Peter J.T. Morris and Anthony S. Travis, "A History of the International Dyestuff Industry", American Dyestuff Reporter, Vol. 81, No.
11, November 1992. Minor editing has been applied. Copyright by the AATCC (www.aatcc.org) and used with permission. Click
images to enlarge.
A History Of The International Dyestuff Industry
By Peter J.T. Morris* and Anthony S. Travis**
Introduction
The preparation and use of dyestuffs is one of the oldest of human activities, as evidenced by the unearthing of ancient fabrics at
archeological sites, as well as accounts in the Bible and works of classical antiquity. Until two centuries ago, the materials and
methods had hardly changed. Then, with the advent of the industrial revolution, chemistry began to play a prominent role in the textile
industry. This led to improvements in existing colorants and their methods of application. This article surveys the prehistory of modem
dyes, the rise of the synthetic dyestuffs industry during the nineteenth century, when science-based innovations led to artificial
products, and the changes brought about in the twentieth century by the challenge of novel fibers, increasing chemical knowledge, and
fluctuating economic conditions.
Dyestuffs before William Perkin invented Mauve
The Orient, the Occident, and Colonial America. The introduction of cochineal, Turkey red and dyewoods into Europe. The first semi-
synthetic dyes: picric acid and murexide. The structure of the dye industry in the 1840s.
In 1630 a Mr. Higginson of Salem, North Carolina, noted of the local vegetation: “here to be divers roots and berries wherewith the
Indians dye excellent holiday colors that no rain or washing can alter”.1 He, like other colonialists in the New World, marveled at the
remarkable variety of dye-yielding trees and plants that were unknown in the Old World.
Until the arrival of these new sources of dyes, Europe relied almost exclusively on the same colorants that had been in use since
antiquity, such as woad, madder and indigo. Even the methods of application had changed little from those employed by the ancient
Egyptians. Mordants enabled a wide range of colors, especially when used with madder, and different cultures had developed not
altogether different technologies.
Notable progress was made in Europe during the thirteenth and fourteenth centuries, especially by Italian and Venetian dyers.
Merchants from Genoa established the trade in alum, the most important dye mordant, with the Gulf of Smyrna. There was bitter rivalry
with Venice, which brought alum and dyes from the east direct to the low countries. From 1429 Florence also engaged in this trade. By
the fifteenth century alum manufacture was commenced at Tolfa, in Italy.2
*Dr. Peter J. T. Morris is Manager of Research and Residencies at the Science Museum, London SW7 2DD, London, Great Britain. This
paper was written while he was the 1991-1992 Edelstein International Fellow in the History of Chemistry and Chemical Technology at
the Sidney M. Edelstein Center for the History and Philosophy of Science, Technology and Medicine.
** Dr. Anthony S. Travis is Deputy Director at the Sidney M. Edelstein Center for the History and Philosophy of Science, Technology and
Medicine, The Hebrew University of Jerusalem, Givat Ram, Jerusalem, 91 904 Israel, and Senior Research Fellow at the Leo Baeck
Institute London.
In 1548, the first edition of the earliest book devoted exclusively to profession-al dyeing was published in. Venice. This was
Gioanventura Rosetti’s Plictho de larte de tentori che insegn tenger pan[n]i banbasi et sede si Per larthe magiore com per Ie
comvne 3, which included details of dye recipes and techniques employed in Venice, Genoa, Florence, and elsewhere in Italy. In
particular, it provided the most complete record of the dyers craft at the time when the first South American dyewood was becoming
available in Europe.4 Until then three primary colors were employed by dyers. Blue was obtained from indigo, either from woad or the
indigo plant. Reds were available from the Kermes insect, from the root of the madder plant, and from so-called brazilwood imported
from the Far East.
Yellows were extracted from weld, Persian berries, saffron and dyers broom. These colors were combined to afford greens, browns,
violets and other compound shades; they could be varied with the aid of mordants.
Rosetti’s publication did not include cochineal, which only later in the sixteenth century displaced Kermes, mainly as a result of the
voyages of Cortez (from 1523). Cochineal dyeing was improved in Holland around 1630, and the secrets of the new process were
stolen by a German who carried the details to London.
Madder was the basis of Turkey red dyeing, introduced to Europe with the aid of Greek technicians in the eighteenth century. Madder
was also important to the emerging calico printing industries of Amsterdam, Basle, Berlin, Elberfeld, Glasgow, Manchester and
Mulhouse. Textile printing made great demands on the expertise of the colorist, and encouraged the publication of manuals on calico
printing, the first of which was Charles Obrien’s, The British Manufacturers Companion and Calico Printers Assistant, which appeared
in London during 1790.5
Occasionally, an intrepid explorer would return with news of new discoveries. Chinese green, Lo-Kao, was not encountered by the
Europeans until the end of the eighteenth century, and attracted much attention in the 1850s.6 Sometimes, colors had fallen out of use,
and their secrets had been lost, like the fabled biblical blue and Roman purple, first extracted from the murex snail by the ancient
Israelites on the Levantine coast, and then adopted by the Phoenicians and Romans. During the nineteenth century many dyers and
scientists attempted to discover the secrets of the colors of antiquity which were imitated using lichens and the New World’s products.
