Handout: Organic Chemistry Reactions Reactions Organized by Compound Families Alkanes 1. Combustion 2. Halogenation Alkenes and Alkynes 1. Additions: hydrogenation, halogenation, hydrohalogenation, hydration 2. Polymerization Aromatic Compounds Substitutions: nitration, halogenation, sulfonation Alcohols 1. Elimination: dehydration 2. Oxidations Thiols Oxidation Amines Acid-Base reactions Aldehydes and Ketones 1. Addition: Acetal/hemiacetal formation by alcohol addition (Reverse rxn: Acetal hydrolysis with acid) 2. Oxidation and Reduction for aldehydes (*Ketones go through reduction only) Carboxylic Acids 1. Substitutions: esterification, amidation (Reverse rxns: ester hydrolysis with acid or base, amide hydrolysis with acid or base) 2. Acid-base reactions Phosphoric acid and Phosphates Phosphoric acid: Esterification with alcohol Phosphates: Phosphorylation H. Kim for Chem 30B 1 Reactions Organized by Reaction Type Family Reaction Example 1. ADDITION Alkenes and Hydrogenation H H Pd catalyst H H C C + H2 H C C H alkynes H H H H H H Pd catalyst H C C H + 2 H2 H C C H H H Halogenation H H Cl Cl C C + Cl2 (or Br2) H C C H H H H H H Cl Hydro- H H Markonikov’s Rule halogenation C C + HCl (or HBr) H C C H applies: H adds to C H CH3 H CH3 with more Hs already. H OH Hydration H H H+ catalyst C C + H2O H C C H Markonikov’s Rule H CH3 H CH3 applies. Aldehydes Addition of O OH H+ catalyst H3C C H(R) + CH3CH2OH and ketones alcohol to get H3C C H(R) + CH3CH2OH hemiacetals or O CH2CH3 acetals hemiacetal O CH2CH3 H+ catalyst H3C C H(R) + H2O O CH2CH3 acetal 2. SUBSTITUTION NO2 Aromatic Nitration H2SO4 catalyst compounds + HNO3 Halogenation FeCl3 (or FeBr3) catalyst Cl + Cl2 (or Br2) SO3H Sulfonation H2SO4 catalyst + SO3 Carboxylic Esterification O H+ catalyst O + CH CH OH H C C OCH CH + H O acids with alcohol H3C C OH 3 2 3 2 3 2 O Amidation with O heat + CH NH H C C NHCH amine H3C C OH 3 2 3 3 + H2O Phosphoric Phosphoric acid: O O + CH OH + H O acid and Esterification HO P OH 3 HO P OCH3 2 Phosphates with alcohol OH OH Phosphates: O O O O O O - Phosphorylation Adenosine O P O P O P O + ROH Adenosine O P O P O- + RO P O- + Energy - - O O O- O- O- O- H. Kim for Chem 30B 2 3. ELIMINATION Alcohols Dehydration H OH H H2SO4 catalyst H CH3 C C + H C C C + H O H3C C C CH3 3 CH2 2 H3C H H H H H major minor Zaitsev’s Rule applies: More highly substituted alkene is major product. 4. OXIDATION/REDUCTION OH Alcohols Oxidation [O] O [O] O 1º R C H R C H R C OH H aldehyde carboxylic acid OH [O] O 2º R C H R C R R Ketone OH [O] 3º R C H No Rxn R Thiols Oxidation [H] [O] Reverse rxn: R-S-S-R 2 RSH 2 RSH R-S-S-R Aldehydes Oxidation O [O] O R C H R C OH aldehyde carboxylic acid Reduction O [H] OH (also addition) R C H R C H H Ketones Reduction O [H] OH (also addition) R C CH3 R C CH3 H 5. ACID-BASE CH CH NH + H O + – Amines Rxn with water 3 2 2 2 CH3CH2NH3 + OH (Basic) CH CH NH + H O+ + Neutralization 3 2 2 3 CH3CH2NH3 + H2O CH CH NH + HCl + – with strong acid 3 2 2 CH3CH2NH3 Cl to get ammonium Reverse rxn: ammonium + – CH3CH2NH3 Cl + NaOH CH3CH2NH2 + NaCl + H2O ion or salt ion or salt + base Carboxylic Rxn with water O O acids H3C C OH + H2O – + H3C C O + H3O (Acidic) O Neutralization O with strong base H3C C OH (aq) + NaOH (aq) – + H3C C O Na (aq) + H2O to get carboxylic acid salt Phenols Neutralization OH O–Na+ + NaOH (very weakly with strong base + H2O acidic) to get salt H. Kim for Chem 30B 3 Other Reaction Types Family Reaction Example RADICAL REACTIONS Alkanes Combustion (Also heat CH (g) + 2O (g) CO + 2H O + Heat oxidation/reduction 4 2 2 2 reaction) Halogenation light or heat Cl CH CH CH + Cl 3 2 3 2 HCl + CH3CH2CH2Cl + CH3CHCH3 Cl Cl Cl Cl Cl Cl + + CH CCH + CHCH CH + CH CH CH 3 3 2 3 2 2 2 CH2CHCH3 Cl Cl Mixed products Alkenes Polymerization initiator CH3 CH3 CH CH CH H2 H2 3 2 ( C C C C ) H H HYDROLYSIS O O Esters Acid hydrolysis to get H+ catalyst + CH OH (Reverse rxns of carboxylic acid and R C O CH3 + H2O R C OH 3 carboxylic acid alcohol O esterification) Saponification: Base O H2O hydrolysis to get R C O CH3 + NaOH (aq) – + R C O Na + CH3OH carboxylic acid salt and alcohol Amides Acid hydrolysis to get O O H H+ catalyst + H O (Reverse rxns of amine H3C C N CH3 2 H C C OH + CH3NH2 3 carboxylic acid Base hydrolysis to get O O amidation) H H2O amine H3C C N CH3 + NaOH (aq) + CH3NH2 H3C C OH O Acetals Acid hydrolysis to get H H+ catalyst H3C C O CH2CH3 + H O + 2 CH CH OH (Reverse reaction aldehydes of ketones 2 H3C C OH 3 2 of acetal formation (reverse of acetal O CH2CH3 from formation) aldehydes/ketones) *Note that organic chemistry reactions can be classified in several different ways. H. Kim for Chem 30B 4 .