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