浙江大学马成有机化学乙课件 要点

Organic Chemistry (Carey 5th)

CHAPTER 1 Introduction: Structure Determines Properties

1. Concepts:

①Atom, Electron and Orbital

②Ionic, Covalent, Polar Covalent Bond / Electronegativity

③Lewis Structures/ Formal Charge/ Resonance

④The Shapes of Molecules

⑤Hybridization

⑥Inductive effect

⑦Theory of acid and base including Conjugate Acids & Bases/Lewis base & acid/ Br?nsted

base & acid

CHAPTER 2: Hydrocarbon Frameworks. Alkanes and Cycloalkanes

1. Concepts:

①Nomenclature and Conformational Analysis (IUPAC nomenclature involving spirocyclic

and bicyclic compounds, Ethane, Butane, Cyclohexanes and Decalin conformation analysis, Ring strain)

②Diagrams--include Newman projection, Wedge-dash, Sawhorse diagrams

③Reaction Classification/ Reaction Variables/ Reactive Intermediates (cation, anion, radical,

carbene)

④Structures of Carbocation/ Radical/ Carbanion

⑤Reaction mechanism in general: Bond cleavage Models/ Activation Energy, Reaction

Heat/ Thermodynamic Control and Kinetic Control/ Hammond Postulate

2. Reaction:

①Radical Monohalogenation of alkane, Meachanism

②Reaction rate/ Calculating the amounts of products

③General Selectivity of Radical Halogenations (α-position of unsaturated compound:

C H-C=C; C H-C三CH)

CHAPTER 3: Stereochemistry

1. Concepts:

①Isomers: Stereoisomers/ Configurational Stereoisomers of Alkenes/ Chirality (Plane of

Symmetry), Optical Activity ( DL), Stereocenter

②Fischer Projections

③R or S Configuration (Cahn-Ingold-Prelog R/S Notation)

④Racemic mixture; Meso-compound; Diastereomers and Enationmer (including Erythro

and Threo enatiomers)

⑤Properties of Stereoisomers, Resolution

⑥Simple compounds with stereo-centers (C / N / S atoms); C2-axial (biphenyl, allene,);

Cycloalkanes

CHAPTER 4: Alkyl Halides Nucleophilic Substitution and Elimination

1. Concepts:

① Structure and Nomenclature Alkyl Halide

② Nucleophilic reagent (Nu -) and base (B -③ Nucleophilicity and Basity

)

④ Nucleophilic Substitution (SN1 and SN2) and β-Elimination(E1 and E2)

2. Reactions:

① Nucleophilic Substitution: (water, NaCN, halide anion_halogen transformation, alkoxide

ions), pay attention to the stereochemistry.

② Alkyl Halides with AgNO 3③ β-Elimination: Dehydrohalogenation, Saytzeff rule and Hofmann Elimination, pay

attention to steric base and the structure of substrate.

induced the formation cabocation SN1 or E1; compared

with the formation of acetylides from terminal alkynes.

3. Mechanism:

① SN1 and SN2 involved stereochemistry, rearrangements of carbocations, and the effect of

reaction variations such as Nucleophile , Substrate , Leaving group and Solvent

② E1 and E2 involved region-selectivity, stereochemistry, and the effect of reaction

variations such as Bsae , and Substrate .

CHAPTER 5: Alkenes and Their Reactions

1. Concepts:

① Structure and Nomenclature

② Configuration isomers of alkene, Stability

③ Clarify the Electrophile

④ Rearrangement of Carbocation

2. Reactions:

④ Electrophlic Addition of HX, H 2O, Cl 2 and Br 2, Cl 2+H 2⑤ Addition with BH O (or HClO)

3, Hg(AcO)2⑥ Oxidation (KMnO , radical addition of HBr

4, Ozonolysis, HIO 4⑦ Reduction with H )

⑧ Addition of cyclopropane

2

3. Mechanism:

③ Electrophlic Addition to C=C, stereochemistry.

