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N
MeO
HO NH
H
NH2+
NH2H2N
Me
NN
NN
NH2
NH2
NH2
H2N
N
N
NH
H2N
NH
OHN
O
O
O
OH
OH
Synthetic Dyes and the Development of Organic Chemistry
indigo
alizarin
mauveine
Bismarck brown
fuchsin
General References:
Aftalion, F. A History of the International Chemical Industry. Philadelphia: University of Pennsylvania Press, 1991.
Beer, J. J. The Emergence of the German Dye Industry. Urbana, IL: Univeristy of Illinois Press, 1959.
Benfey, O. T. and P. J. T. Morris, eds. Robert Burns Woodward. Philadelphia: Chemical Heritage Foundation, 2001.
Christie, R. M. Colour Chemistry. Cambridge: Royal Society of Chemistry, 2001.
Gordon, P. F. and P. Gregory. Organic Chemistry in Colour. Berlin: Springer Verlag, 1983.
Honigsbaum, M. The Fever Trail: In search of the Cure for Malaria. New York: Farrar, Straus and Giroux, 2001.
Pratt, L. S. The Chemistry and Physics of Organic Pigments. New York: John Wiley and sons, Inc., 1947.
Stork, G.; Deqiang, N.; Fujimoto, A.; Koft, E. R.; Balkovec, J. M.; Tata, J. R.; Dake, G. R. J. Am. Chem. Soc. 2001, 123, 3239.
quinine
------------------------------------------------------------------------------------------
1856 – A synthetic route to quinine?
Gradually came into use in mid-1600s
Isolated in 1820 – Pelletier and Caventou
Extracted from the bark of cinchona tree found in the Andes
By early 1800s, native sources almost exhausted
Prices soared despite cultivation elsewhere
Empirical formula established in 1854 – Adolph Strecker
N
MeO
HO N
H
quinine
H
1
HN
2C10H13N + 3[O]
[O]
KCr2O4
H2SO4
NH2NH2
Me
KCr2O4
H2SO4
C20H24N2O2 + H2O
N
MeO
HO NH
H
N
N
NH
H2N
1856 – Perkin's Easter vacation
Formula, but not structure of quinine known
Perkin attempted oxidation:
quinineWilliam Henry Perkin, age 14
Experiment resulted in v. impure brown powder, but Perkin tried to assess whether the oxidation was general:
+
black sludge
EtOH, reflux
purple crystals = "aniline purple," later mauveineimpurities --------------------------------------------------------------------------------------------------------
OHO2N
NO2
NO2
HN
HN
NH
HN
N
O O
O-NH4+
OO
O
Perkin's sketch of Perkin and Sons dye factory
1857 – An industry began
Current synthetic dyes were unsuitable, but demand was high
picric acid
yellowmade from phenolnot lightfast
murexide
reddish-purplereasonably light-resistantapplication complex and expensivesynthesize from urea and nitric acid
Perkin left school, father risked fortune
Success required establishment of large scale organic chemicals industry
Raw materials to make aniline needed on large scale: benzene, nitric acid, aniline
2
1800-1845 – Coal tar and Justus Liebig set the stage
Liebig's lab in Giessen
In late 1700s coal distilled for tar; after 1812, illuminating gas became desirable, excess coal taraccumulated
Liebig one of the premier educators of all time
Fresenius, Erlenmeyer, Kekulé, Wurtz...
