Alkaloids 37

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    Quinoline AlkaloidsQuinoline Alkaloids CinchonaCinchona Alkaloids Alkaloids

     Cinchona bark contain many alkaloids the majors are:Cinchona bark contain many alkaloids the majors are:

    1- Quinine and Quinidine.1- Quinine and Quinidine.

    2- Cinchonine and Cinchonidine.2- Cinchonine and Cinchonidine.

     Cinchona alkaloids are presentCinchona alkaloids are present as salts with Quinic andas salts with Quinic and

    Cinchotannic acids.Cinchotannic acids.

     They are diacidic bases form two types of salts:They are diacidic bases form two types of salts:

    1- eutral salts !"onoacidic# !less water soluble.1- eutral salts !"onoacidic# !less water soluble.

    2- Acidic salts !$iacidic# water soluble.2- Acidic salts !$iacidic# water soluble.

    OHHO

    OH

    HO COOH

    Quinic acid

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      %oth Quinine and Quinidine& Cinchonine and Cinchonidine%oth Quinine and Quinidine& Cinchonine and Cinchonidine are $iastereoisomers. 'ach pair differs in theare $iastereoisomers. 'ach pair differs in the

    stereochemistry at C-( and C-).stereochemistry at C-( and C-).

    *+C,

    *,

    * *

    *+C,

    *,

    * *

    8 9

    Quinine Quinidine

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    Properties:Pro

    perties:  QuinineQuinine  is ery slihtly soluble in *is ery slihtly soluble in *22,& soluble in,& soluble in

    ethanol& chloroform& ether& ben/ene and other oranicethanol& chloroform& ether& ben/ene and other oranic solents.solents.

     QuinineQuinine is ais a diacidic basediacidic base. 0t forms 2 types of sulfates:. 0t forms 2 types of sulfates:

     Quinine monosulfateQuinine monosulfate  !!neutralneutral andand HH22O insolubleO insoluble#.#.

     Quinine bisulfateQuinine bisulfate  !!acidicacidic andand HH22O solubleO soluble#.#.

     QuinineQuinine  !!l l -isomer# ies-isomer# ies quinidinequinidine  !!d d -isomer# amon-isomer# amon

    other products when warmed with ,* in amylother products when warmed with ,* in amyl

    alcohol.alcohol.  Quinine is leorotatory& while uinidine is de3trorotatoryQuinine is leorotatory& while uinidine is de3trorotatory ..

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    Separation of the 4 AlkaloidsSe

    paration of the 4 Alkaloids

    Powdered Bark

    - Alk . CaO + NaOH + H2O

    - Reflux with benzene &

    - Filtration while hot

    Benene filtrate (Alkaloidal bases)

    dilute H2SO4

    Acidic aqueous la!er (Alkaloidal bisulphates)

      pH to 6.5 with Na2CO3

    Precipitate

    Quinine  uinidine!

    cinchonine " cinchonidineHot water ! Na2CO3

    Quinine  NaOH, ethe#

    Aqueous la!er "ther la!er 

    Cinchonine Quinidine " Cinchonidine

    $HCl  PH=! Na! % &a#t. salt

    $ 'ilte#

    Precipitate #iltrate

    Cinchonidine ta#t#ate Quinidine ta#t#ate

    Aqueous solution !onosulphates)!onosulphate)

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     $ests for identification$ests for identification

    %&%& #luorescence test:#luorescence test: 

    4olution of the alkaloid in o3yenated acids !e. *4olution of the alkaloid in o3yenated acids !e. *224,4,55& *,& *,++  oror phosphoric acid#phosphoric acid#  blue fluorescence !6 e with uinine and uinidine#.blue fluorescence !6 e with uinine and uinidine#.

    2& $halleoquine test:2& $halleoquine test:   Aueous solution of the alkaloidal salt 6 %r  Aueous solution of the alkaloidal salt 6 %r 22  7*7*22, !few drops till the, !few drops till the

    appearance of yellow color# 6 * appearance of yellow color# 6 *

    55,* ,* 

     emerald reen emerald reen

     color color

    !6 e with uinine and uinidine#.!6 e with uinine and uinidine#.

    +-+- 'osequin test ("r!throquinine test):'osequin test ("r!throquinine test):

       Aueous solution of the alkaloidal salt 6 dil *Cl 6 %r  Aueous solution of the alkaloidal salt 6 dil *Cl 6 %r 22 7*7*22, !few drops till the, !few drops till the

    appearance of yellow color# 6 C*Cl  appearance of yellow color# 6 C*Cl++ 6 pot. 8errocyanide 6 *6 pot. 8errocyanide 6 *55,*,*   redred color in the C*Clcolor in the C*Cl++ layer !6 e with uinine and uinidine#.layer !6 e with uinine and uinidine#.