While the new dyewoods enriched the ranges of European dyers, the American dyer’s needs were met by madder, indigo and other
vegetable dyes that were newly cultivated in Virginia from around 1650. Dyes from American woods also displaced those that had been
imported. Fustic, cochineal and dyewoods were brought in from the West Indies, while South Carolina and Georgia became significant
sources of cochineal. The inner bark of the common ash tree afforded an indigo substitute, while from around 1770 Edward Bancroft
found that the inner bark of the American black oak gave the yellow colorant soon known as quercitron.7
The development of the colonial natural dye industry in North America coincided with a transatlantic revolution in methods of
manufacture, especially of textiles. The rapid growth of the textile industry from the end of the eighteenth century came about through
the introduction of mechanized processes, improvements in bleaching, and by the mid-nineteenth century multi-color roller printing.
Notably, chlorine became the bleaching agent of choice. These new processes, and the introduction of steam power, enabled rapid
and large scale production, and were accompanied by unprecedented demand for dyes. This encouraged scientific studies, especially
new methods for applying dyes in printing, and improved extraction processes notably in France. The Emperor Napoleon I signed a
decree calling for madder dyeing on wool to be improved,8 and in the 1820s the newly formed Societe Industrielle de Mulhouse offered
a prize for chemical knowledge about madder This led to the first isolation and analyses of alizarin and purpurin.
The French dyers and printers in Mulhouse and Rouen, and the Germans in Berlin and Elberfeld, had close links with the sites of
greatest consumption Lancashire and south-west Scotland, the hubs of the first great Industrial Revolution. Chemists were attracted to
these areas, and they assisted the dyers and calico printers, who, in turn, began to appreciate the importance of chemistry.
One consequence of these developments was that the study of chemistry became a respectable activity since it offered possibilities for
earning a livelihood.
New sources of dyes were investigated from the 1840s, such as coal tar, the waste of lighting gas works. Nitration of phenol from coal
tar yielded yellow picric acid that was a useful dye for over three decades from around 1850. Justus Liebig and Friednch Wohler in
Giessen had investigated murexide, a purple product obtained from snake excrement, although in the late 1830s its potential as a
dyestuff was not immediately apparent.
The problem, as with many other new colorants, was that there were no known methods available for fixing novel “semi-synthetic”
colors. Neither was the raw material abundant. Moreover, dye recipes were secrets that were not, as far as possible, allowed to
escape from the confines of the dyehouse.
This situation began to change when chemically trained colorists moved around Europe, and sometimes across the Atlantic, picking
up the latest developments and selling their skills to dyers and printers.9 In the 1840s the dye-making industry was in the hands of the
extractors of natural colorants merchants and dyers. The French were particularly successful, and their improved production methods
for madder were investigated and imitated by the Dutch. 10 During the 1850s, French colorists and dye-producers, especially Depoully
in Paris managed to surmount the difficulties of making murexide from abundant South American guano, and of applying it to natural
fibers, and it was adopted in Britain, France and Germany.
Mauve
William Perkin’s discovery of an aniline purple, and why he succeeded.
The study of coal tar products that transformed the world of dye-making was spearheaded by August Wilhelm Hofmann, an assistant of
Liebig.11 During the early 1840s, Hofmann demonstrated the identity of a basic compound obtained from various sources, including
indigo and coal tar. It was soon named aniline from anil, the Arabic for indigo. After 1845 Hofmann and others prepared this aromatic
amino compound in two steps from the coal tar hydrocarbon benzene. There were other coal tar hydrocarbons, such as toluene,
naphthalene and anthracene. These were studied because their amino compounds appeared to be related to the alkaloids, above all
the important drug quinine.
Hofmann, from 1845 director of the Royal College of Chemistry in London, and his students and assistants worked on reactions
leading to a variety of amino compounds, as well as on the analysis of important natural substances, including dyestuffs. In 1853, the
fifteen-year-old William Henry Perkin became one of Hofmann’s students.
After following the introductory course, Perkin was assigned a research project related to coal tar compounds. This was the
preparation of an amino derivative of anthracene. Though the project was a failure, Perkin’s interest in aromatic amino compounds led
to similar experiments with benzene and naphthalene in 1855-56. Among the products were colored substances. Their dyeing
properties were investigated, and noted in the subsequent published reports, which appeared during 1857.
Perkin was also interested in a route to synthetic quinine. He attempted this during the Easter vacation of 1856 in a laboratory that he
had set up in a room at his parents’ East London home. The idea was to bring about condensation of the amine allyltoluidine under
oxidizing conditions with potassium dichromate. The experiment failed. To find out why, Perkin delved into the mysteries of aromatic
oxidations. He treated aniline with the same oxidizing agent. The result, a black precipitate, appeared to be no more promising.
Treatment with alcohol, however, afforded a purple solution which stained a piece of cloth. This color resisted soaping and the action
of light, especially when attached to silk, and Perkin was soon considering its possibilities as a commercial dyestuff.
