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67 Preview of Carbonyl Chemistry Kinds of Carbonyls 1. Aldehydes and Ketones 2. Carboxylic Acid Derivatives Carboxylic Acids E

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67 Preview of Carbonyl Chemistry Kinds of Carbonyls 1. Aldehydes and Ketones 2. Carboxylic Acid Derivatives Carboxylic Acids E Preview of Carbonyl Chemistry O O Kinds of carbonyls C C R H R R' 1. Aldehydes and ketones aldehyde ketone -al -one O 2. Carboxylic acid derivatives O O C C C R O carboxylic acids R OH R OR' R' esters carboxylic acid ester lactone acid chlorides -oic acid -oate cyclic ester acid anhydrides O O O C C C amides R Cl R O R nitriles acid chloride acid anhydride -oyl chloride -oic anhydride O O C R' C R'' R N R N R C N R'' R' amide lactam nitrile -amide cyclic amide -nitrile 132 Carbonyl groups have a significant dipole moment ! - O O O C ! + C C Aldehyde 2.72 D Ketone 2.88 Carboxylic acid 1.74 Acid chloride 2.72 Ester 1.72 Amide 3.76 Nitrile 3.90 Water 1.85 Carbonyl carbons are electrophilic sites and can be attacked by nucleophiles 133 67 Chapter 19: Aldehydes and Ketones: Nucleophilic Addition Reactions Recall: Grignard reaction and hydride reduction Chapter 20: Carboxylic Acids and Nitriles Chapter 21. Carboxylic Acid Derivatives and Nucleophilic Acyl Substitution Reactions O O O + Y: C R Y R Nu R Nu :Nu Y tetrahedral intermediate Y is a leaving group: 134 -Cl (acid chloride), -OR (ester), -NR2 (amide) , -O2CR (anhydride) Chapter 22. Carbonyl Alpha-Substitution Reactions Chapter 23. Carbonyl Condensation Reactions O O O O C C C C C R' C R' ! C R' C R' H E B: Enolate anion E E= alkyl halide or carbonyl compound Chapter 24. Amines Chapter 25. Biomolecules: Carbohydrates H O H C OH HO HO C H HO HO O H C OH HO H C OH OH CH2OH Chapter 26: Biomolecules: Amino Acids, Peptides, and Proteins H - H2O + N CO2H H2N H N CO H H N CO H 2 2 2 2 O Ala Val Ala - Val Carboxylic acids + amino group amides 135 (peptides & proteins) 68 Chapter 27. Biomolecules: Lipids fatty acids, steroids, terpenoids CO2H O HO Aracidonic Acid Cholesterol Camphour Chapter 28: Biomolecules: Heterocycles and Nucleic Acids DNA structure and function, RNA The central dogma: DNA → mRNA → proteins 136 Chapter 19: Aldehydes and Ketones: Nucleophilic Addition Reactions Aldehydes and ketones are characterized by the the carbonyl functional group (C=O) 19.1 Naming Aldehydes and Ketones Aldehydes are named by replacing the terminal -e of the corresponding alkane name with -al The parent chain must contain the -CHO group The -CHO carbon is numbered as C1 If the -CHO group is attached to a ring, name the ring andd add the suffix carboxaldehyde O O O H H H 137 butanal 2-ethyl-4-methylpentanal cyclohexane carboxaldehyde 69 Ketones are named by replacing the terminal -e of the alkane name with –one Parent chain is the longest one that contains the ketone group Numbering begins at the end nearer the carbonyl carbon Non systematic names: 138 Ketones and Aldehydes as Substituents The R–C=O as a substituent is an acyl group is used with the suffix -yl from the root of the carboxylic acid The prefix oxo- is used if other functional groups are present and the doubly bonded oxygen is labeled as a substituent on a parent chain 139 70 19.2 Preparation of Aldehydes Oxidation of primary alcohols with pyridinium chlorochromate (PCC) Chapter 17.8 Ozonolysis of an alkene (with at least one =C-H) Chapter 7.8 electrical + 3 O 2 O O _ Ozone (O3): 2 discharge 3 O O O3, CH2Cl2 O R R 1 3 -78 °C O O O O Zn R1 R3 R 1 R3 O + O R1 R3 R R2 R4 2 O R4 R2 R4 R2 R4 molozonide ozonide + ZnO 1) O3 2) Zn H + O=CH2 O 1) O3 2) Zn O H 140 O Hydroboration of a terminal alkyne (Chapter 8.5) 1) BH , THF 3 O 2) H2O2, NaOH R C C H R H Reduction of an ester with diisobutylaluminum hydride (DIBAH) - not really a reliable reaction. Reduction of a lactone or nitrile to an aldehyde is much better Al H O O [H] O [H] C R C OCH3 R CH2OH R OCH3 C H R H fast H iBu O DIBAL Al H O+ O iBu 3 O C R OCH R C OCH C 3 3 R H H iBu H O+ DIBAL Al iBu 3 O R C N N C C R H R H H 141 71 19.2 Preparation of Ketones Oxidation of secondary alcohols with pyridinium chlorochromate (PCC) or chromic acid (Ch. 17.8) Ozonolysis of an alkene (Chapter 7.8) 1) O3 2) Zn O + O Oxymercuration of a terminal alkyne (methyl