carbonyl1

carbonyl1 - TYPES OF CARBONYL COMPOUNDS� General formula...

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Unformatted text preview: TYPES OF CARBONYL COMPOUNDS� General formula Name Name suffix -al O Aldehyde C R Name General formula O Ester H R C O� Ketone C� R Acid anhydride R' O Carboxylic acid� Acid halide -one R C O O -oyl halide X=halogen C R X O� O R C O C Lactone (cyclic ester) -oic acid H -oic anhydride R Name suffix -oate O O C R' O O Amide R Lactam� (cyclic amide) C N -amide R' R" O C N R' Detergents and "fatty acids" - amphiphilic molecules CO2 hydrophobic hydrophilic CO2H omega-3-fatty acid H2O H2O H2O Phospholipids - Fatty acid esters of glycerol grease OH H2O H2O OH glycerol a triol OH H2O MICELLE O O O O LIPID BILAYER O OPO O NH3 Phosphatidylcholine O Amides in Peptides and Proteins OH O NH2 a OH H2N OH H2N O H2N O glycine OH alanine OH H2N O O O phenylalanine OH H2N glutamic acid asparagine Five of the 20 amino acid building blocks that go into all proteins All a-amino acids Proteins are polyamides H N N H O Each protein is defined by a specific primary sequence of amino acids O O H N N H O CO2H b -Lactam Antibiotics H2N H H Other Penicillins varied at this position S HH N N O HO2C H O Penicillin G H d-lactam� g-lactam NH NH NH O O b N HO2C b-lactam H2N S O 6-Aminopenicillamic acid a H O OH O b-amino acid a H2N H2N g g O b a OH g-amino acid d b OH O d-amino acid SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES� 1. Oxidation of alcohols � ClN H CrO3 R1� OH� H R1 O R2 R1 Na2Cr2O7 will over-oxidize to carboxylic acid O O Na2Cr2O 7� H 2SO4� OH R1 R1 R2 R2 1. R2MgBr 2. pH7 H R1 OH 2. From alkynes O� O 2+ R1 H Hg , H2 O H2 SO 4 R1 Me� R1 H 1. RBH2 2. H2 O2, NaOH R1 H SUMMARY - SYNTHESIS OF ALDEHYDES AND KETONES� 3. Friedel-Crafts Acylation O Cl O R R AlCl3 4. Ozonolysis 1. O3 2. Zn/H3O+ H O O Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 1. Nucleophilic Addition: Reactions with Aldehydes and Ketones (Chapter 19) A.� O R -O Nu H3O+ HO R'� Nu Example: Grignard Reaction� O Section 19.8 HO CH3MgBr + Example: Cyanohydrin Formation O Section 19.7 HO CN HCN H H Nu� Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 1. Nucleophilic Addition A. Hydration and Acetal Formation O H2O HO OH OH O O HO H3O+ Section 19.11 Section 19.6 O R O H + OH OH Electrophilic at C OH R H O R� H No longer electrophilic at C� HO OH OH HO R H OH OH H H2O R HO O R O O H R H O H Protected (masked) aldehyde O Acetals as Protecting Groups for Aldehydes� X H Br O OH OH H H BrMg O + H Br M go O M go O H BrMg electrophile O O O 1. H 2. pH7 H OH O H 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 Wittig Reaction Section 19.12 Ph3PO CH2 O Ph = Phenyl Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 1. Nucleophilic Addition O B. R -O Nu H3O+ H2O Nu Nu R R' Nu R' Overview of Reactions 4/27-5/9 - Reactions with carbonyls 1. Nucleophilic Addition B. continued Example: Imine Formation H O O NH2 H2O H3O+ H NH H H2N H H N H2O NH Sometimes called a Schiff base in biochemistry H NH Section 19.9 SUMMARY - Synthesis of Carboxylic Acids� 1. Oxidative cleavage of alkene R' HO KMnO4 HO O R 2. R O R' Oxidation of 1 alcohols and aldehydes O� R H OH R H R 3. O� Jones Oxidation� OH� H Carboxylation of Grignard Reagents O� RMgBr� CO2� R OH� Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 2. Nucleophilic Acyl Substitution: Reactions with Carboxylic Acid derivatives (Chapter 21) O R -O O Nu Y Y - R Nu Y Nu Y = Leaving Group O LiAlH4 OR O RO-Li+ LiAlH4 H O OR Ester hydride reduction Chapter 17.5 H nucleophilic substitution MeMgBr OH nucleophilic addition O RO-Li+� nucleophilic substitution MeMgBr Me OH Me Me nucleophilic addition� Ester grignard reaction Section 21.6 Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 2. Nucleophilic Acyl Substitution Carboxylic Acid Derivatives Example:Acyl Halide Section 21.4 O OH O Example:Ester Section 21.6 O Cl OH SOCl2 O OEt CH3CH2OH HCl O Cl O NHR2 NR2 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 must have "a " H (pKa 10-20) E+ = electrophile enolate O E OH OH enol OH Br2 O Br O H LDA (base) Alpha Halogenation Section 22.3 OLi Alpha Alkylation Section 22.8 O CH3I LDA = Li N Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 4. Condensation Reactions: Enolate/Enol Chemistry O O O base� R'� R R OH R' R'' O R'' R H Aldol Reaction O H� Section 23.2-23.7 OH O base O CH3 H O EtO Section 23.8-23.9 O O base CH3 H C H2 H� H3C Claisen Condensation H3C CH2 O EtO + O CH2 H3C O H3C OEt C H2 OEt - OEt Key in fatty acid biosynthesis Overview of Reactions 4/27-5/9 - Reactions with carbonyls� 4. Condensation Reactions: Enolate/Enol Chemistry continued� Section 23.11� Michael Reaction O O EtO Me H H O NaOEt O EtO O O Me EtO O Me H H HOEt O Me H Me O O EtO Me H H O H Me ...
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This note was uploaded on 03/02/2012 for the course CHEM 512 at MIT.

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