Synthesis of the Dye, Methyl-Sudan I

Janet Smith

Introduction

1-phenylazo-2-naphthol, also known as Methyl-Sudan I, is a bright red synthetic

diazo dye.1 The diazonium chemistry used in the experiment is where these diazo dyes

get their name.1 One of the uses of diazo dyes is in the dying of fabrics, mainly cotton.

Diazo dyes improve the quality of dyed fabrics and prevent the fabric from fading.2

Methyl-Sudan I is a compound composed of aromatic rings, a nitrogen-nitrogen double

bond, a hydroxyl group, and a methyl group. Its is used often in color solvents, oils,

waxes, gasoline, shoe polish, and floor polishes.3 The dye, Methyl-Sudan-I, is classified

as a Group 3 carcinogen meaning its carcinogenicity to humans cannot be classified.4

In 2005, the dye made international news. More than 470,000 food products in the

United Kingdom were recalled after being contaminated with the dye.3 Despite a law in

the European Union that was enacted in 2003 stating that all dried and crushed or ground

chili entering the European Union must be tested and certified as “free of Sudan,” a chili

powder used to make Worcester sauce by Premier Foods, a large food distribution

company in Europe, contained traces of Methyl-Sudan I.3 Soups, sauces, and ready-made

meals that used the sauce were therefore contaminated as well.3 The chili powder was

thought to be imported from India before passing through to food ingredient companies

and eventually being acquired by Premier Foods.3 The dye slipped past the European

Union’s testing and certification process because, according to the Food Standards

Agency of the European Union, the suppliers are responsible for carrying out the tests for

Methyl-Sudan I.3 The contamination was first discovered in February of 2005, but the

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risk of developing cancer from any of the contaminated products was said to be very

low.3

In this experiment, the synthetic dye, Methyl-Sudan I, was synthesized from p-

toluidine. The p-toluidine reacts with sodium nitrite in hydrochloric acid and water at 0°C

to 5°C to make a solution of diazonium salt.1 The diazonium salt is then made into the

diazo dye, Methyl-Sudan I, through the addition of 2-napthol. The mechanism is shown

below5:

The purpose of this experiment was to synthesize a diazo dye, Methyl-Sudan I,

from p-toluidine. Recrystallization techniques were used to obtain a pure sample and 1H

Nuclear Magnetic Resonance analysis and Ultraviolet-visible spectroscopy analysis was

used to confirm the identity and purity of the product.

Experimental

Methyl-Sudan I. 2-naphthol (78mg) and sodium hydroxide (0.5mL, 3M) were

added to a reaction tube, tube one. The solution was heated slightly to get the 2-naphthol

into solution and then was placed into a beaker of warm water to prevent the 2-naphthol

from “crashing out”. To a second reaction tube, tube two, p-toluidine (54mg),

concentrated hydrochloric acid (0.25mL, 12M), and distilled water (0.5mL) was added

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and then warmed to get the p-toluidine into solution. It was then cooled in an ice bath to

below 0°C, and left there to stay cold. Finally, a solution of sodium nitrite (40mg) and

water (0.5mL) was added to a third reaction tube. This solution was then added drop-wise

to tube two, while keeping tube two below 0°C. This mixture in tube two was stirred

vigorously and allowed to sit for five minutes. The solution was then tested for excess

nitrous acid using potassium-iodide paper. The solution failed the test as a dark purple

color was seen immediately upon contact between the paper and solution. Urea was

added a few pellets at a time and stirred vigorously until the solution passed the test,

producing no color when the solution touched the paper. Finally, the contents of tube one

were added in small amounts to the contents of tube two. The bright red mixture was left

in an ice bath for fifteen minutes, while being agitated every 3 minutes. The solution was

then filtered in a Hirsch funnel and the solid was allowed to dry in a locker. A crude

product of 59mg was collected, which was a 47.2% yield. The melting range of the crude

product was 76°C to 80°C. The crude product was recrystallized from ethanol and after

filtration in a Hirsch funnel and drying, 7mg of pure product was collected. This was a

5.60% yield of pure product. The melting range of the pure product was 128°C to 131°C.

Finally, a thin layer chromatography was performed on the pure product dissolved in

ethanol. One component spot was seen, with an Rf value of 0.548. In order to confirm the

identity purity of the product an Ultraviolet-visible spectroscopy analysis and 1H Nuclear

Magnetic Resonance analysis were performed.

