Reaction Guide

Notes: the organization and contents of this page will undoubtedly change, this is just a start.

 

Reactions of Alkanes

1. Free Radical Chlorination of Alkanes

2. Free Radical Bromination of Alkanes

3. Allylic bromination of alkanes using NBS

Reactions of Alkenes

1. Addition of HBr to Alkenes to give Alkyl Bromides

2. Hydroboration of Alkenes With BH3 to give Alcohols

3. Addition of HCl to Alkenes to give Alkyl Chlorides

4. Addition of HI to Alkenes to give Alkyl Iodides

5. Addition of aqueous acid (“H3O+”) to alkenes to give alcohols

6. Bromination of alkenes to give dibromides using Br2

7. Formation of epoxides from alkenes using m-CPBA.

8. Hydrogenation of alkenes to alkanes using Pd/C and hydrogen

9. Dihydroxylation of alkenes with OsO4 to give vicinal diols

10. Cyclopropanation of alkenes with dichlorocarbenes to give dichlorocyclopropanes

11. Chlorination of alkenes to give dichlorides using Cl2

12. Oxymercuration of alkenes to give alcohols using Hg(OAc)2 and water.

13. Iodination of alkenes to give diiodides using I2

14. Formation of bromohydrins from alkenes using water and Br2 (or also NBS)

15. Formation of chlorohydrins from alkenes using water and Cl2

16. Formation of cyclopropanes from alkenes using methylene carbene (:CH2)

17. Cleavage of alkenes to give ketones/aldehydes using ozone (reductive workup)

18. Cleavage of alkenes to give ketones/carboxylic acids using ozone (oxidative workup)

19. Cleavage of alkenes to give ketones/carboxylic acids using KMnO4

20. Addition of alcohols to alkenes through oxymercuration to form ethers.

21. Dihydroxylation of alkenes to give vicinal diols using cold, dilute KMnO4

22. Additions accompanied by rearrangement: 1,2-Hydrogen shifts

23. Additions accompanied by rearrangement: 1,2-alkyl shifts

Reactions of Alkynes

1. Deprotonation of acetylenes to give acetylide ions

2. SN2 of acetylide ions with alkyl halides

3. Hydroboration of alkynes to give aldehydes

4. Partial reduction of alkynes with Lindlar’s catalyst to give cis-alkenes

5. Partial reduction of alkynes with Na/NH3 to give trans-alkenes

6. Oxymercuration of alkynes with water and mercury to give ketones

7. Addition of hydrochloric acid (HCl) to alkynes (once) to give alkenyl chlorides

8. Addition of hydrochloric acid to alkynes (twice!) to give geminal dichlorides.

9. Addition of hydrobromic acid (HBr) to alkynes (once) to give alkenyl bromides

10. Addition of hydrobromic acid (HBr) to alkynes (twice) to give geminal dibromides.

11. Addition of hydroiodic acid (HI) to alkynes (once) to give alkenyl iodides

12. Addition of hydroiodic acid (HI) to alkynes (twice) to give geminal diiodides

13. Catalytic hydrogenation of alkynes with Pd/C to give alkanes

14. Oxidative cleavage of alkynes with ozone to give carboxylic acids

15. Oxidative cleavage of alkynes with KMnO4 to give carboxylic acids

16. Formation of alkynes from elimination of dibromides using NaNH2.

 

 

Reactions of Epoxides

1. Opening of epoxides under acidic conditions to give trans diols.

2. Opening of epoxides under acidic conditions with nucleophiles.

3. Base-catalyzed opening of epoxides with nucleophiles (SN2)

4. Formation of epoxides from halohydrins

Substitution Reactions

1. SN2 reaction of cyanide ion with alkyl halides to give nitriles

2. SN2 reaction of acetylide ions with alkyl halides

3. SN2 reaction of azide ion with alkyl halides to give alkyl azides

4. SN2 reaction of hydrosulfide ion to alkyl halides to give thiols

5. SN2 reaction between alkoxides and alkyl halides to give ethers (Williamson synthesis)

6. SN2 reaction between thiolates and alkyl halides to give thioethers (sulfides)

7. SN2 reaction between amines and alkyl halides to give ammonium salts.

8. SN2 reaction between carboxylates and alkyl halides to give esters

9. SN2 reaction between hydroxide ions and alkyl halides to give alcohols

10. SN2 reaction between water and alkyl halides to give alcohols

11. SN2 reaction between alkyl halides and Gilman reagents (organocuprates) to give alkanes.

12. SN2 reaction to cleave ethers

13. SN1 reaction between alkyl halides and water to give alcohols. 

13. SN1 reaction between alkyl halides and alcohols to give ethers

14. SN1 reaction cleaving ethers under acidic conditions.

15. SN1 reaction converting alcohols to alkyl chlorides through addition of HCl

16. SN1 reaction converting alcohols to alkyl bromides through addition of HBr

17. SN1 reaction converting alcohols to alkyl iodides through addition of HI

18. Substitution with accompanying rearrangement: 1,2-alkyl shifts

 

Elimination Reactions

1. Formation of alkenes from alkyl halides with strong base (E2 reaction).

2. Conversion of alcohols to alkenes using POCl3

3. Elimination of water from alcohols with acid to form alkenes. 

4. Elimination of alkyl halides to form alkenes (E1)

5. Elimination with rearrangement: 1,2-alkyl shifts

6. The Hoffmann elimination of alkylammonium salts to alkenes

 

 

