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Esquemas de memorizao e resumos

1 Conceitos bsicos

Element # of covalent bonds Element # of covalent bondsH 1 F 1C 4 Cl 1N 3 (or 4) Br 1O 2 I 1

Carga formal: Z = valncia, S = compartilhados, U = no-compartilhados


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Ressonncia

Conceitos quntico-mecnicos


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Hibridizao sp3

Hibridizao sp2


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Hibridizao sp

Resumo de Hibridizao

Teoria VSEPR (RPECV)


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2 Grupos funcionais

Hidrocarbonetos

Ligaes polares


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Mais grupos funcionais


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Resumo de funes orgnicas

Propriedades Fsicas


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IV e qumica orgnica


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3 Reaes Orgnicas e Mecanismos (introduo)

1 Conceitos bsicos


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2 Homlise e Heterlise

3 Reaes cido-Base


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4 Carboctions e carbnions, eletrfilos e nuclefilos


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5 Setas curvas em reaes orgnicas

6 Fora de cidos e Bases de Bronsted-Lowry (pKa)


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7 Prevendo resultado de reaes cido-base

8 Estrutura e Acidez


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9 Mudanas de energia nas reaes e mais explicaes para acidez/basicidade


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10 O efeito do solvente na acidez


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11 Compostos Orgnicos como bases

12 Mecanismo Reacional Sn1

13 cidos e bases em solues no-aquosas


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4 Alcanos e cicloalcanos

1 Conceitos Bsicos

2 Forma dos Alcanos


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3 Nomenclatura IUPAC


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4 Propriedades Fsicas

5 Conformaes


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6 Estabilidade dos cicloalcanos, conformaes e isomeria


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7 Sntese de Alcanos e Cicloalcanos

8 Informaes baseadas em frmulas moleculares e ndices de deficincia de H


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5 Estereoqumica e molculas quirais

1 Quiralidade e Estereoqumica

2 Isomerismo


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3 Nomenclatura de estereoismeros


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4 Propriedades dos enantimeros


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5 Sntese de Molculas Quirais


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6 Molculas com mais de um estereocentro


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7 Estereoisomerismo de compostos cclicos


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8 Reaes e configuraes

9 Separao de enantimeros / Resoluo


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10 Compostos com outros tipos de quiralidades


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6 Substituies Nucleoflicas e Eliminaes (Haletos)

1 Haletos Orgnicos


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2 Reaes de Substituio Nucleoflica (SN2)


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3 Reaes de Substituio Nucleoflica (SN1)


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4 Fatores afetando SN1 e SN2


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5 Sntese orgnica: introduo


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6 Reaes de Eliminao


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7 Substituies e Eliminaes


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8 Resumo


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7 Alcenos, Alcinos e mais conceitos dos hidrocarbonetos

1 - Introduo

2 - Nomenclatura


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3 Estabilidade Relativa


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4 Cicloalcanos

5 Sntese Reaes de Eliminao


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6 Alcinos


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7 Reaes Caractersticas


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8 Sntese Orgnica: conceitos bsicos


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9 Reaes de Adio de Alcenos e outras reaes


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10 Sntese: mais conceitos


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8 RMN e Espectrometria de Massas

1 Ressonncia Magntica Nuclear (RMN) de prtons (RMN-H)


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2 Ressonncia Magntica Nuclear (RMN) de Carbono-13


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3 Tcnicas de RMN bidimensionais

4 Espectrometria de Massas


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9 Reaes Radicalares

1 Conceitos Principais


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2 A reao de alcanos com halognios


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3 Mais conceitos


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10 Alcois e teres

1 Informaes bsicas e gerais


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2 Reaes caractersticas


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3 Sntese de teres


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4 Reaes de teres


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5 Resumo das reaes

6 Alcois e compostos carbonlicos


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11 Sistemas Conjugados Insaturados

1 Introduo e conceitos bsicos


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2 Espectroscopia no Ultravioleta/Visvel (UV-Vis)


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3 Reaes em Sistemas Conjugados