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    ,soquinoline Alkaloids,soquinoline Alkaloids %&%& IpecacuanhaI  pecacuanha AlkaloidsAlkaloids

     Occurrence:Occurrence:

    ,pecac,pecac is the dried roots and rhi/omes ofis the dried roots and rhi/omes of Cephalis ipecacuanhaCephalis ipecacuanha !%ra/ilian!%ra/ilian

    ipecacuanha# oripecacuanha# or Cephalis acuminataCephalis acuminata !Cartaena or ;anama ipecacuanha#!Cartaena or ;anama ipecacuanha#

    8am. ?#& mainly e+etinee+etine !>9- @9 ? of total!>9- @9 ? of total

    alkaloids#& withalkaloids#& with cephalinecephaline andand ps!chotrineps!chotrine ..

    -

    .eO

    'O

    -

    O.e O.e

    H H

    *  e ,etine

    *  H Cephaline

    -

    .eO

    HO

    -

    O.e O.e

    H

    -schot#ine

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     "+etine:"+etine:  0t is0t is non phenolicnon phenolic andand le/orotator!le/orotator!..

    0t contains 2 basic nitroens.0t contains 2 basic nitroens.

     Cephaline:Cephaline:  0t is0t is phenolicphenolic andand le/orotator!le/orotator!..

    0t0t 0i/es e+etine0i/es e+etine onon +eth!lation with (CH+eth!lation with (CH11))22 SOSO44..

     Ps!chotrine:Ps!chotrine: 

    ,ccurs as yellow prisms.,ccurs as yellow prisms.

    0t is0t is phenolicphenolic and iesand ies cephalinecephaline on reductionon reduction..

    0t0t 0i/es e+etine0i/es e+etine onon reduction followed b! +eth!lationreduction followed b! +eth!lation..

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     ,solation of ,peca alkaloids:,solation of ,peca alkaloids:Powdered root and rhio+e - "xt. alcohol,#on$., lead acetate.

    - Filtration

    #iltrate 'esidue  Non$alkaloidal sub.

    - "%ap., dil. HCl & Filtration

    Alkaloidal bases and salts

    #iltrate (Alkaloidal HCl salts)

    - Alk. with NaOH & "xt. with ethe#

    "ther la!er 

    ,etine

    (-henolic alkaloids)

    - H#l !Alkaloidal alt'

    - Alk. (H)*H "xt. ethe#

    Aqueous la!er "ther la!er  

    (-schot#ine) (Cephaline)

    Aqalk solution

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     $ests for identification of ,peca alkaloids:$ests for identification of ,peca alkaloids:

     Alkaloidal solution in *Cl 6 Alkaloidal solution in *Cl 6 Ca h!pochloriteCa h!pochlorite 

      oran0eoran0e color.color.

     "+etine"+etine andand cephalinecephaline 66 #roehd3s#roehd3s reaent:reaent: dirt! 0reendirt! 0reen color !thecolor !the

    color with emetine fades by addition of *Cl#.color with emetine fades by addition of *Cl#.

     Ps!chotrinePs!chotrine 66 #roehd3s#roehd3s reaent:reaent:  pale 0reenpale 0reen color.color.

     CephalineCephaline andand ps!chotrineps!chotrine 66 p p-nitrodia/oben/ene-nitrodia/oben/ene  dye soluble indye soluble in

    a,*a,*  purplepurple color.color.

     Ps!chotrinePs!chotrine 6 conc. *6 conc. *224,4,55 66 *,*,++  cherr! redcherr! red color color ..

     EmetineEmetine  + Liebermann's reagent+ Liebermann's reagent  blackblack color.color.

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     *ses:*ses:

     "+etine"+etine  andand cephaelinecephaeline  haehae antitu+our antitu+our   andand  anti/iralanti/iral  actiity& but are too to3ic for therapeutic use.actiity& but are too to3ic for therapeutic use.

     "+etine and ps!chotrine"+etine and ps!chotrine are mainly used asare mainly used as e+etice+etic

    dru0sdru0s

     The crude dru is used asThe crude dru is used as epectorantepectorant !due to its saponin!due to its saponin content# .content# .

     "+etine"+etine *Cl and $ehydroemetine !$*'# hae an*Cl and $ehydroemetine !$*'# hae an

    antia+oebic effect5antia+oebic effect5 and are used for the treatment ofand are used for the treatment of

    amoebic dysentry andamoebic dysentry and Fasciola.Fasciola.  0peca alkaloids are0peca alkaloids are diaphoreticdiaphoretic& alone or in combination with& alone or in combination with

    opium !e..opium !e.. 6o/er3s6o/er3s powder powder #.#.

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    2& Curare Alkaloids2& Curare Alkaloids  Occurrence:Occurrence:  Curare or 4outh American arrow poison is the dried crude e3tract& obtainedCurare or 4outh American arrow poison is the dried crude e3tra