydrogenation 3 possible pathways
a. Add lots of H2 w/ metal catalyst; alkyne reduced to completely saturated
alkane (Pd too reactive to stop after 1 equivalent of H2 is added)
i. 2 eq H2 added yields alkane, 1 added syn yields cis alkene, 1 added
anti yields trans alkene
b. Lindlar catalyst with 1 equivalent H2 yields cis alkene (stereoselective)
c. Dissolving metal reduction (Na in NH3): H2 added anti, yields trans alkene
(stereoselective)
i. Na in liquid NH3 yields solvated e- that turns solution bright blue
ii. Vinyl C+ intermediate most stable when R groups further apart
therefore trans alkene is favored
2. Alkyne Halogenation Vinyl dibromides/dichlorides
a. Halides may add syn or anti (mixture of cis/trans product); difficult to stop
at dihalide
3. Hydrohalogenation
a. Uses 2 equivalents HX; addition of first equivalent yields vinyl halide,
addition of second equivalent yields geminal dihalide
b. Markovnikovs Rule: Both H add to the same C
c. Peroxides catalyze an anti-Markovnikov addition of HBr across the triple
bond
4. Alkyne Mercuric Ion-Catalyzed Hydration
a. In the presence of a strong acid/Hg2+, elements of H2O add to the triple
bond but the initial product is an unstable enol that rearranges to a ketone
(tautomerization)
i. C=O in keto (acid & base-catalyzed) is much stronger than C=C in
enol
b. Tautomers: Constitutional isomers that differ in C=C location and a H
atom); in equilibrium with each other
5. Hydroboration-Oxidation
a. Enol intermediate; overall result = addition of H2O to triple bond, yielding
a ketone
b. Internal alkyne: reaction yields ketone
c. Terminal alkyne: reaction yields aldehyde
d. Hindered dialkylborane (Sia2BH) used to prevent addition of 2BH3 across
the triple bond; adds once, yielding a vinylborane

6. Alkyne Oxidation
Alkyne KMn O4 (netural ,water ) Diketones
a.

b.
c.

KMnO 4 ,O H( warm water )

Carboxylates (oxidative cleavage)

Alkyne
Alkyne 1.O 3 2. H 2 O Carboxylic acids

Mechanisms
1. E2 Dehydrohalogenation

a. Elimination of Vicinal Dibromides

2. E1 Dehydrohalogenation

a. E1 Acid-Catalyzed Alcohol Dehydration

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3. Electrophilic Addition of HX to an Alkene

4. Free-Radical Addition of HBR to Alkenes

5. Acid-catalyzed Alkene Hydration

6. Oxymercuration-Demercuration of an Alkene

7. Hydroboration-Oxidation of an Alkene

8. Addition of a Halogen (X2) to an Alkene

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9. Halohydrin Formation

Reactions
1. Elimination
a. Zaitsevs Rule
b. E2 Dehydrohalogenation
c. E2 Debromination of Vicinal Dibromides
d. E1 Dehydrohalogenation
e. E1 Acid-Catalyzed Dehydration of Alcohols
2. Reactions of Alkenes
a. Markovnikovs Rule
b. Syn vs. anti addition
c. Hydrohalogenation (reagent = HBr)
i. Markovnikov Hydrohalogenation
ii. Anti-Markovnikov (free radical) hydrobromination; ROOR
initiator
d. Direct Hydration (reagents = H+, H2O)
e. Oxymercuration-Demercuration (anti addition, Markovnikov product,
reagents = Hg(OAc)2, H2O, NaBH4, OH-)
i. Alkoxymercuration-demurcuration if nucleophile is an alcohol
f. Hydroboration-Oxidation (Anti-Markovnikov, syn addition, reagents =
BH3-THF, H2O2, OHg. Halogenation (reagent = X2; anti addition)
h. Halohydrin formation (reagent = X2 in H2O; Markovnikov product, anti
addition)
i. Catalytic Hydrogenation (reagent = H2 in Ni, Pd, Pt)
j. Carbene Addition
i. Diazomethane
ii. Simmons-Smith reaction (reagents = CH2I2, Zn, CuCl)
iii. Alpha Elimination (reagents = CHX3, OH-, H2O)
k. Epoxidation (reagent = peroxyacid eg. mCPBA; use H+, H2O to catalyze
ring-opening to trans-glycol)
i. Use CH3CO3H or HCO3H to go straight to trans-glycol

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l. Syn-Dihydroxylation (reagents = 1) KMnO4 (cold, dilute), H2O, OH- or 2)

OsO4, H2O2)
m. Oxidative cleavage (reagents = warm & conc. KMnO4 or O3, Zn, H2O)
n. Polymerization
i. Cationic
ii. Free-radical
iii. Anionic
o. Olefin metathesis
3. Reactions of Alkynes
a. Acetylide Addition to Carbonyls
i. Addition to formaldehyde yields primary alcohol; N(C) increases
by 1
ii. Addition to aldehyde yields secondary alcohol
iii. Addition to ketone yields tertiary alcohol
b. Catalytic Hydrogenation
i. Use lots of H2 (product mixture, mostly alkane) or Lindlar catalyst
(cis alkene) or NaNH2 (trans alkene)
c. Halogenation to Vinyl Dibromides/Dichlorides (reagent = X2)
d. Hydrohalogenation (reagent = 2 eq. HX); vinyl halide intermediate,
geminal dihalide product
i. ROOR-catalyzed anti-Markovnikov hydrobromination
e. Mercuric Ion-Catalyzed Hydration (reagent = H+/Hg2+, H2O
i. Enol intermediate, ketone product (tautomerization)
f. Hydroboration-Oxidation (reagents = BH3, H2O2, OH-)
i. Sia2BH used to prevent excess BH3 addition
g. Alkyne Oxidation
Alkyne KMn O4 (netural ,water ) Diketones
i.

ii.
iii.

KMnO 4 ,O H( warm water )

Carboxylates (oxidative cleavage)

Alkyne
Alkyne 1.O 3 2. H 2 O Carboxylic acids

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