Synthetic Dyes and the Development of Organic Chemistry
Synthetic Dyes and the Development of Organic Chemistry
Synthetic Dyes and the Development of Organic Chemistry
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1856 – Perkin's Easter vacationFormula, but not structure <strong>of</strong> quinine knownPerkin attempted oxidation:2C 10 H 13 N + 3[O]KCr 2 O 4H 2 SO 4C 20 H 24 N 2 O 2 + H 2 OquinineWilliam Henry Perkin, age 14HHN[O]HOHNMeONExperiment resulted in v. impure brown powder, but Perkin tried to assess whe<strong>the</strong>r <strong>the</strong> oxidationwas general:NNH 2+KCr 2 O 4H 2SO 4black sludgeEtOH, refluxH 2 NNNHNH 2Meimpuritiespurple crystals = "aniline purple," later mauveine--------------------------------------------------------------------------------------------------------1857 – An industry beganCurrent syn<strong>the</strong>tic dyes were unsuitable, but dem<strong>and</strong> was highO 2 NOHNO 2 yellowmade from phenolnot lightfastHNNO 2picric acidOHNOOONmurexideHNNHOO - NH 4+reddish-purplereasonably light-resistantapplication complex <strong>and</strong> expensivesyn<strong>the</strong>size from urea <strong>and</strong> nitric acidPerkin left school, fa<strong>the</strong>r risked fortuneSuccess required establishment <strong>of</strong> large scale organic chemicals industryRaw materials to make aniline needed on large scale: benzene, nitric acid, anilinePerkin's sketch <strong>of</strong> Perkin <strong>and</strong> Sons dye factory2
1800-1845 – Coal tar <strong>and</strong> Justus Liebig set <strong>the</strong> stageIn late 1700s coal distilled for tar; after 1812, illuminating gas became desirable, excess coal taraccumulatedLiebig one <strong>of</strong> <strong>the</strong> premier educators <strong>of</strong> all timeFresenius, Erlenmeyer, Kekulé, Wurtz...Small links between industry <strong>and</strong> chemistry establishedAugust Wilhelm H<strong>of</strong>mann began to analyze coal tar extractsH<strong>of</strong>mann establishes Royal College <strong>of</strong> <strong>Chemistry</strong> in Engl<strong>and</strong> *Liebig's lab in Giessen-----------------------------------------------------------------------------------------------------------H 2 NNH1856-1867 – Post-mauveine developments2Concious search for new dyes – fuchsin found by Emanuel VerguinTriphenylmethine dyes enable systematic syn<strong>the</strong>sis <strong>of</strong> new compounds – H<strong>of</strong>mannProduction <strong>of</strong> mauveine stopped after ten yearsNH 2+rosaniline or fuchsin1867 – value <strong>of</strong> dyes had tripled since 1862 despite price dropsN N NH 2Price per kilo <strong>of</strong> raw materials <strong>and</strong> dyesaniline yellow1862 1867+ HNbenzene 5 fr 70 crosaniline 300 fr 30 fr- O 3 SNHNHaniline blueNOHNNNN[O]H + SO 3 NH 4SO 3 NH 4NOHNNmalachite green3
1858 – Peter Griess <strong>and</strong> <strong>the</strong> azo dyesMore Germans in Engl<strong>and</strong>YNONH 2- ONONH 22 diazotization azo couplingOtto Witt, Heinrich Caro <strong>and</strong> Carl Alex<strong>and</strong>er MartiusVersatile chemistry exploitedHNO 2+-Y - H 2N ONHONOONONO-H + N + N+ H 2 ONOYNONH 2HNNOClN ONNOH+ N O H +N N NH 2NNOH 2+aniline yellowAzo dyes today account for 60-70% <strong>of</strong> dyes used in textile applicationsnitrite anionnitrious acidnitrosoacidium ionnitrosonium cation-H 2 OPeter GriessN N H 2 NNH 2chrysoidineN + NpH important in diazotization aswell as azo couplingdinitrogen trioxidenitrosyl chlorideincreasing acidity----------------------------------------------------------------------------------------------------------1869 – Alizarin, <strong>the</strong>n decline for Engl<strong>and</strong> <strong>and</strong> FranceO OHOalizarinOH1868 – Graebe <strong>and</strong> Liebermann deduce structurePerkin <strong>and</strong> Sons first commercial producers:Class <strong>of</strong> carbonyl dyes – anthraquinones1869 - 1 ton1870 - 40 tons1871 - 220 tonsMadderGraebe <strong>and</strong> Liebermann:Caro, Perkin:OBr 2OBrBrOH2SO4OSO 3 HOOOONaOH, ![O]OBrOOHOHOSO3HSO3HOOHOHBrOOOOBut Engl<strong>and</strong> was on <strong>the</strong> decline:H<strong>of</strong>mann departs in 1865Not enough trained chemistsMinimal state fundingBusiness complacencyLittle cultivation <strong>of</strong> scientific inquiryFrance too:Not enough raw materialsLoss <strong>of</strong> Alsace-Lorraine in 1871Patents for products, not processesPrivate labs did not supply enough trained chemists4
