Chapter 9 Reactions of Alcohols, Ethers, Epoxides, Amines, and Thiols Paula Yurkanis Bruice University of California, Santa Barbara

Contents of Chapter 9 Naming Alcohols Substitution and Dehydration of Alcohols Oxidation of Alcohols Naming Ethers Epoxides Skip Thiols and SAM Methylation Chapter 10

Naming Alcohols Find longest carbon chain containing the alcohol. OH gives attached carbon lowest possible number. Break ties with other substituents if necessary. Substituents are listed in alphabetical order. Chapter 10

Examples Determine longest chain with OH Blue chain is longer; however, Red chain contains OH Notice that numbering starts at alcohol group 2. Name: 2-propyl-1-hexanol Chapter 10

Examples Chapter 10

Conversion of Alcohols to Alkyl Halides Hydrogen halide reactions can be SN1 or SN2 Chapter 10

Mechanism of Substitution Secondary and tertiary alcohols undergo SN1 reaction. Chapter 10

Mechanism of Substitution Primary alcohols undergo SN2 reaction. Primary carbocations are too unstable to be formed. Attack from back-side Chapter 10

Dehydration of Alcohols Zaitsev’s Rule is followed whenever possible Chapter 10

Dehydration of Alcohols Chapter 10

Cr6+ Oxidation of Alcohols Acidic hexavalent chromium removes all  H’s makes C-O bonds PCC removes only one  H and makes an aldehyde from a 10 alcohol Chapter 10

Cr6+ Oxidation of Alcohols Chapter 10

Oxidation by Hypochlorous Acid (HOCl)

Nomenclature of Ethers Common Name: Name of alkyl substituents followed by “ether” methyl isopropyl ether methyl ethyl ether IUPAC Parent alkyl compound with RO substituent. “-yl” is then replaced by “oxy” 2-methoxy-butane 1-ethoxy-2-methylpropane Chapter 10

Substitution Reactions of Ethers Ethers can be cleaved only with HI and HBr, not HCl SN1 and SN2 reactions give opposite regioselectivity; H goes on bulky C in SN2, and less-hindered in SN1 Chapter 10

Epoxides Chapter 10