Reaction Flashcards (Alkenes and Alkynes)

25 Pages·2017·1.98 MB·English

DAT Organic Chemistry Reaction Summary Sheet
Alkene Reactions
Hydrohalogenation
Hydrohalogenation
(with Rearrangement)

Halogenation

Hydrobromination
with Peroxide

Hydration

Hydration (with
Rearrangement)
Bromination in H O
2

Oxymercuration-
Demurcuration

Hydroboration-
Oxidation

Syn-Hydroxylation

Syn-Hydroxylation

Anti-Hydroxylation

Addition of an Alcohol

Bromination in Alcohol

Alkoxymercuration-
Demurcuration

Epoxidation

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Catalytic
Hydrogenation

Ozonolysis (Reducing
Conditions)

Ozonolysis (Oxidizing
Conditions)

Oxidative Cleavage

Alkyne Reactions

Catalytic
Hydrogenation
(Catalytic Reduction)
Reduction to Cis-
Alkene

Reduction to Trans-
Alkene

Hydrohalogenation
with HBr (Terminal

Alkyne)
Hydrohalogenation
with HBr (Internal

Alkyne)
Halogenation with Br
2

Hydration of an
Internal Alkyne

Hydration of a
Terminal Alkyne
(Markovnikov)
Hydration of a
Terminal Alkyne

(Anti-Markovnikov)
S 2 Addition of an
N
Acetylide Ion to an

Alkyl Halide
S 2 Addition of an
N
Acetylide Ion to a
Ketone

S 2 Addition of an
N
Acetylide Ion to an
Epoxide
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Free Radical Halogenation Reactions

Free Radical Halogenation
Br
using Bromine (more Br2
selective) hv or Δ

Free Radical Halogenation
Cl
using Chlorine (less

selective) Cl
Cl
2

hv or Δ Cl

Cl

Allylic/Benzylic
Bromination NBS Br
hv or Δ
or ROOR
NBS
Br
hv or Δ
or ROOR Br

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Grignard Reactions

Addition of a Grignard O OH
1. M g X , Ether
Reagent to an Aldehyde
H 2. H3O+ 2˚Alcohol
Addition of a Grignard
O
Reagent to a Ketone 1. M g X , Ether HO
2. H O+ 3˚Alcohol
3
Addition of a Grignard
O
Reagent to an Ester 1. 2 eq. M g X , Ether HO
3˚Alcohol
O 2. H O+
3

Addition of a Grignard
Reagent to an Acyl Chloride O 1. 2 eq. M g X , Ether HO

Cl 2. H O+
3 3˚Alcohol
Addition of a Grignard
O
Reagent to CO
2 1. CO , Ether
MgX 2
OH
2. H O+
3 Carboxylic Acid
Addition of a Grignard OH
O 1. M g X , Ether
Reagent to an Epoxide
(adds to the less subs. side 2. H O+ 2˚Alcohol (less subs. alcohol)
3
forming the less subs.
alcohol)
Addition of a Grignard O O
1. M g X , Ether
Reagent to a Carboxylic Acid
OH 2. H O+ O MgX
3
Carboxylate
Addition of a Grignard O O
1. M g X , Ether
Reagent to an Amide
NH2 2. H O+ NH MgX
3
Deprotonated Amide
Addition of a Grignard
O
Reagent to a Nitrile 1. M g X , Ether
N
Ketone
2. H O+
3

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Electrophilic Aromatic Substitution (EAS) Reactions

Friedel-Crafts Alkylation Cl
(Rearrangement Possible)
AlCl
3

Cl
AlCl
3

Friedel-Crafts Acylation O O
(No Rearrangement
Cl
Possible)
AlCl3

Bromination
Br
Br
2

FeBr
3
Chlorination
Cl
Cl
2
FeCl
3

Nitration
NO
HNO 2
3
H SO
2 4

Sulfonation SO H SO3
3

H SO
2 4
H SO /Δ
2 4
Formylation
O

CO, HCl H
AlCl
3

EAS with an ortho/para- O/P O/P O/P
directing group on Substituent
Substituent
Benzene
Substituent

EAS with a meta-directing M M
group on Benzene
Substituent
Substituent

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Friedel-Crafts M O
Alkylation/Acylation with a
R Cl or Cl R
meta-directing group or No Reaction
an amine on Benzene AlCl3

NH /NRH/NR O
2 2
R Cl or Cl R
No Reaction

AlCl
3

Benzene Side-Chain Reactions

Side-Chain Oxidation of R 1. KMnO , -OH O
4
Benzene to form Benzoic
2. H O+, Heat
Acid R R 3 OH
or or
or

Na2Cr2O7
H SO
2 4

1. KMnO , -OH
4
2. H O+, Heat
3 Requires free Hydrogen at
No Reaction
or Benzylic position
Na Cr O
2 2 7

H SO
2 4

Wolff-Kishner Reduction O
H NNH or N H , -OH, Heat
2 2 2 4
Clemmensen Reduction O
Zn(Hg), HCl, Heat

