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DYES

DYES

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CHEM 118 Organic Lab II (Spring 2005) Prof.

Swift

MODULE 1: DYE SYNTHESIS & DYEING (Jan 24 – Feb 11) For an interesting account on the history on the dye industry, please read the accompanying section on “Dyes” from Napoleon’s Buttons: How 17 Molecules Changed History, by Penny LeCouteur & Jay Burreson, (Penguin, New York) 2003, p. 162-180. Introduction Since prehistoric times, man has been dyeing cloth. In the next three weeks, you will work in pairs to synthesize a total of five dyes (3 each), and test their adhesion to a variety of natural and synthetic fibers. The structures of the dyes appear in Figure 1. You will each perform your own synthesis and generate your own samples, but can share the dyed fabric samples with your partner. The Dyes During the first week, each pair will synthesize the cationic dyes Malachite Green and Crystal Violet via similar Grignard reactions. Malachite Green will be formed by the reaction between p-dimethylaminophenylmagnesium bromide and methyl benzoate. Crystal Violet is formed by the same reaction, substituting diethyl carbonate for the methyl benzoate. These are examples of mordant dyes. One of the oldest known methods of producing wash-fast dyes involves the use of metallic hydroxides, which form a link or mordant (L. mordere, to bite) between the fabric and the dye. The compounds will be used to dye both regular and mordanted fabric samples. These dyes also have select uses based on their known antifungal properties. The former is sometimes applied to the mouths of babies in neonatal units, while the latter is the active ingredient in anti-ick medications used in home aquariums. During the second week, each pair will synthesize Methyl Orange and Orange II dyes by an azo coupling reaction. Azo dyes are among the most common types of dyes. These are both examples of direct dyes that can either be made in bulk and later applied to a fiber, or can be developed on and in a fiber by combining the reactants in the presence of the fiber. Interestingly, Methyl Orange can be used as an acid/base indicator - while its acid-stable form (pH < 3.2) is red, its alkali stable form (pH >4.4) is yellow due to a change in its protonation state. Orange II is made by coupling diazotized sulfanilic acid with 2-naphthol in alkaline solution; Methyl Orange is prepared by coupling the same salt with N,N-dimethylaniline in a weakly acidic solution. In the third week, each person will synthesize Indigo according to the 1882 method of Baeyer (of asprin fame) by heating o-nitrobenzaldehyde and acetone in the presence of base. Indigo is an example of a vat dye, a term which applies to dyes that are reduced to a colorless (leuco) form, applied to a fiber, and then later oxidized on the surface of the fiber. Indigo is unique in that it can be abraded from the surface of a fabric (think of the knees of old blue jeans), whereas other dyes penetrate the fiber.

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Inc.) you will receive each contain 13 strips of different fibers woven into it. While binding strength is important. (5) Creslan (poly-acrylonitrile). 7) Dacron 54 and 64 (polyester without and with a brightener). Swift (H3C)2N N(CH3)2 N(CH3)2 Cl N(CH3)2 Crystal Violet Cl N(CH3)2 Malachite Green HO NaO3S N N NaO3S N N N O CH3 CH3 N H O Indigo H N Orange II Methyl Orange Figure 1. heat. the fibers are: (1) acetate rayon (cellulose di-or triacetate). In the case of fiber-reactive dyes. There are a smaller number of hydroxyl groups in acetate rayon compared to cotton. additional factors must be considered.6 (polyamide). the dyes may be covalent bonded to the fiber. though these are not concerns to be taken into account in our experiments. you should be able to see quite clearly the marked differences in shade produced by the same dye on different types fibers. The Fibers After each of these dyes has been synthesized. for a dye to be commercially viable as a textile colorant. Resistance to light. A natural fiber such as cotton has a surface area of about 5 acres per pound. The pieces of Multifiber fabric (Testfabrics. The molecular structures of most of these fibers are provided in Figure 2. (8) nylon 6.CHEM 118 Organic Lab II (Spring 2005) Prof. (10) silk (polyamide). and/or hydrogen bonding. (9) Orlon 75 (poly-acrylonitrile). (6. When dyes are absorbed from solution (usually aqueous) onto the surface of the fiber. and (13) wool (polyimide). Below the black thread starting at the top. Molecular structures of the dyes to be synthesized. Acetate rayon is cellulose (from any source) in which about two of the hydroxyl groups in each unit have been acetylated so that it can be solubilized in acetone and then spun into fiber. Nylon (which we’ll synthesize in the next module) is a polyamide and made 2 . (11) polypropylene. Cotton is pure cellulose. In these experiments. van der Waals forces. the dye penetrates the fiber’s pores. (12) viscose rayon (regenerated cellulose). (4) cotton. you will test their ability to directly stain a variety of fibers that have been woven into a piece of Multifiber fabric. These dyes and most other dyes are non-covalently bound to the fiber by a combination of intermolecular interactions including electrostatic forces. (2) SEF (Monsanto’s modacrylic Self-Extinguishing Fiber). The stronger the intermolecular interactions are between the dye and fiber. the better the dye will adhere. and washing are important commercial considerations. (3) Arnel (cellulose triacetate).