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1
H-NMR Data (see attached): Obtained using 36mg of product in deuterated chloroform

solvent on a 60MHz spectrometer.

Significant Peaks
Observed Splitting Pattern, Type of Hydrogen
1.25ppm Singlet, unknown

1.55ppm Singlet, —CH3

2.164ppm Singlet, acetone impurity

2.45ppm Doublet, unknown

3.80ppm Singlet, unknown

6.80ppm Singlet, —OH

7.0ppm to 7.75ppm Too difficult to determine because of many

different sets of overlapping equivalent
hydrogen atoms, Aromatic ring—H

UV-Vis Data (see attached):

Absorption (nm)
216nm
256nm
454nm
658nm

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Results and Discussion:

The 1H-NMR spectrum showed significant peaks at 1.55ppm, 6.80ppm, and

7.0ppm to 7.55ppm. There were also significant peaks at 1.25ppm, 2.164ppm, 2.45ppm,

and 3.80ppm. However all of these peaks were impurities since the structure of methyl-

sudan I, would not result in peaks in these regions of the spectrum. The peak at 2.164ppm

was most likely a result of an acetone impurity caused by the cleaning of the 1H-NMR

tube between this use and the last use. The significant peaks that corresponded to the

structure of methyl-sudan I, were seen at 1.55ppm, 6.80ppm, and 7.0ppm to 7.55ppm.

The peaks between 7.0ppm and 7.55ppm were a result of the aromatic rings in the

structure. Since there were nine arene protons, the integral value for this set of peaks was

set at nine. The small singlet peak seen at 6.80ppm corresponded to the hydroxyl group in

the structure, but an integral value was not taken here because this peak was so close to

the peaks corresponding to the arene protons. The integral value looked to be about one,

however, which was correct since there was only one hydroxyl proton. The singlet peak

seen at 1.55ppm corresponded to the methyl group and had an integral value of 2.56,

which is approximately three, the correct value.

This spectrum was very hard to read and was very poor quality. This could have

resulted from many different errors during the experiment and analysis of the product.

The synthesis may not have been carried out properly because there were a large number

of temperature constraints, which are difficult to regulate for an entire experiment. The
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H-NMR tubes may not have been properly cleaned after their last use resulting in a side

reaction and impurities. Other sources of human error or machine error also could have

been factors.

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 Although the 1H-NMR analysis showed that the product may have had quite a few

impurities, melting point determination using a Mel-Temp device in the laboratory

showed that the product was very pure. The crude product had a melting range of 76°C to

80°C, which is very far away from the theoretical melting point of 131°C, showing that

the crude product was very impure. The pure product had a melting range of 128°C to

130°C, which compared very favorably to the accepted value of 131°C, showing the

product was very pure. The thin-layer chromatography also showed the product was very

pure because only one spot was seen on the developed TLC plate, showing that only one

component was present in the mixture.

The UV-Vis analysis showed the molar absorbivity of Methyl-Sudan I to be

32172L/mol*cm. The Uv-Vis also showed a large band of absorption at 454nm, which

corresponds to the red color of the dye.

Overall the synthesis of methyl-sudan I was moderately successful. The synthesis

only produced a 5.60% product yield. The 1H-NMR analysis showed a few impurities,

yet the melting range showed that the product was almost completely pure. Finally, the

UV-Vis analysis confirmed the light being absorbed by the product produced the

observed red color.

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 References
1
“Synthesis of the Dye, Methyl-Sudan I” handout. Retrieved from Williamson, K.L.,

Macroscale and Microscale Organic Experiments. 2nd Edition. 1994, Houghton

Mifflin, Boston. Revised 10/18/07

2
Types of synthetic dyes. Retrieved from http://hubpages.com/hub/Types-of-Synthetic-

Dyes
3
Q&A: Sudan I. (2005, February 21). Retrieved from http://news.bbc.co.uk/2/hi/health/

4285285.stm
4
World Health Organization, International Agency for Research on Cancer. (2008).

Overall evaluations of carcinogenicity to humans Lyon, France: Retrieved from

http://monographs.iarc.fr/ENG/Classification/crthgr03.php
5
McMurry, J. (2008). Organic chemistry. Belmont, CA: Brooks/Cole, Cengage Learning.