Alizarin

FromWikipedia,thefreeencyclopedia

Alizarinor1,2dihydroxyanthraquinone(also
knownasMordantRed11andTurkeyRed[1])isan
organiccompoundwithformulaC14H8O4thathas
beenusedthroughouthistoryasaprominentreddye,
principallyfordyeingtextilefabrics.Historicallyit
wasderivedfromtherootsofplantsofthemadder
genus.[2]In1869,itbecamethefirstnaturalpigment
tobeduplicatedsynthetically.[3]

Alizarin

Alizarinisthemainingredientforthemanufactureof
themadderlakepigmentsknowntopaintersasRose
madderandAlizarincrimson.Alizarininthemost
commonusageofthetermhasadeepredcolor,but
thetermisalsopartofthenameforseveralrelated
nonreddyes,suchasAlizarineCyanineGreenand
AlizarineBrilliantBlue.Anotableuseofalizarinin
moderntimesisasastainingagentinbiological
researchbecauseitstainsfreecalciumandcertain
calciumcompoundsaredorlightpurplecolor.
Alizarincontinuestobeusedcommerciallyasared
textiledye,buttoalesserextentthan100yearsago.
Names

Contents
1
2
3
4
5
6
7

History
Structureandproperties
Applications
Seealso
References
Furtherreading
Externallinks

IUPACname
1,2dihydroxy9,10anthracenedione
Othernames
1,2Dihydroxyanthraquinone,Turkeyred,
Mordantred11,AlizarinB,Alizarinred
Identifiers
CASNumber

72480(http://www.commonc
hemistry.org/ChemicalDetail.as
px?ref=72480)

History
Madderhasbeencultivatedasadyestuffsince
antiquityincentralAsiaandEgypt,whereitwas
grownasearlyas1500BC.Clothdyedwithmadder
rootpigmentwasfoundinthetombofthePharaoh
TutankhamunandintheruinsofPompeiiandancient
Corinth.IntheMiddleAges,Charlemagne
encouragedmaddercultivation.Madderwaswidely
usedasadyeinWesternEuropeintheLateMedieval
centuries.[4]In17thcenturyEngland,alizarinwas

ChEBI

CHEBI:16866(https://www.eb
i.ac.uk/chebi/searchId.do?chebi
Id=16866)

ChEMBL

ChEMBL55814(https://www.e
bi.ac.uk/chembldb/index.php/co
mpound/inspect/ChEMBL5581
4)

ChemSpider

6056(http://www.chemspider.c
om/ChemicalStructure.6056.ht
ml)

usedasareddyefortheclothingoftheparliamentary
NewModelArmy.Thedistinctiveredcolorwould
continuetobewornforcenturies(thoughalso
producedbyotherdyessuchascochineal),giving
EnglishandlaterBritishsoldiersthenicknameof
"redcoats".
Themadderdyestuffis
combinedwithadyemordant.
Accordingtowhichmordant
alizarincolor
used,theresultingcolormaybe
anywherefrompinkthrough
purpletodarkbrown.Inthe
18thcenturythemostvaluedcolorwasabrightred
knownas"TurkeyRed".Thecombinationof
mordantsandoveralltechniqueusedtoobtainthe
TurkeyRedoriginatedintheMiddleEastorTurkey
(hencethename).Itwasacomplexandmultistep
techniqueinitsMiddleEasternformulation,some
partsofwhichwereunnecessary.[5]Theprocesswas
simplifiedinlate18thcenturyEurope.By1804,adye
makerGeorgeFieldinBritainhadrefinedatechnique
tomakelakemadderbytreatingitwithalum,andan
alkali,[6]thatconvertsthewatersolublemadder
extractintoasolid,insolublepigment.Thisresulting
madderlakehasalongerlastingcolor,andcanbe
usedmoreefficaciously,forexamplebyblendingit
intoapaint.Overthefollowingyears,itwasfound
thatothermetalsalts,includingthosecontainingiron,
tin,andchromium,couldbeusedinplaceofalumto
givemadderbasedpigmentsofvariousothercolors.
Thisgeneralmethodofpreparinglakeshasbeen
knownforcenturies[7]butwassimplifiedinthelate
18thandearly19thcenturies.