Except for the terminal acid and amine groups. This agent helps form a stronger link between the fabric and the dye. Wool and silk are polypeptides cross-linked with disulfide bridges. glutamic acid and lysine) provide many polar groups in wool and silk. R=H. has few polar centers within the polymer.g. After 5 min. Similarly Dacron. The tannic acid was fixed to the cloth by transferring the cloth to a hot bath made from 20mg of potassium antimonyl tartrate (tartar emetic) in 20mL of water. the dye Turkey Red (alizarin) is red with an aluminum mordant.CHEM 118 Organic Lab II (Spring 2005) Prof. For instance. to bite). The color of the final product depends on both the dye used and the mordant. mordere. R=OAc) O N H R H N O N H Polyacrylonitrile (Orlon) R O n O O OCH2CH2 n O R Wool (R = amino acid residue) Polyethylene glycol terephthalate (Dacron) Figure 2. This is one of the oldest known methods of producing wash-fast colors. there are no strongly polar centers in nylon. Pieces of cloth were then immersed in 0. They were prepared by allowing regular test fabric strips to stand in a nearly boiling solution of 0. a polyester made by polymerizing ethylene glycol and terephthalic acid. Orlon is a polymer of acrylonitrile.. Molecular structures of the fibers to be dyed. HOH2C O HO O RO O OR HOH2C O OH O O (CH2)4 n O H H n CH2 CH C N n N(CH2)6 N Nylon Cellulose (Cotton. usually a metal hydroxide.1g of tannic acid in 50mL of water for 30min. such as tannic acid. Acetate rayon. The acidic and basic amino acids (e. to the fibers. also function as mordants. the cloth was wrung out and dried as much as possible. 3 . and brownish-red with a chromium mordant. violet with an iron mordant. Other substances. One way to make dyes adhere to fibers more effectively is to apply a mordant (L. Some mordanted pieces of test fabric have been prepared ahead of time and will be available for use during the first week of experiments only. Swift by polymerizing adipic acid and hexamethylenediamine.1M solutions of mordants (either ferrous sulfate or copper sulfate) and kept at the boiling point for about 15-20min.