Perkin sent samples of his colorant to Pullars of Perth, dyers of piece goods with connections throughout Europe, who reported
favorably of the novel substance.12 Purple was a popular color, but the alternatives, made from lichens and the guano-derived
murexide, were not fast to light, especially in the acidic atmospheres of industrial cities.
Perkin wisely filed a patent for his new invention during August 1856, and, in October, left the Royal College of Chemistry to pursue its
improvement.
It was in January 1857 that an East London silk dyer named Thomas Keith reported the superior qualities of the aniline color. This
encouraged Perkin, his father, and brother Thomas Dix to construct a small factory to manufacture aniline purple at Greenford Green,
north-west of London. The first batch of finished product was shipped to Thomas Keith in December 1857. The Perkins were in
business.
Unfortunately, the product proved difficult to sell, except for the limited application of dyeing silk, because of the difficulties of attachment
to cotton. Consequently, there was little enthusiasm from the calico printers in Lancashire and Scotland.
Nevertheless, purple had become the leading color of fashion in Paris and London, probably because of the introduction of a fast and
brilliant lichen dye, French purple, manufactured by a firm in Lyon. Perkin was under pressure to develop a suitable mordant for cotton,
which he achieved at the same time as Robert Pullar. Then the product had to be sold to the printers, which required considerable
travel throughout Britain and trials in the factories of potential consumers. These succeeded, and the synthetic color, at first named
Tyrian Purple, after the fabled Levantine dye, became a success early in 1859.13
The production of the new color required plentiful supplies of aniline, made in two steps—nitration and reduction—from benzene,
which was distilled from coal tar. At first the process apparatus was made of glass, but when demand picked up the Perkins
introduced small hand stirred iron equipment. These reactors were scaled up, and mechanized, by Edward Chambers Nicholson of
the South London chemical manufacturer Simpson, Maule & Nicholson; the partners were also former students of Hofmann. Perkin
would not license his patented process to other firms in Britain, which meant that new progress was made elsewhere. Lyon dyers,
who specialized in silks, were soon experimenting with the aniline reaction. They and innovative Parisian firms, such as Depoully and
Castelhaz, manufactured aniline purple on a considerable scale from the end of 1858, as did one or two German firms. This caused
widespread use in the fashion centers of Europe. In Britain, aniline purple was renamed mauve (French for the mallow flower) during
the spring of 1859, when it reached a peak of popularity.
Fuchsine
A range of synthetic dyestuffs appears in Britain and France. Specialist companies enter the field.
At the same time as mauve was becoming popular a second aniline color, a brilliant red called fuchsine (after the fuchsia flower),
appeared from the factory of the Renard Freres, a dyeing partnership based in Lyon. It was the invention of Francois Emmanuel
Verguin, who had joined the Renards early in 1859. The oxidizing agent was stannic chloride, and the product was on sale from May of
that year.
During the winter of 1859-60, Nicholson in London discovered a better route to the red, in which arsenic acid was employed in the
oxidative condensation of commercial aniline. Henry Medlock, another former student of Hofmann, and consultant to a firm of dyers in
Coventry, came across an almost identical process.
In January 1860, Medlock filed his patent, just one week before Nicholson. In October, rights to Medlock’s arsenic acid process were
purchased from the Coventry firm by Simpson, Maule & Nicholson, which marketed the red as roseine, although it was more generally
known as magenta in Britain, after the battle of that name.
The third aniline dye was discovered in 1860 by Charles Girard and Georges de Laire, chemical assistants of Jules Theophile Pelouze
at the Paris Mint. Pelouze, an expert in the extraction and reactions of benzene, owned a factory for the preparation of this hydrocarbon
and the intermediates nitrobenzene and aniline at Brentford, near London.
While working at Brentford on the aniline red reaction, Girard and de Laire came across a mixture that afforded a blue colorant. They
found that the best method was to heat aniline with the red. This was patented early in 1861, and their aniline dye patents were soon
acquired by the Renards, who also bought the interests of Pelouze. The Renards were closely connected with Simpson, Maule &
Nicholson, which in 1862 was granted a license to manufacture the blue in Britain.
Hofmann was the scientific consultant to the two firms, and studied the constitution of aniline red and blue.14 Thereafter, the growth of
the aniline dye industry was closely linked to Hofmann’s work with amino compounds.
Hofmann analyzed the blue for Nicholson, and in May 1863 revealed to the scientific world that it was triphenylated aniline red. This
suggested the possibility of colors from other substitutions on the red. He investigated alkylation and came across brilliant violets. The
process was patented, licensed to Simpson’s firm, the Renards, and a German manufacturer.
The violets became known as Hofmann’s violets, and from 1864 displaced Perkin’s mauve. Unlike the earlier aniline colors, which had
been discovered through empirical methods on the shop floor or in factory laboratories, the Hofmann’s violets were a consequence of
theory based scientific research. Hofmann’s later research into aniline dyes demonstrated that aniline red (fuchsine, magenta,
roseine, etc.) was not a product from aniline alone, but from a mixture of toluene and aniline. Moreover, Nicholson found that
sulfonation imparted the important property of solubility to aniline blue.
