Organic Chemistry, 6th edition Paula Yurkanis Bruice Chapter 17 Carbonyl Compounds I Reactions of Carboxylic Acids and Carboxylic Derivatives Brian L. Groh Minnesota State University, Mankato Mankato, MN Bruice: Organic Chemistry, © 2011 Pearson Education, Inc.

Which of the following compounds is propanoic anhydride? 17.2 Which of the following compounds is propanoic anhydride? Bruice: Organic Chemistry, © 2011 Pearson Education, Inc.

Which of the following compounds is propanoic anhydride? 17.2 Which of the following compounds is propanoic anhydride? Propanoic anhydride is made of two 3-carbon acids. Bruice: Organic Chemistry, © 2011 Pearson Education, Inc.

Bruice: Organic Chemistry, © 2011 Pearson Education, Inc. 17.6 Which carboxylic acid derivative is most readily hydrolyzed by aqueous base? E Carboxylic acid derivatives hydrolyze by the same mechanism and at the same approximate rate. Bruice: Organic Chemistry, © 2011 Pearson Education, Inc.

Bruice: Organic Chemistry, © 2011 Pearson Education, Inc. 17.6 Which carboxylic acid derivative is most readily hydrolyzed by aqueous base? Best leaving group = fastest hydrolysis E Carboxylic acid derivatives hydrolyze by the same mechanism and at the same approximate rate. Bruice: Organic Chemistry, © 2011 Pearson Education, Inc.

Under basic conditions, in nucleophilic acyl substitution, _____. 17.7 Under basic conditions, in nucleophilic acyl substitution, _____. protonation of the carbonyl group is followed by nucleophilic attack loss of the leaving group is followed by formation of an acylium ion an SN2 mechanism is followed the nucleophile must be a weaker base than the leaving group nucleophilic addition to the carbonyl is followed by loss of a leaving group Bruice: Organic Chemistry, © 2011 Pearson Education, Inc.

Under basic conditions, in nucleophilic acyl substitution, _____. 17.7 Under basic conditions, in nucleophilic acyl substitution, _____. protonation of the carbonyl group is followed by nucleophilic attack loss of the leaving group is followed by formation of an acylium ion an SN2 mechanism is followed the nucleophile must be a weaker base than the leaving group nucleophilic addition to the carbonyl is followed by loss of a leaving group Protonation doesn’t occur under basic conditions. Bruice: Organic Chemistry, © 2011 Pearson Education, Inc.

Bruice: Organic Chemistry, © 2011 Pearson Education, Inc. 17.10 Which of the following carboxylic acid derivatives could be used in this reaction? For X = -Br -Cl -OC(=O)CH3 -OCH3 Any of the above Bruice: Organic Chemistry, © 2011 Pearson Education, Inc.

Bruice: Organic Chemistry, © 2011 Pearson Education, Inc. 17.10 Which of the following carboxylic acid derivatives could be used in this reaction? For X = -Br -Cl -OC(=O)CH3 -OCH3 Any of the above All of these derivatives are more reactive than the amide product. Bruice: Organic Chemistry, © 2011 Pearson Education, Inc.

Bruice: Organic Chemistry, © 2011 Pearson Education, Inc. 17.13 Upon aqueous hydrolysis of 18O labeled ethyl acetate, which oxygen(s) will be labeled in the final reaction mixture after mild acidification? Bruice: Organic Chemistry, © 2011 Pearson Education, Inc.

Bruice: Organic Chemistry, © 2011 Pearson Education, Inc. 17.13 Upon aqueous hydrolysis of 18O labeled ethyl acetate, which oxygen(s) will be labeled in the final reaction mixture after mild acidification? Nucleophilic attack by hydroxide occurs at the acyl group resulting in loss of the 18O labeled ethoxy group. Bruice: Organic Chemistry, © 2011 Pearson Education, Inc.

Which compound is the product of the reaction sequence? 17.21 Which compound is the product of the reaction sequence? Bruice: Organic Chemistry, © 2011 Pearson Education, Inc.

Which compound is the product of the reaction sequence? 17.21 Which compound is the product of the reaction sequence? Acid => acid chloride => ester => amide, which is stable toward reaction with water. Bruice: Organic Chemistry, © 2011 Pearson Education, Inc.