Small links between industry and chemistry established
August Wilhelm Hofmann began to analyze coal tar extracts
Hofmann establishes Royal College of Chemistry in England*
-----------------------------------------------------------------------------------------------------------
OH
N N
N
N
[O]
-O3S
N
N
OH
NH
+HN
NH
H+
SO3NH4
SO3NH4
N
N
NH2+
NH2H2N
NN
NH2
1856-1867 – Post-mauveine developments
Concious search for new dyes – fuchsin found by Emanuel Verguin
Triphenylmethine dyes enable systematic synthesis of new compounds – Hofmann
Production of mauveine stopped after ten years
1867 – value of dyes had tripled since 1862 despite price drops
rosaniline or fuchsin
malachite green
aniline blue
aniline yellow
1862 1867
benzene 5 fr 70 c
rosaniline 300 fr 30 fr
Price per kilo of raw materials and dyes
3
NH2
N O
Y
-O
NO
NH2
-Y-
HNO2
H2+
NN
O
HON
O
ON
ON
O
-H+
N+
N
+H2O
NO
HN
NO
YN
O
NH2
ClN
O
NN
OH
+NO
H+
NN
NH2
NN
OH2+
-H2O
NN
NH2H2N
N+
N
1858 – Peter Griess and the azo dyes
Peter Griess
More Germans in England
2 diazotization azo coupling
aniline yellow
Otto Witt, Heinrich Caro and Carl Alexander Martius
Versatile chemistry exploited
Azo dyes today account for 60-70% of dyes used in textile applicationschrysoidine
increasing acidity
pH important in diazotization as well as azo coupling
nitrite anion
dinitrogen trioxide
nitrious acidnitrosoacidium ion nitrosonium cation
nitrosyl chloride
----------------------------------------------------------------------------------------------------------
O
O
Br2
O
O
OH
OH
O
O
Br
Br
O
O
OH
OH
O
O
Br
Br
NaOH, !
O
O
SO3H
SO3H
O
O
H2SO4
O
O
OH
OH
[O]
O
O
SO3H
1869 – Alizarin, then decline for England and France
Madder
alizarin
1868 – Graebe and Liebermann deduce structure
Perkin and Sons first commercial producers:
Class of carbonyl dyes – anthraquinones
But England was on the decline:
Hofmann departs in 1865Not enough trained chemistsMinimal state fundingBusiness complacencyLittle cultivation of scientific inquiry
France too:
Not enough raw materialsLoss of Alsace-Lorraine in 1871Patents for products, not processesPrivate labs did not supply enough trained chemists
1869 - 1 ton1870 - 40 tons1871 - 220 tons
Caro, Perkin:Graebe and Liebermann:
4
CIBA, Sandoz
BASF
German industry on the rise
Decentralization – lack of investment necessitated imitation, competition among small states
Patent situation – laws difficult to enact, foreign technology not protected, competition increased
Geography – raw materials, transportation in Rhein river valley
Education – the Liebig tradition supplied fresh ideas, trained chemists
Unification in 1871 – Patent Act of 1876 arrived at the right time
Business – ties between industry and universities established quickly
Bayer
Kalle,Höchst
AGFA
--------------------------------------------------------------------------------------------------------
Education – Universities and the Technische Hochschule
1809 Univeristy of Berlin – model for a modern university:
Liebig's pedagogical model:
1860s – glut of doctoral students led to technische hochschule:*
Ties with professors highly sought after by companies
SeminarsSemestersVernacularProfessional training, productive citizens
Close relationship with professor, whose enthusiasm evoked admiration and loyaltyFull enthusiasm for studies – 6 days/wk, 12-15 hrs/dayCompetitive atmosphere among students"ample opportunities of witnessing, in a comparatively short time, a vast variety of processes which are being constantly carried on in an institution consisting of a great number of experimentalists" (Hofmann, 1849)
Proximity to state centersTies with state and industryIncluded education in other fieldsStimulated improvements at universities (v. similiar by 1900)
5
OBr
HO
Br
BrO
BrCO2H
1870s – Heinrich Caro exemplifies industrial and academic cooperation
Heinrich Caro
As director of research at BASF, Caro tirelessly fostered ties with academics
1868 – Graebe and Liebermann consult Caro regarding alizarin
1873 – Adolf von Baeyer and Caro collaborate on research program They discover eosin Martius at Agfa discovers secret formula with the help of Hofmann
1876 – Caro stymied again with chrysoidine by Martius and Hofmann*
1876 – Griess supplied Caro with samples from azo coupling reactions