Jmol3Dmodel

Interactiveimage(http://chema
pps.stolaf.edu/jmol/jmol.php?m
odel=O%3DC2c1ccccc1C%2
8%3DO%29c3c2ccc%28O%29
c3O)

KEGG

C01474(http://www.kegg.jp/en
try/C01474)

PubChem

6293(https://pubchem.ncbi.nl
m.nih.gov/compound/6293)

UNII

60MEW57T9G(http://fdasis.nl
m.nih.gov/srs/srsdirect.jsp?regn
o=60MEW57T9G)

InChI
SMILES

Properties
Chemicalformula

C14H8O4

Molarmass

240.21gmol1

Appearance

orangeredcrystalsorpowder

Density

1.540g/cm3

Meltingpoint

279to283C(534to541F
552to556K)

Boilingpoint

430C(806F703K)

Solubilityinwater

slightlytosparinglysoluble

Acidity(pKa)

6.94
Hazards

Safetydatasheet

ExternalMSDS(http://ptcl.che
m.ox.ac.uk/MSDS/AL/alizarin.
html)

Rphrases
R36R37R38
In1826,theFrenchchemistPierreJeanRobiquet
Sphrases
S26S36
foundthatmadderrootcontainedtwocolorants,the
[8]
Relatedcompounds
redalizarinandthemorerapidlyfadingpurpurin.
Thealizarincomponentbecamethefirstnaturaldye
Relatedcompounds anthraquinone,anthracene
tobesyntheticallyduplicatedin1868whenthe
Exceptwhereotherwisenoted,dataaregivenfor
GermanchemistsCarlGraebeandCarlLiebermann,
materialsintheirstandardstate(at25C[77F],
workingforBASF,foundawaytoproduceitfrom
100kPa).
[9]
anthracene. Aboutthesametime,theEnglishdye
verify(whatis ?)
chemistWilliamHenryPerkinindependently
Infoboxreferences
discoveredthesamesynthesis,althoughtheBASF
groupfiledtheirpatentbeforePerkinbyonlyoneday.
Thesubsequentdiscovery(madebyBroennerandGutzhowin1871)thatanthracenecouldbeabstracted
fromcoaltarfurtheradvancedtheimportanceandaffordabilityofalizarin'sartificialsynthesis.[10]

Thesyntheticalizarincouldbeproducedforafractionofthecostofthenaturalproduct,andthemarket
formaddercollapsedvirtuallyovernight.Theprincipalsynthesisentailedoxidationofanthraquinone2
sulfonicacidwithsodiumnitrateinconcentratedsodiumhydroxide.Alizarinitselfhasbeeninturn
largelyreplacedtodaybythemorelightresistantquinacridonepigmentsdevelopedatDuPontin1958.

Structureandproperties
Alizarinisoneoftendihydroxyanthraquinoneisomers.Itsmolecularstructurecanbeviewedasbeing
derivedfromanthraquinonebyreplacementoftwoneighboringhydrogenatoms(H)byhydroxylgroups
(OH).
Itissolubleinhexaneandchloroform,andcanbeobtainedfromthelatterasredpurplecrystals,
m.p.277278C.[2]
AlizarinchangescolordependingonthepHofthesolutionitisin,therebymakingitapHindicator.[11]

Applications
AlizarinRedisusedinabiochemicalassaytodetermine,quantitativelybycolorimetry,thepresenceof
calcificdepositionbycellsofanosteogeniclineage.Assuchitisanearlystagemarker(days1016of
invitroculture)ofmatrixmineralization,acrucialsteptowardstheformationofcalcifiedextracellular
matrixassociatedwithtruebone.
Alizarin'sabilitiesasabiologicalstainwerefirstnotedin1567,whenitwasobservedthatwhenfedto
animals,itstainedtheirteethandbonesred.Thechemicalisnowcommonlyusedinmedicalstudies
involvingcalcium.Free(ionic)calciumformsprecipitateswithalizarin,andtissueblockcontaining
calciumstainredimmediatelywhenimmersedinalizarin.Thus,bothpurecalciumandcalciuminbones
andothertissuescanbestained.Theprocessofstainingcalciumwithalizarinworksbestwhen
conductedinbasicsolution.[12]
Inclinicalpractice,itisusedtostainsynovialfluidtoassessforbasiccalciumphosphatecrystals.[13]
Alizarinhasalsobeenusedinstudiesinvolvingbonegrowth,osteoporosis,bonemarrow,calcium
depositsinthevascularsystem,cellularsignaling,geneexpression,tissueengineering,and
mesenchymalstemcells.[12]Ingeology,itisusedasastaintoindicatethecalciumcarbonateminerals,
calciteandaragonite.[14]
Madderlakehadbeeninuseasaredpigmentinpaintingssinceantiquity.[15]

