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    Diazonium Salts

    Uploaded by

    Deepak Kumar Sharma
    1) Diazonium salts can be synthesized from aromatic amines and used to couple to form azo dyes or undergo replacement reactions through various methods such as Sandmeyer reactions. 2) Aromatic diazonium ions react with nucleophiles like halides, cyanide, hydroxide or hydride to install new substituents on the aromatic ring. 3) Separation of ortho- and para- isomers can be difficult if their boiling points are too close, so physical properties or experience must be consulted to determine if separation is feasible.

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    Diazonium Salts

    Uploaded by

    Deepak Kumar Sharma
    160 views20 pages
    1) Diazonium salts can be synthesized from aromatic amines and used to couple to form azo dyes or undergo replacement reactions through various methods such as Sandmeyer reactions. 2) Aromatic diazonium ions react with nucleophiles like halides, cyanide, hydroxide or hydride to install new substituents on the aromatic ring. 3) Separation of ortho- and para- isomers can be difficult if their boiling points are too close, so physical properties or experience must be consulted to determine if separation is feasible.

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    1) Diazonium salts can be synthesized from aromatic amines and used to couple to form azo dyes or undergo replacement reactions through various methods such as Sandmeyer reactions. 2) Aromatic diazonium ions react with nucleophiles like halides, cyanide, hydroxide or hydride to install new substituents on the aromatic ring. 3) Separation of ortho- and para- isomers can be difficult if their boiling points are too close, so physical properties or experience must be consulted to determine if separation is feasible.

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    160 views20 pages

    Diazonium Salts

    Uploaded by

    Deepak Kumar Sharma
    1) Diazonium salts can be synthesized from aromatic amines and used to couple to form azo dyes or undergo replacement reactions through various methods such as Sandmeyer reactions. 2) Aromatic diazonium ions react with nucleophiles like halides, cyanide, hydroxide or hydride to install new substituents on the aromatic ring. 3) Separation of ortho- and para- isomers can be difficult if their boiling points are too close, so physical properties or experience must be consulted to determine if separation is feasible.

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    Diazonium salts

    synthesis

    HNO3
    NO2
    H2SO4

    H2, Ni

    HONO
    N N NH2

    benzenediazonium ion
    Diazonium salts, reactions
    1. Coupling to form azo dyes
    2. Replacements
    a) -Br, -Cl, -CN
    b) -I
    c) -F
    d) -OH
    e) -H
    f) etc.
    coupling to form azo dyes

    G N2

    + G N N

    an azo dye
    G = OH, NH2,
    NHR, NR2, etc.

    CH3
    H3C N + N2 SO3H

    N,N-dimethylaniline CH3
    H3C N N N SO3H

    methyl orange
    Sandmeyer

    Ar-N2+ + CuCl  Ar-Cl + N2

    Ar-N2+ + CuBr  Ar-Br + N2

    Ar-N2+ + CuCN  Ar-CN + N2


    Ar-N2+ + KI  Ar-I + N2

    Ar-N2+ + HBF4  Ar-F + N2

    Ar-N2+ + H2O, H+  Ar-OH + N2

    Ar-N2+ + H3PO2  Ar-H + N2


    CuCl

    Cl
    CuBr
    NO2

    Br
    CuCN

    CN
    NH2

    KI
    I
    N2

    HBF4
    F

    H2O,H+
    OH

    H3PO2
    Br
    NaCN
    NR

    NO2 NH2
    HNO3 H2/Ni

    H2SO4

    NaNO2
    HCl

    C N N2
    CuCN
    benzonitrile
    I2, Fe
    NR

    NO2 NH2
    HNO3 H2/Ni

    H2SO4

    NaNO2
    HCl

    I N2
    KI
    iodobenzene
    Br
    NaOH
    NR

    NO2 NH2
    HNO3 H2/Ni

    H2SO4

    NaNO2
    HCl

    OH N2
    H2O,H+
    phenol
    p-bromotoluene

    CH3 CH3 CH3


    Br2,Fe Br
    +

    Br
    bp 185oC bp 182oC

    You cannot separate a mixture of ortho and para-


    bromotoluene in a reasonable purity. Their bp's are
    too close together!
    CH3 CH3 CH3

    HNO3 H2/Ni
    + ortho-
    H2SO4
    bp 222oC
    NO2 NH2

    bp 238oC NaNO2
    HCl
    A mixture of ortho & para-
    nitrotoluenes is separable in
    a reasonable yield and purity CH3 CH3
    CuBr

    Br N2
    In syntheses, you may no longer assume that you can
    separate a pure para isomer from an ortho/para
    mixture. Either look up the physical properties of
    the compounds or rely on experience gained in the
    homework as to which mixtures are separable and
    which ones are not!
    m-bromotoluene
    CH3 CH3 CH3

    HNO3 H2/Ni
    + ortho-
    H2SO4
    bp 222oC
    NO2 NH2

    bp 238oC
    (CH3CO)2O

    CH3 CH3 CH3


    H2O,OH- Br2,Fe

    Br  Br
    NH2 NHCOCH3 NHCOCH3

    CH3 CH3
    HONO H3PO2

    Br Br
    N2
    m-bromophenol

    NO2 NO2
    HNO3 Br2,Fe
    H2SO4
    Br

    H2/Pt

    OH N2 NH2
    H2O NaNO2

    H+ H+
    Br Br Br
    p-toluic acid

    CH3 CH3 CH3

    HNO3 H2/Ni
    + ortho-
    H2SO4
    bp 222oC
    NO2 NH2

    bp 238oC NaNO2
    HCl

    CH3 CH3 CH3


    H2O, H+ CuCN
    heat
    COOH CN N2
    1,2,3-tribromobenzene

    NO2 NH2 NHCOCH3

    HNO3 H2/Ni (CH3CO)2O

    H2SO4

    TAR! HNO3
    H2SO4

    NH2 NH2 NHCOCH3


    Br Br Br2 (aq) H2O, OH-
    + ortho-
    heat
    NO2 NO2 NO2

    HONO
    H3PO2

    N2 Br Br Br
    Br Br Br Br Br Br Br Br
    CuBr H2 HONO
    Ni H3PO2
    NO2 NO2 NH2
    1,3,5-tribromobenzene

    NO2 NH2
    HNO3 H2/Ni

    H2SO4

    polybromination Br2 (aq)

    N2 NH2
    Br Br H3PO2 Br Br HONO Br Br

    Br Br Br
    Spectroscopy of amines

    Infrared: N—H stretch 3200 – 3500 cm-1


    1o often two bands 2o one band 3o no bands
    N—H bend
    1o strong bands 650-900 cm-1(broad) and 1560-1650 cm-1

    nmr: N—H 1-5 ppm (often broad and low)


    p-toluidine

    N—H
    stretch

    N—H bend
    NH2 c
    p-ethylaniline
    d

    CH2CH3
    b a

    d c b a

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