AZO DYES

Presented By:
Hasnain M Raza M.Phil Organic Chemistry hmraza100@gmail.com
Institute of chemistry University of the Punjab Lahore Pakistan
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CONTENTS

Introduction Constructing The Azo LinkageGeneral synthesis of Azo Dyes Classification of Azo dyes Applications of Azo dyes Health and Safety Aspects

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INTRODUCTION TO DYE
A dye is a colored substance that has an affinity to the substrate to which it is being applied. The dye is generally applied in an aqueous solution, and may require a mordant to improve the fastness of the dye on the fiber. Chemical affinity is defined as electronic properties by which dissimilar chemical species are capable of forming chemical compounds. It can also refer to the tendency of an atom or compound to combine by chemical reaction with atoms or compounds of unlike composition
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AZO DYESINTRODUCTION

There are more than 100,000 commercially available dyes whilst over 7 x 105 metric tons of dyestuffs are produced annually. Amongst the synthetic dyes, azo dyes are the largest group and it is estimated more than half of the annually produced amounts of dyes (for the year 1994 worldwide azo dyes production as 1 million tons) are azo dyes.
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Azo dyes are basically characterized by the presence of one or more azo linkages (-N = N-). The azo group is attached to two groups, of which at least one, but more usually both, are aromatic and more difficult to biodegrade in nature. They exist in the trans form in which the bond angle is 120 , the nitrogen atoms are sp2 hybridized. Hence, during the synthesis of azo dyes and dyeing process in industries, dyes that are lost to the industries wastewater remain recalcitrant. Consequently affect photosynthetic activity in aquatic life due to the reduced light penetration.
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Aryl azo compounds have vivid colours, especially reds, oranges, and yellows. Therefore, they are used as dyes, azo dyes for example Disperse Orange 1. Some azo compounds, e.g. methyl orange, are used as acid-base indicators due to the different colours of their acid and salt forms. The development of azo dyes was an important step in the development of the chemical industry.
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Disperse Orange 1 (4anilino-4'nitroazobenzene) is a dye of the azobenzene class. Disperse Orange 1 contains approximately 25% dye by weight, with the remaining mass consisting of NaCl and other salts.
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RESONANCE IS RESPONSIBLE FOR COLOUR IN AZO DYES

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Constructing The Azo Linkage....... The cetral feature of Azo Dyes Just in two steps

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Almost without exception, azo dyes are made by diazotization of a primary aromatic amine followed by coupling of the resultant diazonium salt with an electron-rich nucleophile . A diazomum salt is a weak electrophile and hence reacts only with highly electron rich species such as amino and hydroxy compound.

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STEP 1) Diazonium Salt formation

Reaction of primary arylamines with nitrous acid results in the formation of relatively stable arenediazonium salts.

This reaction occurs through the intermediacy of an N-nitrosoamine The N-nitrosoamine is converted to a diazonium ion in a series of steps

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H. M.Raza MPhil PUIC H. M.Raza MPhil PUIC Lhr Lhr

STEP 2) Coupling Reactions of Arenediazonium

Salts Arenediazonium ions react as electrophiles with highly reactive aromatic compounds such as phenol and aromatic tertiary amines The reaction is called a diazo coupling reaction

The Diazo component often contains electronaccepting substituents, and the Coupling group contains electron-donating substituent.

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COUPLING WITH PHENOL OCCURS BEST IN

SLIGHTLY ALKALINE SOLUTION

The alkaline solution produces a phenoxide ion that couples more rapidly If the solution is too alkaline, a nonreactive diazohydroxide is produced

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PHENOL AND ANILINE DERIVATIVES UNDERGO

COUPLING ALMOST EXCLUSIVELY AT THE PARA POSITION UNLESS THIS POSITION IS BLOCKED.

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The azo coupling results in compounds which are highly conjugated and which often absorb light in the visible region + The -SO Na group is added to the molecule 3 to confer water solubility and to link the dye to the polar fibers of wool, cotton etc. Orange II is made from 2-naphthol

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DIAZO COMPONENTS
Diazo components for the production of azo dyes can be divided into the following groups of aromatic amines: Aniline and Substituted Anilines. Examples: Toluidines, nitroanilines. Naphthylamines and Naphthylaminesulfonic Acids.and

Diamines H2N-A -NH2

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DIAZOTIZATION METHODS
Depending on the basicity and solubility of the amines being diazotized, the following diazotization methods find industrial use: a) Direct Diazotization. The primary aromatic amine is dissolved or suspended in aqueous hydrochloric or sulfuric acid, and a concentrated aqueous sodium nitrite solution is added. An excess of 2.5-3 equivalents of acid per equivalent of amine is used. A temperature of 0-5C is maintained by adding ice.

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B) INDIRECT

DIAZOTIZATION

Amines with sulfonic or carboxylic acid groups are often difficult to dissolve in dilute acid. Therefore, the amine is dissolved in water or a weak alkali, and the calculated amount of sodium nitrite solution is added to this amine solution which is stirred into the ice-cooled acid solution already in the vessel. The acid can also be added to the amine-nitrite mixture already at hand. c) Diazotization of Weakly Basic Amines Weakly basic amines are dissolved in concentrated sulfuric acid and diazotized with nitrosylsulfuric acid (NO HS0 4-) , which is easily prepared from solid sodium nitrite and concentrated sulfuric acid.

