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DAT Organic Chemistry Reaction Summary Sheet Alkene Reactions

Hydrohalogenation

Hydrohalogenation (with Rearrangement)

Halogenation

Hydrobromination with Peroxide

Hydration

Hydration (with Rearrangement)

Bromination in H2O

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 Br2

Hydration of an Internal Alkyne

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

SN2 Addition of an Acetylide Ion to an Alkyl Halide

SN2 Addition of an Acetylide Ion to a Ketone

SN2 Addition of an Acetylide Ion to an Epoxide

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Free Radical Halogenation Reactions Free Radical Halogenation using Bromine (more selective)

Free Radical Halogenation using Chlorine (less selective)

Allylic/Benzylic Bromination

Br2

hv or Δ

Br

NBShv or Δor ROOR

Br

NBShv or Δor ROOR

Br

Br

Cl2hv or Δ

Cl

Cl

Cl

Cl

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Grignard Reactions

Addition of a Grignard Reagent to an Aldehyde

2˚Alcohol

Addition of a Grignard Reagent to a Ketone

3˚Alcohol

Addition of a Grignard Reagent to an Ester

3˚Alcohol

Addition of a Grignard Reagent to an Acyl Chloride

3˚Alcohol

Addition of a Grignard Reagent to CO2

Carboxylic Acid

Addition of a Grignard Reagent to an Epoxide (adds to the less subs. side forming the less subs. alcohol)

2˚Alcohol (less subs. alcohol)

Addition of a Grignard Reagent to a Carboxylic Acid

Carboxylate

Addition of a Grignard Reagent to an Amide

Deprotonated Amide

Addition of a Grignard Reagent to a Nitrile

Ketone

MgXOH

O1. , Ether

2. H3O+ O

O

MgX

MgXNH2

O1. , Ether

2. H3O+ NH

O

MgX

1. CO2, Ether

2. H3O+MgX

O

OH

MgX1. , Ether

2. H3O+

OHO

MgX1. , Ether

2. H3O+

O HO

MgXO

O 1. 2 eq. , Ether

2. H3O+

HO

MgXCl

O 1. 2 eq. , Ether

2. H3O+

HO

MgXO1. , Ether

2. H3O+N

MgX1. , Ether

2. H3O+H

O OH

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Electrophilic Aromatic Substitution (EAS) Reactions

Friedel-Crafts Alkylation (Rearrangement Possible)

Friedel-Crafts Acylation (No Rearrangement Possible)

Bromination

Chlorination

Nitration

Sulfonation

Formylation

EAS with an ortho/para-directing group on Benzene

EAS with a meta-directing group on Benzene

ClAlCl3

ClAlCl3

FeCl3

ClCl2

O/P

Substituent

O/P O/PSubstituent

SubstituentM

Substituent

M

Substituent

ClAlCl3

OO

H2SO4

NO2HNO3

AlCl3

CO, HCl

O

H

FeBr3

BrBr2

H2SO4

SO3SO3H

H2SO4/Δ

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Friedel-Crafts Alkylation/Acylation with a meta-directing group or an amine on Benzene

