WWU -- Chemistry Nucleophilic Substitution Reactions: Reactions and Synthetic Applications

WWU -- Chemistry Assignment for Chapter 12 l Read Sections 12.0 through 12.4 l SKIP Pages 1108 (bottom) through 1112 (Sect. 12.4) l New material on N-bromosuccinimide reactions l SKIP Sections 12.5 through 12.6 l Read Sections 12.7 through 12.8 l SKIP Section 12.9 l Read Sections through l SKIP Section l Read Sections through end of chapter l ORGANIC NOMENCLATURE: Alcohols and Ethers

WWU -- Chemistry Problem Assignment l In-Text Problems –12-1 through 12-8 –12-12 through –12-27 through –12-34 through l End-of-Chapter Problems –40 through 42 –46 through 54 –57 through 61 –63 through 75

WWU -- Chemistry General Rules for Nomenclature l Choose the longest continuous chain of carbon atoms which includes the carbon atom bearing the functional group. This chain will identify the parent hydrocarbon. l Number the parent carbon chain from the end nearest the functional group, irrespective of other substitution. l Indicate the substituents by name and number. Assign a number to the carbon atom bearing the functional group. l Combine all parts into one word, using correct punctuation.

WWU -- Chemistry General Rules for Nomenclature (continued) l Show the presence of the functional group by replacing the -e of the alkane ending (sometimes the -ane) with the appropriate ending for the functional group. Show the position of the functional group by inserting a number into the name immediately before the name of the parent chain.

WWU -- Chemistry Block Diagram for Nomenclature

WWU -- Chemistry Nucleophilic Substitution

WWU -- Chemistry Nucleophilic Substitution

WWU -- Chemistry Assisted Nucleophilic Substitution

WWU -- Chemistry Assisted S N 2: Mechanism

WWU -- Chemistry Assisted S N 1: Mechanism

WWU -- Chemistry Alcohol + Hydrogen Halide l This method is best with tertiary alcohols l This reaction works very slowly with primary and secondary alcohols. l Rearrangements are possible!

WWU -- Chemistry Neopentyl Alcohol + Lucas Reagent

WWU -- Chemistry Alcohols + Phosphorus Halides

WWU -- Chemistry Alcohol + Phosphorus Halide l This method is best for primary and secondary alcohols. l This method is generally unsuccessful with tertiary alcohols l Rearrangements do not happen with this method.

WWU -- Chemistry Preparation of Tosylates TsCl R-OTs

WWU -- Chemistry Which Alkyl Halide Should I Use? l If the halide is a better leaving group, the reaction will go in higher yield. I - > Br - > Cl - l If the halide is cheaper, the reaction will be more economical. Cl - > Br - > I -

WWU -- Chemistry Which Alkyl Halide Should I Use? (Part Two) l Best compromise… Alkyl bromides! l Exception: For CH 3 —X, use Methyl iodide

WWU -- Chemistry Addition of Hydrogen Halides to Double Bonds This reaction follows Markovnikov’s Rule Chapter 8, Section 8.4

WWU -- Chemistry Free Radical Halogenation of Alkanes Chapter 3, Section 3.17

WWU -- Chemistry Allylic Halogenation with N-Bromosuccinimide

WWU -- Chemistry Mechanism – Step 1

WWU -- Chemistry Mechanism – Step 2

WWU -- Chemistry Mechanism – Step 3

WWU -- Chemistry Mechanism – Step 4

WWU -- Chemistry Halogenation at a Benzylic Position

WWU -- Chemistry Benzylic Substitution – Mechanism Step 2

WWU -- Chemistry Conversion of Alkyl Halides to Alcohols SN1SN1 SN2SN2

WWU -- Chemistry Synthesis of Ethers

WWU -- Chemistry Williamson Ether Synthesis SN2SN2

WWU -- Chemistry General Reaction of Epoxides

WWU -- Chemistry Under Acidic Conditions…

WWU -- Chemistry Reactions of Epoxides

WWU -- Chemistry More Reactions of Epoxides

WWU -- Chemistry Reactions of Epoxides in Basic Medium

WWU -- Chemistry Reactions of Epoxides in Acidic Medium

WWU -- Chemistry Synthesis of Heliannuol E Hydrolyze to remove methyl group.

WWU -- Chemistry Synthesis of Heliannuol C Hydrolyze to remove methyl group.

WWU -- Chemistry Synthesis Problem #1

WWU -- Chemistry Outline the Mechanism

WWU -- Chemistry HBr or PBr 3 ???

WWU -- Chemistry Synthesis Problem #2

WWU -- Chemistry Synthesis of MTBE (Methyl tert-Butyl Ether)

WWU -- Chemistry Synthesis Problem #3

WWU -- Chemistry Reactions of Epoxides

WWU -- Chemistry More Reactions of Epoxides

WWU -- Chemistry What are the Products?

WWU -- Chemistry Synthesis Problem #4

WWU -- Chemistry The Synthesis Problem from Hell!

WWU -- Chemistry Try this! Plus any additional needed reagents and solvents

WWU -- Chemistry

Change in Assignment (August 11, 2004) l Include the following sections: –12.9 –12.10 –12.11 –12.14 –12.15