a salt that is usually insoluble in ether. Example of a dye binding to a mordanted fiber. In this second step of the reaction.. However. and a solution of the Grignard reagent is formed. an intermediate tertiary alcohol is formed. Grignard reagents react readily with water. in a simple acid/base reaction. a carbon-carbon bond-forming reaction by which almost any alcohol may be formed from appropriate alkyl halides and carbonyl compounds. Another useful trick to start the reaction is to add a few drops of CH3I or a small crystal of I2. The Grignard reagent is not isolated but most often reacts immediately with a carbonyl compound to give the magnesium alkoxide. are among the most common. Finally. an ester will be slowly (the reaction is endothermic!) added to the Grignard reagent. alcohols. When either of the resultant alkoxide salts is hydrolyzed with HCl. The great versatility of this reaction lies in the wide range of compounds that can undergo the reaction. initially has a coat of oxide on the outside. The reaction will begin at exposed surfaces. Thus. this compound immediately loses a molecule of water. Before embarking on this second step. Once the exothermic reaction starts. The Grignard reagent is easily formed by reaction of an alkyl halide (in particular a bromide) with magnesium metal in anhydrous diethyl ether or THF. The Grignard reagent is a strong base and a strong nucleophile. so the reactants and apparatus must all be completely dry and free of acidic protons. Reactions with ketones and aldehydes. thiols. amines. in the form of a coarse powder. find a partner and decide which compound each of you will synthesize. Crushing the turnings (on a piece of weighing paper) under absolutely dry solvent in the presence of an organic halide exposes a fresh unoxidized surface. which is believed to convert a small amount of halide to (the more reactive) iodide. As a base it will react with all protons that are more acidic than those found on alkenes and alkanes. Swift O Alizarin O O O H 2O Cr O OH2 O ll Ce se ulo Figure 3. giving tertiary and secondary alcohols. it proceeds easily – the magnesium dissolves. Malachite Green is synthesized in a similar fashion by reacting one mole of methyl benzoate and two moles of the Grignard reagent. Part A (work in pairs): Grignard Synthesis of Crystal Violet or Malachite Green1 In 1912 Victor Grignard received the Nobel prize in chemistry for his work on the reaction that bears his name.CHEM 118 Organic Lab II (Spring 2005) Prof. The first step in the synthesis of both dyes is to form a Grignard reagent from pdimethylaminophenyl bromide. the alkoxide formed is reacted with acidified ice water to give a covalent. Products will be exchanged at the end. otherwise the reaction will not start. respectively. etc. Crystal Violet is formed when one mole of diethyl carbonate is added to three moles of the Grignard reagent. ether-soluble alcohol and the ionic water-soluble magnesium salt. as evidenced by a slight turbidity in the solution and the evolution of bubbles. The magnesium metal. leaving a highly stable colored 4 .

Obtain the following reagents before setting up the reaction: 2. Reaction scheme for the Grignard synthesis of Crystal Violet and Malachite Green. 0. pour 2-3mL of THF through the condenser. Place the drying tube at the top. Swift carbocation. Keep the THF covered with parafilm or a rubber stopper. 30mL of dry tetrahydrofuran (THF). and this conjugation is responsible for the colors of these dyes. All glassware used in this experiment must be dry because the Grignard reagents are very water sensitive. Fit the condenser to the flask and adjust the water so that it flows gently through the condenser.40g Mg turnings. Prepare a drying tube filled with anhydrous calcium chloride ahead of time.5g of 4-bromo-N. and 2-3 small crystals of iodine. 5 . Procedure Making the Grignard reagent (whole class) 1. Both dyes are highly conjugated. and discard these rinses in the flammable waste container. Once the glassware is rinsed. The positive charge is extensively delocalized due to the overlap of the orbitals on the cationic center with the conjugated π-system of the benzene rings and even the paradimethylamino groups.CHEM 118 Organic Lab II (Spring 2005) Prof.Ndimethylaniline. 2. N(CH3)2 H3CH2C O O O Br Mg N(CH3)2 THF N(CH3)2 N(CH3)2 MALACHITE GREEN O OCH3 (H3C)2N OMgBr HCl Cl (H3C)2N MgBr H3CH2C N(CH3)2 (H3C)2N OMgBr HCl Cl (H3C)2N CRYSTAL VIOLET N(CH3)2 N(CH3)2 N(CH3)2 Figure 4. the reagents need to be added quickly and the apparatus assembled to minimize exposure to atmospheric moisture. 3. The visible λmax can be obtained from the UV/Vis spectrum. Rinse a 50-mL round-bottom flask with 2-3mL of THF.