The Renards and Simpson, Maule & Nicholson attempted to control the French and British markets with monopolies based on their
patents. A major court case that commenced in Paris during early 1860 was resolved in March 1863, when judgment was given in favor
of the Renards. This was a controversial decision. The Renards now controlled all processes to the red, and, therefore, had a
monopoly over the supply of its derivatives, aniline blue and the Hofmann’s violets. Simpson, Maule & Nicholson was less fortunate.
This firm lost its aniline red patent case in 1865, although it managed to retain the monopoly on aniline blue.
Once the red process became public property in Britain, the dye industry there expanded. It was Thomas Holliday, son of the tar distiller
Read Holliday of Huddersfield, who had battled against Simpson, Maule & Nicholson to make free the arsenic acid process for aniline
red, and after 1865 his business grew rapidly. This also assisted Ivan Levinstein, from Berlin, who in 1865 began the manufacture of
magenta at Blackley, Manchester; Levinstein’s factory was a forerunner of the present ICI Specialties.
Litigation and the outcomes of patent disputes were also spurs to new innovative activities. Since routes based on the oxidations of
aniline with arsenic acid were held up in Britain (except at Nicholson’s firm) until early 1865, because of injunctions, phenol-based
colors, naphthalene colors, modifications of mauve, and exploitation of Peter Griess’s discovery, what was later called the diazo
reaction, were all investigated. Heinrich Caro, a German colorist at Roberts, Dale & Co. in Manchester, the main rival of Simpson,
Maule & Nicholson, was instrumental in directing research that led to all these colors.15
Aniline Black
Caro invented a process for mauve in 1860, whereby copper salts were used as oxidants. It became the sole competitor to Perkin’s
dichromate reaction and the Manchester-made mauve was used in Lancashire and Scotland from around 1862. From the residue of
the reaction, Roberts, Dale & Co. extracted a black colorant suited to cotton printing. However, in 1862 it was used only to a limited
extent by printers in Britain because of the corrosive action on printing machinery. It was more widely applied on the mainland of
Europe, where wooden block printing was still popular.
The original discovery of aniline black was made in 1859 by John Lightfoot of Accrington, north of Manchester. He established that the
direct application of aniline in the presence of an oxidizing agent to cotton, using the engraved copper plates of cylinders of printing
machinery, gave a fast and brilliant black, but, again, this was not wholly satisfactory because of the corrosion problem. Lightfoot
eventually patented his process early in 1863. For mainland Europe and the United States patent rights were assigned to J.J. Muller-
Pack of Basle.
In 1864 Charles Lauth in Paris came out with the first of the improvements that were to make aniline black printing possible with
machinery. This was through the use of insoluble copper salts. For the remainder of the nineteenth century, aniline black printing and
dyeing was carried out on a vast scale.16
Alkylation and phenylation of aniline
Since the Renards retained exclusive control over the production of aniline red, blue and violet, chemists in Paris and Lyon also sought
out new reactions on coal tar products. In addition, the Renards, which became Societe La Fuchsine in 1864 (backed by the Credit
Lyonnais bank), had problems with pollution from large scale arsenic acid oxidation (from around 1862). For these reasons, amino
group hydrogens of aniline and toluidine were replaced by phenyl and alkyi groups prior to oxidation. This work, inspired by Hofmann’s
publications on the constitutions of aniline colors, led to the introduction of reactions carried out at high pressures and temperatures by
Poirrier in Paris (alkylation, 1866), which enabled the Renards’ patents to be circumvented. It also led to the introduction of less
poisonous oxidants. In Britain, Levinstein and Holliday used the substitution reactions to bypass the blue and violet processes
licensed to Simpson, Maule & Nicholson.
By 1864, the price of aniline red had fallen to about ten per cent of the 1860 levels, which reflected both the improved methods of large
scale production and the high level of competition. A wide range of colors, including yellows, brown, and grey were available from
commercial aniline.
Table 1
Prices of aniline dyes as quoted in France, 1860-1867, fr. per kg. unless otherwise indicated ( 1₤ =24-25 fr.)
11, November 1992. Minor editing has been applied. Copyright by the AATCC (www.aatcc.org) and used with permission. Click
images to enlarge.
A History Of The International Dyestuff Industry
By Peter J.T. Morris* and Anthony S. Travis**
Introduction
The preparation and use of dyestuffs is one of the oldest of human activities, as evidenced by the unearthing of ancient fabrics at
archeological sites, as well as accounts in the Bible and works of classical antiquity. Until two centuries ago, the materials and
methods had hardly changed. Then, with the advent of the industrial revolution, chemistry began to play a prominent role in the textile
industry. This led to improvements in existing colorants and their methods of application. This article surveys the prehistory of modem
dyes, the rise of the synthetic dyestuffs industry during the nineteenth century, when science-based innovations led to artificial
products, and the changes brought about in the twentieth century by the challenge of novel fibers, increasing chemical knowledge, and
fluctuating economic conditions.
