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Organic Chemistry Lecture Outline Carbonyl-Containing Functional Groups FUNCTIONAL GROUPS CONTAINING CARBONYL GROUPS A carbonyl group has a carbon atom doubly bonded to an oxygen atom. 1. The carbon atom of a carbonyl group is sp2 hybridized. 2. A carbonyl group is polarized with the oxygen atom bearing a partial negative and the carbon bearing a partial positive charge. 3. The carbon atom of a carbonyl group is electrophilic. The following functional groups contain a carbonyl group. ALDEHYDES AMIDES KETONES ESTERS IMIDES ACID CHLORIDES ANHYDRIDES CARBOXYLIC ACIDS GENERAL TYPES OF REACTIONS CARBONYL GROUPS UNDERGO 1. NUCLEOPHILIC ADDITION REACTIONS: Occurs with all types of carbonyls 2. NUCLEOPHILIC ACYL SUBSTITUTIONS: Occurs with acids, acid chlorides,amides, esters, anhydrides, imides 3. ALPHA-SUBSTITUTION REACTIONS: Occurs with all carbonyls that bear an alpha hydrogen atom 4. CARBONYL CONDENSATION REACTIONS: Occurs between two carbonyl groups ALDEHYDES AND KETONES Aldehydes and ketones are carbonyl-containing functional groups. The structures and reactivity of these functional groups are similar. Aldehydes have a hydrogen atom and a carbon atom bonded to the carbonyl carbon. Ketones have two carbon atoms bonded to the carbonyl carbon. The carbonyl carbon of both aldehydes and ketones is electrophilic. Aldehyde Ketone O O δ δ H H atom C atom C atom C atom NOMENCLATURE OF ALDEHYDES AND KETONES IUPAC The parent of an aldehyde or ketone is the longest, continuous carbon chain that contains the carbonyl carbon of the functional group. The parent name reflects the total number of carbon atoms in the chain (2 carbons = ethan, 3 carbons = propan, etc..). The parent chain is numbered from one end of the chain, so as to give the carbonyl carbon the lowest possible number. For aldehydes, this means the carbonyl carbon will always be the number 1 carbon. Substituents are assigned a number to indicate their position on the parent chain. Substituents are named to reflect the number of carbon atoms of the substituent. Substituents are placed in alphabetical order. The “-AL” suffix is used for aldehydes, the “–ONE” suffix is used for ketones. O O O CH3 H 3-methylbutanal 4-methylhexanone Cl 4-chloro-2-methylcyclohexanone Organic Chemistry Lecture Outline Carbonyl-Containing Functional Groups COMMON There are many common names that are used to describe aldehydes and ketones. Some of these are: O O O CH3 H O H methylethyl ketone Acetophenone Benzaldehyde O O H H3C Formaldehyde H CH3 Acrolein Acetone REACTIONS TO PREPARE ALDEHYDES & KETONES ALDEHYDES 1. Oxidation of Alcohols O PCC H OH O Jones Reagent 2. OH Reduction of Esters DIBAL is used to reduce esters to aldehydes Ester Aldehyde O O O DIBAL R R OR OR + OR R H H HOH H 3. Tetrahedral Intermediate ROH Hydration of Terminal Alkynes H2B H C C CH3 = H H2B H BH3 H CH3 H CH3 Transition State O H H2O2 NaOH HO H H H CH3 Aldehyde H CH3 Enol Organic Chemistry Lecture Outline Carbonyl-Containing Functional Groups KETONES 1. Oxidation of Alcohols O PCC O OH Jones Reagent O Na2Cr2O7 2. Friedel-Crafts Acylation Cl Cl Al Cl Al O Cl O Cl X R X R AlX3 O O H R 3. R Hydration of Terminal Alkynes H H + H C C CH3 H3O H CH3 H Most Stable Carbocation H OH2 CH3 Oxonium ion O H OH H H CH3 Ketone H CH3 Enol CARBOXYLIC ACIDS, ESTERS AND AMIDES Carboxylic acids, esters and amides are carbonyl-containing functional groups. The structures and reactivity of these functional groups are similar. Carboxylic acids have a hydroxyl group (-OH) and a carbon atom bonded to the carbonyl carbon. Esters have an alkoxide group (-OR) and a carbon atom bonded to the carbonyl carbon. Amides have an amino group (-NH2, -NHR, -NR2) and a carbon atom bonded to the carbonyl carbon. The carbonyl carbon of all of these functional groups is electrophilic, but not as electrophilic as aldehydes and ketones. Organic Chemistry Lecture Outline Carbonyl-Containing Functional Groups Ester Carboxylic Acid O O HO hydroxyl group Primary Amide δ RO Secondary Amide O H2N amino group Alkoxide group C atom δ C atom Tertiary Amide O O δ RHN C atom amino group δ R2N C atom amino group δ C atom STERIC AND ELECTRONIC EFFECTS OF CARBONYL COMPOUNDS Steric Effects Steric effects influence the reactivity of the electrophilic carbonyl carbon in nucleophilic acyl addition and nucleophilic acyl substitution reactions. Carbonyl groups bonded to large, bulky substituents (eg., tertiary carbons) react slower with nucleophiles than carbonyl groups with smaller, less bulky substituents. Electronic Effects Electronic effects influence the reactivity of the electrophilic carbonyl carbon in nucleophilic acyl addition and nucleophilic acyl substitution reactions. Substituents with lone pair electrons assiociated with them can donate electrons into the pi system, making the electrophilic carbonyl carbon less positive and less reactive with a nucleophile. Carbonyl-containing functional groups like carboxylic acids, esters and amides that have substituents with lone pairs (O or N atoms) react slower than aldehydes and ketones due to this electronic effect.