6. Crystal Violet synthesis (other ½ class) 8. 7. and add 2. swirling after each drop. Each strip contains 13 different types of fabric. 10. Cool the flask to room temperature. One of the strips is untreated. Put on gloves before starting the dye synthesis. Using a Pasteur pipette. Pour the reaction mixture into a 150mL beaker.0mL of THF to the vial. add the ester solution drop by drop. Remove a small aliquot of either Crystal Violet or Malachite Green and add it to 20mL of boiling water. Clamp a round-bottomed flask in place. 10. 15. 11. and 2-3 small crystals of iodine. Weigh 0. Pour the reaction mixture into a 150mL beaker. After the addition is complete. swirling after each drop. Maintain a gentle reflux for 30 minutes. Malachite Green synthesis (½ class) 8. temporarily remove the condenser. 12. replace the condenser and heat the reaction mixture to reflux for 5 minutes. Collect a UV/Vis spectrum on a small diluted portion of your solution and record the λ of the maximum absorbance. Dye the mordanted cloth in this bath for 5-10 min at a temperature just below the boiling point.5g of 4-bromo-N. Weigh 0. 12. 9. Swift 4. You will each receive two different strips of Multifiber fabric. After the addition is complete. Scrape the Mg turnings on a piece of weighing paper to expose a fresh surface and add these to the RBF.0mL of THF to the vial. add the ester solution drop by drop. replace the condenser and heat the reaction mixture to reflux for 5 minutes. 25mL of dry tetrahydrofuran (THF). the other has been pretreated with a mordant (note the slightly different tinge of color). Cool the reaction flask in a beaker of tap water until it reaches room temperature.N-dimethylaniline. The initial dark color fades and is replaced by the greyish solution typical of Grignard reagents. some bubbling will occur as the residual magnesium reacts with the acid. 6 . Measurement of UV-Vis spectra (whole class) 13. Slowly add 5mL of 5% HCl solution to the beaker with stirring. Slowly add 5mL of 5% HCl solution to the beaker with stirring. Dyeing Test fabric strips (whole class) 14. 9. Cool the flask to room temperature. some bubbling will occur as the residual magnesium reacts with the acid. Using a Pasteur pipette.CHEM 118 Organic Lab II (Spring 2005) Prof. 11. 5.30g of diethyl carbonate into a small vial (set in a beaker so that it willnot tip over) and add 1. Cover with a watch glass to minimize evaporation. Heat the reaction with a 70-75oC water bath.21g of methyl benzoate into a small vial (set in a beaker so it will not tip over) and add 1.

Cut each strip in half and give one to your partner. Leave dyed fabric strips in your drawer for comparison with other dyed cloths in subsequent weeks. Neutralize the acid washings with sodium carbonate before pouring them down the sink or pouring them into the container for aqueous inorganic waste. For the synthesis of Orange II and Methyl Orange. diethyl carbonate and methyl benzoate are irritants. Remove dye stains on the beaker. Avoid contact with skin. Before embarking on the second step. Wear gloves while dyeing the fabric samples and cleaning the glassware that contained the dye. blot and dry. clothing and anything else they contact. SAFETY INFO: 4-Bromo-N. and then coupling the salt to an aromatic phenol (or a different methylated amine) via an electrophilic aromatic substitution reaction. wash the dyed cloth under running water with soap. Sulfanilic acid exists as a zwitterion in aqueous solution.N-dimethylaniline. Wearing old clothes to lab is highly recommended. eyes and clothing. PRE-LAB QUESTIONS: 1. consult with your partner to determine which compound each of you will synthesize. CLEANUP: The dye solution should be poured into an aqueous inorganic waste container in the hood. Dye stains on glassware can be removed with a few milliliters of 6M HCl then washing with water. Why is this good advice? 2. 17. Why is it important to not overheat your THF in the water bath? 4. The TA will instruct you to keep the bottle of tetrahydrofuran (THF) closed at all times except when you are dispensing reagents. Dye another piece of cloth that has not been mordanted and compare the two. They are typically formed in a two-step reaction . Like last week.by first oxidizing an aromatic amine to a diazonium salt. The procedures for the electrophilic aromatic addition are similar on paper. Why is the ester added dropwise to the Grignard reagent? Part B (work in pairs): Synthesis of Azo Dyes Orange II or Methyl Orange2 Probably the most common type of dyes are the azo dyes.CHEM 118 Organic Lab II (Spring 2005) Prof. products will be exchanged at the end. but additional information on the mechanisms can be found in Wade chapters 17 & 19. In each case. The mechanisms of these reactions will be covered in greater detail during recitation. everyone will form the same diazonium salt of sulfanilic acid in the first step according to the reaction scheme in Figure 5. but a bit different in 7 . Why are the magnesium turnings scraped on a piece of weighing paper and not just in the round bottom flask? 3. using glass rods. allow as much of the dye to drain back into the beaker as possible and then. The dyes made in this experiment will stain skin. Swift 16. if necessary. There are literally thousands of them.