Dyestuffs before William Perkin invented Mauve
The Orient, the Occident, and Colonial America. The introduction of cochineal, Turkey red and dyewoods into Europe. The first semi-
synthetic dyes: picric acid and murexide. The structure of the dye industry in the 1840s.
In 1630 a Mr. Higginson of Salem, North Carolina, noted of the local vegetation: “here to be divers roots and berries wherewith the
Indians dye excellent holiday colors that no rain or washing can alter”.1 He, like other colonialists in the New World, marveled at the
remarkable variety of dye-yielding trees and plants that were unknown in the Old World.
Until the arrival of these new sources of dyes, Europe relied almost exclusively on the same colorants that had been in use since
antiquity, such as woad, madder and indigo. Even the methods of application had changed little from those employed by the ancient
Egyptians. Mordants enabled a wide range of colors, especially when used with madder, and different cultures had developed not
altogether different technologies.
Notable progress was made in Europe during the thirteenth and fourteenth centuries, especially by Italian and Venetian dyers.
Merchants from Genoa established the trade in alum, the most important dye mordant, with the Gulf of Smyrna. There was bitter rivalry
with Venice, which brought alum and dyes from the east direct to the low countries. From 1429 Florence also engaged in this trade. By
the fifteenth century alum manufacture was commenced at Tolfa, in Italy.2
*Dr. Peter J. T. Morris is Manager of Research and Residencies at the Science Museum, London SW7 2DD, London, Great Britain. This
paper was written while he was the 1991-1992 Edelstein International Fellow in the History of Chemistry and Chemical Technology at
the Sidney M. Edelstein Center for the History and Philosophy of Science, Technology and Medicine.
** Dr. Anthony S. Travis is Deputy Director at the Sidney M. Edelstein Center for the History and Philosophy of Science, Technology and
Medicine, The Hebrew University of Jerusalem, Givat Ram, Jerusalem, 91 904 Israel, and Senior Research Fellow at the Leo Baeck
Institute London.
In 1548, the first edition of the earliest book devoted exclusively to profession-al dyeing was published in. Venice. This was
Gioanventura Rosetti’s Plictho de larte de tentori che insegn tenger pan[n]i banbasi et sede si Per larthe magiore com per Ie
comvne 3, which included details of dye recipes and techniques employed in Venice, Genoa, Florence, and elsewhere in Italy. In
particular, it provided the most complete record of the dyers craft at the time when the first South American dyewood was becoming
available in Europe.4 Until then three primary colors were employed by dyers. Blue was obtained from indigo, either from woad or the
indigo plant. Reds were available from the Kermes insect, from the root of the madder plant, and from so-called brazilwood imported
from the Far East.
Yellows were extracted from weld, Persian berries, saffron and dyers broom. These colors were combined to afford greens, browns,
violets and other compound shades; they could be varied with the aid of mordants.
Rosetti’s publication did not include cochineal, which only later in the sixteenth century displaced Kermes, mainly as a result of the
voyages of Cortez (from 1523). Cochineal dyeing was improved in Holland around 1630, and the secrets of the new process were
stolen by a German who carried the details to London.
Madder was the basis of Turkey red dyeing, introduced to Europe with the aid of Greek technicians in the eighteenth century. Madder
was also important to the emerging calico printing industries of Amsterdam, Basle, Berlin, Elberfeld, Glasgow, Manchester and
Mulhouse. Textile printing made great demands on the expertise of the colorist, and encouraged the publication of manuals on calico
printing, the first of which was Charles Obrien’s, The British Manufacturers Companion and Calico Printers Assistant, which appeared
in London during 1790.5
Occasionally, an intrepid explorer would return with news of new discoveries. Chinese green, Lo-Kao, was not encountered by the
Europeans until the end of the eighteenth century, and attracted much attention in the 1850s.6 Sometimes, colors had fallen out of use,
and their secrets had been lost, like the fabled biblical blue and Roman purple, first extracted from the murex snail by the ancient
Israelites on the Levantine coast, and then adopted by the Phoenicians and Romans. During the nineteenth century many dyers and
scientists attempted to discover the secrets of the colors of antiquity which were imitated using lichens and the New World’s products.
While the new dyewoods enriched the ranges of European dyers, the American dyer’s needs were met by madder, indigo and other
vegetable dyes that were newly cultivated in Virginia from around 1650. Dyes from American woods also displaced those that had been
imported. Fustic, cochineal and dyewoods were brought in from the West Indies, while South Carolina and Georgia became significant
sources of cochineal. The inner bark of the common ash tree afforded an indigo substitute, while from around 1770 Edward Bancroft
found that the inner bark of the American black oak gave the yellow colorant soon known as quercitron.7
The development of the colonial natural dye industry in North America coincided with a transatlantic revolution in methods of
manufacture, especially of textiles. The rapid growth of the textile industry from the end of the eighteenth century came about through
the introduction of mechanized processes, improvements in bleaching, and by the mid-nineteenth century multi-color roller printing.
