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    Heterocyclics

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    pawanaana
    This document summarizes key information about heterocyclic compounds. It begins by defining heterocycles as ring compounds containing elements other than carbon, such as oxygen, nitrogen, and sulfur. It then discusses different systems for naming heterocycles and provides examples of common heterocyclic ring structures. The document notes that aromatic heterocycles like pyrrole, furan, and thiophene are very reactive due to resonance stabilization. It also summarizes common reactions for several important heterocycles like pyridine, including electrophilic aromatic substitution, nucleophilic aromatic substitution, and reduction reactions.

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    Heterocyclics

    Uploaded by

    pawanaana
    169 views28 pages
    This document summarizes key information about heterocyclic compounds. It begins by defining heterocycles as ring compounds containing elements other than carbon, such as oxygen, nitrogen, and sulfur. It then discusses different systems for naming heterocycles and provides examples of common heterocyclic ring structures. The document notes that aromatic heterocycles like pyrrole, furan, and thiophene are very reactive due to resonance stabilization. It also summarizes common reactions for several important heterocycles like pyridine, including electrophilic aromatic substitution, nucleophilic aromatic substitution, and reduction reactions.

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    This document summarizes key information about heterocyclic compounds. It begins by defining heterocycles as ring compounds containing elements other than carbon, such as oxygen, nitrogen, and sulfur. It then discusses different systems for naming heterocycles and provides examples of common heterocyclic ring structures. The document notes that aromatic heterocycles like pyrrole, furan, and thiophene are very reactive due to resonance stabilization. It also summarizes common reactions for several important heterocycles like pyridine, including electrophilic aromatic substitution, nucleophilic aromatic substitution, and reduction reactions.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    169 views28 pages

    Heterocyclics

    Uploaded by

    pawanaana
    This document summarizes key information about heterocyclic compounds. It begins by defining heterocycles as ring compounds containing elements other than carbon, such as oxygen, nitrogen, and sulfur. It then discusses different systems for naming heterocycles and provides examples of common heterocyclic ring structures. The document notes that aromatic heterocycles like pyrrole, furan, and thiophene are very reactive due to resonance stabilization. It also summarizes common reactions for several important heterocycles like pyridine, including electrophilic aromatic substitution, nucleophilic aromatic substitution, and reduction reactions.

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    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    of 28

    Heterocycles

    Ring compounds with elements other than carbon in the ring. The most common elements to appear in heterocyclic compounds are oxygen, nitrogen and sulfur. The aliphatic heterocycles are similar to the open chain analogues, ethers, amines and sulfides. The aromatic heterocycles are similar to other aromatic compounds.

    Heterocyclic Nomenclature Replacement nomenclature (IUPAC recommended 1957) Oxygen Sulfur Nitrogen oxa thia aza

    Lowest number assigned to the hetero atom with the highest precedence: O > S > N

    S thiacyclobutane

    NH

    1-oxa-3-azacyclopentane

    Hantzsch-Widman (1888) Suffixes ring with nitrogen Ring members unsatd satd 3 4 5 6 7 -irine ete ole ine -iridine etidine olidine perhydro__ine ring without nitrogen unsatd satd irene ete ole in irine etane olane ane epane