ketone) + (Chapter 8.5) HgSO4, H3O O R C C H R CH3 methyl ketone O + O HgSO4, H3O R C C R R + R1 1 2 2 R2 -or- R1 hydroboration 142 Friedel-Crafts acylation (aryl ketone) Chapter 16.4 O O C R Cl R AlCl3 Reaction of an acid chloride with a Gilman reagent (diorganocopper lithium, cuprates) Chapter 10.9 ether H3C _ + 2 CH3Li + CuI Cu Li + LiI H3C Gilman's reagent (dimethylcuprate, dimethylcopper lithium) O O C R Cl + (H3C)2CuLi C R CH3 143 72 19.3 Oxidation of Aldehydes and Ketones + Chromic acid (CrO3/H3O ) oxidizes aldehydes to carboxylic acids Silver oxide, Ag2O, in aqueous ammonia (Tollens’ reagent) oxidizes aldehydes to carboxylic acids O AgO2 O NH4OH, H2O C C + Ag R H R OH Precipitated Ag(0) forms a silver mirror: chemical test for aldehydes 144 19.4 Nucleophilic Addition Reactions of Aldehydes and Ketones Nucleophiles: w/ a formal negative charge Neutral: must have a lone pair of electrons OH O H-A O O H-A OH -HOH Nu C C C C C C Nu Nu Nu-H Nu-H Nu: :Nu-H 145 73 19.5 Relative Reactivity of Aldehydes and Ketones aldehydes are more reactive toward nucleophilic addition than ketones. In general aromatic aldehydes (benzaldehydes) are less reactive because of resonance with the aromatic ring 19.6 Nucleophilic Addition of H2O: Hydration Water can reversibly add to the carbonyl carbon of aldehydes and ketones to give 1,1-diols (geminal or gem-diols) OH O + H2O C C R OH R R R - H2O 146 R= H, H 99.9 % hydrate O + H O OH R= CH3, H 50 % 2 C R C R= (H3C)3C, H 20 % R R OH - H2O R R= CH3, CH3 0.1 % The rate of hydration is slow, unless catalyzed by acid or base Base-catalyzed mechanism (Fig. 19.4): hydroxide is a better nucleophile than water Acid-catalyzed mechanism (Fig. 19.5): protonated carbonyl is a better electrophile Does adding acid or base change the amount of hydrate? 147 74 The hydration is reversible Hydration is a typical addition reaction of aldehydes and ketones 148 19.7 Nucleophilic Addition of HCN: Cyanohydrin Formation Aldehydes and unhindered ketones react with HCN to give cyanohydrins (mechanism: p. 694) Equilibrium favors cyanohydrin formation O H C N OH C R R' pKa ~ 9.2 R C N R' The nitrile of a cyanohydrin can be reduced to an amine or + hydrolyzed (with H3O ) to a carboxylic acid (Ch. 20.9) LiAlH OH 4 OH + OH or B2H6 H3O C R C C OH CH2NH2 R C N R C R' R' R' O 149 75 19.8 Nucleophilic Addition of Grignard Reagents and Hydride Reagents: Alcohol Formation (also see Chapters 17.6 & 17.5) Preparation of alcohols from ketones and aldehydes MgX MgX OH O H O+ O R-MgX O 3 C C C R ether C R R: M M OH O O H O+ M-H O 3 C C C C H H H: Note: the mechanism (arrow pushing) is not much different than for the hydration of carbonyls O O H OH OH + :OH C C C OH OH :OH H OH2 O OH OH OH + C + H3O C C C OH OH 150 :OH 2 H :OH2 19.9 Nucleophilic Addition of Amines: Imine and Enamine Formation Primary amines, RNH2, will add to aldehydes and ketones followed by lose of water to give imines (Schiff bases) Secondary amines, R2NH, react similarly to give enamines, after lose of water and tauromerization (ene + amine = unsaturated amine) 151 76 Mechanism of Formation of Imines Imines are isoelectronic with a carbonyl Fig. 19.8 O O H2N NH-opsin H HN + retinal G-protein coupled Lys-opsin receptor N H + h! opsin N G-protein Cascade H 152 Chapter 19.15: Please read Pyridoxal Phosphate (Vitamin B6) Involved in amino acid biosynthesis, metabolism and catabolism - R CO2 - R CO2 NH2 H O N Imine - H2O 2 OH (Schiff base) 2 OH O PO O3PO 3 + H2O N N H H Pyridoxal phosphate dependent enzymes L-DOPA decarboxylase HO CO2 HO NH3 NH HO 3 HO Dopamine CO2 aromatic amino acid HO NH decarboxylase 3 HO NH3 N N H H Serotonin 153 77 Related C=N derivatives NO2 H NO2 N H OH NH2 N N O N H2NOH O2N NO2 hydroxylamine 2,4-dinitrohydrazine -H2O -H2O oxime 2,4-dinitrophenylhydrazone Enamine Formation: Mechanism (Fig. 19.10) 154 19.10 Nucleophilic Addition of Hydrazine: The Wolff–Kishner Reaction Reduction of aldehydes and ketones to a methylene group (CH2) with hydrazine (H2NNH2) and base (NaOH) NH2 H H N O H H -N H2N-NH2, 2 NaOH H2, Pd/C H2O General reduction of ketones Chapter 16.11 and aldehydes to -CH2 Limited to aryl ketones O H2N-NH2, NaOH, H2O H3CO H3CO H N-NH , O 2 2 NaOH, H2O H H2N-NH2, O NaOH, H2O HO2C CO2H HO2C CO2H 155 Mechanism: Fig 19.11 (p.
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