Benzene Side-Chain Reactions

Side-Chain Oxidation of Benzene to form Benzoic Acid

Requires free Hydrogen at Benzylic position

Wolff-Kishner Reduction

Clemmensen Reduction

Zn(Hg), HCl, HeatO

Zn(Hg), HCl, Heat NH2NO2

H2NNH2 or N2H4, -OH, HeatO

M

AlCl3

Cl R

O

R Cl or No Reaction

NH2/NRH/NR2

AlCl3

Cl R

O

R Cl or No Reaction

1. KMnO4, -OH2. H3O+, Heat

O

OH

Na2Cr2O7

H2SO4

orR R

R

or or

1. KMnO4, -OH2. H3O+, Heat

Na2Cr2O7

H2SO4

orNo Reaction

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Hydride Reduction Reactions

Reduction of an Aldehyde to a 1˚Alcohol

Reduction of a Ketone to a 2˚Alcohol

Reduction of a Carboxylic Acid to a 1˚Alcohol

Reduction of an Ester to a 1˚Alcohol

Reduction of an Ester to an Aldehyde

Reduction of an Acyl Chloride to a 1˚Alcohol

Reduction of an Acyl Chloride to an Aldehyde

Reduction of an Amide to an Amine

Hoffmann Rearrangement

Reduction of a Nitrile to an Amine

H

O 1. NaBH4, EtOH

2. H3O+ H

OH

H

O 1. LiAlH4, EtOH

2. H3O+ H

OH

O 1. NaBH4, EtOH

2. H3O+

OH

O 1. LiAlH4, EtOH

2. H3O+

OH

OH

O 1. LiAlH4, EtOH

2. H3O+ H

OH

Cl

O 1. LiAlH4, EtOH

2. H3O+ H

OH

1. LiAlH4, EtOH

2. H3O+NH2N

O

O 1. LiAlH4, EtOH

2. H3O+ H

OH

OH

LiAlH[OC(CH3)3]3O

Cl

O

H

O

O 1. DIBAL-H, -78°C

2. H2O H

O

NH2

O 1. LiAlH4, EtOH

2. H3O+ NH2

NH2

O 1. Br2

2. NaOHNH2

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Alcohol Reactions

Conversion of a 2˚/3˚Alcohol to an alkyl halide via SN1

Conversion of a 1˚/2˚Alcohol to an alkyl bromide via SN2

Conversion of a 1˚/2˚Alcohol to an alkyl chloride via SN2

Conversion of an Alcohol to a Tosylate Ester (OTs)

Retention of Stereochemistry

Acid-catalyzed Dehydration of an Alcohol

Zaitsev’s Rule

Chromic Acid Oxidation of a 1o Alcohol to a Carboxylic Acid

Chromic Acid Oxidation of a 2o Alcohol to a Ketone

Chromic Acid Oxidation of an Aldehyde to a Carboxylic Acid

PCC or DMP Oxidation of a 1o Alcohol to an Aldehyde

PCC or DMP Oxidation of a 2o Alcohol to a Ketone

OH PBr3 Br

OH HX X

OH HX X

OH SOCl2Cl

Pyridine

H

OH PBr3H

Br

H

OH SOCl2H

Cl

Pyridine

OH H3O+

H

OH

OH

O

H2SO4

Na2Cr2O7orCrO3

OH O

H2SO4

Na2Cr2O7orCrO3

H

O

OH

O

H2SO4

Na2Cr2O7orCrO3

OH TsCl OTs

H

OH

H

OPCC or DMP

OH OPCC or DMP

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Ether and Epoxide Reactions

Williamson Ether Synthesis via SN2

Acid-catalyzed Cleavage of Ethers when one side is 2˚/3˚ (Nucleophile attacks more substituted side via SN1)

Acid-catalyzed Cleavage of Ethers when neither side is 2˚/3˚ (Nucleophile attacks less substituted side via SN2)

Acid-catalyzed Ring Opening of Epoxides (Nucleophile attacks more substituted side)

Base-catalyzed Ring Opening of Epoxides (Nucleophile attacks less substituted side)

Aldehyde and Ketone Reactions

Nucleophilic Addition to an Aldehyde or Ketone

Addition of water to an Aldehyde or Ketone forming a Hydrate

Base-catalyzed addition of an Alcohol to an Aldehyde or Ketone forming a Hemi-acetal/Hemi-ketal

Acid-catalyzed addition of an Alcohol to an Aldehyde or Ketone forming a Acetal/Ketal (Protecting Group, reversed by H3O+)

Acid-catalyzed addition of Ethylene Glycol to an Aldehyde or Ketone forming a Acetal/Ketal (Protecting Group, reversed by H3O+)

OHBr

Br HO

O HClOH

Cl

OHBr

Br HO

HBrO OHBr

C or H

O

C or H

HO OO

HO

C or H

O

C or H

HONucleophileH3O+

Nucleophile

C or H

O

H3O+ or -OH

H2OC or H

HO OH

C or H

O

C or H

O O

H3O+

H3O+

HOOH

C or H

O

C or H

O O

HO

H3O+

H3O+

OHNaH, Na, or K Cl

O O

O OCH3HOCH3

OOH

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Addition of a 1˚ Amine to an Aldehyde or Ketone forming an Imine (Reversed by H3O+)

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

Double bond forms on more substituted end for Ketones

Addition of a Wittig Reagent to an Aldehyde or Ketone

Michael Addition to an α, β Unsaturated Ketone

Michael Addition to an α, β Unsaturated Ketone with a Gilman Reagent (Organocuprates)

C or H

O

C or H

N

H3O+

H2N

H3O+

C or H

O

H3O+

NH

H3O+

C or H

N

C or H

O

C or H

PPh3

O O

O O

or -CN, HNR2, HSR etc.

O

O

O O(CH3CH2CH2)2CuLi

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Alpha Addition/Substitution Reactions

Self Aldol Condensation and Enone Formation

Mixed Aldol Condensation and Enone Formation

Self Claisen Condensation

Mixed Claisen Condensation

Dieckmann Cyclization (Intramolecular Claisen Condensation)

Acetoacetic Ester Synthesis

Malonic Ester Synthesis

H

O-OH, H2O

O OH H3O+, NaOH

Δ

O O

O O -OH, H2OO

HO

H3O+, NaOH

Δ

O

O

O

2O1.