Reactions of Alkyl Halides

1. Formation of Grignard reagents from alkyl halides.

2. Formation of Grignard reagents from alkenyl halides.

3. Protonation of Grignards with acid to give alkanes.

4. Formation of Gilman reagents from alkyl halides.

5. Formation of organolithium reagents from alkyl halides

Reactions of Alcohols and Thiols

1. Formation of ethers from alcohols, base and alkyl halides (Williamson ether synthesis)

2. Protection of alcohols as silyl ethers.

3. Deprotonation of alcohols to give alkoxides.

4. Protonation of alcohols to give oxonium ions.

5. Conversion of alcohols into tosylates using TsCl

6. Conversion of alcohols to alkyl chlorides using SOCl2

7. Conversion of alcohols to alkyl bromides using PBr3

8. Oxidation of secondary alcohols to ketones using PCC (and related reagents)

9. Oxidation of primary alcohols to aldehydes using pyridinium chlorochromate (PCC)

10. Oxidation of primary alcohols to carboxylic acids using chromic acid (H2CrO4) or potassium permanganate (KMnO4)

11. Formation of disulfides from thiols.

Reactions of Dienes

1. Diels Alder reaction

2. Polymerization of dienes

Reactions of Aromatics (Arenes)

1. Nitration of aromatics to give nitroarenes

2. Reduction of aromatic ketones to alkanes with Pd/H2

3. Bromination of alkylbenzenes to form benzylic bromides

4. Oxidation of aromatic alkanes with KMnO4 to give carboxylic acids.

5. Reduction of nitroarenes to give aromatic amines

6. Friedel-Crafts acylation of arenes

7. Friedel-Crafts alkylation of arenes

8. Sulfonylation of arenes to give sulfonic acids

9. Chlorination of arenes to give chloroarenes

10. Bromination of arenes to give bromoarenes

11. Iodination of arenes to give iodoarenes

Reactions of Aldehydes and Ketones

1. Formation of acetals from aldehydes and ketones

2. Hydrolysis of acetals to give aldehydes and ketones

2. Addition of Grignard reagents to ketones to give tertiary alcohols

3. Addition of Grignard reagents to aldehydes to give secondary alcohols.

4. Addition of Grignard reagents to formaldehyde to give primary alcohols

5. Addition of sodium borohydride (NaBH4) to aldehydes to give primary alcohols

6. Addition of sodium borohydride (NaBH4) to ketones to give secondary alcohols

7. Addition of lithium aluminum hydride (LiAlH4) to aldehydes to give primary alcohols

8. Addition of lithium aluminum hydride (LiAlH4) to ketones to give secondary alcohols

9. Addition of primary amines to aldehydes and ketones to give imines.

10. Reduction of ketones and aldehydes to alkanes using hydrazine (Wolff Kishner reaction)

11. Addition of phosphorus ylides to aldehydes and ketones to give alkenes (Wittig Reaction)

12. Addition of enolates to aldehydes and ketones to give aldols (Aldol Reaction)

13. Addition of secondary amines to aldehydes and ketones to give enamines

14. Addition of hydrogen cyanide to aldehydes and ketones to give cyanohydrins

15. Oxidation of aldehydes with Ag2O to form carboxylic acids (Tollens reaction)

16. Oxidation of aldehydes with Cr to form carboxylic acids

17. Hydrolysis of imines to obtain aldehydes and ketones

18. Keto-enol tautomerism

19. The Clemmensen reduction of ketones/aldehydes to alkanes

20. Formation of hydrates from aldehydes and ketones

21. The Haloform reaction

22. Formation of enolates from aldehydes/ketones and base

23. Alkylation of enolates

24. Formation of thioacetals from aldehydes and ketones

Reactions of α,β-unsaturated carbonyl compounds (“enones”)

1. 1,4-addition of enolates to enones (the Michael reaction)

2.  1,4-addition of organocuprates to enones (Gilman reagents)

3. 1,4-addition of other nucleophiles to enones

Reactions of carboxylic acids

1. Formation of carboxylate ions from carboxylic acids using base

2. Formation of carboxylic acids from Grignard reagents and CO2

3. Conversion of carboxylic acids to acid chlorides using SOCl2

4. Reduction of carboxylic acids to primary alcohols using LiAlH4

5. Fischer esterification: conversion of carboxylic acids to esters using alcohols and acid catalyst

6. Decarboxylation of β-keto carboxylic acids

Reactions of esters

1. Reduction of esters to primary alcohols using DIBAL

2. Addition of Grignard reagents to esters to give tertiary alcohols

3. Reduction of esters to primary alcohols using LiAlH4

4. Hydrolysis of esters to carboxylic acids using aqueous acid

5. Transesterification of esters using alkoxides

6. The Claisen and Dieckmann condensations of enolates with esters

Reactions of Acid Halides

1. Conversion of acid halides to esters using alcohols

2. Conversion of acid halides to ketones using organocuprates (Gilman reagents)

3. Conversion of acid halides to anhydrides using carboxylates

4. Conversion of acid halides to amides using amines

5. Reduction of acid halides to aldehydes using LiAlH(O-tBu)3

 

Reactions of Amides

1. Dehydration of amides to nitriles using P2O5

Reactions of Nitriles

1. Addition of Grignard reagents to nitriles to give ketones (after hydrolysis)

2. Reduction of nitriles to primary amines using LiAlH4

3. Hydrolysis of nitriles to give carboxylic acids using aqueous acid

 

Miscellaneous

1. Reduction of thioketals to alkanes using Raney Nickel

2. Alkylation of enamines

3. Oxidative cleavage of 1,2-diols (vicinal diols) to give carbonyl compounds