反応例 19.2 芳香族ジアゾニウム塩の反 応

反応例   19.2  芳香族ジアゾニウム塩の反 応 

(1) -NH

-OH

NH₂ OH

1) HCl/NaNO

2) EtOCS

K/45˚C 3) KOH then H

SO

63-75%

D. S. Tarbell, D. K. Fukushima Org. Synth. Coll. Vol. 3, 809

NH₂

NO₂

OH

NO₂

1) H

SO

/NaNO

2) H

SO

/H

O/160 ˚C

85-88%

R. H. F. Manske

Org. Synth. Coll. Vol. 1, 404

NO₂

CHO

SnCl₂

NH₂

CHO

HCl

OH

CHO

1) NaNO₂/HCl 2) H₂O/ !

R.B. Woodward,

Org. Synth. Coll. Vol. 3, 453

51~56%

NH₂ Br

OH Br

1) H

SO

/NaNO

2) H

O

80-92%

H. E. Ungnade, E. F. Orwoll Org. Synth. Coll. Vol. 3, 130

Ph NH₂ Ph

Ph

!

Ph OH Ph

Ph

HNO₂/H₂O K. Dimroth, A. Berndt, H.. Perst, C. Reichardt, Org. Synth.

Coll. Vol. 5, 1130.

Ar–NH₂

4-CH₃ : 2-CH₃-5-NO₂ :

2-CH₃-6-NO₂ : 4-Br:

2-PhCO:

2-Me₂NCO:

Ar–N₂⁺ HSO₄^– Ar–OH

NaNO₂, H₂SO₄ Cu(NO₃)₂ Cu₂O, H₂O

phenol yield / % 93

95 80 87 76~85

54

T. Cohen, A.G. Dietz, J.R. Miser, J. Org. Chem., 42, 2053 (1977).

(2) -NH

-F (Schiemann

)

NH₂ F

1) HCl/NaNO

2) HBF

3) heat

51-57%

D. T. Flood

Org. Synth. Coll. Vol. 2, 295

NH₂ EtO₂C

F EtO₂C

1) HCl/NaNO

2) HBF

3) heat

G. Schiemann, W. Winkelm Eler Org. Synth. Coll. Vol. 2, 299 84-89%

H₂N NH₂

1) HCl/NaNO

2) HBF

3) heat

80–81.5%

G. Schiemann, W. Winkelmöler, Org. Synth. Coll. Vol. 2, 188.

NH₂ Br

F Br

1) HCl/NaNO

2) HPF

3) 165 ˚C

K. G. Rutherford, W. Redmond Org. Synth. Coll. Vol. 5, 133 69-73%

(3) -NH

-Cl (Sandmeyer

)

NH₂

NO₂

Cl

NO₂

1) HCl/NaNO

2) CuCl W. W. Hartman, M. R. Brethen

Org. Synth. Coll. Vol. 1, 162 68-73%

NH₂ Cl

1) HCl/NaNO

2) CuCl

74-79%

C. S. Marvel, S. M. McElvain Org. Synth. Coll. Vol. 1, 170

O₂N NO₂ NH₂

O₂N NO₂

1) H

SO

/NaNO

2) HCl/Cu

Cl

F. D. Gunstone, S. H. Tucker Org. Synth. Coll. Vol, 4, 160 71-74%

NO₂

CHO

Cl

CHO

1) SnCl

/HCl

2) NaNO

/HCl 3) CuCl/HCl

85-88%

J. S. Buck, W. S. Ide

Org. Synth. Coll. Vol. 2, 130

(3) -NH

-Br (Sandmeyer

)