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12 Sistemas Aromticos



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2 Caractersticas do benzeno


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3 Sistemas aromticos conceitos mais gerais


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4 Espectroscopia de compostos aromticos


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4 Reaes de compostos aromticos


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13 Aldedos e Cetonas


2 Snteses e reaes


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3 Identificao de cetonas e aldedos


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14 cidos Carboxlicos e Derivados



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2Reaes no carbono carbonlico


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3 Reaes de condensao e de adio conjugada em compostos carbonlicos


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15 Aminas

1 Conceitos bsicos


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2 Reaes


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3 Anlise de Aminas


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4 Mais reaes


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16 Mais reaes aromticas


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Reaes dos compostos orgnicos

1 Algumas reaes importantes, por classes de compostos

Alcanos

Aquecimento

X2 (Cl, Br ou F)Aquecimento ou

hv

Aquecimento

Craqueamento

Combusto

Halogenao

+ etc.

X

CO2 + H2O

Alcenos

H

Br2

m CPBA

HBr

1 - Hg(OAc)2, H 2O

2 - NABH4

Br2, ROH

H2, Pd/C

Br H

Br

Br

H

O

Br H

H

HO H

Br H

OH

H H

H

R 2NH

RO-

HO H

NR2

HO H

OR

Halogenao

AdioMarkovinkov

Epoxidao

OximercuriaoDesmercuriao

Formao deHalolcool

ReduaoCataltica

BH3, THF

Hidroborao

B(CHCH3CHCH3CH3)3

1 - B2H6, 2- H2O2

HidrataoAnti-Markovnikov

H

OH

H2SO4, H2O

HidrataoMarkovnikov

H

HO

KMnO4 dil.

Oxidao Branda

H

OHHO

OsO4

Oxidao Branda

H

OHHO

1 - O3 2 - H2O

Ozonlise

O

H

O


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Alcinos

Adio deorganometlico

FormaodeGrignard

FormaodeAcetileto

H2, Pd/C

Reduo

Li

R

R

RLi, THF, -78CR= H

MgXRMgX, THF

NaNH2, -78 C - Na+

R

HX

Adio Eletroflica

R

X

X

BH3

Hidroborao

R3 B

Alcois

R1 R2

SN1Somente

eficiente paratercirio

R3

OH

HBr

R1 R2

R3

Br

SN2Reao deMitsonobu

H Nu, Ph3P, DEAD

R1 R2

R3

Nu

Oxidao

H2Cr2O7

R1 R2

O

Oxidao

PCC

R1 R2

O

Desidratao

H2SO4

R1 R2

R3

+R1

R2

R3O

R3

R1

R2


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Aldedos

1 - NaCN, H2SO4

AdioNucleoflica

O

H

Adio de Organometlicos

AdiodeGrignard

OH

H

ROH, c. ou base

Equlibrio deHemiacetal

NaHSO3, banho de gelo

Adio de bissulfito

RNH2, H+ cat.

Formao de imina

NH3, H2, Ni, Presso

Reduo Aminativa

NaBH4

Reduocom boroidreto

OH

NH2

2 - H2O

1 - RLi, THF

2 - H2O

1 - RMgBr, Et2O

2 - H2O

CN

OH

R

OH

R

OH

OR

OH

SO3-Na+

N

R

NaCN, NH4Cl

Sntese deAminocido de Strecker

NH2

H

CN H2O, H+ NH2

H

CO2H

c.ou Base

Enolizao

OH


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Cetonas

1 - NaCN, H2SO4

AdioNucleof lica

O

Adio de Organometlicos

AdiodeGrignard

OH

ROH, c. ou base

Equlibrio deHemiacetal

NaHSO3, banho de gelo

Adio de bissulfito

RNH2, H+ cat.

Formao de imina

Formao de enamina

NH3, NaCNBH3

Reduo Aminativa

Sal de Fosfnio, NaH

Reao de Wittig

NaBH4

Reduocom boroidreto

OH

NH2

2 - H2O

1 - RLi, THF

2 - H2O

1 - RMgBr, Et2O

2 - H2O

R1

HN

R2 , H+ cat.

