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TYPES OF CARBONYL COMPOUNDS�

General Name Name General Name Name formula suffix formula suffix O O -al -oate C C R' R H R O O� O C -one C � O R R' (cyclic ester) Carboxylic O -oic C H O acid� R O C R' -amide Acid O R N X= -oyl R" C halide halide O R X � C R' Acid O O� -oic (cyclic amide) N anhydride anhydride C C R O R Detergents and "fatty " - amphiphilic molecules CO2H

CO2 omega-3-fatty hydrophobic hydrophilic acid

H2O

H2O Phospholipids - 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 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 phenylalanine asparagine glutamic acid

Five of the 20 building blocks that go into all proteins All a-amino acids

Proteins are 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 AND � 1. Oxidation of � Cl- Na Cr O will over-oxidize to O 2 2 7 N H CrO3 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

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 O O

Cl R R

AlCl3

4.

1. O3

+ 2. Zn/H3O O O H Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 1. : Reactions with Aldehydes and Ketones (Chapter 19)

A.� O -O Nu + HO Nu H3O �

R R'�

Nu

Example: � Section 19.8

O HO CH3 MgBr +

Example: 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 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 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. 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: Formation

O H H2O H O + H3O NH2 NH H

H2N

H H H2O H

N NH NH

Sometimes called a Schiff in Section 19.9 SUMMARY - Synthesis of Carboxylic Acids� 1. Oxidative cleavage of

R' KMnO4 HO HO O O R R R'

2. Oxidation of 1 alcohols and aldehydes O�

O� R H

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 =

O O OH LiAlH LiAlH4 4 Ester 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: 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: /

O O O H

+ E = O must have "a " H enolate electrophile (pKa 10-20 ) E OH OH

enol

OH O Br2 Alpha 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 Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 4. Condensation Reactions: Enolate/Enol Chemistry continued� 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