NH₂ Br

1) NaNO₂/HBr 2) Cu

L.A. Bigelow

Org. Synth. Coll. Vol. 1, 135 43~47%

NH₂ Br

L. A. Bigelow

Org. Synth. Coll. Vol. 1,136 70-73%

1) H

SO

/NaNO

2) HBr/CuBr

NH₂ Cl

Br Cl

J. L. Hartwell

Org. Synth. Coll. Vol. 3, 185 1) HBr/NaNO

2) CuBr/HBr/heat

89-95%

(4) -NH

-I

NH₂ I

1) NaNO₂/HCl 2) KI/H₂O

74~76%

H.J. Lucas, E.R. Kennedy Org. Synth. Coll. Vol. 2, 351

NH₂ HO

I HO

1) H

SO

/NaNO

2) KI/Cu (cat)/80 ˚C F. B. Dains, F. Eberly Org. Synth. Coll. Vol. 2, 355 69-72%

CO₂H

NH₂ I

CO₂H

1) HCl/NaNO

2) KI

!"#$#%&'()*+,-./012 3456789:;7<=>?@AAA>?BCDD

I

NO₂ I

NH₂

I

NO₂ I

I

1) NaNO₂/H₂SO₄

3) KI/H₂O

65~70%

R.B. Sandin, T.L. Cairns, Org. Synth. Coll. Vol. 2, 604

2) H₃PO₄

(5) -NH

-CN (Sandmeyer

)

NH₂ CN

1) HCl/NaNO

2) CuCN

64-70%

H. T. Clarke, R. R. Read Org. Synth. Coll. Vol. 1, 514

NH₂ CN

1) HCl/NaNO

2) CuCN

64-70%

H. T. Clarke, R. R. Read Org. Synth. Coll. Vol. 1, 514

(6) -NH

-NO

NH₂ O₂N

NO₂

O₂N

67-82%

1) HBF

/NaNO

2) NaNO

/Cu/H

O E. B. Starkey

Org. Synth. Coll. Vol. 2, 225

NH₂

NO₂

NO₂

NO₂ 1) NaNO₂/H₂SO₄/AcOH

2) NaNO₂/H₂O/Copper sulfites

52–60%

H.H. Hodgson, A.P. Mahadevan, E.R. Ward, Org. Synth. Coll. Vol. 3, 341.

(7)

NO₂

NH₂

NO₂

N₃ 1) NaNO₂/H₂SO₄

2) NaN₃ G.D. Mendenhall, P.A.S. Smith, Org. Synth., Coll. Vol. 5, 829.

CO₂H

NH₂ SH

CO₂H

1) HCl/NaNO

2) Na

S

3) Zn/AcOH

71-84%

C. F. H. Allen, D. D. MacKay Org. Synth. Coll. Vol. 2, 580

NH₂

CH₃

S

CH₃

OEt S

SH

CH₃

1) NaNO₂/HCl 2) EtOCS₂K, 40~45 ˚C

1) KOH/EtOH/ ! 2) H₂SO₄/H₂O

63~75%

D.S. Tarbell, D.K. Fukushima, Org. Synth. Coll.Vol. 3, 809.

NH₂

CF₃

SO₂Cl

CF₃

1) HCl/NaNO

2) SO

/CuCl/AcOH/HCl

68-79%

R. V. Hoffman

Org. Synth., 60, 121 (1983) (Collective Volume 7, page 508)

NH₂

1) NaNO₂/HCl 2) Se/KOH

Se

H.M. Leicester

Org. Synth. Coll. Vol. 2, 238 79~86%

NH₂ AsO₃H₂

1) HCl/NaNO

2) Na

AsO

/CuSO

3) HCl

39-45%

R. H. Bullard, J. B. Dickey Org. Synth. Coll. Vol. 2, 494

(8)

NH₂

O₂N

KOH

O2N O₂N

Cl

1) NaNO₂/HCl 2) CH₂=CH-CH=CH₂

G.A, Ropp, E.C. Coyner Org. Synth. Coll. Vol. 4, 727

57~62%

(9) -NH

-H

H₂N

NH₂

1) HCl/NaNO

2) H

PO

N. Kornblum

Org. Synth. Coll. Vol. 3, 295 76-82%

H₂N MeO

OMe NH₂

MeO

OMe

1) HCl/NaNO

2) H

PO

66-78%

N. Kornblum

Org. Synth. Coll. Vol. 3, 295

(10)

NH₂ CO₂H

N CO₂H

N

NMe₂

H. T. Clarke, W. R. Kirner Org. Synth. Coll. Vol. 1, 374 1) HCl/NaNO

2) PhNMe

62-66%

ONa

NaO N N NH₂

1) HCl/NaNO

2)

NH₂

SO₃H

N(CH₃)₂

N N N(CH₃)₂ HO₃S

1) NaNO

2)

NH₂

3 eq.

1) 1 eq.NaNO₂/HCl 2) 2 eq. NaOAc

N N HN

82~85%

W.W. Hartman, J.B. Dickey Org. Synth. Coll. Vol. 2, 163