CHM 234| Study guide 4
CHM 234| Study guide 4 CHM 234
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This 9 page Study Guide was uploaded by Alvin Notetaker on Wednesday April 27, 2016. The Study Guide belongs to CHM 234 at Arizona State University taught by Pillai in Fall 2015. Since its upload, it has received 30 views. For similar materials see General Organic Chemistry II in Chemistry at Arizona State University.
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Date Created: 04/27/16
CHM 234 Study Guide 3 Aldehydes and Ketones : Reaction of Acid Chloride Nomenclature and ICPAC Reaction Between Acid Chloride and Preparing aldehyde/ketone Organometallic Reagent Relative reactivity for aldehyde and ketone Oxygen Nucleophile : Acid Anhydrides : Hydrate Formation Preparation and Reactions Acetal Formation Acetylation with Acetic Anhydride Ester: Cyclic Acetal and reverse Preparation via S2 Stable Hemiacetal N Nitrogen Nucleophile: Preparation via Fischer Esterification Primary amine Preparation via Acid Chloride Secondary amine Reaction of Ester WolfKishner Reduction Acidcatalyzed Hydrolysis Hydrolysis of Acetals, Imines, Enamines Aminolysis of Ester Sulfur Nucleophile: Reduction of Ester Convert to alkane Grignard Reaction with Ester Hydrogen (Hydride) Nucleophile : Amide : Reagent Hydrolysis of Amides (acid and base) Reduction of Amides Carbon Nucleophile : Grignard Reaction Nitriles Cyanohydrin Formation Preparation via SN Witting Reaction Preparation via Amides BaeyerVilliger Oxidation of Aldehyde and Hydrolysis of Nitriles (acid and base) Grignard reaction of Nitriles Ketone Priority for placement/migrant of the oxygen atom Reduction of Nitriles Carboxylic acid: Alpha Carbon Chemistry: Enols and Nomenclature Enolates: Common name αcarbon Naming the carboxylic salts αhydrogen Preparing Carboxylic acid Increase in stability when αhydrogen is Carboxylation of Grignard Reagent removed Reaction of Carboxylic Acid Enolates Carboxylic acid derivatives: Forming Enolates Nomenclature Alpha Halogenation of Enol and Enolates Reactivity of Carboxylic Acid Derivatives and The HellVolhardZelinski Reaction why? BasePromoted halogenation Nucleophilic Acyl Substitution Halogenation of Methyl Ketone Acid Halide: (Haloform reaction) Preparation and Reaction of Acid Chloride Aldol Reaction and reverse Hydrolysis of Acid Chloride Alcoholysis of Acid Chloride Aminolysis of Acid Chloride Answers: Aldehydes and Ketones : Nomenclature and ICPAC: ● Aldehyde: “al” ● Ketone” one” Preparing aldehyde/ketone: ● Oxidation of secondary alcohol ○ PCC with CH2Cl2 ○ Na2Cr2O7 with H2SO4 ● Ozonolysis of alkenes ○ 1) O3 with 2) DMS ● Acidcatalyzed hydration of terminal alkynes ○ H2SO4, H2O with HgSO4 ○ goes to more substituted ○ enol to keto ● Hydroborationoxidation of terminal alkynes ○ 1) R2BH with 2) H2O2, NaOH ○ goes to less substituted ● FriedelCrafts Acylation ○ ketone with a halide with Al(halide)3 Relative reactivity: (most to least) 1. Formaldehyde 2. Aldehyde 3. Ketone Oxygen Nucleophile : Hydrate Formation ● Steric effect ● Electronic effect Acetal Formation ● Reagent: ○ 2 ROH with [H+] (ketone to two ester group) Cyclic Acetal and reverse ● Reagent: ○ ketone with (CH2)2(OH)2 (forms a cyclic compound) ● Act as a protection Stable Hemiacetal ● Reagent: ○ H+ (forms a cyclic compound) ● One compound that has a ketone and an alcohol group ● The partial negative oxygen in the alcohol group bonds itself with the carbon of the ketone Nitrogen Nucleophile: Primary amine ● For double bond CN ● Reagent: ○ Trace acid ○ [H+] ○ TsOH Secondary amine ● Forms double bond CC WolfKishner Reduction ● Reduction from carbonyl to alkane ● Reagent: ○ N2H2 and then KOH/H2O Acetals ● Forms carbonyl and alcohol group Imines ● Forms carbonyl and amine Enamine ● Forms carbonyl and amide Sulfur Nucleophile : Convert ketone to alkane ● Reagent: (after protecting) ○ H2 with Raney Ni Hydrogen (Hydride) Nucleophile : Hydrogen (Hydride) Nucleophile ● Reagent ○ 1. LAH with 2. H2O ○ NaBH with MeOH Carbon Nucleophile : Grignard Reaction ● Reagent: ○ RMgBr with H2O Cyanohydrin Formation ● Reagent: ○ HCN with KCN (Ketone to nitrile) ○ 1. LAH with 2. H2O (Nitrile to amine) ○ H+ (Nitrile to carboxylic acid) Witting Reaction ● Reagent: ○ carbonyl with phosphonium (P(C6H5)3) ● A S 2 prefer less hindered molecule. N (Note: Just look at the phosphonium. It prefers the less hindered segment.) BaeyerVilliger Oxidation of Aldehyde and Ketone ● Reagent: ○ Peroxyacid Priority for placement/migrant of the oxygen atom: ● H>3°>2°Phenyl>1°>methyl Carboxylic acid : Nomenclature and ICPAC for Carboxylic acid ● Remove “e” with “oic acid” Common name ● Position is labeled with Greek letter starting at the carbon of the acid. Naming the carboxylic salts ● First name the cation ● Name the anion by replacing “ic acid” with “ate” Preparing Carboxylic acid ● Oxidation Cleavage of Alkynes ○ 1. O3 with 2. H2O ● Oxidation of Primary Alcohol ○ Na2Cr2O7 with H2SO4, H2O ● Oxidation of Alkylbenzenes ○ Na2Cr2O7 with H2SO4, H2O ● Hydrolysis of Nitriles ○ H+ with heat Carboxylation of Grignard Reagent Reagent: ● 1. CO2 with 2. H3O+ Reaction of Carboxylic Acid Reagent: ● 1. LAH with H3O+ ● BH3THF Carboxylic acid derivatives X Name Cl Acid halide COOR Acid anhydride OR Ester NH Amide 2 Nitrile, RCN, is a acid derivative Carboxylic acid derivatives : Nomenclature for Carboxylic acid derivatives Naming Acid Halide Replace “ic acid” with “yl halide” Naming Acid Anhydride Replace “acid” with “anhydride” Naming Easter Replace “ic acid” or “oic acid” with “ate” Naming Amide Replace “ic acid” or “oic acid” with “amide” If the amide group have a alkyl group substituents, their names are place with a “N” as the locant. Naming Nitrile Replace “ic acid” with “oniltrile” Reactivity of Carboxylic Acid Derivatives Most to least 1. Acid halide 2. Acid anhydride 3. Ester 4. Amide Nucleophilic Acyl Substitution ● Acid starts with proton transfer ● Base Start with nucleophilic attack Acid Halide: Preparation and Reaction of Acid Chloride ● Reaction with carboxylic acid ● Reagent: ○ SOCl2 Hydrolysis of Acid Chloride ● Acid chloride to carboxylic acid Alcoholysis of Acid Chloride ● Reagent: ○ ROH and pyridine Aminolysis of Acid Chloride ● Reagent: ○ (2 eq.) NH3 ○ (2 eq.) RNH2 ○ (2 eq.) R2NH Reaction of Acid Chloride ● Reagent: ○ 1. ex. LAH with 2. H2O To stop of aldehyde: ● Reagent: ○ 1. LiAl(OR)3H and 2. H2O Reaction Between Acid Chloride and Organometallic Reagent ● Reagent: ○ 1. ex. RMgBr with 2. H3O+ Acid Anhydrides : Preparation and Reactions ● Acetic anhydride is the only anhydride that can be form at high temperature. ● All reactions are the same as acid chloride Acetylation with Acetic Anhydride ● Reagent: ○ ROH ■ Form ester ○ RNH2 ■ Forms amide Ester: Via S2 N ● Reagent: ○ 1. NaOH with 2. CH3I (carboxylic acid to ester) Via Fischer Esterification ● Reagent: ○ CH3OH with H3O+ (carboxylic acid to ester with the R group on the alcohol) Via Acid Chloride ● Reagent: ○ ROH with pyridine (Acid chloride to easter) Reaction of Ester ● Saponification ● Reagent: ○ NaOH with H3O+ ( ester to carboxylic acid) Acidcatalyzed Hydrolysis ● Reagent ○ H3O+ (ester to carboxylic acid) Aminolysis of Ester ● Reagent: ○ NH3 (ester to amide and alcohol) Reduction of Ester ● Reagent: ○ 1. LAH with 2. H2O (form hydroxyl group) ○ 1. DIBAH with 2. H2O (form aldehyde) Grignard Reaction with Ester ● Reagent: ○ 1. ex. RMgBr with 2. H3O+ (ester to alochol and two Rs group) Amide : Hydrolysis of Amides (base and acid) ● Reagent ○ H3O+ (amide to carboxylic acid) ○ NaOH, H2O with H3O+ (amide to carboxylic acid) Reduction of Amides ● Reagent: ○ 1. ex. LAH with 2. H2O (amide to amine) Nitriles Preparation via S2 N ● Reagent: ○ 1. NaCN (alkyl halide to nitrile) Preparation via Amides ● Reagent: ○ 1. SOCl2 ( amide to nitrile) Hydrolysis of Nitriles ● Reagent ○ H3O+ (Nitrile to carboxylic acid) ○ NaOH, H2O with H3O+ (Nitrile to carboxylic acid) Grignard reaction of Nitriles ● Reagent: ○ 1. ex. RMgBr with 2. H3O+ (Nitrile to ketone) Reduction of Nitriles ● Reagent: ○ 1. ex. LAH with 2. H2O (Nitrile to amine) Alpha Carbon Chemistry: Enols and Enolates : αcarbon ● Carbon adjacent to a carbonyl carbon. αhydrogen ● Hydrogen bonded to αcarbon Increase in stability when αhydrogen is removed 1. Creates a delocalized electron 2. Delocalized electrons moves to the more electronegative atom, oxygen. Enolates ● Is the resonancestabilisation when deprotonation of the alpha position. Forming Enolates ● Reagent: ○ LDA ○ NaH Alpha Halogenation of Enol and Enolates ● Reagent: ○ Br2 with H3O+ ● Forms one halogen on the αcarbon ● Reaction with ketone The HellVolhardZelinski Reaction ● Reagent: ○ 1. PBr3, Br2 with 2. H2O ● Forms one halogen on the αcarbon ● Reaction with carboxylic acid BasePromoted halogenation ● Reagent: ○ Br2 with OH ● Forms two halogen on the αcarbon Halogenation of Methyl Ketone (Haloform reaction) ● Reagent: ○ (ex.) I2 with OH ● Can be with any halogen. Aldol Reaction and reverse ● Two of the same compound react with base (OH) and water to make a carboncarbon bond on the αcarbon.
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