71

Experiment
SynthesisofSudanI
11

Objectives
1) TosynthesizeSudanIdyebydiazotization/couplingreactionsofanilinewithnaphthol.
2) Torecrystallizeandcharacterizetheproductbymeasuringitsmeltingpoint.

Introduction
Dyeswereinusebeforerecordedhistory.Indigo,apigmentextractedfromaplant,was
used to dye burial cloths for Egyptian mummies over 4,000 years ago. Indigo is used today to
dye blue jeans. Tyrian purple was derived from Mediterranean mollusks. Approximately 9,000
molluskswereneededtogiveonegramofthedye.
American Indians used cochineal, a scarlet dye extracted from the dried bodies of
insects, to color their baskets and clothing. The red dye alizarin, extracted from madder root,
was known to the ancient Egyptians and Persians. Alizarin was used to dye the red coats of
BritishsoldiersintheAmericanRevolution,theredcapsandtrousersofFrenchsoldiersinthe
FrenchRevolution,andtheviolinsofAntonioStradivari.Structuresforthesedyesareshownin
Figure1.

Figure1
Examplesofdyes

72

Colored compounds absorb some, but not all, wavelengths of visible light. When one
looks at the light reflected from a colored object, the eye sees white light minus the
wavelengths absorbed by the object. Therefore, a colored object appears as the color
complementarytothewavelengthsitabsorbs.
Functional groups that absorb light are called chromophores. They are typically highly
conjugated systems containing several double bonds and one or more characteristic groups
suchasazo(N=N),nitro(NO
2
),andcarbonyl(>C=O).
Anazodyeisdefinedbyhavinganazolinkage(N=N)aspartofitschromophore. Azo
dyesaremadeintwosteps.First,aprimaryaromaticamineisreactedtogiveadiazoniumsalt,
as shown in Equation 1. Second, the diazonium salt is reacted or coupled with a strongly
activatedaromaticsystem,suchasphenoxide,asshowninEquation2.

Thefirststep,theformationofdiazoniumsalts,iscalleddiazotization.Thereactionwas
discoveredin1858byPeterGriess,whosubsequentlydiscoveredseveralreactionsofthisnew
compound.Themostimportantmethodforthepreparationofdiazoniumsaltsistreatmentof
primaryaminessuchasanilinewithnitrousacid(HNO
2
)preparedfromsodiumnitrite(NaNO
2
)
andamineralacid(e.g.HCl)(Scheme1).Adetaileddiazotizationreactionmechanismisshown
intheScheme2.

Scheme1Generationofnitrousacidandnitricoxidecation(NO
+
)
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Scheme2Mechanismfordiazotizationofprimaryamine

Primaryaliphaticaminesreactwithnitrousacidto givehighlyunstablediazoniumsalts
which spontaneously decompose to N
2
gas and carbocations (Scheme 3). The carbocations
react further to produce a mixture of alkenes, alcohols or alkyl halides, with alcohols as the
majorproduct.Thisreactionisoflittlesyntheticimportancebecausethediazoniumsaltistoo
unstable,evenundercoldconditions.

Scheme3Degradationofaliphaticdiazoniumsalt

Primaryaromaticaminescanformdiazoniumsaltswhicharestableatlowtemperature.
In aqueous solution these salts are unstable at temperatures higher than +5 C; the N
+
N
group tends to leave as N
2
, i.e. nitrogen gas. One can isolate diazonium compounds as
tetrafluoroborate (BF
4

) salts, which are relatively stable at room temperature. In general,

diazonium compounds are not isolated and once prepared, used immediately in further
reactions.
Anazocouplingisareactionbetweenadiazoniumcompoundandananiline,phenolor
other aromatic compound which produces an azo compound. In this reaction the diazonium
salt is an electrophile and the activated arene is a nucleophile in an electrophilic aromatic
substitution. In most cases, including the example in Equation 2, the diazonium compound is
also aromatic. The product absorbs longer wavelengths of light than the reactants because of
increasedconjugation.
74
NH
2
HCl
NH
3
+
Cl
-
aniline
anilinium
chloride
diazotization
(NaNO
2
+ HCl)
N
N
+
Cl
-
benzene diazonium
chloride
N
N
+
Cl
-
benzene diazonium
chloride
+
OH
-naphthol
NaOH
coupling
OH
N
N
Sudan-1
(1-phenyl-azo-2-naphthol)

Scheme4SynthesisofSudanI

In this experiment, an azo dye called SudanI will be synthesized from aniline and
naphthol (Scheme 4). SudanI is also commonly known as CI Solvent Yellow 14 and Solvent
Orange R. It is a lysochrome, a diazoconjugate dye systematically named 1phenylazo2
naphthol.SudanIisapowderedsubstancewithanorangeredappearance.Itismainlyusedto
color waxes, oils, petrol, solvents and polishes. Sudan I has also been adopted for coloring
various foodstuffs, including particular brands of curry powder and chili powder, although the
use of SudanI in foods is now banned in many countries because it has been classified as a
category3carcinogenbytheInternationalAgencyforResearchonCancer.

ExperimentalProcedure

1) Placeabout0.2gofanilineinapreweighed10mLroundbottomflask.Recordtheactual
weightofaniline.
2) Add 1 mL of distilled water and 10 drops of concentrated HCl. Swirl the flask in an ice
waterbath.
3) Toacleananddrytesttube,place1mLof10%NaNO
2
(fromburette).Chillthissolutionin
theicewaterbath.
4) Weigh 0.15 g of naphthol in a 50 mL beaker. Add 1 mL of 10% NaOH and 2 mL of
distilledwater.Stirthemixturewithaglassroduntilahomogeneoussolutionoccurs.Chill
thissolutionintheicewaterbath.
5) When all three mixtures are cooled to about 0 C, use a dropper to transfer the NaNO
2

solution into the roundbottom flask containing the aniline solution. Stir the mixture
75
thoroughly. Do not add the NaNO
2
solution too fast because the internal temperature
shouldbebelow10C.
6) Transfer the reaction mixture from the roundbottom flask into the beaker containing
naphthol.Stirthemixturetoavoidaggregationofredprecipitates.
7) Stirthemixtureintheicewaterbathfor35minutes.
8) Vacuumfiltertheprecipitatesandwashthefiltratewithcoldwater.
9) Allowtheprecipitatestodryonthevacuumfiltrationsetforafewminutes.Transferthis
productintoa50mLErlenmeyerflask.
10) Recrystallizethecrudeproductinethanol.
11) Vacuumfilterthecrystalsandwashthemwithcoldethanol.
12) Drythecrystalsonapreweighedwatchglass.
13) Weighandrecordtheyieldoftherecrystallizedproduct.
14) Determinethemeltingpointoftheproduct.
15) Submittheproductinaplasticbagtoyourinstructor.

LaboratorySafetyPrecaution
1) Wearsafetygogglesandlabcoatatalltimeswhileworkinginthelaboratory.
2) Anilineistoxicandirritating.
3) Sodiumnitriteisatoxicoxidizer.
4) Concentratedhydrochloricacidistoxic.Naphtholisirritating.
5) Sodiumhydroxideistoxicandcorrosive.
6) Ethanolisflammableandirritating.Keepawayfromflamesandotherheatsources.
7) Washyourhandsthoroughlywithsoapordetergentbeforeleavingthelaboratory.