German industry on <strong>the</strong> riseBayerAGFAKalle,HöchstBASFCIBA, S<strong>and</strong>ozDecentralization – lack <strong>of</strong> investment necessitated imitation, competition among small statesPatent situation – laws difficult to enact, foreign technology not protected, competition increasedGeography – raw materials, transportation in Rhein river valleyEducation – <strong>the</strong> Liebig tradition supplied fresh ideas, trained chemistsUnification in 1871 – Patent Act <strong>of</strong> 1876 arrived at <strong>the</strong> right timeBusiness – ties between industry <strong>and</strong> universities established quickly--------------------------------------------------------------------------------------------------------Education – Universities <strong>and</strong> <strong>the</strong> Technische Hochschule1809 Univeristy <strong>of</strong> Berlin – model for a modern university:SeminarsSemestersVernacularPr<strong>of</strong>essional training, productive citizensLiebig's pedagogical model:Close relationship with pr<strong>of</strong>essor, whose enthusiasm evoked admiration <strong>and</strong> loyaltyFull enthusiasm for studies – 6 days/wk, 12-15 hrs/dayCompetitive atmosphere among students"ample opportunities <strong>of</strong> witnessing, in a comparatively short time, a vast variety <strong>of</strong>processes which are being constantly carried on in an institution consisting <strong>of</strong> a greatnumber <strong>of</strong> experimentalists" (H<strong>of</strong>mann, 1849)1860s – glut <strong>of</strong> doctoral students led to technische hochschule: *Proximity to state centersTies with state <strong>and</strong> industryIncluded education in o<strong>the</strong>r fieldsStimulated improvements at universities (v. similiar by 1900)Ties with pr<strong>of</strong>essors highly sought after by companies5
1870s – Heinrich Caro exemplifies industrial <strong>and</strong> academic cooperationAs director <strong>of</strong> research at BASF, Caro tirelessly fostered ties with academics1868 – Graebe <strong>and</strong> Liebermann consult Caro regarding alizarin1873 – Adolf von Baeyer <strong>and</strong> Caro collaborate on research programThey discover eosinMartius at Agfa discovers secret formula with <strong>the</strong> help <strong>of</strong> H<strong>of</strong>mannHeinrich Caro1876 – Caro stymied again with chrysoidine by Martius <strong>and</strong> H<strong>of</strong>mann *1876 – Griess supplied Caro with samples from azo coupling reactions1878 – Emil <strong>and</strong> Otto Fischer (under von Baeyer) solve structure <strong>of</strong> triphenylmethine dyes, butonly with help from CaroHOBrOBrOBrCO 2 HBrEosinA. W. H<strong>of</strong>mannAdolf von BaeyerEmil Fischer------------------------------------------------------------------------------------------1870-1890 – Rise <strong>of</strong> <strong>the</strong> industrial research laboratory <strong>and</strong> <strong>the</strong> Bayer exampleResearch labs enabled acceleration <strong>of</strong> research by consolidating resourcesTeamsFacilitiesAcademically trained scientists in management positionsBayer was slower to innovate than o<strong>the</strong>r major german firmsBy 1882, a full research staff was still not established1884 –Duisberg enables Bayer to compete with AgfaCarl DuisbergDuisberg spontaneously evolves into a research directorPrimitive labs replaced with Duisberg design <strong>of</strong> new building, layout adopted almost universally*Also quality control, library, conferences, product testingIn 1896, 1 in 70 dyes approved for productionBy 1900, 1 in 200 dyes marketedca. 1905, 1 in 300 dyes marketedNH 2SO 3 NaNNN N NH 2benzopurpurin 4BSO 3NaBayer laboratories after Duisberg6
Back to <strong>the</strong> mosquitoH1918 – Paul Rabe takes quinotoxine to quinineMeOONHMeOHOHNNN1944 Woodward <strong>and</strong> Doering's planquinotoxineHONRabeONHHNHMeOMeOHOHNNquinotoxineOhomeroquineneHON7-hydroxyisoquinoline----------------------------------------------------------------------------------------Woodward's Quinotoxine syn<strong>the</strong>sisNHHONCH2OpiperidineMeOHHONNMeOH/NaOMe220 °C, 10h64%HONMeOON7-hydroxyisoquinoline1. H 2, PtOAcOH2. Ac 2O, MeOH95% (for 2 steps)HONOH 2 Raney NiquantHOONOHONEtOH/NaOEtEtONO68%mixture <strong>of</strong> isomersH36% cis recrystallizedHONHNOMeI, K 2 CO 3EtOHNHNO1. 60% NaOH40 °C2. KOCNHCrO 3N NH2O1. 0.1 N HCl!2. AgO, H 2 SHNHEtOOH90%EtOOH42%HOOHquantHO HOhomeroquineneOOEt1. EtOH, HCl2.BzCl, K 2CO 396%EtOHHNOPhMeONNaOEt, !MeOEtOOOHHNOPh6 N HCl, !50% (2 steps)quinotoxineON9
ConclusionsONHHOHNMeOMeONNquinotoxineWhile dye chemistry is a limited field, it facilitated <strong>the</strong> development <strong>of</strong> organicchemistry, chemical industry, chemical education as we know <strong>the</strong>m today.10