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D)

DIAZOTIZATION IN ORGANIC SOLVENTS.

The water-insoluble or sparingly soluble ammine is dissolved in glacial acetic acid or other organic solvents and, where necessary, diluted with water. After the addition of acid it is diazotized in the usual manner with sodium nitrite solution. Nitrosylsulfuric acid, nitrosyl chloride, alkyl nitrites, or nitrous gases can also be used instead of sodium nitrite. Temperature, pH, and the concentration of the diazotizing solution often have a considerable effect on the progress of diazotization. Physical properties (distribution, particle size) and the addition of emulsifiers and dispersing agents influence the diazotization of slightly soluble amines.

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CERTAIN AROMATIC AMINES REQUIRE SPECIAL

DIAZOTIZING PROCESSES

o-Diamines, such as 1,2-phenylenediamine and 1,8naphthylenediamine, undergo cyclization during the normal diazotization process to form triazoles;

Benzotriazole Naphtho[1,8]triAzole(PerLazimine) The desired bis-diazotization with o-,m-, and p phenylenediamine is achieved in glacial acetic acid with nitrosylsulfuric acid. 1,8-Naphthylenediamine can be bis-diazotized in an excess of acid.
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IMPORTANT

Diazonium compounds are generally stable only in aqueous solution at low temperatures. When heated, they frequently decompose by eliminating nitrogen to form the corresponding phenol. Some amines, however, can be diazotized at temperatures up t0 40 0C. Metal ions also accelerate the decomposition of diazonium compounds. Therefore, diazotization is usually carried out in wooden vats or iron stirring vessels with an acid-proof lining or rubber coating.
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COUPLING COMPONENTS
The most important coupling components can be divided into the following groups. Where there are several possibilities for coupling, the preferred coupling positions are marked by bold arrows and the other possible coupling positions by ordinary arrows.

Anilines , diarninobenzenes :

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Electron-donating substituents in the aniline, such as methyl or methoxy groups, especially at the rneta position, promote coupling; the tendency to couple thus increases in the order ; aniline< o -toluidine< -toluidine< -anisidine< cresidine<l-amino-2,5-dimethoxy-benzene (aminohydroquinone dimethyl ether) to the extent that without formation of the diazoamino compound, the last three bases are attached almost quantitatively in the desired position, i.e., at the 4-posi-tion relative to the amino group.

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Phenols, Naphthols. and many more coupling reagents

The readiness of the phenols to couple increases with increasing number of hydroxyl groups, for example, in the following series:

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How Azo Dyes are formed . Just Wait For a Moment

synthesis of 2-Nphthol Orange and 1-Naphthylamine Red

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DEMONSTRATION EXPERIMENT
AZO DYE FORMATION OBJECTIVES: DIAZOTATION, COUPLIN

Chemicals: sulfanilic acid 1-naphthylamine 2-naphthol sodium nitrite 2 N NaOH 2 N H2SO4

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THE FOLLOWING SOLUTIONS ARE

PREPARED

Sulfanilic acid solution: 1.7 g of sulfanilic acid in 50 mL in of 2 N H2SO4 Sodium nitrite solution: 0.6 g of NaNO2 in 10 mL of dist. H2O 1-Naphthylamine solution: 0.7 g of 1naphthylamine in 50 mL of 2 N H2SO4 2-Naphthol solution: 0.7 g of 2-naphthol in 50 mL of 2 N NaOH

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Glass wares crystallizing dish 3 beakers 250 mL beaker 100 mL 3 volumetric pipets 50 mL volumetric pipet 10 mL 2 petri dishes 3 pipet bulbs 3 glass stirring rods

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Hazards and safety precautions:

Azo dyes are toxic and may cause genetic mutations.

1-Naphthylamine is absorbed through skin and the respiratory and intestinal tract. It is toxic and carcinogenic. Sulfanilic acid may act as a skin, eye or respiratory irritant. May act as a sensitizer. 2-Naphthol is harmful if swallowed or inhaled. May be harmful in contact with the skin. Eye, skin and respiratory irritant. Sodium nitrite is toxic if swallowed. Severe eye irritant. Respiratory and skin irritant. May act as a carcinogen for chronic exposure Safety goggles and protective gloves must be worn. Good ventilation required! The 1-naphthylamine solution of phenol and the sodium nitrite solution should be made under a fume hood!

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Experimental procedure:

A crystallizing dish is half filled with ice. Four beakers containing the following solutions are placed in a ice bath:

beaker 1: 50 mL of an acidic solution of sulfanilic acid beaker 2: 10 mL of an aqueous solution of sodium nitrite beaker 3: 50 mL of an acidic solution of 1naphthylamine

beaker 4: 50 mL of an alkaline solution of 1-naphthol

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The sulfanilic acid solution is mixed with the aqueous solution of sodium nitrite while stirring. Equal volumes of the mixture are poured into the beakers 3 and 4. Results: The solutions in the beakers turn red.

