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Synthesis of a Diazo Dye

Lucas Man
TA Michelle Portillo
Synthetic #2 Formal Final Report

Abstract
Diazo dyes are important synthetic dyes based on diazonium chemistry. In this
experiment, the diazo dye Methyl-Sudan I was synthesized in a two-step process by Iirst
synthesizing the diazonium salt oI p-Toluidine and then reacting the diazonium salt with 2-
naphtholate in basic conditions to produce the diazo dye in 21.3 puriIied yield. The dye was
characterized by melting point, UV/Vis, 60 MHz and 400 MHz
1
H NMR analyses.

Introduction
Diazonium salts are important intermediates oI a variety oI reactions that involve
halogenation or the synthesis oI conjugated azo compounds that can be used as dyes or
pigments.
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The creation oI aromatic halides, Ior example, involves diazotization oI an aromatic
amine to generate a diazonium salt; the halide ion will then displace the diazo group in the
Sandmeye reaction to generate the aromatic halide.
1, 2
In addition to halides, diazonium salts can
also react with activated aromatics with carbonyl or amine groups.
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The azo compounds that are
synthesized in these reactions oIten absorb light in the visible spectrum due to their high degrees
oI conjugation and are used as synthetic dyes.
P-Toluidine is commonly used in diazotization reactions due to its aromatic amine group
as well as its methyl group in the para position that can provide additional Iunctionality in
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Iollow-up reactions. Due to the ease in generating its diazonium salt, p-toluidine is used in the
synthesis oI a wide range oI synthetic organic dyes, pharmaceutical products and pesticides
involving diazotization and azo coupling reactions.
3
Similarly, 2-naphthol is oIten used in the
synthesis oI azo dyes and a variety oI other compounds
4
as it is easily activated under basic
conditions to generate 2-naphtholate, which readily reacts with diazonium salts.
The diazonium salt oI p-toluidine can thus be reacted with 2-naphtholate in an azo
coupling reaction to produce an azo dye. The complete mechanisms oI the diazotization,
activation oI 2-naphthol and the azo coupling reaction are shown in Scheme 1.
1,5
The reaction is
a multi-step process: the diazotization occurs Iirst as sodium nitrate reacts with a strong acid to
produce nitrous acid, which reacts with water to generate a nitrosonium ion.
1,5
The lone pair
electrons on nitrogen oI p-toluidine attacks the nitrosonium ion and through a series oI reactions
and a tautomerization, eventually yields the diazonium ion.
1,5









In step two, 2-naphthol Iirst reacts with strong base to Iorm 2-naphtholate.
5,6,7
The
negative charge on 2-naphtholate is delocalized through resonance Iorms and can be placed on
carbon 2 making a carbanion.
5,6
The carbanion then attacks the diazonium ion in the coupling
reaction to yield the azo compound.
5,6

Scheme 1A - Reaction scheme Ior the diazotization oI p-Toluidine and azo coupling with 2-
Naphthol
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In this experiment, the azo compound Methyl-Sudan I was synthesized using reaction
scheme 1 as shown above. The purpose was to utilize the diazotization reaction oI p-Toluidine to
produce a diazonium salt that can react with 2-naphtholate to create a dye that absorbed
electromagnetic wavelengths in the visible light ranges. Melting point, NMR and UV/Vis
spectrophotometer characterization were carried out to veriIy the production oI the azo dye.

Experimental
All chemicals were obtained Irom the common shelI and hooded shelI in the lab room or
acquired Irom the stockroom and used without puriIication. All reactions were carried out in a
Scheme 1B - Electron-pushing diagram Ior the diazotization and azo coupling reactions involving
p-Toluidine and 2-naphthol
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hood. The
1
H proton NMR spectrums were taken on both a 60 MHz and 400 MHz NMR
spectrometer. Melting point analysis was perIormed using a Mel Temp II melting point apparatus
without corrections Ior barometric pressure.

!toluidine diazonium salt. P-toluidine (100 mg, 0.933 mmol) was mixed with 12M HCl (0.5
mL) and 1mL distilled H
2
O in a 10mL Erlenmeyer Ilask while gently warmed in a water bath
and stirred with a 0.5 inch micro-stir bar. Solution was kept in ice bath at 0-5C aIter all solids
have dissolved. Sodium nitrite (80 mg, 1.159 mmol) was dissolved in 1mL H
2
O in a reaction,
and the sodium nitrite solution was added to the p-toluidine/HCl solution in dropwise Iashion
while maintaining the temperature at 0-5C. The acidity oI the diazonium salt solution was tested
with potassium iodide/starch paper and adjusted to neutral pH by adding urea crystals.

Sodium 2aphtholate. 2-naphthol (160 mg, 1.1098 mmol) was mided with 3M NaOH (1.5
mL) in a reaction tube and gently warmed in water bath to dissolve all solids.

MethylSudan I azo dye. 2-naphtholate solution was slowly added to the diazonium salt
solution in small amounts. Temperature oI the diazonium salt solution was maintained at 0-5C
at all times. The orange-red precipitate (192 mg, 78.7 crude yield) was collected in a Hirsch
Iunnel by vacuum Iiltration. The collected crystals were redissolved in 95 ethanol in a warm
water bath and recrystallized. The product was isolated as a bright red crystalline powder (52
mg, 27.1 recovery, 21.3 yield); Melting point 92C (decomposed to brown viscous liquid);
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H NMR (60 MHz, CDCl3) o 8.737 (s, 1H), 7.819 (m, 14H), 2.416 (s, 3H), 2.171 (s, 1H);
1
H
NMR (400 MHz, CDCl3) o 8.6166 (d, 1H), 7.7362 (d, 1H), 7.6844 (d, 2H), 7.6326 (d, 2H),
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7.5751 (t, 1H), 7.4082 (t, 1H), 7.2951 (dd, 2H), 6.9345 (d, 1H), 3.037 (s, 3H); UV/Vis (95
Ethanol) 480 nm (0.53294), 418 nm (0.48781), 318 nm (0.27835).