Br2, HOAc

HalogenaoVia Enolato

O

t-BuOK

FormaodeEnol ter

OMe

CN

OH

R

OH

R

OH

OR

OH

SO3-Na+

N

R

N

R1 R2

Br


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cidos Carboxlicos

SOCl2/ PCl5 / (COCl)2

SubstituioNucleof lica

ROH, H+

NH3O

OH


Reaocido-Base

O

Cl

O

R

O

O- NH4+

HCl

Reaocido-Base

+OH Cl-

OH

BH3, THF

Reduo OH

Anidridos

H2O


ROH

NH3

O

O

O



O

OH

O

OR

O

NH2

steres

H2O, c. ou base

SubstituioNucleoflica

RMgX

NH3

O

OR

SubstituioNucleoflica

Subst.Nucl.e Reduo

O

OH

OH

R

LiAlH4 ou LiBH4

Reduo

DIBAL, Hex, - 70 C

Reduo

R

OH

O

H

O

NH2


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Cloretos de cido

H2O


ROH

NH3

O

Cl



O

OH

O

OR

O

NH2

RCO2-


R2CuLi

Substit. Nucl.com Cupratos

Formao de Amidade Weinreb

O

O

O

R

O

N

HN

O

R

O

OMe

teres

HBr ou HCl conc.

Clivagem

H2SO4

O2

O

Eliminao

Autoxidao

X

O

O

Amidas

H2O, c. ou bas. fort

Reduo

O

NH2

O

OH

LiALH4

Reduo NH2


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Compostos Carbonlicos a,b-Insaturados

KCN, HCN

ProdutoTermodinmico

R2NH+

ROH, c. ou base

O

R

Adio Conjugada

Adio Conjugada

O

R

RSH

Adio Conjugada

HX

Adio Conjugada

NaBH4, R = H

Reduo

NaBH4

Reduo

RMgX, CuCl

Adio Conjugadacom CuCl

NaBH4, CeCl3

Reduo

KCN, HCN

ProdutoCintico

OH

R

CN

CN

O

R

NR

O

R

OR

O

R

SR

O

R

X

OH

OH

R

O

R

R

OH

R

Aminas

R1 R2Formao deAmida Terciria

NH2 CH2=O , NaCNBH3

R1 R2

N

Nitrilas

1 - DIBAL, -70 C

CN2 - H2O, H

+

H

O


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Haletos de Alquila

X

Mg, THF

Formao deGrignard

Li, EtOH

Formao deorganoltio

EtOH, base fraca

Substituio

EtOH, Base f orte

Eliminao

MgX

Li

OEt

Nitrocompostos

NO2

H2, Pt ou Pd

Reduo NH

Compostos de Grignard

MgX

Adio deGrignard

Adio de Grignard

Formao dec. Carb. do CO2

R1R2

O

R

R1

HO

R2

R MgX

1 - Co2, Et2O2 - H+

OH

O

Organoltios

X

Adio deorganometlico

Adio deOrganometlico

Ortolitiao

RX

TrocaHalognio- Ltio

MgBr2,THF

Transmetalao

CeCl,T HF

Transmetalao

R1R2

O

R

OR

R1

HO

R2

R Li

OR

Li

R Li

MgBr

CeCl2


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Benzeno

Bromao

Br2, AlCl3

Br

Nitrao

HNO3, H2SO4

NO2

Sulfonao

H2SO4 + SO3

SO2 OH

Alqulao deFriedel-Craf ts

RX + AlCl3

R

Acilao deFriedel-Craf ts

RCOCl + AlCl3

ReduoCataltica

H2, Ni, 50C, 100 atm

O

R

Ortolitiao

RLiLi

OH OH


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2 Informaes importantes sobre classes de reaes

1 SN1, SN2, E1, E2 e E1cb


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2 Substituio Eletroflica Aromtica