2. H3O+

O O

O

O

OO1.

2. H3O+

O O O

O

O OO1.

2. ClO3.

4. Cl5. H3O+, Δ

O

CO2 HO

O O

O OO1.

2. ClO3.

4. Cl5. H3O+, Δ

HO

O

CO2 2 HO

H

O

2-OH, H2O

H

O OH H3O+, NaOH

Δ H

O

O

2-OH, H2O O OH H3O+, NaOH

Δ

O

O1.

2. H3O+ O

O

O O

O O O

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DAT Organic Chemistry Reaction Details Sheet Rearrangements Details When carbocations form, H’s and CH3’s can do a 1,2-shift to generate a more stable carbocation intermediate 1,2-Hydride Shift

1,2-Methyl Shift

Alkene Reactions Details Hydrohalogenation

What’s added: H+ and Br- Regioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible (methyl and hydride shifts) Mechanism:

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Halogenation

What’s added: 2 Br atoms Regioselectivity: N/A Stereoselectivity: Anti Intermediate: Bromonium ion Rearrangement: Not possible Mechanism:

Hydrobromination with Peroxide

What’s added: H× and Br× Regioselectivity: Anti-Markovnikov Stereoselectivity: N/A Intermediate: Radical Rearrangement: Not possible Mechanism:

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Hydration

What’s added: H+ and OH- Regioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible (methyl and hydride shifts) Mechanism:

Bromination in H2O

What’s added: Br+ and OH- Regioselectivity: Markovnikov Stereoselectivity: Anti Intermediate: Bromonium ion Rearrangement: Not possible Mechanism:

Oxymercuration-Demurcuration

What’s added: H+ and OH- Regioselectivity: Markovnikov Stereoselectivity: Anti Intermediate: Mercurinium ion bridge Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction

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Hydroboration-Oxidation

What’s added: H+ and OH-

Regioselectivity: Anti-Markovnikov Stereoselectivity: Syn Intermediate: Hydroxy-boranes Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Syn-Hydroxylation

or What’s added: 2 OH groups Regioselectivity: N/A Stereoselectivity: Syn Intermediate: N/A Rearrangement: Not possible Mechanism:

Anti-Hydroxylation

What’s added: 2 OH groups Regioselectivity: N/A Stereoselectivity: Anti Intermediate: N/A Rearrangement: Not possible Mechanism: Epoxidation then reaction with aqueous acid or base. In acidic conditions, the H2O attacks the more highly-substituted C:

In basic conditions, H2O attacks the less highly-substituted C:

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Addition of an Alcohol

What’s added: H+ and OR-

Regioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible Mechanism:

Bromination in Alcohol

What’s added: Br+ and OR- Regioselectivity: Markovnikov Stereoselectivity: Anti Intermediate: Bromonium ion Rearrangement: Not possible Mechanism:

Alkoxymercuration-Demurcuration

What’s added: H+ and OCH3

-

Regioselectivity: Markovnikov

Stereoselectivity: Anti Intermediate: Mercurinium ion Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction

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Epoxidation

What’s added: O Regioselectivity: N/A Stereoselectivity: Syn Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Do know that a commonly-used peroxy acid is m-CPBA:

Catalytic Hydrogenation

What’s added: 2 H atoms Regioselectivity: N/A Stereoselectivity: Syn Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Ozonolysis in Reducing Conditions

What’s added: 2 O atoms Regioselectivity: N/A Stereoselectivity: N/A Intermediate: N/A Rearrangement: N/A Mechanism: You do not need to know the mechanism for this reaction Do know that the C=C double bond gets “sawed” in half, and an O atom is placed on the end of each new piece. Note: (CH3)2S is often abbreviated “DMS” for dimethyl sulfide.

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Ozonolysis in Oxidizing Conditions

What’s added: Multiple O atoms Regioselectivity: N/A Stereoselectivity: N/A Intermediate: N/A Rearrangement: N/A Mechanism: You do not need to know the mechanism for this reaction Do know that the C=C double bond gets “sawed” in half, and an O atom is placed on the end of each new piece. Then, one of the H’s attached to the alkene C’s gets replaced by an –OH group.

Oxidative Cleavage

What’s added: Multiple O atoms Regioselectivity: N/A Stereoselectivity: N/A Intermediate: N/A Rearrangement: N/A Mechanism: You do not need to know the mechanism for this reaction Do know that the C=C double bond gets “sawed” in half, and an O atom is placed on the end of each new piece. Then, one of the H’s attached to the alkene C’s gets replaced by an –OH group.

