ORGANIC CHEMISTRY-STUD.SOLNS.MAN+SG(LL)
ORGANIC CHEMISTRY-STUD.SOLNS.MAN+SG(LL)
4th Edition
ISBN: 9781119659587
Author: Klein
Publisher: WILEY
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Chapter 25, Problem 59PP

(a)

Interpretation Introduction

Interpretation:

The products formed in the given set of transformation need to be predicted.

Concept introduction:

α -bromination of carboxylic acid in presence of bromine and a catalytic amount of phosphorous tribromide to form α -bromocarboxylic acid is known as Hell-Volhard-Zelinsky reaction.  The formed α -bromocarboxylic acid when treated with ammonia gives α -aminocarboxylic acid as the product.

ORGANIC CHEMISTRY-STUD.SOLNS.MAN+SG(LL), Chapter 25, Problem 59PP , additional homework tip  1

(b)

Interpretation Introduction

Concept introduction:

Strecker synthesis is a process in which the aldehyde reacts with ammonium chloride and alkali cyanide to form α -aminonitrile.  The formed α -aminonitrile is undergoes hydrolysis to give the respective amino acids.  The general scheme can be shown as,

ORGANIC CHEMISTRY-STUD.SOLNS.MAN+SG(LL), Chapter 25, Problem 59PP , additional homework tip  2

Steps involved in Strecker synthesis are,

  • Protonation of carbonyl
  • Nucleophilic attack of ammonia to form imine
  • Attack of cyanide to form α -aminonitrile
  • Hydrolysis to give α -aminoacid

(c)

Interpretation Introduction

Concept introduction:

Amidomalonate synthesis is a process in which a halide is converted to an amino acid with two new carbon atoms (comes from amidomalonate).  By use of this method a new alkyl groups can be introduced.  A general scheme of this synthesis is shown below,

ORGANIC CHEMISTRY-STUD.SOLNS.MAN+SG(LL), Chapter 25, Problem 59PP , additional homework tip  3

Steps involved in amidomalonater synthesis are,

  • Deprotonation of α carbon in amidomalonate
  • Alkylation of enolate
  • Hydrolysis of ester using aqueous acid
  • Decarboxylation at high temperature

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2. Write a complete mechanism for the reaction shown below. NaOCH LOCH₁ O₂N NO2 CH₂OH, 20 °C O₂N NO2
4. Propose a synthesis of the target molecules from the respective starting materials. a) b) LUCH C Br OH
The following mechanism for the gas phase reaction of H2 and ICI that is consistent with the observed rate law is: step 1 step 2 slow: H2(g) +ICI(g) → HCl(g) + HI(g) fast: ICI(g) + HI(g) → HCl(g) + |2(g) (1) What is the equation for the overall reaction? Use the smallest integer coefficients possible. If a box is not needed, leave it blank. + → + (2) Which species acts as a catalyst? Enter formula. If none, leave box blank: (3) Which species acts as a reaction intermediate? Enter formula. If none, leave box blank: (4) Complete the rate law for the overall reaction that is consistent with this mechanism. (Use the form k[A][B]"..., where '1' is understood (so don't write it) for m, n etc.) Rate =

Chapter 25 Solutions

ORGANIC CHEMISTRY-STUD.SOLNS.MAN+SG(LL)

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