④ Bromonium ion

4. Emphasis:

Oxidation with KMnO

4

CHAPTER 6: Alkynes and Reaction of Alkynes

1. Concepts:

① Structure and Nomenclature

② The acidity of terminal alkynes

③ Stabilities of Carbocations

2. Reactions:

① Electrophlic Addition of HX, H 2O, Cl 2 and Br 2

②Addition with BH3, HgSO

4

③Reaction of acetylide, which was derived from the reaction of terminal Alkynes with

strong base, Ag, and Cu.

④Reduction with H2(Lindlar’s Pd, ), Na/NH3

(l)

3. Synthesis:

①From actylide

②From Alkyl halids (1,2-dihalo compounds, vinyl halides) via elemination

4. Emphasis:

The elimination of vinyl halides

CHAPTER 7: Conjugation in Alkadienes and Allylic Systems

1. Concepts:

①Conjugation (π–π, p –π, σ–π)

②The strength of conjugation

③Resonance

④Allylic Systems

⑤Molecular Orbitals

2. Reactions:

①Preparation of Conjugated Dienes

②Electrophilic Addition of Conjugated Dienes (1,2- and 1,4 addition)

③Diels-Alder Reaction

④Reaction of allylic system: NBS, SN2

CHAPTER 8: Alcohols and Reactions

1. Concepts:

①Structure and Nomenclature

2. Reactions:

①Williamson Ether Synthesis

)

②Halogenation (HX and PX3, SOCl2

③Dehydration

④Leaving group transformation (Sulfonate and Halide for Substitution, pay attention to the

stereochemistry), and the corresponding substituted/elimination reaction (depending on the existence of base or nucleophile).

⑤Oxidation

⑥Reaction of 1,2-diol: Oxidation, Pinacol Rearrangement (pay attention to the tendency of

group, anti-shift)

CHAPTER 9: Aromaticity and Reactions of Benzene

1. Concepts:

①Aromatic and Anti-aromatic (Resonance Energy, Stabilities, Hückel's Rule, MO theory

②Clarify aromatic compounds (involving annulenes, Hetercycle compounds π-electron rich

and poor systems, ions)

③Electronic effects (inductive effect and conjugated effect)

④Nomenclature of Benzene, Naphthalene, Biphenyl, Annulenes, and other Hetercycle

compounds (furan, pyrrole, imidazole, pyridine, thiophene, thiazole).

⑤Effect of aromatic stabilization on reactions of benzenen (and other aromatic compounds)

2. Reactions:

①Electrophilic Aromatic Substitution of benzene (Halogenation, Nitration, Sulfonation,

)

FC-Alkylation, FC-Acylation, chloromethylation

3. Mechanism:

①Electrophilic Aromatic Substitution

CHAPTER 10: Benzene Derivatives and the Reactions of Substituted Benzenes

1. Concepts:

①Benzene Derivatives (Phenol, Aniline, Benzene Halide, benzoic acid) and Nomenclature

②Directing effects in Electophilic Aromatic Substitution ( EAS)

③Activation or deactivation

④Cumulative effects of the substituents

2. Reactions:

①Electophilic Aromatic Substitution of substituted benzene (Halogenation, Nitration,

Sulfonation, FC-Alkylation, Acylation), pay attention to the effects of sustitutents

②EAS Reactions of Naphthalene

③The Reaction of Benzylic Systems (Radically halogenated, Oxidation at a Benzylic

position, Nucleophilic substitution, Elimination, Addition)

④Nucleophilic Substitution of Aryl Halides (two path, Addition–Elimination, Elimination

–Addition, benzyne)

3. Synthesis

①Substituted benzene

CHAPTER 11: Aldehydes and Ketones Nucleophilic Addition to C=O

1. Concepts:

⑤Structure and Nomenclature

⑥Reactivity of Carbonyl group

⑦Diastereoselectivity in Nucleophilic Addition Reaction of acyclic substrates (Cram

Modle)

2. Reactions:

②Nucleophilic Addition to C=O (Different nucleophiles: C, N, O, S)