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Alkynes Reactions Details Catalytic Hydrogenation

What’s added: 4 H atoms Regioselectivity: N/A Stereoselectivity: Anti Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Reduction to Cis-Alkene

What’s added: 2 H atoms Regioselectivity: N/A Stereoselectivity: Syn Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Reduction to Trans-Alkene

What’s added: 2 H atoms Regioselectivity: N/A Stereoselectivity: N/A Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Hydrohalogenation with HBr (Terminal Alkyne)

What’s added: 1 H atom and 1 halogen atom (can be F, Br, I, or Cl) per equivalent of HX Regioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible Mechanism: The halogen goes to the C with fewer H’s

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Hydrohalogenation with HBr (Internal Alkyne)

What’s added: 1 H atom and 1 halogen atom (can be Cl or Br) per equivalent of HX Regioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: Carbocation Rearrangement: Possible Mechanism: Same as for terminal alkynes, but yields a mixture of two products because both intermediates are equally stable Halogenation with Br2

What’s added: 2 halogen atoms (can be F, Br, I, or Cl) Regioselectivity: N/A Stereoselectivity: Anti Intermediate: Bromonium ion Rearrangement: Not possible Mechanism:

Hydration of an Internal Alkyne

What’s added: 1 O atoms Regioselectivity: N/A Stereoselectivity: N/A Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Do know that this reaction produces enols, which then tautomerize to form ketones.

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Hydration of a Terminal Alkyne (Markovnikov)

What’s added: 1 O atom Regioselectivity: Markovnikov Stereoselectivity: N/A Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Do know that this reaction produces Markovnikov enols, which then tautomerize to form ketones.

Hydration of a Terminal Alkyne (Anti-Markovnikov)

What’s added: 1 O atom Regioselectivity: Anti-Markovnikov Stereoselectivity: N/A Intermediate: N/A Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Do know that this reaction produces Anti-Markovnikov enols, which then tautomerize to form aldehydes.

SN2 Addition of an Acetylide Ion to an Alkyl Halide

What’s added: additional C atoms (-R of alkyl halide) Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Acetylide Ion Rearrangement: Not possible Mechanism: Deprotonation, then alkylation via SN2 reaction

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SN2 Addition of an Acetylide Ion to a Ketone

What’s added: 2 additional alkyl groups and 1 –OH group Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Acetylide Ion Rearrangement: Not possible Mechanism: Deprotonation, then addition of a ketone via SN2 reaction

SN2 Addition of an Acetylide Ion to an Epoxide

What’s added: 2-hydroxylpropane (from epoxide) Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Acetylide Ion Rearrangement: Not possible Mechanism: Deprotonation, then addition of 2-hydroxyl propane via SN2 reaction

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Free Radical Halogenation Reaction Details Free Radical Halogenation using Bromine (more selective)

What’s added: 1 Br atom Regioselectivity: Most Substituted Product Stereoselectivity: N/A Intermediate: Radical Intermediate Rearrangement: Not possible Mechanism: Formation of bromine and carbon radicals and them joining to create an alkyl halide 1. Initiation

2. Propagation

3. Termination

Br Br hv or ΔBr Br

Br Br Br Br

Br2

hv or Δ

Br

H

BrHBr

Br BrBr

Br

alkyl halide

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Free Radical Halogenation using Chlorine (less selective)

What’s added: 1 Cl atom Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Radical Intermediate Rearrangement: Not possible Mechanism: Formation of chlorine and carbon radicals and them joining to create alkyl halides 1. Initiation

2. Propagation

3. Termination

Cl2hv or Δ

Cl

Cl

Cl

Cl

Cl Cl hv or ΔCl Cl

ClHCl

Cl Cl Cl

alkyl halide

H

Cl

Cl HCl

Cl ClCl

alkyl halide

Cl

H

Cl Cl Cl Cl

H

ClHCl

Cl ClCl

Cl

alkyl halide

Cl HCl

Cl ClCl

alkyl halideCl

H

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Allylic/Benzylic Bromination

What’s added: 1 Br atom Regioselectivity: N/A Stereoselectivity: N/A Intermediate: Allylic Radical Intermediate Rearrangement: Not possible Mechanism: You do not need to know the mechanism for this reaction Note: this reaction results in the formation of allylic radical intermediates which resonate and thus allow for the formation of multiple products.

NBShv or Δor ROOR

Br

NBShv or Δor ROOR

Br

Br

NBShv or Δor ROOR

BrBr

allylic radical intermediatesBr

Br