Preparation of Methyl Orange Background Reading: Small Scale Syntheses, pp 363 (azo dyes). McMurry, ., !

rganic "hemistry, #th $d., pp %&&'3 (()')is spectroscopy) and *+,'% (diazonium ions and their coupling reactions) -6th $d.: pp +.3'6, *,#'/,0 Summary 1he 2irst step is called 3diazotization.4 Sodium sul2anilate reacts 5ith sodium nitrite in hydrochloric acid (i.e., nitroso cation) to 2orm an unsta6le 3diazonium salt.4 1he second step is the 3diazonium coupling reaction.4 1he diazonium ion is used in situ, and reacts 5ith 7,7'dimethylaniline to 2orm the acidic azo dye. 1he crude dye 5ill then 6e isolated, and used to create dyed nylon 2a6ric. Reaction Scheme
SO3H 2 NH2 + NH3 SO3 -

SO3- +Na

Na2CO3

2 NH2

CO2

H2O

Sulfanilic Acid (zwitterion)

Sodium Sulfanilate

SO3- +Na HCl / NO2-

SO3- +Na Sodium Sulfanilate Diazonium Chloride N N

+

NH2

Cl

SO3- +Na

N(CH3)2

+
N N
+

CH3COOH

Na+ -O3S

N N

N(CH3)2

Cl

N N-Dimeth!laniline

"eth!l Oran#e

Mechanism 8iazotization:
H3O+ O N OH nitrou$ acid -H2O O N OH2+ O N
+

nitro$o ion

HO3S

H N : H

+N

O HO3S

H N H
+

N O

OH2

HO3S N-Nitro$oamine H2O

N H

N O

H3O+ HO3S N N O HO3S N N OH H3O+

Diazoh!dro%ide

HO3S

.. N

.. N OH2+

HO3S

Diazonium (electro&hile)

8iazo "oupling:
Na+ -O3S N
+

.. CH 3 N CH3

Na+ -O3S

.. .. N N H

N(CH3)2+

OH2

Na+ -O3S

.. .. N N

.. N(CH3)2

"eth!l Oran#e (azo d!e)

"olor 1heory 1he 2irst real attempt to interpret the color o2 dyes in terms o2 chemical structure 5as made 6y !tto 9itt in ,.#6. :e proposed that dyes consist o2 con;ugated '6onded systems, called chromophores, and salt'2orming groups, called au<ochromes, 5hich are polar su6stituents that modi2y their colors. = chromophore is a simple, unsaturated, e' 5ithdra5ing group attached to an aromatic ring system. 1he e<tended con;ugation due to the chromophore decreases $ (and increases ma<) o2 the > transition, so that the ma< is in the ?isi6le range. $<amples include nitro ('7!/), azo ('7@7'), car6onyl ("@!), and nitrile ('"7). =n au<ochrome is an e' donating group (6y resonance) attached to an aromatic ring system. 1hese also change $ and ma<. $<amples include hydro<yl ('!:) and amino groups ('7:/, '7:R, and A7R/). 1he 2unction o2 a dye is primarily to create a particular color or hue in association 5ith the 2a6ric or su6strate. Both natural 2i6ers (like 5ool, silk, and cotton) and synthetic su6strates (like nylon) can 6e dyed. 8yeing is generally carried out in aBueous solution, and the process o2 attaching a dye molecule to the 2i6er is called adsorption. 8yes that are attracted to the te<tile 6y physical 2orces (physical adsorption, or physadsorption), and ha?e a direct attachment to the 2i6er (chemical adsorption, or chemisorption), are called direct dyes. =cid dyes, like methyl orange and tartrazine, are 5ater'solu6le anions (anionic dyes) that 2orm ionic 6onds 6et5een the dye and the 2i6er. Both 5ool and nylon are amide macro'molecules that ha?e terminal amino ('7:/) and acid ('"!!:) groups. 1hese can 2orm ionic 6onds 5ith the dye molecules. =s 5ith amino acids, these groups o2ten e<ist as z5itterions, that is the molecule has 6oth a positi?ely'charged group ('7:3C) and negati?ely'charged group ('"!!'). =nionic (or acid) dyes ha?e AS!3' groups that 2orm ionic 6onds, or salt linkages, 5ith the A 7:3C groups on the 2i6ers.

