TYPES OF CARBONYL COMPOUNDS� General Name Name General Name Name formula suffix formula suffix O O -al Ester -oate Aldehyde C C R' R H R O O� O Ketone C -one Lactone C � O R R' (cyclic ester) Carboxylic O -oic C H acid O acid� R O Amide C R' -amide Acid O R N X=halogen -oyl R" C halide halide O R X Lactam� C R' Acid O O� -oic (cyclic amide) N anhydride anhydride C C R O R Detergents and "fatty acids" - amphiphilic molecules CO2H CO2 omega-3-fatty hydrophobic hydrophilic acid H2O H2O Phospholipids - Fatty acid esters H2O of glycerol grease OH glycerol H2O OH a triol H2O OH H2O MICELLE O O O O O LIPID BILAYER O PO O NH3 Phosphatidylcholine O OH Amides in Peptides and Proteins O NH a 2 OH OH OH OH H N OH H2N H2N 2 H2N H2N O O O O O glycine alanine phenylalanine asparagine glutamic acid Five of the 20 amino acid building blocks that go into all proteins All a-amino acids Proteins are polyamides O O H H N N N N H H O O CO2H Each protein is defined by a specific primary sequence of amino acids b-Lactam Antibiotics Other Penicillins varied at this position H H H N S 2 H H H N S N O O H N HO2C O H Penicillin G 6-Aminopenicillamic acid HO2C b-lactam g-lactam d-lactam� NH NH NH O O O a b O g a H N H2N OH 2 OH H2N OH d b b O g a O b-amino acid g-amino acid d-amino acid SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES� 1. Oxidation of alcohols � Cl- Na Cr O will over-oxidize to O 2 2 7 N H CrO3 carboxylic acid H R1� OH� R1 O R2 O R 1. R2MgBr 2 Na2Cr2O7� H SO OH 2 4� R H 2. pH7 R1 R1 R2 1 R1 OH 2. From alkynes O� 2 + O Hg , H2O R H 1. RBH2 R1 1 H2SO4 R1 H R1 Me� H 2. H2O2, NaOH SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES� 3. Friedel-Crafts Acylation O O Cl R R AlCl3 4. Ozonolysis 1. O3 + 2. Zn/H3O O O H Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 1. Nucleophilic Addition: Reactions with Aldehydes and Ketones (Chapter 19) A.� O -O Nu + HO Nu H3O � R R'� Nu Example: Grignard Reaction� Section 19.8 O HO CH3 MgBr + Example: Cyanohydrin Formation Section 19.7 O HO CN HCN H H Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 1. Nucleophilic Addition A. Hydration and Acetal Formation OH O H2O HO OH O HO O O + H3O Section 19.6 Section 19.11 O R H O O H+ R H Electrophilic at C OH OH � No longer electrophilic at C� HO OH OH OH HO OH OH R H H2O O R H HO R H O O O Protected (masked ) aldehyde R H R H Acetals as Protecting Groups for Aldehydes� M go H H Br BrMg O X O H+ OH OH H o H Br Mg BrMg O O O O O 1. electrophile H 2. pH7 H H OH O + H2O/H OH O O Overview of Reactions 4/27-5/9 - Reactions with carbonyls 1. Nucleophilic Addition A. CH3-Br BuLi P P CH3 P CH2 O triphenyl phosphine Ph3P CH2 Wittig Reaction Ph PO O 3 Ph = Phenyl Section 19.12 Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 1. Nucleophilic Addition Nu B. O -O Nu + H O Nu H3O 2 R R' R R' Nu Overview of Reactions 4/27-5/9 - Reactions with carbonyls 1. Nucleophilic Addition B. continued Example: Imine Formation O H H2O H O + H3O NH2 NH H H2N H H H2O H N NH NH Sometimes called a Schiff base in biochemistry Section 19.9 SUMMARY - Synthesis of Carboxylic Acids� 1. Oxidative cleavage of alkene R' KMnO4 HO HO O O R R R' 2. Oxidation of 1 alcohols and aldehydes O� O� R H Jones Oxidation� OH R OH� H R H 3. Carboxylation of Grignard Reagents O� CO2� RMgBr� R OH� Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 2. Nucleophilic Acyl Substitution: Reactions with Carboxylic Acid derivatives (Chapter 21) O -O Nu O R Y Y R Nu Y- Nu Y = Leaving Group O O OH LiAlH LiAlH4 4 Ester hydride reduction OR H H Chapter 17.5 RO-Li+ nucleophilic substitution nucleophilic addition MeMgBr O MeMgBr OH O Me Ester grignard reaction Section 21.6 - + Me Me OR RO Li � nucleophilic substitution nucleophilic addition� Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 2. Nucleophilic Acyl Substitution Carboxylic Acid Derivatives Example:Acyl Halide Section 21.4 Example:Ester Section 21.6 O OH O Cl O OH O OEt SOCl2 CH3 CH 2 OH HCl O Cl O NR2 NHR2 Example:Amide Section 21.7 Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 3. Alpha Substitution: Enolate/Enol Chemistry O O O H + E = O must have "a " H enolate electrophile (pKa 10-20 ) E OH OH enol OH O Br2 Alpha Halogenation Section 22.3 Br Alpha Alkylation O OLi O Section 22.8 LDA (base) CH3I Li N H LDA = Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 4. Condensation Reactions: Enolate/Enol Chemistry O O O O base� R' OH R R R'� R'' R'' R H Aldol Reaction Section 23.2-23.7 OH O O base O O H3C C H H� CH3 H CH2 H2 H3C H� Claisen Condensation Section 23.8-23.9 O O O O base + OEt- O H3C C OEt EtO CH3 EtO CH2 H2 H C OEt 3 Key in fatty acid biosynthesis Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 4. Condensation Reactions: Enolate/Enol Chemistry continued� Michael Reaction Section 23.11� O O O O O O NaOEt EtO Me EtO Me EtO Me O H H H H HOEt Me O H Me O O EtO Me H H O H Me .