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MECHANISTIC ASPECTS:

Diazotation: When primary aryl amines are reacted with nitrous acid (generated from NaNO2 in combination with H2SO4 ) a reaction occurs which makes a diazoniumion (1). The reaction takes place under freezing conditions.

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Coupling reaction: The diazotized sulfanilic acid reacts with 2naphthol and 1-naphthylamine to produce an acidic and basic azo dye alternatively (2). The azo coupling represents an electrophilic aromatic substitution. The diazonium cation is a relatively weak electrophile. So the aromatic ring which it attacks must have a activating group such as - OH and - NH2. Electron withdrawing groups on the aromatic ring of the diazonium ion facilitate the substitution
reaction. .

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Electrophilic substitution of 2-naphthol occurs preferentially at the 1-position. The NH2 group in 1-naphthylamine activates the 2- and 4-position

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Industries Also Use Two Steps to Synthesize Azo Dyes

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LAYOUT OF AZO DYE MANUFACTURING

PLANT 1, storage tanks for liquid starting materials; 2, storage drums for solid starting materials; 3, diazotisation vessel; 4, coupling component vessel; 5, ice machine; 6, coupling vessel; 7. isolation vessel; 8. filter presses; 9, filtrate to waste liquor treatment plant; 10, dryers; 11, emptying of dyestuffs for feeding to the mill; 12, outgoing air purification plant.

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H. M.Raza MPhil PUIC H. M.Raza MPhil PUIC Lhr Lhr

CLASSIFICATION OF AZO DYES

Classification based on number of Azo groups Monoazo dyes Disazo, Trisazo, or, more rarely, four (tetrakisazo) or more (polyazo) azo groups Classification based on Application Method Reactive Azo Dyes,Disperse,Direct,Cationic,Anionic and Metallised Azo Dyes

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AZO DYES ARE USED IN

Textile Dying Leather tanning. Fur Dying Paper industries Food Flavors Ink Dyes Photographic Dyes As Indicators Thermal and Ink Jet Printing Optical Data Storage Biomedical Applications Comestics

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Do You Know ? Azo Dyes are present in many things of daily use ! Imparting them beautiful colours

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MONOAZO DYES
Color Additive FD&C Red No. 40 R1 R2

FD&C Yellow No. 5

FD&C Yellow No. 6

D&C Orange No. 4

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MONOAZO DYES

Color Additive

R1

R2

D&C Red No. 6

D&C Red No. 7

D&C Red No. 34

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MONOAZO DYES
Color Additive R1 R2____________

D&C Red No. 36

D&C Red No. 31

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DISAZO DYES

Color Additive

R1

R2

R3

D&C Brown No. 1

D&C Red No. 17

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THESE MATERIALS ARE SOME OF THE MORE FAMILIAR COLORS OF OUR ENVIRONMENT

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AZO DYESHEALTH AND SAFETY ASPECTS

Azo dyes though make our life beautiful by a broad spectrum of colors ,at the same time they are hazardous and cause health and environmental problems . Hazards of Azo Dyes 1)Some azo dyes are toxic. 2)Some cause sensitization..Dermatologists have reported cases of skin reactions caused by textile azo dyes. 3)Mutagenicity Ames test is commercially used as a first screening for the mutagenicity of a dye .
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Several of the azo dyes are mutagenic and including 4-phenylazoaniline and N-methyl and N,N-dimetyhl-4-phenylazoaniline (Sparado, 1992). Their chemical structures are based on azobenzene and the azo naphthol derivatives. e.g. Amaranth = Acid Red 27 = FD&C Red 2 4)Environmental pollution 5)Carcinogenicity

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In an international conference held in Wurzburg, Germany in October 1992, an incident was reported where 15 workers were working in distilling 2naphthylamine plant. Long term of exposure to 2-naphthylamine caused all of these 15 workers to develop bladder cancer. Over the years epidemiological studies have shown the evidence that long-term occupational exposure to certain aromatic amines such as benzidine, 4aminobiphenyl and 2-naphthylamine, that are used in dye industries increases the risk of developing cancer.
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Azo dyes can be reduced by azoreductases in liver cells, skin surface microflora, kidney cells and intestinal bacteria and thus aromatic amines (aryl amines) are released. Walker (1970) pointed out that the metabolism of azo dyes in mammal (dog) occurred when the result showed the product of azo dye (sulphanilic acid) was found in the urine of dogs after they consumed Orange I.

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A study carried out by Hildenbrand et al. (1999) on reduction of azo dyes in cell cultures showed that the addition of a dye, Resacor Blue 2F, to kidney cells and liver cells produced a carcinogenic aromatic amine 3,3Dimethoxybenzidine.

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LEGISLATION.SAFETY ASPECTS
A number of laws and regulations providing health and environmental protection during manufacture ,use and storage of chemicals have been made esp. in advance countries (like EPA). Dyes are registered and their quality is checked before use.

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Any Question

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Thanks

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