Chapter_18 - P1 PCX/SRB JWDD052-18 P2 xxx JWDD052-Solomons-v3 Printer Hamilton 21:10 18 CARBOXYLIC ACIDS AND THEIR DERIVATIVES NUCLEOPHILIC

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P1: PCX/SRB P2: xxx Printer: Hamilton JWDD052-18 JWDD052-Solomons-v3 June 12, 2007 21:10 18 CARBOXYLIC ACIDS AND THEIR DERIVATIVES: NUCLEOPHILIC ADDITION- ELIMINATION AT THE ACYL CARBON SOLUTIONS TO PROBLEMS 18.1 (a) 2-Methylbutanoic acid (b) ( Z )-3-Pentenoic acid or ( Z )-pent-3-enoic acid (c) Sodium 4-bromobutanoate (d) 5-Phenylpentanoic acid (e) ( E )-3-Ethyl-3-pentenoic acid or ( E )-3-Ethylpent-3-enoic acid 18.2 Acetic acid, in the absence of solvating molecules, exists as a dimer owing to the formation of two intermolecular hydrogen bonds: CH 3 CH 3 C O O H O O C H At temperatures much above the boiling point, the dimer dissociates into the individual molecules. 18.3 (a) OH F O (F is more electronegative than H ) (b) OH F O (F is more electronegative than Cl ) (c) Cl OH O (Cl is more electronegative than Br ) (d) OH O F (F is closer to CO 2 H) (e) F OH O (F is closer to CO 2 H) 361
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P1: PCX/SRB P2: xxx Printer: Hamilton JWDD052-18 JWDD052-Solomons-v3 June 12, 2007 21:10 362 CARBOXYLIC ACIDS AND THEIR DERIVATIVES (f) (CH 3 ) 3 N + O OH [(CH 3 ) 3 + N is more electronegative than H ] (g) CF 3 O OH (CF 3 is more electronegative than CH 3 ) 18.4 (a) The carboxyl group is an electron-withdrawing group; thus, in a dicarboxylic acid such as those in Table 18.3, one carboxyl group increases the acidity of the other. (b) As the distance between the carboxyl groups increases, the acid-strengthening, inductive effect decreases. 18.5 (b) O O O 2 N (d) N CH 3 CH 3 (c) OCH 3 CH 3 O O (a) O OCH 3 (e) CN O (f ) OCH 3 O OCH 3 (i) O Br Br (g) O O O O (j) O O O O (h) O H N CH 3 CH 3 O O 18.6 (a) (1) KMnO 4 , OH , heat (2) H 3 O + + CO 2 O OH
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P1: PCX/SRB P2: xxx Printer: Hamilton JWDD052-18 JWDD052-Solomons-v3 June 12, 2007 21:10 CARBOXYLIC ACIDS AND THEIR DERIVATIVES 363 (1) Cl 2 /NaOH (2) H 3 O + (d) (1) KMnO 4 , OH , heat (2) H 3 O + O (b) (c) Mg Et 2 O CO 2 H 3 O + OMgBr Br MgBr O H O (f) OH O OH O OH O OH + CHCl 3 (e) (1) KMnO 4 , OH , heat (2) H 3 O + (1) KMnO 4 , OH (2) H 3 O + OH O OH O 18.7 These syntheses are easy to see if we work backward using a retrosynthetic analysis before writing the synthesis. 1) CO 2 2) H 3 O + Mg Et 2 O OH O C 6 H 5 MgBr C 6 H 5 (a) OH O C 6 H 5 Br C 6 H 5 OO C MgBr C 6 H 5 + Retrosynthetic analysis Br C 6 H 5 Synthesis
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P1: PCX/SRB P2: xxx Printer: Hamilton JWDD052-18 JWDD052-Solomons-v3 June 12, 2007 21:10 364 CARBOXYLIC ACIDS AND THEIR DERIVATIVES (b) O OH Br OO C + (c) (d) O OH MgBr C + Br O OH Br MgBr C + 1) CO 2 2) H 3 O + Mg Et 2 O 1) CO 2 2) H 3 O + Mg Et 2 O Br O OH MgBr C + O OH O OH 1) CO 2 2) H 3 O + Mg Et 2 O C + Retrosynthetic analysis Retrosynthetic analysis Retrosynthetic analysis Synthesis Synthesis Synthesis MgBr C + MgBr Br Br MgBr (e) O OH MgBr C + Br O OH 1) CO 2 2) H 3 O + Mg Et 2 O MgBr Br Retrosynthetic Analysis Synthesis
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P1: PCX/SRB P2: xxx Printer: Hamilton JWDD052-18 JWDD052-Solomons-v3 June 12, 2007 21:10 CARBOXYLIC ACIDS AND THEIR DERIVATIVES 365 18.8 C 6 H 5 OH O C 6 H 5 OH O C 6 H 5 C 6 H 5 Br O C 6 H 5 OH C 6 H 5 CN C 6 H 5 Br CN H 3 O + heat 1) CN 2) H 3 O + , Δ OH O Br (a) 1.
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This note was uploaded on 09/10/2008 for the course CHE 321 taught by Professor Fowler/sampson during the Spring '08 term at SUNY Stony Brook.

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Chapter_18 - P1 PCX/SRB JWDD052-18 P2 xxx JWDD052-Solomons-v3 Printer Hamilton 21:10 18 CARBOXYLIC ACIDS AND THEIR DERIVATIVES NUCLEOPHILIC

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