Chapter 17. Aldehydes and Ketones - Sonic.net

Chapter 17. Aldehydes and Ketones - Sonic.net

Aldehydes and Ketones carbonyl compounds O carbonyl group structure, bonding and physical properties Review of methods of preparation of aldehydes and ketones hydration of alkynes Friedel-Crafts acylation of aromatic compounds

Overview of reactions of carbonyl compounds reduction to alcohols addition of organometallic reagents addition of oxygen, nitrogen, sulfur and phosphorus nucleophiles reduction of carbonyl to methylene (Clemmensen or Wolff-Kishner) Nucleophilic addition to carbonyls Nucleophilic addition to carbonyls

OH O + Z Z Synthesis of Alcohols Reduction of Carbonyl Compounds Synthesis of Alcohols Reduction of Carbonyl Compounds

O C OH reducing agent C H Synthesis of Alcohols Reduction of Carbonyl Compounds O C OH

reducing agent C H H2/cat., NaBH4, LiAlH4 O 1. LiAlH 4/ether 2. H2O OH

lithium aluminum hydride (LAH) O + Li AlH3 H O + Li AlH3 H

Li+ -AlH3 O H O O CH3CH2CCH2CH2COCH2CH3 1. LiAlH 4/ether 2. H2O CH3CH2CHCH2CH2CH2OH OH

O O CH3CH2CCH2CH2COCH2CH3 NaBH4/H2O sodium O borohydride CH3CH2CHCH2CH2COCH2CH3 OH Synthesis of Alcohols Using Organometallic Reagents

O C RMgX + O MgX C R + H3O OH

C R O C RMgX + O MgX C R O

C MgX R + H3O OH C R O CH3(CH2)8CH2MgBr + HCH

1. ether + 2. HO 3 CH3(CH2)8CH2CH2OH O COCH3 + 2 CH3MgBr 1. ether + 2. HO 3

OH CCH3 CH3 O COCH3 CH3 MgBr O +MgBr C OCH3 CH3

O COCH3 O +MgBr C OCH3 CH3 CH3 MgBr O C CH3

-OCH 3 O C CH3 CH3 MgBr O +MgBr C CH3

CH3 O C CH3 CH3 MgBr O +MgBr C CH3 CH3 + H

OH CCH3 CH3 MgBr + O 1. THF + 2. H3O CH2CH2OH

Hydration of aldehydes and ketones O + + H or H2O OH

OH OH An example O + Cl H Cl Cl

+ H2O H3O OH Cl Cl Cl H OH

Addition of alcohols: hemiacetal and acetal formation Addition of alcohols: hemiacetal and acetal formation O + + ROH OH

H3O OR hemiacetal or hemiketal Addition of alcohols: hemiacetal and acetal formation OH +

+ ROH OR hemiacetal OR H3O OR acetal Mechanism of acetal formation O

+ H OH2 OH + + O R

O R H OH R O H H O+ R Mechanism of acetal formation + R

R O O R O H OR + H3O + OR

O+ H R O H H An example HO O +

HO pTosOH toluene O O Addition of ammonia and amines: imine and enamine formation O +

+R NH2 R OH H N NH R

O + +R H NH R' H

OH H N R R' R N R' Examples

O + CH NH 3 2 N + H3O N CH 3

N Examples O H N + (CH3)2NH +

H3O CH3 N CH 3 H N Examples O

+ H3O + N H The Wittig Reaction R CH2X +

Ph3P: RCH2 PPh 3 + - X O B:

R H RCH PPh 3 + YLIDE An example Br + Ph3P: NaOH

PPh 3 + O The mechanism Br + Ph3P: PPh 3 H

Br Mechanism, cont. PPh 3 H Br ylide PPh 3

OH Mechanism, cont. PPh 3 + PPh 3 O O

oxaphosphetane Mechanism, cont. PPh 3 O Formation of cyanohydrins O -

1) CN OH + 2) H3O C N Example Glc Glc O H

C N Reduction of carbonyls to alkanes Clemmensen reduction Wolff-Kishner reduction Desulfurization of thioketals Nucleophilic Addition to a,bUnsaturated Carbonyls Nuc +

Nuc OH O Nuc OH Nucleophilic Addition to a,bUnsaturated Carbonyls Strong nucleophiles add 1,2 kinetic control Weaker nucleophiles add 1,4 thermodynamic control Nucleophilic Addition to a,bUnsaturated Carbonyls

O KCN H2O Nucleophilic Addition to a,bUnsaturated Carbonyls O OH KCN H2O NC

O NC Nucleophilic Addition to a,bUnsaturated Carbonyls O +(CH3CH2)2CuLi H2O Et2O Nucleophilic Addition to a,bUnsaturated Carbonyls O

O +(CH3CH2)2CuLi H2O Et2O CH3CH2

Recently Viewed Presentations

  • Empower your team - National Career Development Conference

    Empower your team - National Career Development Conference

    Empower your team . Organizational Structure. Carolyn Warkentin, B.A., C.A.E. Executive Director. South Essex Community Council "An empowered organization is one in which individuals have the knowledge, skills, desire and opportunity to personally succeed in a way that leads to...
  • Blueprint reading - Mediapolis Community School

    Blueprint reading - Mediapolis Community School

    Alphabet of lines. Universal language of technician, architect, & engineer. Basis of all construction drawings. Many different line types, thicknesses, and applications. Understanding Line Types. Object lines. Also known as visible lines.
  • BOT DE presentation

    BOT DE presentation

    Canvas is used in 93% of our credit classes this semester. This continues a steady, slight year-to-year increase in the use of a course management system - the transition did not impact that. Child Development department now offering a Zero...
  • Quantum Numbers  n, l, m, and s  Used

    Quantum Numbers n, l, m, and s Used

    Nitrogen. 1s2 2s2 2p3. Hund's Rule. Orbitals. of . equal energy. are each . occupied. by one . electron. before any . orbital. is occupied by a . second electron ...
  • Model Transformations An overview Pierre-Alain Muller INRIA Pierre-alain.muller@irisa.fr

    Model Transformations An overview Pierre-Alain Muller INRIA [email protected]

    Model Transformations An overview Pierre-Alain Muller INRIA [email protected] Model Transformations @ Google Outline MDE basic principles What is a model-transformation?
  • Lesson 1: Length English vs. Metric Units Which

    Lesson 1: Length English vs. Metric Units Which

    English vs. Metric Units. Which is longer? A. 1 mile or 1 kilometer. B. 1 yard or 1 meter. C. 1 inch or 1 centimeter. 1.6 kilometers. 1 mile. 1 yard = 0.9144 meters
  • 3.06 Acquire foundational knowledge of business laws ...

    3.06 Acquire foundational knowledge of business laws ...

    3.06 Acquire foundational knowledge of business laws & regulations to understand their nature & scope. ... Uniform Commercial Code (UCC) - Sale and lease contracts ... 3.06 Acquire foundational knowledge of business laws & regulations to understand their nature &...
  • Law of Treaties

    Law of Treaties

    (john.h jackson, status of treaty in domestic legal system: policy analisys, ajil 86, april 1992, hal. 315) uu no. 15/2001 tentang merk adalah implementasi dari trademark law treaty uu no 6/1996 tentang perairan adalah act of transformation atau implementation dari...