Discussion
The diazotization reaction involving p-toluidine and nitrous acid in water yields a
diazonium salt that can react with 2-naphtholate to produce a bright red azo dye Methyl-Sudan I.
In this experiment, these reactions were carried out to yield Methyl-Sudan I in 21.3 yield. The
product was Iirst precipitated in 78.7 crude yield and then recrystallized in 27.1 recovery.
The loss oI yield during recrystallized was most likely the result oI the dye staining the Iiltering
apparatus and thus being unable to be extracted. Furthermore, the recrystallization procedure was
delicate and careIul heating was essential to prevent the dye Irom decomposing. Thus there may
have been an excess oI solvent used, and some oI the dye may still have remained in solution
when vacuum Iiltration was used to extract the crystallized products.
However, enough oI the product was isolated to perIorm melting point, NMR and
UV/Vis characterizations. Using a Mel Temp II apparatus, the dye was Iound to decompose at
around 92C to a dark brown viscous liquid (Notebook pages, Supplemental InIormation),
thereIore no accurate melting point was Iound. UV/Vis absorbance characterization (Figure 1,
Supplemental InIormation) shows that the product did absorb wavelengths in the visible light
ranges, with absorbance peaks at 480 nm and 418 nm. These wavelengths correspond to the
violet-blue range oI colors in the visible spectral
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and the absorbance oI these colors will result in
the transmittance oI red-orange colors, corresponding to the bright red appearance oI the dye.
Characterizations with 60 MHz and 400 MHz
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H NMR Iurther veriIy the synthesis oI
Methyl-Sudan I. The 60 MHz
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H NMR spectrum (Figure 2, Supplemental InIormation) contains
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a peak at 2.418 ppm, integral value oI 3, corresponding to the methyl group oI Methyl-Sudan I.
Peaks between 7.819 and 6.846 ppm with integral value oI 14 correspond to the aromatic
hydrogens oI the azo compound with some contribution Irom solvent signals. The peaks at 8.737
and 8.578 ppm correspond to the hydrogen on the carbon adjacent to the alcohol group.
The 400 MHz
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H NMR spectrum (Figure 3, Supplemental InIormation) provides a much
clearer characterization oI the compound. The splitting patterns and integral values clearly
correspond to the protons in methyl-sudan I. The doublet at 8.6166 ppm, integral oI 1
corresponds to the hydrogen on the carbon adjacent to the alcohol group due to the de-shielding
eIIect oI the oxygen atom. The doublet at 7.7362, integral oI 1 corresponds to the hydrogen on
the second carbon away Irom the alcohol. The doublet at 7.6844, integral oI 2, indicates the two
chemically identical hydrogens on the carbons adjacent to the carbon bonded to the nitrogen. The
doublet at 7.6326, integral oI 1, represents the hydrogen on the second ring oI the 2-naphthol
moiety oI the compound, 2 carbons away Irom the carbon bonded to the nitrogen. The triplet at
7.5751, integral oI 1, corresponds to the hydrogen split by 2 adjacent hydrogens 4 carbons away
Irom the nitrogen. The other triplet, at 7.4082 ppm, integral oI 1 corresponds to the other
hydrogen that is split by 2 adjacent hydrogens, 5 carbons away Irom the nitrogen and oxygen
atoms. The doublet oI doublets at 7.2951, integral value oI 2, corresponds to the 2 hydrogens on
the carbons adjacent to the carbon bonded to the methyl group.
The 400 MHz
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H NMR provides clear evidence Ior the synthesis oI methyl-sudan I in
this experiment. The relatively accurate integral values as well as lack oI additional signals
indicate that the product is very pure. UV/Vis absorbance characterization Iurther veriIies that
the product is a dye absorbing visible light wavelengths corresponding to the violet-blue end oI
the spectrum
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. The purity oI the product shows that the reaction was very clean with Iew by-
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products. However the low percent yield and percent recovery show that recrystallization was
not eIIicient and puriIication could be improved.

onclusions
The production oI synthetic azo dyes using diazotization reactions and azo coupling
reactions is common in the chemical industry. P-toluidine and 2-naphthol are both commonly
used Ior such syntheses. This experiment successIully synthesized one such azo dye, methyl-
sudan I in 21.3 yield by reacting the diazonium salt oI p-toluidine with 2-naphtholate. The dye
was veriIied to absorb wavelengths in the visible light range by UV/Vis characterization, and its
structure was Iurther conIirmed with proton NMR characterization.
The 78.7 crude yield and only 27.1 recovery indicate that much oI the product was
lost during puriIication. A large amount oI the dye was absorbed by the Iilter papers used during
the vacuum Iiltration procedure. The absorbed dye could potentially be recovered by placing the
Iilter papers in 95 ethanol, redissolving the dye and then evaporating the solvent although this
process may leave impurities behind as well. Another possibility to increase yield is to use larger
amounts oI starting materials; the percent yield could be increased as proportionately less oI the
product would be lost.

Acknowledgements
The author would like to thank Michelle Portillo and Dr. Rummel Ior their help in the lab
with steup and procedures. Thanks also to Chris Fenning Ior instrument room help and analysis
oI NMR spectra, and thanks to the stockroom staII Ior providing equipment and necessary
chemicals.
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#eferences
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