Seealso
Alizarineink
Aniline
1,2,4Trihydroxyanthraquinoneorpurpurin,anotherreddyethatoccursinmadderroot
Hydroxyanthraquinone
Dihydroxyanthraquinone
Listofdyes
Listofcolors(compact)

References

1.SigmaAldrichCatalog:Alizarin(http://www.sigmaaldrich.com/cat
alog/ProductDetail.do?lang=en&N4=122777%7CSIAL&N5=SEA
RCH_CONCAT_PNO%7CBRAND_KEY&F=SPEC)
2.Theprimarymadderspeciesfromwhichalizarinhistoricallyhas
beenobtainedisRubiatinctorum.SeealsoVankar,P.S.Shanker,
R.Mahanta,D.Tiwari,S.C.(2008)."EcofriendlySonicator
DyeingofCottonwithRubiacordifoliaLinn.Using
Biomordant".DyesandPigments76(1):207212.
doi:10.1016/j.dyepig.2006.08.023.
3.Bien,H.S.Stawitz,J.Wunderlich,K.(2005),"Anthraquinone
DyesandIntermediates",Ullmann'sEncyclopediaofIndustrial
Chemistry,Weinheim:WileyVCH,
doi:10.1002/14356007.a02_355
4.Manyexamplesoftheuseoftheword"madder",meaningthe
rootsoftheplantRubiatinctorumusedasadye,aregiveninthe
MiddleEnglishDictionary(http://quod.lib.umich.edu/cgi/m/mec/
medidx?type=id&id=MED26444&egs=all&egdisplay=compact),
JohannesVermeer,Christinthe
adictionaryoflatemedievalEnglish.
HouseofMarthaandMary,165456.
5.Lowengard,S.(2006)."IndustryandIdeas:TurkeyRed".The
TheredblouseofMaryispaintedin
CreationofColorin18thCenturyEurope.GutenbergE.org.
madderlake
ISBN9780231503693.Additional18thcenturyhistoryat"Turkey
RedDyeinginBlackleyTheDelaunayDyeworks".
ColorantsInHistory.org.
6.GeorgeField'snotesareheldattheCourtauldInstituteofArt.See"FIELD,George(?17771854)".Retrieved
20120804.
7.Thompson,D.V.(1956).TheMaterialsandTechniquesofMedievalPainting.Dover.pp.115124.ISBN0
486203271.
8.See:
PierreJeanRobiquetandJeanJacquesColin(1826)"Surunnouveauprincipeimmdiatdesvgtaux
(lalizarin)obtenudelagarance"(http://books.google.co.tz/books?id=uLk3AAAAMAAJ&pg=PA407#
v=onepage&q&f=false)(Onanewsubstancefromplants(alizarin)obtainedfrommadder),Journalde
pharmacieetdessciencesaccessoires,2ndseries,12:407412.
JeanJacquesColinandPierreJeanRobiquet(1827)"Nouvellesrecherchessurlamatiercolorantede
lagarance"(http://books.google.com/books?id=JZU5AAAAcAAJ&pg=PA225#v=onepage&q&f=false)
(Newresearchintothecoloringmaterialofmadder),Annalesdechimieetdephysique,2ndseries,34:
225253.
9.Note:
In1868,GraebeandLiebermannshowedthatalizarincanbeconvertedintoanthracene.See:C.Graebe
andC.Liebermann(1868)"UeberAlizarin,undAnthracen"(http://gallica.bnf.fr/ark:/12148/bpt6k9066
7r/f56.image.langEN)(Onalizarinandanthracene),BerichtederDeutschenchemischenGesellschaftzu
Berlin,1:4951.
In1869,GraebeandLiebermannannouncedthattheyhadsucceededintransforminganthraceneinto
alizarin.See:C.GraebeandC.Liebermann(1869)"UeberknstlicheBildungvonAlizarin"(http://gall
ica.bnf.fr/ark:/12148/bpt6k906683/f20.image.langEN)(Ontheartificialformationofalizarin),Berichte
derDeutschenchemischenGesellschaftzuBerlin,2:14.
ForGraebeandLiebermann'soriginalprocessformakingalizarinfromanthracene,see:Charles
GraebeandCharlesLiebermann,"Improvedprocessofpreparingalizarine,"(http://pdfpiw.uspto.gov/.
piw?Docid=00095465&homeurl=http%3A%2F%2Fpatft.uspto.gov%2Fnetacgi%2FnphParser%3FSect
1%3DPTO1%2526Sect2%3DHITOFF%2526d%3DPALL%2526p%3D1%2526u%3D%25252Fnetahtm
l%25252FPTO%25252Fsrchnum.htm%2526r%3D1%2526f%3DG%2526l%3D50%2526s1%3D009546
5.PN.%2526OS%3DPN%2F0095465%2526RS%3DPN%2F0095465&PageNum=&Rtype=&SectionNu
m=&idkey=NONE&Input=View+first+page)U.S.Patentno.95,465(issued:October5,1869).(See
alsotheirEnglishpatent,no.3,850,issuedDecember18,1868.)
AmoreefficientprocessformakingalizarinfromanthracenewasdevelopedbyCaro,Graebeand
Liebermannin1870.See:H.Caro,C.Graebe,andC.Liebermann(1870)"UeberFabrikationvon
knstlichemAlizarin"(http://gallica.bnf.fr/ark:/12148/bpt6k90670n/f363.image.langEN)(Onthe
manufactureofartificialalizarin),BerichtederDeutschenchemischenGesellschaftzuBerlin,3:359