=cid'Base Dndicator Eroperties o2 Methyl !range

H OH2 .. .. N N .. N(CH3)2
+

Na+ -O3S

"eth!l Oran#e (Azo D!e) &H) *+* (!ellow w/ ma% , *-2 nm) De&rotonation (OH-) (rotonation (H3O+)

H Na+ -O3S

.. N N +

.. N(CH3)2

Helianthin ((rotonated D!e) &H. 3+2 (red w/ ma% , /0- nm)

'e$onance

Na+ -O3S

.. N N H

+ N(CH3)2

Erocedure Eretreatment 6e2ore 8iazotization ,. 8issol?e ,./ g anhydrous 7a/"!3 5ith %& ml 8D :/! in a ,/%'ml $rlenmeyer 2lask using a stir 6ar. /. =dd 3.6 g anhydrous sul2anilic acid, and heat solution 5ith a hot 5ater 6ath until dissol?ed. (Dt may still appear cloudy.) 3. Fra?ity 2ilter i2 solids are present, then rinse paper 5ith 3'% ml o2 hot 5ater. 8iscard 2iltered solids, and cool 2iltrate to room temperature. 8iazotization Reaction +. =dd ,.% g 7a7!/ to 2iltrate, and stir until dissol?ed. %. =dd % ml conc. :"l to a +&&'ml 6eaker containing /% ml o2 (%&G H %&G) ice 5ater 5hile stirring. "aution: "onc. acids are corrosi?eI 6. Eour sul2anilate solution into +&&'ml 6eaker 5ith :"l solution, and place 6eaker in an ice 6ath. 1he diazonium salt 5ill 2orm as a 5hite solid. "oupling Reaction #. !6tain /.# g o2 7,7'dimethylaniline (d @ &.*6 gHml) in a ,&'ml graduated cylinder, and pour directly into the +&&'ml 6eaker. 9ash cylinder 5ith /.&'ml conc. acetic acid, and add contents to +&&'ml 6eaker. Stir 2or ,%'/& min at /&'/%o" to ensure complete reaction. "aution: 7,7'dimethylaniline is to<ic and is readily a6sor6ed through the skinI :andle only 5ith glo?esI Dt is also ?olatile, and needs to remain completely in the hood until trans2er is completeI .. Slo5ly add 3& ml o2 ,&G 7a!:. "heck p: o2 aBueous phase. =dd additional 7a!: solution, i2 necessary, until 6asic. Dsolation o2 "rude 8ye *. :eat to 6oiling 5ith hot plate 2or ,&',% minutes. 9hen most o2 dye is dissol?ed, add ,& g 7a"l (salting out), then cool crude reaction mi<ture in an ice 6ath. ,&. )acuum 2ilter, and 5ash dye t5ice 5ith ,& ml cold, saturated 7a"l solution. 8iscard 2iltrate in sink (J,,& ml aB salt 5aste). ,,. Remo?e &.% g o2 dye, and dry remainder in o?en o?ernight to o6tain yield. 8ying 7ylon Ka6ric ,/. Elace &.% g o2 dye in a 6eaker 5ith 3&& ml o2 tap 5ater. =dd ,& ml o2 ,%G 7a/S!+ and % drops o2 conc. :/S!+, then heat to 6oiling. "aution: "onc. acids are corrosi?eI ,3. =dd nylon 2a6ric to 6ath and stir 2or %',& minutes. 1hen, remo?e dyed 2a6ric and rinse 5ell 5ith 5ater.

8ata 1o "ollect Rather than only pasting reactions and mechanisms into the report, descri6e the mechanisms Bualitati?ely in a paragraph or t5o. 8etermine theoretical yield G 6y 2inding moles o2 the product and o2 the t5o reagents. =lso, attach a portion o2 the dyed 2a6ric to your report.

Eost'La6 Muestions ,. (se the name o2 the azo compound on pg *+% o2 McMurry -pg */,, 6th $d.0 to name our product more systematically. (:ints: Erecede name 5ith 3sodium4, and end name 5ith 3sul2onate4. =lso, precede 3dimethyl4 5ith 37,7'4 inside the parentheses.) /. Suppose 5e 5anted to create the azo compound sho5n on pg *+%. 9hat are the common and systematic names o2 the aromatic compound that reacts 5ith :7!/ to create the 6enzenediazonium 6isul2ateN 3. 8escri6e electronically 5hich part o2 the methyl orange molecule can 6eha?e like a BrOnsted 6ase. (See acid'6ase indicator diagram.) +. $<plain electronically 5hy dyes are colored and ho5 the added proton on methyl orange changes the color (ma<). (See color theory discussion, as 5ell as pp %&/'+ in, McMurry -pp +.%'6, 6th $d.0.) %. :o5 does methyl orange attach to the nylon 2a6ricN