    epine perhydro__epine epin

    You must know the * names

    O
    * oxirane ethylene oxide oxacyclopropane

    S
    * thiirane ethylene sulfide thiacyclopropane

    N H
    * aziridine ethylene imine azacyclopropane

    N N
    diazirane

    N 1-azirine

    N O

    oxaziridine oxazacyclopropane

    O
    oxetane oxacyclobutane

    S
    thietane thiacyclobutane

    NH
    azetidine azacyclobutane

    N
    azete azacyclobutadiene

    N
    1-azetine 1-azacyclobutene

    O
    * furan oxole oxacyclopentandiene

    S
    * thiophene thiole thiacyclopentandiene

    N H * pyrrole

    O O
    1,3-dioxolane 1,3-dioxacyclopentane

    O
    * tetrahydrofuran

    N H
    * pyrrolidine azacyclopentane

    N N H N N H
    imidazole

    N N H N

    pyrazole

    1,2,4-triazole

    N O
    oxazole

    N O N S
    thiazole

    isooxazole

    O
    4-hydropyran

    O
    4-pyrone

    2-pyrone

    O O
    * 1,4-dioxane

    H N N H
    * piperidine

    N H
    piperazine

    N N N N
    pyrimidine

    N N
    pyrazine

    pyridazine

    O N
    * pyridine

    N H
    * morpholine

    5 6 7 8

    4 3

    6 7

    N
    1

    N2
    8 1

    * quinoline

    * isoquinoline

    N H
    * indole

    Aromatic heterocycles

    N H pyrrole

    O furan

    S thiophene

    Aromatic! EAS very, very reactive resonance stabilization energy ~ 22-28 Kcal/mole sp2 N H 6 pi electrons no unshared pair on Nitrogen very weak base Kb = 10-14

    N H

    strong acids N H pyrrole CH3CO2-NO2+

    polymer!

    (CH3CO)2O, 5oC SO3 pyridine, 90o C6H5-N2+Cl-

    N H

    NO2

    N H

    SO3H

    N H

    N N

    CHCl3, KOH N H pyrrole N H H2O O CH=O

    HCN, HCl (CH3CO)2O 250o

    N H Br Br N H

    C CH3 Br Br

    Br2, EtOH 0o

    CH3CO2NO2 O furan pyridine:SO3 O C6H5N2+ O (CH3CO)2O, BF3 O N SO3H O NO2

    C CH3

    1. HCN, HCl O furan Br2 dioxane HgCl2 CH3CO2Na O HgCl CH3COCl O O Br 2. H2O O CH=O

    I2 O

    C CH3

    less reactive, can use acids S H2SO4 S CH3CO2NO2 (CH3CO)2O Br2, benzene I2, HgO S I S NO2 SO3H

    Br

    Br

    Why EAS 2-position?

    2-

    H N H H Y N H H

    H Y N H

    H Y

    3-

    N H

    N H

    H2, Ni N H 250o N H Kb = 10-3 2o amine H2, Ni O 50o O THF

    Kb = 10-14

    Pyridine N N N 6 pi electrons, sp2, flat aromatic, resonance stabilization energy ~ 23 Kcal/mole Kb = 2.3 X 10-9
    4 3 2 5

    N
    1

    CH3 N

    -picoline

    Pyridine Reactions:

    important solvent & base (~ 3o amine)

    1) EAS (much less reactive than benzene ~ nitro)


    KNO3, H2SO4, 370
    o

    NO2
    3% yield

    N H2SO4, SO3, HgSO4 220o, 24 hours

    N SO3 N H Br2, 300o N Friedel-Crafts no reaction Br + N Br Br

    Deactivated to EAS due to electronegativity of Nitrogen Directs beta due to destabilization of alpha and gamma H H Y N H N Y H Y Y N H Y H Y

    N N N

    N Y

    H Y

    H Y

    Pyridine, reactions 2) Nucleophilic aromatic substitution


    NaNH2 N N NH2

    phenyl lithium N

    H2O N

    NH3, 200o N Cl NH3, 200o N N N Br N NH2 NH2 H N Z Z

    Br N

    NH3, 200o

    NR

    activated to nucl. arom. subts. directs alpha & gamma

    Pyridine, reactions 3) As base Kb = 2.3 X 10-9


    HBr N N H CH3I N N CH3 4o salt I Br

    Pyridine, reactions 4) reduction


    H2, Pt N HCl, 25o, 3 atm. N H piperidine Kb = 2 X 10-3 aliphatic 2o amine

    Polynuclear Heteroaromatics
    EAS
    6 7 8 5 4 3 2 6 7

    EAS
    5 4 3

    N
    1

    N
    8 1

    NAS

    quinoline
    4 5 6 7 3 2

    NAS isoquinoline

    EAS

    N H

    indole

    Skraup synthesis of quinoline

    NH2 +
    aniline

    NO2 H2C OH HC OH H2C OH


    glycerol

    +
    nitrobenzene

    H2SO4

    + H2O N

    The nitrobenzene is not only the solvent, but is also one of the reactants.

    H2C OH HC OH H2C OH

    H+ -H2O

    HC O CH + CH2
    acrolein

    NH2
    H+

    O H C CH2 CH2 N H OH H C CH2 CH2 N H

    H
    -H2O

    OH
    EAS

    N H NO2

    N H NH2 + N

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