NO2 Zn(Hg), HCl, Heat NH2

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Hydride Reduction Reactions

Reduction of an Aldehyde to O 1. NaBH , EtOH OH
4
a 1˚Alcohol
H 2. H O+ H
3

O OH
1. LiAlH , EtOH
4
H 2. H O+ H
3
Reduction of a Ketone to a O 1. NaBH , EtOH OH
4
2˚Alcohol
2. H O+
3

O OH
1. LiAlH , EtOH
4
2. H O+
3
Reduction of a Carboxylic O OH
1. LiAlH , EtOH
4
Acid to a 1˚Alcohol
OH 2. H O+ H
3
Reduction of an Ester to a
O OH
1. LiAlH , EtOH
1˚Alcohol 4
OH
O 2. H O+ H
3
Reduction of an Ester to an
Aldehyde O 1. DIBAL-H, -78°C O
O 2. H O H
2
Reduction of an Acyl
O OH
Chloride to a 1˚Alcohol 1. LiAlH4, EtOH
Cl 2. H O+ H
3
Reduction of an Acyl O O
LiAlH[OC(CH ) ]
Chloride to an Aldehyde 3 33
Cl H
Reduction of an Amide to an
O
1. LiAlH , EtOH
Amine 4
NH2 2. H3O+ NH2
Hoffmann Rearrangement O
1. Br
2
NH
NH 2
2 2. NaOH
Reduction of a Nitrile to an
1. LiAlH , EtOH
4
Amine N NH
2
2. H O+
3

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Alcohol Reactions

Conversion of a 2˚/3˚Alcohol to an alkyl OH X
HX
halide via S 1
N

OH X
HX

Conversion of a 1˚/2˚Alcohol to an alkyl OH Br
PBr
3
bromide via S 2
N H H

OH Br
PBr
3

Conversion of a 1˚/2˚Alcohol to an alkyl OH Cl
SOCl
2
chloride via S 2
N H Pyridine H

OH Cl
SOCl
2

Pyridine

Conversion of an Alcohol to a Tosylate Ester
OH OTs
TsCl
(OTs) Retention of Stereochemistry
Acid-catalyzed Dehydration of an Alcohol
OH
H O+
3 Zaitsev’s Rule

Chromic Acid Oxidation of a 1o Alcohol to a
Na Cr O
Carboxylic Acid 2 2 7
or
OH O
CrO
3
H H2SO4 OH
Chromic Acid Oxidation of a 2o Alcohol to a
Ketone Na2Cr2O7
or
OH O
CrO
3

H SO
2 4
Chromic Acid Oxidation of an Aldehyde to a
Na Cr O
Carboxylic Acid 2 2 7
or
O CrO O
3

H H2SO4 OH

PCC or DMP Oxidation of a 1o Alcohol to an
OH O
PCC or DMP
Aldehyde
H H
PCC or DMP Oxidation of a 2o Alcohol to a
OH O
PCC or DMP
Ketone

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Ether and Epoxide Reactions

Williamson Ether Synthesis via S 2
N
NaH, Na, or K Cl
OH O O
Acid-catalyzed Cleavage of Ethers when
HBr
one side is 2˚/3˚ (Nucleophile attacks O Br HO
more substituted side via SN1)

HBr
O Br HO
Acid-catalyzed Cleavage of Ethers
when neither side is 2˚/3˚ (Nucleophile O HBr OH
attacks less substituted side via S 2) Br
N
Acid-catalyzed Ring Opening of Epoxides
(Nucleophile attacks more substituted Cl
O HCl
side) OH
Base-catalyzed Ring Opening of OH
O OCH
Epoxides (Nucleophile attacks less 3 O
HOCH
substituted side) 3

Aldehyde and Ketone Reactions

Nucleophilic Addition to an Aldehyde or O
Nucleophile HO Nucleophile
Ketone
C or H H O+ C or H
3
Addition of water to an Aldehyde or O HO OH
H O
Ketone forming a Hydrate 2
C or H C or H
H O+ or -OH
3
Base-catalyzed addition of an Alcohol O HO O
O
to an Aldehyde or Ketone forming a
C or H C or H
Hemi-acetal/Hemi-ketal HO
Acid-catalyzed addition of an Alcohol O H O+ O O
3
to an Aldehyde or Ketone forming a
C or H C or H
Acetal/Ketal (Protecting Group, reversed HO
by H O+)
3
H3O+
Acid-catalyzed addition of Ethylene OH
O
HO O O
Glycol to an Aldehyde or Ketone forming
a Acetal/Ketal (Protecting Group, C or H H O+ C or H
reversed by H O+) 3
3

H O+
3

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Addition of a 1˚ Amine to an Aldehyde or O N
H N
2
Ketone forming an Imine (Reversed by
H O+) C or H H3O+ C or H
3

H O+
3

Addition of a 2˚ Amine to an Aldehyde or O N N
Ketone forming an Enamine (Reversed H
by H3O+) C or H H3O+ C or H

H O+
3

Double bond forms on more substituted end for Ketones
Addition of a Wittig Reagent to an
O PPh
3
Aldehyde or Ketone
C or H C or H

Michael Addition to an α, β Unsaturated O O
Ketone O O

or -CN, HNR ,
2
HSR etc.
O
O
Michael Addition to an α, β Unsaturated
O O
Ketone with a Gilman Reagent (CH CH CH ) CuLi
3 2 2 2
(Organocuprates)

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