Swift how they are executed experimentally.CHEM 118 Organic Lab II (Spring 2005) Prof. 2. and stir until it is dissolved. 8 .N-dimethylaniline in a weakly acidic solution. To make Orange II.5% sodium carbonate solution. Cool the solution under tap water.47g of sodium nitrite. Synthesis of Orange II and Methyl Orange via azo coupling reactions. Step 1: NH NH3 Na2CO3 NH2 + CO2 + H2O SO3Na N 2 HCl NaNO2 N Cl 2 SO3H SO3 SO3 Step 2: OH O3S NaOH OH N N N N SO3Na ORANGE II METHYL ORANGE CH3 N CH3 acetic acid O3S N N NaO3S N N CH3 OH NaO3S NH N (Red Form pH <= 3. the diazonium salt of sulfanilic acid is coupled with 2-naphthol in alkaline solution in the second step. the salt is coupled with N. add 0.2) N CH3 H CH3 CH3 N (Yellow Form pH >= 4. To make Methyl Orange.2g of sulfanilic acid in 12. In a 50-mL Erlenmeyer flask dissolve (with boiling if necessary) 1. These dyes will then be used to dye regular Multifiber fabric strips (the mordanted cloth gives pretty similar results).4) Figure 5.5 mL of 2. Procedure Formation of the diazonium salt (whole class) 1.

Pour (with stirring) the suspension of diazotized sulfanilic acid into the 2-naphthol solution.3mL of concentrated hydrochloric acid. 9. The product is not collected but is used in the preparation of Orange II or Methyl Orange dye while in suspension. wash the material from the filter paper and funnel with water. Orange II crystallizes from aqueous alcohol as a dihydrate complex (i. cool further by stirring and collect the product on a Buchner funnel. and allow crystallization to proceed. Avoid a large excess of water. Pour the filtrate into an Erlenmeyer flask. set the beaker in a pan of ice water. In a 250 mL beaker.CHEM 118 Organic Lab II (Spring 2005) Prof. after 5-10min.7g. Add 2. add 25-30mL of ethanol.5g of ice and 1. it can be obtained in a fairly satisfactory form by adding saturated sodium chloride solution to a hot. 10. dissolve 0. Rinse the Erlenmeyer flask with a small amount of water and add it to the beaker. The crude yield is thus not significant. the nitrile. add it to the flask. and bring the cake into solution at the boiling point. and the material need not be dried before being purified. It is more stable than most diazonium salts and will keep for a few hours. Swift 3. rinse the filter flask with a small quantity of water. The product dries slowly and contains about 20% of sodium chloride.e. 2H2O) and allowance for this should be made in calculating the yield. 6. C16H11N2O4SNa . 7. This particular azo dye is too soluble to be crystallized from water. 8. 9 . bring this all into solution by heating and stirring. Cool to 80oC. Filter by suction through a Buchner funnel that has been preheated on the steam bath. separates easily from the solution because a considerable excess of sodium ion from the carbonate. but the best crystals are obtained from aqueous ethanol.9g of 2-naphthol in 5mL of cold 3M sodium hydroxide solution. Orange II synthesis (½ class) 4. 11. The yield of pure. heat the mixture until the solid dissolves.5mL) to prevent separation of solid during filtration. Pour the solution into a flask containing about 7. but use enough (about 12. If the water of hydration is eliminated by drying at 120oC the material becomes fiery red. and if greater than 15mL evaporate by boiling. The filtration can be somewhat slow. being a sodium salt. and the alkali is present. 12. Cool the solution well before collecting the product. 5. estimate the volume. Rinse the beaker with mother liquor and wash finally with a little ethanol. crystalline material is about 1. When near room temperature. and let the solution cool undisturbed. Coupling occurs very rapidly and the dye. Use saturated sodium chloride solution rather than water for rinsing the material out of the beaker and for washing the filter cake free of the dark-colored mother liquor. Stir the crystalline paste thoroughly to effect good mixing and.5g of sodium chloride to further decrease the solubility of the product. filtered solution in water and cooling. In a minute or two a powdery white precipitate of the diazonium salt should separate and the material is then ready for use. Transfer the filter cake to a beaker.

