Лекция 16 - chem.msu.su electro2_Arom).pdf · NH2 Br Br Br Br2 NH2 O O O HN O HN O HN O HBr Br

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Text of Лекция 16 - chem.msu.su electro2_Arom).pdf · NH2 Br Br Br Br2 NH2 O O O HN O HN O HN O HBr...

16 .

Docendo discimus ,

. . . , , ( ) .. . . . . . S, (). . -. . . - . - . , , . -. . . . , . . - ( ), ( , ) . -. . , .

ZZ

H Cl

B:

Z

Cl

-Cl+-Cl-FeCl3-

+ HCl + FeCl3

B: = Cl- FeCl4-

+

FeCl3

FeBr3

Br

Cl

Cl

Br

+ Cl2 +

(45 %) (55 %)

+ Br2 +

(65 %) (35 %)

25 C

Cl

FeCl3

Br Br

Br

FeBr3

Cl

Cl

Br

Br

Cl

Cl

Br

Br

+ Cl2 +

(70 %) (30 %)

+ Br2 +

(86 %) (13 %)

25 C

25 C

+

(1 %)

NO2

FeBr3

OAlBr3

NO2

Br

OBr

+ Br2

(90 %)

25 - 30 C+ HBr

25 - 30 C+ Br2 + HBr

(75 %)

NO2

FeCl3

NO2

Cl+ Cl2 40 - 50 C

+ HCl

NH2Br

Br

Br Br2

NH2O

O

OHN

O

HN

O

HN

O

H BrBr

Br

AcOH

Br2

HN

O

Br

HN

O

Br

HClEtOH, H2O

NH2

Br

AcOH, 0 C

H2N

H2N

HOOC

I2

ICl

H2N I

H2N I

HOOC

I2 + HgO I2 +Hg(OAc)2

I2 + AgOAc I2 + Ag2SO4

H3CO

H3CO

CHCl3H3CO

H3CO

I

+ CF3COOAg + I2 20 C

85 - 90 %

O2NI2 + AgOTf

I2 / HNO3

O2N

I

I100 C

(60 %)

O

O

O

OMe

O

O

O

I

I

I

I

I I

IOMe

I

I2 + HNO3

I2 + SO3

I2 + HNO3 + H2SO4

F2 ! !

- -

PhCH3

OPhH

CS2

CH2Cl2

OO

O

O

O

Ac2O / AlCl3 (85 %)

AcCl / AlCl3 (88 %)

AcCl / AlCl3 (92 %)

AcCl / AlCl3(90 %)

OCl

AlCl3CH2Cl2

O1-

AlCl3CH2Cl2

O O2N COCl

COCH3

O

O

O NO2

+ CH3COCl (70 %)

+ PhCOCl + CF3SO3H60 C (90

%)

+ CF3SO3H+

(84 %)

OH

CO2H

OCOR OAlCl2R

O

AlCl3

OAlCl2

OCOCH3CO2H

OH

COR

Ac2O / H2SO4

+ RCO+

o- -

O

O

O

O

AlCl3

O

CO2H

HO R R

H+ S

R

HO2C

+NH2NH2 / KOH

NH2NH2 / KOH

- H2O

RMgBr(R = )

Pd / C (R = H)

-

O

O

O

AlCl3

O

HOO

H2SO4

O

O

Zn

O

O

O

O

+

9,10-

+

O

O

OO

OH

O

AlCl3

H2SO4 O NaBH4 OH

R

OHH2SO4

[O]

RMgBr

H2SO4[O]

O

OH

R

Zn / Hg / HCl

H

Hh [O]

-

Y+

Y

Y- H+

Y

X

X-

H Y

X H

Y+

X-

H Y

-HX

B

Y

- HB+

-HX

Br2

HNO3ROH

H Br

Br H

O2N H

H OR

- HBr

- ROH

Br

Br

NO2

Br

- H2

9,10--9,10-

9-

9,10-

9-

-

M

Cl

Cl

ClBrR

RCl AlCl3RCl AlCl3 R AlCl4

ArH + RXAlCl3 (.)

RBr + MCl3

R + AlCl4+

ArR + HX

Cl

Cl

BF3

AlCl3 Cl

Br+ FCH2CH2Br 20 C, 4 .

+ HF

(94 %)

+50 C

AlCl3 / C6H6+ + HCl

(35 %) (65 %)

ClAlCl3

+ 2- 30 C

(80 %)

Cl

AlCl3

ClCl3Al

(50%)

H OSO3H

OH

Me HSO4

OH

Me

H

OH

Me

OH

Me

+

OH

BF360 C+ +

(56 %) (27 %)

OH

H3PO4*P2O5 S, t C

- H2S

HO

2

AlCl3; HCl

H3PO4+250 C; 25

+80 - 120 C; 10

( )

OH

HCHONaOH

OH

CH2OHH+

OH

OH

OH OH

x

x

x- -

OH

HCHONaOH

OHOH OH OH

-4-OH

4

H

O H

HCl H

HO H

MeO

HO

H

Cl

MeOCl

Cl

Cl

HOHCl

Cl

CCl4

AlCl3

CHCl3

AlCl3Ph

Ph PhH

Cl

-

AlCl3

C OCuCl

Cu2Cl2

H C O + AlCl4

ArH + CO + HCl ArCHO + HCl(70 - 90 %)

ClSO3H + HCOOH HCl + CO + H2SO4

HCl + + AlCl3

AlCl3

ClAlCl3

AlCl3

Cu2Cl2

Cu2Cl2Cl CHO

CHO

CHO + CO + HCl

40 C

+ CO + HCl

50 C

(80 %)

(70 %)

+ CO + HCl30 C

(60 %)50 .

-

OR Zn(CN)2HCl

OR

OR

CH NH

R'

NH2

Cl

Cl

H2O

H2O

OR

OR

CH O

R'

O

o- -

R'CN

HCl / ZnCl2(R = )

o- -

HO OH

OH

HO

C NMe

C6H6HO CHO

HO OH

OH

O

Zn(CN)2 + HCl

(99 %)

+1) HCl / Zn (CN)2

2) H2O

(60 %)

-

AcONa

(H3C)2N

H2O

HN(CH3)2

O

(H3C)2NCl

O P

O

ClCl

P

O

ClClCl

(H3C)2NN(CH3)2

H H2O

(H3C)2NH

N(CH3)2

Cl

(CH3)2N C PO2Cl2Cl

(H3C)2NO

H

Cl-

+ ClCH=N(CH3)2

+

( )

(99 %)

HN

O POCl2Cl-

H

O

H O CH3

O

ArH + HF

OBF3

HF

O+ HF

0 C+ CH3COOH

ArCHO + HF

ArCHOR

Cl

H2OArCHOArH + Cl2CHOR 20 C; 15

TiCl4 / CH2Cl2

(70 - 90 %)

H3O+

OH

NaOH

OH

CO2H

ONa

CO2

Ac2O

OH

CO2Na

O

CO2H

O

pKa 10

ONa

CO2

OK

CO2

OH

KO2C

OH

CO2Na

5 , 180 0C

5 , 220 0C

16 . F2 ! !