Contents STRUCTURE AND SYNTHESIS 10 OF ALCOHOLS 425 10-1 Introduction 425 10-2 Structure and Classification of Alcohols 425 10-3 Nomenclature of Alcohols and Phenols 427 10-4 Physical Properties of Alcohols 430 10-5 Commercially Important Alcohols 433 10-6 Acidity of Alcohols and Phenols 435 10-7 Synthesis of Alcohols:Introduction and Review 438 Summary:Previous Alcohol Synth 43 188 llic Reagents fo c Reagentst Key Mechanism 10-1 Grianard Reactions 443 Summary:Grignard Reactions 450 Reagents Reduction 10-10 Side Re: 10-11 Carbonyl Group:Synthesis of 1and Mechanism 10-2:Hydride Reduction of a Carbonyl Group 454 Summary:Reactions of LiAlH4 and NaBH4 455 Summary:Alcohol Syntheses by Nucleophilic Additions to Carbonyl Groups 457 10-12 Thiols(M ercaptans)458 EssentialTerms 46 Study Problems 462 11 REACTIONS OF ALCOHOLS 467 467 Oxidation State hols and Related Functional Groups hols 11-3 11-4 Alcohols 472 cal Oxidation of Alcohols 474 115 Alcohols as Nucleophiles and Electrophiles;Formation ofTosylates 476 Summary:SN2 Reactions OfTosylate Esters 478 11-6 Reduction of Alcohols 478 11-7 Reactions of Alcohols with Hydrohalic Acids 479 Mechanism 11-1:Reaction of aTertiary Alcohol with HBr(SN1)480 c-2:Reaction of a Primary Alcohol with 11-8 Reactic ns of Alcohols with Phospho s Halides 484 ns of alcohols with Th I Chloride 485 11-9 Mechanism 11-3:Reaction of Alcohols with PBr3 485 11-10 hanism 11-4:(Review):Acid-Catalyzed Dehydration of an Alcohol 487 Problem-Solving Strategy:Pr posing Reaction Mechanisms 491 11-11 10s49 Rearrangement 495 x Contents 10 STRUCTURE AND SYNTHESIS OF ALCOHOLS 425 10-1 Introduction 425 10-2 Structure and Classification of Alcohols 425 10-3 Nomenclature of Alcohols and Phenols 427 10-4 Physical Properties of Alcohols 430 10-5 Commercially Important Alcohols 433 10-6 Acidity of Alcohols and Phenols 435 10-7 Synthesis of Alcohols: Introduction and Review 438 Summary: Previous Alcohol Syntheses 438 10-8 Organometallic Reagents for Alcohol Synthesis 440 10-9 Addition of Organometallic Reagents to Carbonyl Compounds 443 Key Mechanism 10-1: Grignard Reactions 443 Summary: Grignard Reactions 450 10-10 Side Reactions of Organometallic Reagents: Reduction of Alkyl Halides 451 10-11 Reduction of the Carbonyl Group: Synthesis of 1° and 2° Alcohols 453 Mechanism 10-2: Hydride Reduction of a Carbonyl Group 454 Summary: Reactions of LiAIH4 and NaBH4 455 Summary: Alcohol Syntheses by Nucleophilic Additions to Carbonyl Groups 457 10-12 Thiols (Mercaptans) 458 Essential Terms 461 Study Problems 462 11 REACTIONS OF ALCOHOLS 467 11-1 Oxidation States of Alcohols and Related Functional Groups 467 11-2 Oxidation of Alcohols 469 11-3 Additional Methods for Oxidizing Alcohols 472 11-4 Biological Oxidation of Alcohols 474 11-5 Alcohols as Nucleophiles and Electrophiles; Formation of Tosylates 476 Summary: SN2 Reactions Of Tosylate Esters 478 11-6 Reduction of Alcohols 478 11-7 Reactions of Alcohols with Hydrohalic Acids 479 Mechanism 11-1: Reaction of a Tertiary Alcohol with HBr (SN1) 480 Mechanism 11-2: Reaction of a Primary Alcohol with HBr (SN2) 480 11-8 Reactions of Alcohols with Phosphorus Halides 484 Reactions of Alcohols with Thionyl Chloride 485 11-9 Mechanism 11-3: Reaction of Alcohols with PBr3 485 11-10 Dehydration Reactions of Alcohols 487 Mechanism 11-4: (Review): Acid-Catalyzed Dehydration of an Alcohol 487 Problem-Solving Strategy: Proposing Reaction Mechanisms 491 11-11 Unique Reactions of Diols 494 Mechanism 11-5: The Pinacol Rearrangement 495