Rinse the test tube with a small quantity of water and add it to the beaker. 8. CLEANUP: The organic crystallization filtrate should be placed in the organic solvents container. the dye bath is prepared from 50mg of Orange II or Methyl Orange. Remove the fabric from the dye bath. Acids and bases should always be dispensed carefully in the hood. allow it to cool. and then wash it thoroughly with soap under running water before drying it. The filtrate from the reaction should be poured into an aqueous inorganic waste container in the hood. collect the product on a Buchner funnel. Dissolve a small amount of dye in aqueous solution and record the λmax. 0. Neutralize the acid washings with sodium carbonate before pouring them down the sink or 10 . Swift Methyl Orange synthesis (other ½ class) 4. Methyl Orange and Orange II. Stir well and heat the mixture to the boiling point.8mL of N. 15mL of water. 9. The crude product need not be dried but can be crystallized from water after making preliminary solubility tests to determine the proper conditions. so always use in solution. When cooled thoroughly. Some diazonium salts are explosive when dry. Dye stains on glassware can be removed with a few milliliters of 6M HCl then washing with water. For the direct dyes. thoroughly mix 0. using saturated sodium chloride solution rather than water to rinse the flask and to wash the dark mother liquor from the filter cake. 5. To the suspension of diazotized sulfanilic acid contained in a 250mL beaker. and 5 drops of 3M sulfuric acid in a 30mL beaker.) Dyeing Test fabric strips (whole class) 14. 6. Stir and mix thoroughly and within a few minutes the red. Place the beaker in a pan of ice and water and allow the solution to cool undisturbed.25-1. when a large part of the dye should dissolve.5mL of 3M sodium sulfate solution. (note: not every person’s sample must be measured if time runs short. Place a piece of test fabric (without mordant) in the bath for 5 min at a temperature near the boiling point. Those working with Methyl Orange should measure the λmax in different solutions with pH > 5 and < 3. In a test tube. The yield is about 1. Measurement of UV-Vis spectra (whole class) 13. SAFETY INFO: Avoid skin contact with diazonium salts. A stiff paste should result in 5-10min and 9mL of 3M sodium hydroxide solution is then added to produce the orange sodium salt.5g. but everyone in the section should have the λmax recorded for each sample type.N-dimethylaniline and 0.CHEM 118 Organic Lab II (Spring 2005) Prof.63mL of glacial acetic acid. add (with stirring) the solution of dimethylaniline acetate. acid-stable form of the dye should separate. 7.