Notably, chlorine became the bleaching agent of choice. These new processes, and the introduction of steam power, enabled rapid
and large scale production, and were accompanied by unprecedented demand for dyes. This encouraged scientific studies, especially
new methods for applying dyes in printing, and improved extraction processes notably in France. The Emperor Napoleon I signed a
decree calling for madder dyeing on wool to be improved,8 and in the 1820s the newly formed Societe Industrielle de Mulhouse offered
a prize for chemical knowledge about madder This led to the first isolation and analyses of alizarin and purpurin.
The French dyers and printers in Mulhouse and Rouen, and the Germans in Berlin and Elberfeld, had close links with the sites of
greatest consumption Lancashire and south-west Scotland, the hubs of the first great Industrial Revolution. Chemists were attracted to
these areas, and they assisted the dyers and calico printers, who, in turn, began to appreciate the importance of chemistry.
One consequence of these developments was that the study of chemistry became a respectable activity since it offered possibilities for
earning a livelihood.
New sources of dyes were investigated from the 1840s, such as coal tar, the waste of lighting gas works. Nitration of phenol from coal
tar yielded yellow picric acid that was a useful dye for over three decades from around 1850. Justus Liebig and Friednch Wohler in
Giessen had investigated murexide, a purple product obtained from snake excrement, although in the late 1830s its potential as a
dyestuff was not immediately apparent.
The problem, as with many other new colorants, was that there were no known methods available for fixing novel “semi-synthetic”
colors. Neither was the raw material abundant. Moreover, dye recipes were secrets that were not, as far as possible, allowed to
escape from the confines of the dyehouse.
This situation began to change when chemically trained colorists moved around Europe, and sometimes across the Atlantic, picking
up the latest developments and selling their skills to dyers and printers.9 In the 1840s the dye-making industry was in the hands of the
extractors of natural colorants merchants and dyers. The French were particularly successful, and their improved production methods
for madder were investigated and imitated by the Dutch. 10 During the 1850s, French colorists and dye-producers, especially Depoully
in Paris managed to surmount the difficulties of making murexide from abundant South American guano, and of applying it to natural
fibers, and it was adopted in Britain, France and Germany.
Mauve
William Perkin’s discovery of an aniline purple, and why he succeeded.
The study of coal tar products that transformed the world of dye-making was spearheaded by August Wilhelm Hofmann, an assistant of
Liebig.11 During the early 1840s, Hofmann demonstrated the identity of a basic compound obtained from various sources, including
indigo and coal tar. It was soon named aniline from anil, the Arabic for indigo. After 1845 Hofmann and others prepared this aromatic
amino compound in two steps from the coal tar hydrocarbon benzene. There were other coal tar hydrocarbons, such as toluene,
naphthalene and anthracene. These were studied because their amino compounds appeared to be related to the alkaloids, above all
the important drug quinine.
Hofmann, from 1845 director of the Royal College of Chemistry in London, and his students and assistants worked on reactions
leading to a variety of amino compounds, as well as on the analysis of important natural substances, including dyestuffs. In 1853, the
fifteen-year-old William Henry Perkin became one of Hofmann’s students.
After following the introductory course, Perkin was assigned a research project related to coal tar compounds. This was the
preparation of an amino derivative of anthracene. Though the project was a failure, Perkin’s interest in aromatic amino compounds led
to similar experiments with benzene and naphthalene in 1855-56. Among the products were colored substances. Their dyeing
properties were investigated, and noted in the subsequent published reports, which appeared during 1857.
Perkin was also interested in a route to synthetic quinine. He attempted this during the Easter vacation of 1856 in a laboratory that he
had set up in a room at his parents’ East London home. The idea was to bring about condensation of the amine allyltoluidine under
oxidizing conditions with potassium dichromate. The experiment failed. To find out why, Perkin delved into the mysteries of aromatic
oxidations. He treated aniline with the same oxidizing agent. The result, a black precipitate, appeared to be no more promising.
Treatment with alcohol, however, afforded a purple solution which stained a piece of cloth. This color resisted soaping and the action
of light, especially when attached to silk, and Perkin was soon considering its possibilities as a commercial dyestuff.
Perkin sent samples of his colorant to Pullars of Perth, dyers of piece goods with connections throughout Europe, who reported
favorably of the novel substance.12 Purple was a popular color, but the alternatives, made from lichens and the guano-derived
murexide, were not fast to light, especially in the acidic atmospheres of industrial cities.
Perkin wisely filed a patent for his new invention during August 1856, and, in October, left the Royal College of Chemistry to pursue its
improvement.
It was in January 1857 that an East London silk dyer named Thomas Keith reported the superior qualities of the aniline color. This
encouraged Perkin, his father, and brother Thomas Dix to construct a small factory to manufacture aniline purple at Greenford Green,
north-west of London. The first batch of finished product was shipped to Thomas Keith in December 1857. The Perkins were in
business.
Unfortunately, the product proved difficult to sell, except for the limited application of dyeing silk, because of the difficulties of attachment
to cotton. Consequently, there was little enthusiasm from the calico printers in Lancashire and Scotland.
