反応例 16.2 芳香族求電子置換反 応における配向性

反応例 16.2  芳香族求電子置換反 応における配向性 

参考文献： 

鈴木仁美，“有機反応 Ⅱ 芳香族化合物”丸善（1984）． 

L.M. Stock, H.C. Brown, Adv. Phys. Org. Chem., 1, 35 (1963).

K. Schofield, “Aromatic Nitration,” Cambridge Univ. Press (1980).

R.O.C. Norman, R. Taylor, “Electrophilic Substitution in Benzenoid Compounds,”

Elsevier (1956).

G.A. Olah, “Friedel-Crafts Chemistry,” Wiley (1973). 

ニトロ化   

トルエン 

CH₃

SO₂

NO₂⁺BF₄^–/

CH₃ NO₂

CH₃

O₂N CH₃

O₂N

+ +

HNO₃-H₂SO₄, 25 ˚C 25 ˚C

61.0 3.7 30.9

65.4 2.8 31.8

AcONO₂/Ac₂O, 30 ˚C 58.4 4.4 37.2  

アルキル置換体  R

CH₂CH₃ CH(CH₃)₂ C(CH₃)₃

R NO₂

R

O₂N R

O₂N

+ +

AcONO₂/Ac₂O 0 ˚C

R = CH₃ 58.1 3.7 38.2

45.9 3.3 50.8

28.0 4.5 67.5

10.0 6.8 83.2  

種々の置換体  Y

CN CF₃

I

NO₂ F Cl Br

CO₂H COMe

CO₂Et NHAc

NMe₃⁺ Ph

Y NO₂

Y

O₂N Y

O₂N

+ +

Y = OMe HNO₃-H₂SO₄, 45 ˚C 31 2 67

AcONO₂/Ac₂O, 10 ˚C 71^a) <0.5 28 HNO₃-H₂SO₄, 25 ˚C

AcONO₂/Ac₂O, 20 ˚C

19.4 2.1 78.5

67.8^a) 2.5 29.7

HNO₃-H₂SO₄, 25 ˚C – 89 11

HNO₃-H₂SO₄, 25 ˚C HNO₃-H₂SO₄, 25 ˚C HNO₃-H₂SO₄, 25 ˚C HNO₃-H₂SO₄, 25 ˚C

13 0.6 86

35 0.9 64

43 0.9 56

45 1.3 54

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HNO₃-H₂SO₄, 25 ˚C 26.4 71.6 <2

HNO₃, 0 ˚C 18.5 80.2 1.3

HNO₃, 0 ˚C 17 81 <2

HNO₃-H₂SO₄, 0 ˚C 6 91 3

HNO₃-H₂SO₄, 25 ˚C 6.1 91.8 2.1

HNO₃, 30 ˚C 27.7 66.4 5.9

AcONO₂/Ac₂O, 25 ˚C 68 – 32

トルエンの種々の反応   

CH₃

Cl⁺ Br⁺ SO₃(H⁺)

CH₃ E

CH₃

E CH₃

E

+ +

HNO₃/MeNO₂, 25 ˚C 61.7 1.9 36.4

E⁺ = NO₂⁺

Cl₂/HOAc, 25 ˚C 59.8 0.5 39.4

Br₂/HOAc-H₂O, 25 ˚C 32.9 0.3 66.8

H₂SO₄/H₂O, 25 ˚C 36 4.5 29  

MeCO

PhCO

Me

PhCH

Me

CH

MeCOCl, AlCl

/ C

H

Cl

, 25 ˚C

1.2 1.3 97.6

PhCOCl, AlCl

/ PhNO

, 25 ˚C

7.2 1.1 91.7

MeBr, AlBr

/ PhCH

, 0~5 ˚C

53.7 17.3 28.9

PhCH

Cl, AlCl

/ MeNO

, 25 ˚C

43.5 4.5 52.0

Me

CHCl, GaCl

/ MeNO

, 25 ˚C

46.9 17.4 35.7

塩素化   

Y

Me Cl Br CN CF₃ NO₂

Y Cl

Y

Cl Y

Cl

+ +

Y = OMe 34.9 – 65.1

74.7 2.2 23.1

36.4 1.3 62.3

39.7 3.4 56.9

23.2 73.9 2.9

15.7 80.2 4.1

17.6 80.9 1.5

Cl⁺

R.O.C. Norman, C.K. Radda, J. Chem. Soc., 3610 (1961).  

Friedel-Crafts アルキル化   

Y

EtBr, GaBr

Et

Y

Et Y

Et

+ +

C

H

Cl

, 25 ˚C

33.3 25.6 41.1

Y = Ph

Y = Cl 42.2 15.9 41.9

Y PhCH₂Cl, AlCl₃

CH₃ CH₂CH₃

F Cl Br

Y CH₂Ph

Y

PhCH₂ Y

PhCH₂

+ +

MeNO₂, 25 ˚C

43.5 4.5 52.0

42.4 5.0 52.6

33.0 0.6 66.4

66.8

32.5 0.7

85.1

14.7 0.2

Friedel-Crafts アシル化   

アセチル化 

Y MeCOCl, AlCl₃

Ph CH₃ CH₂CH₃ CH(CH₃)₂ C(CH₃)₃

F Cl

Br

Y COMe

Y

MeCO Y

MeCO

+ +

C₂H₄Cl₂, 25 ˚C

Y = OMe 100

97.3

1.2 1.3 97.6

0.3 2.7 97.0

0 3.0 97.0

0 3.8 96.2

– –

– –

0 0.5 99.5

– – 100

– – 100

スルホン化   

Y H₂SO₄

CH₂CH₃ CH(CH₃)₂ C(CH₃)₃ F

Cl Br

Y SO₃H

HO₃S Y Y

HO₃S

+ +

Y = CH₃ 30 2.4 68

89% H₂SO₄, 25 ˚C

90~95% H₂SO₄, 25 ˚C

90~95% H₂SO₄, 12 ˚C

16.3 – 83.7

2.8 – 97.2

0 7.7 92.3

0.5 0.14 99.4

0.4 0.2 99.4

~100  

クロロメチル化   

Y CH₂O, HCl

CH₂CH₃ CH(CH₃)₂ C(CH₃)₃ F

Cl Br

Y CH₂Cl

Y

ClCH₂ Y

ClCH₂

+ +

Y = CH₃ 45 1.1 54

conc. HCl 60~70 ˚C

HCl-ZnCl₂/ CCl₄, 50 ˚C

29 1.9 69

12 3.2 84

~0.1 5.8 94

11 – 89

37 – 63

58

42 –