Co Che Phan Ung Huu Co Chuong I

7/30/2019 Co Che Phan Ung Huu Co Chuong I

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C CH

PHN NG HU C


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PHN LOI PHN NG HU C

4 loi chnh1. Phn ng th (Substitution)

H NO2HNO3

H2SO4


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2. Phn ng tch (elimination)

CC

H

H

H

H

Br

HKOH

HBrCC

H

H

H

H

PHN LOI PHN NG HU C


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3. Phn ng cng (addition)

PHN LOI PHN NG HU C

C C

H

H

H

H

Br Br + CCl4 C C

Br H

Br

H

H

H


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4. Phn ng chuyn v (rearrangement)

PHN LOI PHN NG HU C

C CH

H

H

C

C C CH3

CH3

H3C

H3C

CH3H3C

H3C

H+


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PHN LOI PHN NG HU C


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PHN LOI PHN NG HU C


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C ch phn ng

Da vo cch t lin kt cng ha tr:c 3 c ch chnh:

1. C ch phn ng ion: tc cht hoc

cht trung gian hoc sn phm l ion.

+SO3H+

SO3H

H

+

SO3H

Benzenesulfonic acid (95%)


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2.C ch phn ng gc t do

cht trung gian mang in t l gi l

gc t do (free radical hocradical).

X:

: :

+ H : R X:

::

: H R.+

Alkyl radicalAlkane

C ch phn ng


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3. C ch ng b (pericyclic)

ch c s phn b li cc orbital lin kt.

C ch phn ng

CyclohexeneDiene alkene Cyclic transition state

+


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D ly v ng ly

1. S D LY (Heterolysis) Thng xy ra i vi cc lin kt bphn cc

Cn mt tc nhn h tr c thtch ri hai ion ra

A B A+

+ B-

Ions

Heterolytic bond cleavage

A B A

B

-Y Y


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2. S NG LY (Homolysis)

A B A

Radicals

Homolytic bond cle

R O O R

Dialkyl peroxide

heat

alkoxyl radicals

2 R O

X Xheat or light

2 X

Gc t do alkoxyl


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ng ly

D ly

D ly


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Bond-Making


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ACID-BASE

BRNTED-LOWRY Acid: cht c th cho mt proton H+

Base:cht c th nhn mt proton H+

H O

H

+ H Cl H O

H

H+

Cl-

+

Base

(proton acceptor)Acid

(proton donor)

Conjugate acid

of H2O

Conjugate base

of HCl


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Hng s acid Ka. Acid cng mnh khi Kacng ln v ngc li

Gi tr pKa = - log Ka.Acid cng mnh khi Ka

cng ln hay pKacng nh. Trong mt cp acid-base: dng acid cng

mnh (pKanh) th dng base lin hp ca

n cng yuv ngc li.

HA + H2O H3O+

+ A-

Ka =

H3O+

A-

HA

Ka


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nh hng ca dung mi

AH + Sol: A:() + SolH(+)

an acid solvent conjugate conjugate

base acid

Dung miAcid Base lin hp Acid lin hp


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NH HNG CA pH N CU TRC


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NH HNG CA pH N CU TRC

pKa (RCOOH) = 5

pKa (RNH3) = 10+


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ACID & BASE HU C

C

O

O HH3C O

H

H

+ CO

OH3C O

H

H

+ H+

Acetic acid

A carboxylic acid(acid)

Water

(base)

Acetate ion

(conjugate baseof acetic acid)

Hydronium ion

(conjugate acidof water)

N

H

HR

+O

H

H

+ H+

Hydronium ion

(acid)

N

H

H

H

H O

H

H

Water

(conjugate base of H3O+)

+

Amine1o

(base)

Alkylammonium ion

(conjugate acid of amine)


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ACID & BASE HU C


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Phn ng acid-base

Trong phnng acid-base: dng acid mnhsphnngvidng base mnh v cho rasnphm l cc dng acid v base yuhn

C

O

OH3C+H

Acetic acid

pKa = 4.74

CH3CH2OH

Ethanol

C

O

OH3C+

Acetic acid

(acid)

CH3CH2OH2+

Protonated ethanol

pKa = - 2.5


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KHI NIM ACID-BASE THEO LEWIS

Acid:Cht c kh nng nhncc i in t

Base:Cht c kh nng chocc i in t

+

+

-

+H+

Lewis acid

(electron -pair

acceptor)

Lewis base

(electron-pair

donor)

NH3 NH3H

AlCl

Cl

Cl

NH3 AlClCl

Cl

+NH3

Lewis base

(electron-pair

donor)

Lewis acid

(electron -pair

acceptor)

Base LewisAcid Lewis

Base LewisAcid Lewis


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Bt k mt cht no trong c nguyn tthiu in t u c tnh acid Lewis

V d: BF3, AlCl3, ZnCl2, FeCl3,

+

+-

+

+

R O H ZnCl2 R O ZnCl2

H

Br Br FeBr3 Br Br FeBr3-

KHI NIM ACID-BASE THEO LEWIS


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ACID-BASE THEO LEWIS


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Reactive IntermediatesCHT TRUNG GIAN PHN NG


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S d ly mt lin kt gia carbon v mt nguyn t bt

k c th to thnh:

Carbocation: ion dngvi in tch dng trn C

Carbanion: ion mvi in tch m trn C

C Z

C + + Z-

Carbocation

C Z

heterolysis

heterolysisC - Z++

Carbanion

D ly

D ly


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Nguyn t carbon thiu in t C lai ha sp2

C tnh acid Lewis

Cht thn in t(electrophile)

CARBOCATION

R2C R1 R1

R3

R2

1200

1200

1200

Oblique view Top view

R3


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*BcCarbocat ion

C+ O H

H

C O H

H

+

Carbocation

(Lewis acid)

Water

(Lewis base)

H3C C

CH3

CH3

+ H3C C

CH3

H

+

CH2+

~~ CC

CH

H

H

H

H

+ H3C C

H

H

+ H C

H

H

+

Carbocation 3

2 1

benzyl allyl methyl

~~

CARBOCATION


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CARBOCATION

Carbocation bn

Alcol bc 3


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CARBOCATIONALKYL

Orbital p trng

Orbital


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CARBOCATIONALKYL


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CARBOCATIONALKYL

Carbocation khng th

t cu trc phng

CARBOCATION ALLYL


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CARBOCATIONALLYL


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CARBOCATION BENZYL


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Mt s Carbocation l acid Lewis

CARBANION


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CARBANIONIon m cha carbon ha tr 3

L nhng base Lewis mnhPhn ng vi proton H+hoc nhng tm mang

in tch dng (thiu in t)

L cht thn hch (Nucleophile)

C-

H A

C AH+ +

-

Carbanion Lewis acid

C-

C L

C LC+ +-

Carbanion Lewis acid

CARBENE V CARBENOID


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CARBENE V CARBENOID

Phn t trung ha in cha C ha tr 2

C trng thi lai ha sp2 L cht thn in t v nguyn t carbon cn

mt i in t t c cu bt b bn vng.

CH2

N N+ heat or light

Diazomethane Methylene Nitrogen

CH2 N N+

C

H

HC

R

RR

sp2 orbital

+

Vacant p orbital

A carbocationMethylene (a carbene)

C

H

H

H

sp3

A carbanion


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VIT C CH PHN NG


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VIT C CH PHN NG


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In reactions where the distribution of electrons

is not symmetrical, the direction in which curved

arrows are drawn may be significant.


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This is not a plausible

mechanism

Co Che Phan Ung Huu Co Chuong I

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