In this experiment. Synthetic indigo is very insoluble in water. The acetone enolate anion adds to the aldehyde to produce an intermediate hydroxy ketone that that been isolated and identified. OH HO HO O OH H O ferment OH N H O air O2 O N H Indigo H N O N H Indican N H Indoxyl Figure 6. His 1882 synthesis of indigo starts with o-nitrobenzaldehyde.a. F. During this process the water-soluble indoxyl permeates the fibers and is air oxidized to form the intense blue. Swift pouring them into the container for aqueous inorganic waste. was extracted and subsequently cleaved to form glucose and another colorless compound. This is typically 11 .CHEM 118 Organic Lab II (Spring 2005) Prof. Why might it be better to measure the UV/Vis spectrum of a dilute sample rather than a concentrated one? Part C (work in pairs): Synthesis of Indigo3 The original source of indigo was the leaves of the tropical plants of the Indigofera species. a colorless compound. The fermented brew containing indoxyl was typically then transferred to a large open vat. you will prepare indigo by an almost forgotten method developed by J. Adolf von Baeyer (of asprin fame). When cut leaves are fermented in water. that precipitates inside the fibers of the cloth. Why must the diazonium salt be added to a cold solution of 2-naphthol (for Orange II) when the same diazonium salt can be added to a room temperature solution of N. PRE-LAB QUESTIONS: 1. Why is the filter cake rinsed with saturated sodium chloride solution instead of water? 3. W. if necessary. but it is a good method for quickly generating the small quantities needed here. and the mixture beaten with large sticks to aerate the solution. Remove dye stains on the beaker.N-dimethylaniline (for Methyl Orange)? 2. The next steps are unknown (but in the lab report you will be asked to propose a viable mechanism). Reactions associated with the isolation of indigo from plant sources. indoxyl. indigo. This is not the method used commercially.k. It must first be chemically reduced to a basesoluble yellow dihydro derivative (a. water insoluble dimer. “indigo white” or the leuco form). which is heated in acetone and base. the cloth added. indican. Indigo has been produced commercially by chemical synthesis since 1897.

(The following dyeing experiments can be run on a larger scale if people want to pool their samples together. the dye will be oxidized back to the original blue indigo. 7. 5. CHO O H 3C base O CH3 H2C CH3 OH O base NO2 NO2 Indigo Figure 7. Swift done with a chemical reducing agent such as sodium hydrosulfite. Chill the flask in an ice bath. Upon removal of the solution and exposure to air. 4. 8. 9. 2. 3.) 12 . Procedure Indigo Synthesis and Dyeing (half class) 1.25 g (3 pellets) sodium hydroxide in 5 mL of water (About 12 M NaOH). Laboratory synthesis of Indigo. Transfer the filter paper to a paper towel and allow it to air dry while you prepare for the next step. Place 6 mL acetone and 0.75 g (0. Remove from heat and allow the flask to cool. 6. Continue to reflux for another 20 min.0017 mole) of o-nitrobenzaldehyde in a 25 mL round bottom flask. Oxidation/reduction of blue and white Indigo. Just scale the reagents accordingly.5 mL portions of a solution of 0.CHEM 118 Organic Lab II (Spring 2005) Prof. Add 10 mL of water and swirl the contents to mix them. The fabric can then be dipped in the alkaline solution of the reduced dye so that the dye impregnates the cloth. Attach a reflux condenser and heat the flask in a water bath until the solution refluxes gently. Collect the solid on a Buchner funnel and wash the dark blue precipitate with a little water and several small portions of acetone. O ONa H N Na2S2O4 + NaOH O2 (air) N H N H ONa O Colored blue form (Water insoluble) N H Colorless leuco form (Water soluble) Figure 8. Add through the condenser over a period of 5 min 0.