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3 Reaes na carbonila

Adio Nucleoflica

Trajetria de Burgi-Dunitz


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Reaes com organometlicos


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Adio Conjugada


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Substituio Nucleoflica


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Substituio Nucleoflica com perda do oxignio

Reaes Eletroflicas


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4 Reaes cido-Base


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5 Reaes de Oxidao e Reduo


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6 Grupos Protetores


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3 Reaes orgnicas nomeadas

Acetoacetic Ester Synthesis

Acyloin Condensation

Alder-Ene Reaction (Ene Reaction)

Aldol Addition (Aldol Reaction)


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Mechanism of the Aldol Addition

Aldol Condensation


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Azo Coupling

Baeyer-Villiger Oxidation

Balz-Schiemann Reaction

Beckmann Rearrangement

Bergman Cyclization (Bergman Cycloaromatization)


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Birch Reduction

Blaise Reaction

Brook Rearrangement

Brown Hydroboration

Cannizzaro Reaction

Corey-Bakshi-Shibata Reduction (Itsuno-Corey Reduction)

Claisen Rearrangement


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Claisen Condensation

Clemmensen Reduction

Corey-Fuchs Reaction

Corey-Kim Oxidation

Corey-Seebach Reaction (Seebach Umpolung)

Cross Metathesis

Curtius Rearrangement

Dakin Reaction


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Delpine Reaction

Dess-Martin Oxidation

Diazotisation

Dieckmann Condensation

Diels-Alder Reaction


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Directed ortho Metalation (DOM)

Epoxidation (Prilezhaev Reaction)

Fischer Esterification (Fischer-Speier Esterification)

Favorskii Reaction

Fischer Indole Synthesis

Friedel-Crafts Acylation

Friedel-Crafts Alkylation


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Friedlaender Synthesis

Fries Rearrangement

Fukuyama Coupling

Fukuyama Reduction

Gabriel Synthesis


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Grignard Reaction (Grignard Reagents)

Grubbs Reaction (Olefin Metathesis)

Haloform Reaction

Heck Reaction

Hell-Volhard-Zelinsky Reaction

Henry Reaction


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Hofmann Elimination

Hofmann's Rule

Horner-Wadsworth-Emmons Reaction (Wittig-Horner Reaction)

Ireland-Claisen Rearrangement


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Iwanow Reaction (Ivanov Reaction)

Jacobsen Epoxidation (Jacobsen-Katsuki Epoxidation)

Jones Oxidation

Kochi Reaction

Kolbe Electrolysis


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Kolbe Nitrile Synthesis

Kolbe-Schmitt Reaction

Kumada Coupling

Lawesson's Reagent

Leuckart Thiophenol Reaction

Luche Reduction


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Mannich Reaction

Markovnikov's Rule

Anti-Markovnikov

McMurry Reaction

Michael Addition

Mitsunobu Reaction


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Mukaiyama Aldol Addition

Nazarov Cyclization (Nazarov Reaction)

Negishi Coupling

Nozaki-Hiyama Coupling (Nozaki-Hiyama-Kishi Reaction)

Nucleophilic Substitution (SN1 SN2)

Nucleophilic substitution is the reaction of an electron pair donor (the nucleophile, Nu)

with an electron pair acceptor (the electrophile). An sp3-hybridized electrophile must

have a leaving group (X) in order for the reaction to take place.


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Mechanism of Nucleophilic Substitution

The term SN2 means that two molecules are involved in the actual transition state:

The departure of the leaving group occurs simultaneously with the backside attack by

the nucleophile. The SN2 reaction thus leads to a predictable configuration of the

stereocenter - it proceeds with inversion (reversal of the configuration).

In the SN1 reaction, a planar carbenium ion is formed first, which then reacts further

with the nucleophile. Since the nucleophile is free to attack from either side, this

reaction is associated with racemization.

In both reactions, the nucleophile competes with the leaving group. Because of this,

one must realize what properties a leaving group should have, and what constitutes a

good nucleophile. For this reason, it is worthwhile to know which factors will

determine whether a reaction follows an SN1 or SN2 pathway.