Nevertheless, purple had become the leading color of fashion in Paris and London, probably because of the introduction of a fast and
brilliant lichen dye, French purple, manufactured by a firm in Lyon. Perkin was under pressure to develop a suitable mordant for cotton,
which he achieved at the same time as Robert Pullar. Then the product had to be sold to the printers, which required considerable
travel throughout Britain and trials in the factories of potential consumers. These succeeded, and the synthetic color, at first named
Tyrian Purple, after the fabled Levantine dye, became a success early in 1859.13
The production of the new color required plentiful supplies of aniline, made in two steps—nitration and reduction—from benzene,
which was distilled from coal tar. At first the process apparatus was made of glass, but when demand picked up the Perkins
introduced small hand stirred iron equipment. These reactors were scaled up, and mechanized, by Edward Chambers Nicholson of
the South London chemical manufacturer Simpson, Maule & Nicholson; the partners were also former students of Hofmann. Perkin
would not license his patented process to other firms in Britain, which meant that new progress was made elsewhere. Lyon dyers,
who specialized in silks, were soon experimenting with the aniline reaction. They and innovative Parisian firms, such as Depoully and
Castelhaz, manufactured aniline purple on a considerable scale from the end of 1858, as did one or two German firms. This caused
widespread use in the fashion centers of Europe. In Britain, aniline purple was renamed mauve (French for the mallow flower) during
the spring of 1859, when it reached a peak of popularity.
Fuchsine
A range of synthetic dyestuffs appears in Britain and France. Specialist companies enter the field.
At the same time as mauve was becoming popular a second aniline color, a brilliant red called fuchsine (after the fuchsia flower),
appeared from the factory of the Renard Freres, a dyeing partnership based in Lyon. It was the invention of Francois Emmanuel
Verguin, who had joined the Renards early in 1859. The oxidizing agent was stannic chloride, and the product was on sale from May of
that year.
During the winter of 1859-60, Nicholson in London discovered a better route to the red, in which arsenic acid was employed in the
oxidative condensation of commercial aniline. Henry Medlock, another former student of Hofmann, and consultant to a firm of dyers in
Coventry, came across an almost identical process.
In January 1860, Medlock filed his patent, just one week before Nicholson. In October, rights to Medlock’s arsenic acid process were
purchased from the Coventry firm by Simpson, Maule & Nicholson, which marketed the red as roseine, although it was more generally
known as magenta in Britain, after the battle of that name.
The third aniline dye was discovered in 1860 by Charles Girard and Georges de Laire, chemical assistants of Jules Theophile Pelouze
at the Paris Mint. Pelouze, an expert in the extraction and reactions of benzene, owned a factory for the preparation of this hydrocarbon
and the intermediates nitrobenzene and aniline at Brentford, near London.
While working at Brentford on the aniline red reaction, Girard and de Laire came across a mixture that afforded a blue colorant. They
found that the best method was to heat aniline with the red. This was patented early in 1861, and their aniline dye patents were soon
acquired by the Renards, who also bought the interests of Pelouze. The Renards were closely connected with Simpson, Maule &
Nicholson, which in 1862 was granted a license to manufacture the blue in Britain.
Hofmann was the scientific consultant to the two firms, and studied the constitution of aniline red and blue.14 Thereafter, the growth of
the aniline dye industry was closely linked to Hofmann’s work with amino compounds.
Hofmann analyzed the blue for Nicholson, and in May 1863 revealed to the scientific world that it was triphenylated aniline red. This
suggested the possibility of colors from other substitutions on the red. He investigated alkylation and came across brilliant violets. The
process was patented, licensed to Simpson’s firm, the Renards, and a German manufacturer.
The violets became known as Hofmann’s violets, and from 1864 displaced Perkin’s mauve. Unlike the earlier aniline colors, which had
been discovered through empirical methods on the shop floor or in factory laboratories, the Hofmann’s violets were a consequence of
theory based scientific research. Hofmann’s later research into aniline dyes demonstrated that aniline red (fuchsine, magenta,
roseine, etc.) was not a product from aniline alone, but from a mixture of toluene and aniline. Moreover, Nicholson found that
sulfonation imparted the important property of solubility to aniline blue.
The Renards and Simpson, Maule & Nicholson attempted to control the French and British markets with monopolies based on their
patents. A major court case that commenced in Paris during early 1860 was resolved in March 1863, when judgment was given in favor
of the Renards. This was a controversial decision. The Renards now controlled all processes to the red, and, therefore, had a
monopoly over the supply of its derivatives, aniline blue and the Hofmann’s violets. Simpson, Maule & Nicholson was less fortunate.
This firm lost its aniline red patent case in 1865, although it managed to retain the monopoly on aniline blue.
Once the red process became public property in Britain, the dye industry there expanded. It was Thomas Holliday, son of the tar distiller
Read Holliday of Huddersfield, who had battled against Simpson, Maule & Nicholson to make free the arsenic acid process for aniline
red, and after 1865 his business grew rapidly. This also assisted Ivan Levinstein, from Berlin, who in 1865 began the manufacture of
magenta at Blackley, Manchester; Levinstein’s factory was a forerunner of the present ICI Specialties.