③Baeyer-Villiger Oxidation of Ketone (Mechanism, migration tendencies of groups)

④Reduction (Complex Metal Hydrides, Wolff-Kishner Reduction, Clemmensen Reduction,

Catalytic Hydrogenation, Cannizzaro Reaction)

3. Mechanism:

①Nucleophilic Addition to C=O

CHAPTER 12: Carboxylic Acids and Derivatives Nucleophilic Acyl Substitution Reaction

1. Concepts:

①Structure and Nomenclature (Carboxylic acid, Ester, Amide, Acyl halide, Anhydride)

②Reactivity of Carboxylic Acids and Derivatives

③Properties: the acidity of Carboxylic Acids, the m.p. and b.p. of Carboxylic Acids and

their Derivatives

2. Reactions:

①Nucleophilic Acyl Substitution Reaction (hydrolysis, alcoholysis, aminolysis)

②Reduction (Complex Metal Hydrides)

③Reactions with organometallic reagents (Alkyl lithium reagents and Grignard’s reagents)

④Decarboxylation

⑤Rearrangements of Cationic or Electron Deficient Nitrogen (Beckmann Rearrangement,

Hofmann Rearrangement, Curtius Rearrangement)

CHAPTER 13: Enol and Enolate-Reactions at theα-Carbon of Carbonyl Compounds

1. Concepts:

①the acidity of hydrogen on α- carbon; tautomer, enol and enolate; the stability of enol and

enolate ion

②Vinylagous Systems (Hydroxyl Acidity)

2. Reactions:

①α- halogenation, Haloform reaction, Aldol (cross) condensation, Mannich Reaction

②Ester condensation (Claisen condensation, Dieckmen condensation, Cross ester-ketone

condensation), Reformatsky Reaction, Darzens Reaction

③Robinson annulation, Michael Reaction, α-carbon alkylation (ketone, active methylene

systems)

3. Synthesis:

①From active methylene systems (Substituted Acetone Synthesis, Substituted Acetic Acid

Synthesis)

CHAPTER 15: Amines and the Reaction of Amines

1. Concepts:

①Nomenclature (Quaternary Ammonium salts , Quaternary Ammonium Hydroxide)

②Structure, Basicity and Acidity

③Phase-Transfer Catalysis

④Cis-, trans-configuration of imine

2. Reactions:

①Preparation of Amines (Alkylation, Gabriel Primary Amine Synthesis, Reduction of

Azides, Nitriles, Nitroarene, Imine)

②Nitrosation of amines

③Synthetic Transformations of Aryl Diazonium Salts, Azo-coupling

④Quaternary Ammonium Hydroxide and Hofmann Elimination

3. Synthesis:

①The synthesis of Amine (Reduction, alkylation, Gabriel synthesis)

②Aryl Diazonium Salts, Azo-coupling

CHAPTER 16: Phenol and Benzoquinone

1. Concepts:

①Nomenclature

②Structure, Acidity of Phenol

2. Reactions:

①Substitution of the Hydroxyl Hydrogen (ether synthesis)

②Electrophilic Substitution of the Phenol Aromatic Ring

③React with Br

2

④Acylation of Phenols

⑤Oxidation of Phenols

CHAPTER 17 Ethers and Epoxides

1. Concepts:

①Nomenclature and properties

②Crown ether

2. Reactions:

①Acid-Catalyzed Cleavage of Ethers

②The Williamson Ether Synthesis

③Preparation of Epoxides (Oxidation, Darzens Reaction, Intramolecular Williamson

Ether Synthesis), pay attention to the stereochemistry!

④Nucleophilic Ring-Opening Reactions of Epoxides (Acidic and Basic-condition), pay

attention to the stereochemistry!

CHAPTER 18 Introduction of Analytical Chemistry

①1H-NMR Chemical Shift, Number of signals, Splitting pattern, Coupling Constant

②IR functional groups (Carbonyl, Hydroxy and Amino group)