1878 – Emil and Otto Fischer (under von Baeyer) solve structure of triphenylmethine dyes, but only with help from Caro
Adolf von Baeyer Emil Fischer
Eosin
A. W. Hofmann ------------------------------------------------------------------------------------------
NN
NH2
SO3NaN
NNH2
SO3Na
1870-1890 – Rise of the industrial research laboratory and the Bayer example
Research labs enabled acceleration of research by consolidating resources Teams Facilities Academically trained scientists in management positions
Bayer was slower to innovate than other major german firms
By 1882, a full research staff was still not established
1884 –Duisberg enables Bayer to compete with Agfa
Duisberg spontaneously evolves into a research director
Primitive labs replaced with Duisberg design of new building, layout adopted almost universally*
Also quality control, library, conferences, product testing
Bayer laboratories after Duisberg
Carl Duisberg
benzopurpurin 4B
In 1896, 1 in 70 dyes approved for productionBy 1900, 1 in 200 dyes marketed ca. 1905, 1 in 300 dyes marketed
6
O
OH
HNO2
HNO3
NH
O
N
HO
O
OHNO2
Sn-HCl
Zn-HCl
NH
O
NH2
O
OHNH2
FeCl3
-H2O
NH
O
O
NH
O
Cl
O
OH
O
NH2
OH
O
Cl
OH
O
NH
O
OH
NH
OH
O
OH
-CO2
NH
OH
O
O
O
NH3
NH
O
O
NaOCl
NH
HN
O
O
Indigo side note
indigofera tinctoria
Natural sources were not quickly overcome due to synthetic challenges1869- von Baeyer proposes correct structure, synthesized 11 years later
von Baeyer:
isatin
PCl3, P,
indigo
1893 – Heumann's first commercially viable synthesis for BASF
NaOH200 °C
Indigo
H2SO4, !HgSO4
Hofmannrearrangement
Air
---------------------------------------------------------------------------------------------------------
The industry up to the war – paving the way for IG Farben
Expansion Germany's coal tar dye exports:
Quantity in tons Value in thousands of marks
1882 8,363 69,3061887 14,666 55,534
1892 23,202 70,976
1897 35,510 90,896
1902 59,862 138,582
1907 79,215 186,515
1912 93,671 209,166
Other fields
Pharmaceuticals – growth of medicine Heavy chemicals and organic intermediates – industrial efficiency Photography Nitrogen fixation – BASF fertilizers and munitions Isoprene polymerization – Bayer synthetic rubber
Chemistry in the serviceof industry
7
------------------------------------------------------------------------------------------
War, cartel formation and IG Farben
Intensification of competition led to profits inadequate for investment
1881 – first alizarin cartel fixed price and allocated market
1900 – second alizarin cartel allowed prices of some products to remain low, in exchange for an international monopoly
Duisberg pushes for fusion of research laboratories, but emphasizes decentralization
1904 – Bayer, BASF, and Agfa, and Höchst and Casella merged as two syndicates
1914 – war turned the industry to explosives, nitrogen and rubber
1916 – exigencies of war brought about merger of the two syndicates to IG Farben
Agreement, stratification, planning enabled further growth of cartel during and after the war
1925 – cartel became a full trust triggering further expansion
Facilitated WW2
IG Farben administrative building - 1928 8
N
MeO
HO N
NHO
N
MeO
O
NH
N
MeO
O
NH
NH
O
HO
H
H
N
MeO
HO N
H
H
Back to the mosquito
1918 – Paul Rabe takes quinotoxine to quinine
1944 Woodward and Doering's plan
Rabe
homeroquinene
7-hydroxyisoquinoline
quinotoxine
quinotoxine
----------------------------------------------------------------------------------------
NHO
N
ONHO
O
EtO
H
H
N
O
EtO
H
H
Ph
O
NHO
O
NHO
N
N
MeO
O OEt
N
ON
O
EtO
H
H
NaOEt, !
NHO
O
N
MeO
O
NO
H
O
PhEtO
H
NHO
CrO3
N NH2
O
O
HO
H
H
NO
OH
H
N
MeO
O
NH
NH
O
HO
H
H
Woodward's Quinotoxine synthesis
CH2Opiperidine
MeOH
7-hydroxyisoquinoline
1. H2, PtOAcOH2. Ac2O, MeOH
MeOH/NaOMe220 °C, 10h
64%
95% (for 2 steps)
H2 Raney Niquant
mixture of isomers36% cis recrystallized
EtOH/NaOEtEtONO
68%
MeI, K2CO3
EtOH
90%
1. 60% NaOH 40 °C2. KOCN
42%
1. 0.1 N HCl!
2. AgO, H2S
homeroquinene
quant
1. EtOH, HCl2.BzCl, K2CO3
96%
6 N HCl, !quinotoxine
50% (2 steps)
9
Conclusions
N
MeO
HO N
N
MeO
O
NH
quinotoxine
H
While dye chemistry is a limited field, it facilitated the development of organic chemistry, chemical industry, chemical education as we know them today.
10