Litigation and the outcomes of patent disputes were also spurs to new innovative activities. Since routes based on the oxidations of
aniline with arsenic acid were held up in Britain (except at Nicholson’s firm) until early 1865, because of injunctions, phenol-based
colors, naphthalene colors, modifications of mauve, and exploitation of Peter Griess’s discovery, what was later called the diazo
reaction, were all investigated. Heinrich Caro, a German colorist at Roberts, Dale & Co. in Manchester, the main rival of Simpson,
Maule & Nicholson, was instrumental in directing research that led to all these colors.15
Aniline Black
Caro invented a process for mauve in 1860, whereby copper salts were used as oxidants. It became the sole competitor to Perkin’s
dichromate reaction and the Manchester-made mauve was used in Lancashire and Scotland from around 1862. From the residue of
the reaction, Roberts, Dale & Co. extracted a black colorant suited to cotton printing. However, in 1862 it was used only to a limited
extent by printers in Britain because of the corrosive action on printing machinery. It was more widely applied on the mainland of
Europe, where wooden block printing was still popular.
The original discovery of aniline black was made in 1859 by John Lightfoot of Accrington, north of Manchester. He established that the
direct application of aniline in the presence of an oxidizing agent to cotton, using the engraved copper plates of cylinders of printing
machinery, gave a fast and brilliant black, but, again, this was not wholly satisfactory because of the corrosion problem. Lightfoot
eventually patented his process early in 1863. For mainland Europe and the United States patent rights were assigned to J.J. Muller-
Pack of Basle.
In 1864 Charles Lauth in Paris came out with the first of the improvements that were to make aniline black printing possible with
machinery. This was through the use of insoluble copper salts. For the remainder of the nineteenth century, aniline black printing and
dyeing was carried out on a vast scale.16
Alkylation and phenylation of aniline
Since the Renards retained exclusive control over the production of aniline red, blue and violet, chemists in Paris and Lyon also sought
out new reactions on coal tar products. In addition, the Renards, which became Societe La Fuchsine in 1864 (backed by the Credit
Lyonnais bank), had problems with pollution from large scale arsenic acid oxidation (from around 1862). For these reasons, amino
group hydrogens of aniline and toluidine were replaced by phenyl and alkyi groups prior to oxidation. This work, inspired by Hofmann’s
publications on the constitutions of aniline colors, led to the introduction of reactions carried out at high pressures and temperatures by
Poirrier in Paris (alkylation, 1866), which enabled the Renards’ patents to be circumvented. It also led to the introduction of less
poisonous oxidants. In Britain, Levinstein and Holliday used the substitution reactions to bypass the blue and violet processes
licensed to Simpson, Maule & Nicholson.
By 1864, the price of aniline red had fallen to about ten per cent of the 1860 levels, which reflected both the improved methods of large
scale production and the high level of competition. A wide range of colors, including yellows, brown, and grey were available from
commercial aniline.
Table 1
Prices of aniline dyes as quoted in France, 1860-1867, fr. per kg. unless otherwise indicated ( 1₤ =24-25 fr.)
|
Year Month |
Firm |
Red |
Purple |
Blue |
Violet |
Notes |
|
|
|
|
|
|
|
|
|
1859 |
Casthelaz ( |
|
3,000-4,000 |
|
|
powder |
|
|
Depoully ( |
|
60 |
|
|
paste |
|
|
Depoully |
|
100/l |
|
|
solution |
|
|
|
|
|
|
|
|
|
1860 |
Iager (Barmen) |
1,500 |
|
|
|
solid |
|
Feb. |
Fayolle ( |
100 |
|
|
|
paste |
|
May |
|
60 |
|
|
|
paste |
|
“ |
Depoully |
1,250 |
900 |
|
|
solid |
|
Nov. |
|
400 |
|
|
|
dry |
|
“ |
|
700 |
|
|
|
dry, sol. in
water |
|
“ |
|
400 |
|
|
|
‘pure’ |
|
“ |
|
60 |
50 |
|
|
paste |
|
“ |
|
18/l |
|
|
|
solution |
|
Dec. |
|
|
500 |
|
|
solid |
|
|
|
|
|
|
|
|
|
1861 |
|
|
|
|
|
|
|
Jan. |
Simpson,
Maule & Nicholson
( |
|
|
400 |
|
solid |
|
“ |
Renards |
|
|
300 (bleu de
Lyon) |
|
solid |
|
Feb. |
Poirrier ( |
|
300 (bleu
d’aniline) |
|
|
solid |
|
|
Depoully |
700 |
|
|
|
solid |
|
|
Renards |
800 |
|
|
|
solid |
|
July |
Renards |
800 |
|
|
|
solid |
|
|
Iager |
700 |
|
|
|
solid |
|
|
Depoully |
500 |
|
|
|
solid |
|
|
|
|
|
150 |
|
|
|
Aug. |
Renards |
600 |
|
|
|
solid |
|
Sept. |
Renards |
|
|
600 (bleu
Imperial) |
|
solid |
|
Dec. |
Renards |
|
|
600 (bleu
de |