360.
10.Brnner,J.Gutzkow,H.(1871)."VerfahrenzurDarstellungvonAnthracenausdemPechvon
Steinkohlentheer,undzurDarstellungvonFarbstoffenausAnthracen"[ProcessforPreparingAnthracene
fromCoalTarPitch,andPreparationofDyeStuffsfromAnthracene].DinglersPolytechnischesJournal(in
German)201:545546.
11.Meloan,S.N.Puchtler,H.Valentine,L.S.(1972)."AlkalineandAcidAlizarinRedSStainsforAlkali
SolubleandAlkaliInsolubleCalciumDeposits".ArchivesofPathology93(3):190197.PMID4110754.
12.Puchtler,H.Meloan,S.N.Terry,M.S.(1969)."OntheHistoryandMechanismofAlizarinRedSStains
forCalcium".TheJournalofHistochemistryandCytochemistry17(2):110124.doi:10.1177/17.2.110.
PMID4179464.
13.Paul,H.Reginato,A.J.Schumacher,H.R.(1983)."AlizarinRedSStainingasaScreeningTesttoDetect
CalciumCompoundsinSynovialFluid".ArthritisandRheumatism26(2):191200.
doi:10.1002/art.1780260211.PMID6186260.
14.Green,O.R.(2001).AManualofPracticalLaboratoryandFieldTechniquesinPalaeobiology.Springer.
p.56.ISBN9780412589805.
15.Schweppe,H.,andWinter,J.MadderandAlizarininArtistsPigments.AHandbookofTheirHistoryand
Characteristics,Vol3:E.W.Fitzhugh(Ed.)OxfordUniversityPress1997,p.111112

Furtherreading
Schweppe,H.,andWinter,J."MadderandAlizarin",inArtistsPigments.AHandbookofTheir
HistoryandCharacteristics,Vol3:E.W.Fitzhugh(Ed.)OxfordUniversityPress1997,p.109
142

Externallinks
Moleculeoftheday:Alizarin(http://scienceblogs.com/moleculeoftheday/2007/04/alizarin_not_so
_mad_for_madder.php)
Madderlake(http://colourlex.com/project/madderlake/),Colourlex

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