Very good leaving groups, such as triflate, tosylate and mesylate, stabilize an incipient

negative charge. The delocalization of this charge is reflected in the fact that these ions

are not considered to be nucleophilic.


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Hydroxide and alkoxide ions are not good leaving groups; however, they can be

activated by means of Lewis or Brnsted acids.

Epoxides are an exception, since they relieve their ring strain when they undergo

nucleophilic substitution, with activation by acid being optional:

Triflate, tosylate and mesylate are the anions of strong acids. The weak conjugate

bases are poor nucleophiles. Nucleophilicity increases in parallel with the base

strength. Thus, amines, alcohols and alkoxides are very good nucleophiles. Base

strength is a rough measure of how reactive the nonbonding electron pair is; thus, it is

not necessary for a nucleophile to be anionic.

Under substitution conditions, amines proceed all the way to form quaternary salts,

which makes it difficult to control the extent of the reaction.


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However, as a nucleophile's base strength and steric hindrance increase, its basicity

tends to be accentuated. If there are abstractable protons at the -position of the

electrophile, an elimination pathway can compete with the nucleophilic substitution.

An additional factor that plays a role is the character of the solvent. Increasing

stabilization of the nucleophile by the solvent results in decreasing reactivity. Thus,

polar protic solvents will stabilize the chloride and bromide ions through the formation

of hydrogen bonds to these smaller anions. Iodide is a comparatively better

nucleophile in these solvents. The reverse behavior predominates in aprotic polar

media.

The solvent also plays an important role in determining which pathway the reaction

will take, SN1 versus SN2. It may safely be assumed that a primary-substituted leaving

group will follow an SN2 pathway in any case, since the formation of the corresponding

unstable primary carbenium ion is disfavored. Reaction by the SN1 pathway is highly

probable for compounds with tertiary substitution, since the corresponding tertiary

carbenium ion is stabilized through hyperconjugation:

The better the solvent stabilizes the ions, the more probable that the reaction will

follow an SN1 pathway (e.g., in polar protic solvents such as water/acetone). The more

highly substituted is the incipient carbenium ion, the more probable that the reaction

will follow an SN1 pathway. The more unreactive the nucleophile, the more probable it

becomes that a reaction with secondary and tertiary electrophiles will follow an SN1

pathway. A weaker nucleophile is not as effective in the backside attack, since this

location is sterically shielded, especially in the case of tertiary substrates. Carbenium

ions are planar and therefore less sterically hindered, and are naturally more reactive

as electrophiles than the uncharged parent compound.

The hydrolysis oftert-butyl chloride is a typical SN1 reaction:


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Oppenauer Oxidation

Ozonolysis (Criegee Mechanism)

Paal-Knorr Furan Synthesis

Paal-Knorr Pyrrole Synthesis

Passerini Reaction


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Peterson Olefination

Reformatsky Reaction

Ring Closing Metathesis (RCM)

Ring Opening Metathesis (Polymerization) - ROM(P)

Ritter Reaction


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Robinson Annulation

Saytzeff's Rule

Saytzeff Rule implies that base-induced eliminations (E2) will lead predominantly to

the olefin in which the double bond is more highly substituted, i.e. that the product

distribution will be controlled by thermodynamics.

The use of sterically hindered bases raises the activation energy barrier for thepathway to the product predicted by Saytzeff's Rule. Thus, a sterically hindered base

will preferentially react with the least hindered protons, and the product distribution

will be controlled by kinetics.

Shapiro Reaction

Sharpless Aminohydroxylation (Sharpless Oxyamination)


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Sharpless Dihydroxylation

Sharpless Epoxidation

Stille Coupling

Strecker Synthesis


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Suzuki Coupling

Swern Oxidation

Van Leusen Reaction

Wacker-Tsuji Oxidation

Weinreb Ketone Synthesis

Williamson Synthesis


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Wittig Reaction

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