Though the syntheses you performed these past three weeks have already been reported in the chemical literature previously. lets pretend they haven’t. (i. not 5) as though it were an experimental section of a journal article you plan to submit. Note what happens during the drying process. Check to make sure the pH is neutral. before diluting the dye bath with a large quantity of water and flushing it down the drain. (400 words max) 2. Remove the strips with a pair of tweezers. Write up succinct experimental procedures for the syntheses you performed these past two weeks. what is it about the chemical structures of the dye and the fabric that make dyeing effective)? Briefly compare and contrast the effectiveness of dyeing for each dyefabric combination.e. (600 words max) 13 . merely suspended.25% hypochlorite solution) to the dye bath to oxidize it to the starting material. the liquid will always appear to be dark blue due to a film of the oxidized dye on the surface of the solution.CHEM 118 Organic Lab II (Spring 2005) Prof. PRE-LAB QUESTIONS: 1. To increase the intensity of the dye.25% hypochlorite solution) to the dye bath to oxidize it to the starting material. What can you conclude about the associations between dye and fabric on the basis of molecular structure (i. Note: You may want to create and refer to a data table to discuss this topic succinctly. 11. CLEANUP: Add household bleach (5. Why is it important to not overheat your acetone in the water bath? Lab Report Short writing assignments (should be typed) 1. and stir the mixture until a yellow to green solution of the “indigo white” forms. Place the multifiber strips in the solution and heat gently for 5 minutes. I’m looking for 3 syntheses each. a bit of soap should be added to the dye bath. Add all but a small sample of the blue indigo prepared. it is not easy to state exactly how much of this reducing agent should be used. Add household bleach (5. the process may be repeated several times with no drying. (To disperse the dye in water. Because Na2S2O4 decomposes on storage. Check to make sure the pH is neutral. 14.e. Note: From the top. The mixture can be diluted with water and flushed down the drain. rinse them with water and allow them to dry. Swift 10. before diluting the dye bath with a large quantity of water and flushing it down the drain. and 1 g of fresh sodium dithionate (Na2S2O4) in a 250 mL beaker. Place 50 mL of water and 2.5 mL of 10% sodium hydroxide. Heating the solution gently for a few minutes may help to improve the reduction. The blue color should be fully formed in about 5 minutes. Although the liquid appears blue the dye is not dissolved. If the mixture remains definitively blue.) 12. it may be necessary to add more reducing agent (in small portions) until the solution changes color. 13. The mixture can be diluted with water and flushed down the drain.

Williamson. (250 words max) Questions (handwritten or typed) 1.e. Propose a chemically plausible mechanism (curved arrow notation) for the synthesis of indigo shown in Figure 7. Morrill and D. 3 C. The color change (red – yellow) is due to transition from one chromophore (azo group) to another (quinoid system). Draw out the mechanism for the synthesis of Crystal Violet using curved arrow notation. Jr. (Prentice Hall. Neckers. Interestingly.H. Methyl Orange can be used as an acid/base indicator . Using arrow notation. 2nd Ed. Wilcox. F. Experimental Organic Chemistry A Balanced Approach: Macroscale and Microscale (W. Organic Experiments 8th Ed..while its acid-stable form (pH < 3.F. you should list them all. C.2) is red. C.4) is yellow. and M. Wilcox. i. its alkali stable form (pH >4. F. NY) 1998. Experimental Organic Chemistry: A Small-Scale Approach. 1 14 . and indicate the one that was determined most recently based on the references. (Houghton Mifflin. what experimental question would you be most interested in asking? Briefly describe an experiment(s) that could be performed to address the question you asked. Mohrig. CH3 NaO3S N N N CH3 H+ OHNaO3S H N CH3 N N CH3 Yellow at at pH > 4.4 Red at pH < 3.) 4.CHEM 118 Organic Lab II (Spring 2005) Prof. Fieser. K. 2. Swift 3. C. Hammond. draw a mechanism showing how the yellow form is converted to the red form in the presence of acid.2 3. If this is the case. T. If there were extra time (a few hours or possible a third week) allotted to this dye module. Freeman. N.L. What are the Beilstein registry numbers and melting points of Crystal Violet and Indigo? (note: sometimes an organic compounds will have multiple melting points listed in Beilstein. Englewood Cliffs. R. NJ) 1988. 2 L. NY) 1998. what are logical steps that could convert the hydroxyketone to indigo in the presence of base? J.

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