Perkin, William Henry

PERKIN, WILLIAM HENRY

(b. London, England, 12 March 1838; d. Sudbury, England, 14 July 1907)

synthetic organic chemistry, physical organic chemistry.

Perkin was the son of George Fowler Perkin, a builder and contractor. He became interested in chemistry at an early age and in 1851 was sent to the City of London school, where—although science was not part of the curriculum—he was able to attend the weekly lectures on chemistry given by one of the classmaters during the dinner hour. Perkin’s father was opposed to his making a career in chemistry, but he was encouraged by his master, Thomas Hall, through whose intercession he was enrolled in the Royal College of Science when he was fifteen. Perkin attended the lectures of the German chemist A. W. von Hofmann and, by the end of his second year at the college, was appointed Hofmann’s assistant.

Perkin established his own laboratory at home at about the same time; one of his first pieces of private research was concerned with a coloring material. With Arthur H. Church he began to investigate the reduction products of dinitrobenzene and dinitronaphthalene. From the latter, Perkin and Church obtained a colored substance that they named “nitrosonaphthalene,” which proved to be one of the first of the azo-dyes derived from naphthalene to be manufactured. They subsequently patented their process. Perkin’s major discovery, that of mauve, the first synthetic dyestujj, occurred shortly thereafter, during the Easter vacation of 1856, when Perkin was only eighteen.

Hofmann had previously remarked to Perkin on the desirability of synthesizing quinine. Taking up the problem Perkin (basing his experiments on the idea, now understood to be unsound, that the structure of a chemical compound could be determined from the molecular formula alone) first treated toluidine with bichromate of potash, then repeated the process with an aniline salt. From the latter he obtained not quinine but a dirty, dark-colored precipitate. Some special instinct caused him to examine this precipitate further, and he discovered it to have coloring properties. From it he succeeded in isolating mauve, or aniline purple, the first dyestuff to be produced commercially from coal-tar. Almost immediately he sent a sample to a firm of dyers in Perth, with the request that they try it for coloring silk. In reply he received a letter that said, “If your discovery does not make the goods too expensive, it is decidedly one of the most valuable that has come out for a long time.”

Perkin thus decided to patent his method for manufacturing the new dyestuff. His father agreed to provide financial support, although Hofmann had tried to discourage the venture, and a factory building was begun at Greenford Green in June 1857. Aming the initial problems that the manufacturers faced was the refining of suitable raw materials; the eighteen-year-old Perkin had to work out a method of converting nitrobenzene to aniline and to devise not only a new technique but also a new apparatus. Nonetheless Perkin’s “Tyrian purple” was being used in London dyehouses within six months, and shortly thereafter other firms in England and France were engaged in its production. Many other produres for making mauve were soon patented. These represented only slight modifications of Perkin’s original process, but fortunately for Perkin none of these newer methods yielded mauve as cheaply as his “bichromate method.

Perkin’s discovery gave impetus to a new coal-tar dyestuffs industry. Perkin was able to keep his factory working at a profit in spite of the discovery of a number of other new coloring materials by a number of other chemists; in 1864 he himself introduced a new method for the alkylation of magenta, which allowed him to compete with the manufacturers of other violet dyes.

In 1868 the German chemists Graebe and Liebermann announced that they had synthesized alizarin, the natural coloring matter of madder; their process, however, was too expensive to be of more than scientific interest. Within a year Perkin worked out two new methods to manufacture alizarin more cheaply; both used coal-tar products, one being based upon dichloroanthracene and the other upon the sulfonic acid of anthraquinone. Synthetic alizarin soon replaced rose madder as the prome red dye, both in England and on the Continent. By the end of 1869 Perkin’s company had made a ton of alizarin, and by 1871 they were manufacturing 220 tons a year.

Perkin had always hoped to devote himself completely to pure science, and by 1873 he found that his factory and patents could guarantee him the means for a modest retirement. The following year, when he was thirty-six, he sold his factory and turned full time to the research in pure chemistry that he had conducted concurrently with his industrial work. He had already made significant contributions to organic chemistry, even while burdened by commerce; in 1858, a year after his factory had opened, he had discovered that aminoacetic acid with ammonia. By 1860, in collaboration with B. F. Duppa, he had established the relationships between tartaric, fumaric, and maleic acids and had accomplished the synthesis of cinnamic acid from dibromo succinic acid. About 1867 he began to investigate the action of acetic anhydride on aromatic aldehydes, which led him to the method of synthesizing unsaturated acids by what is now known as “Perkin’s synthesis”-a method that he applied, within a year of its discovery, to synthesizing coumarin. This line of investigation culminated, after Perkin’s retirement from the dyestuffs industry, in his discovery that cinnamic acid could be synthesized from benzaldehyde—a discovery that made possible the first synthesis of indigo by Baeyer and Caro.

Upon retiring from business Perkin had a new house built at Sudbury and converted the old, adjacent one into a laboratory, where he continued to work almost until the time of his death. In 1881 he became interested in the magnetic rotatory polarization of certain organic compounds and so developed his investigations that the examination of this property became an important tool in considering questions of molecular structure. Perkin devoted the last twently-five years of his life to this physica aspect of organic chemistry; he was commended for his work by Professoe Bruehl, himself one of the pioneers of the application of optical methods to the determination of chemical constitutions, who there was little, almost nothing, known of this subject, certainly nothing of practical use to the chemist. You created a new branch of science.…”

Perkin’s personal life was essentially uneventful. His devotion to his work and his family was so complete that, aside from participating in the activities of several scientific societies, he took no part in outside affairs. He was married twice; in 1859 to Jemima Harriet Lissett, who died in 1862, then in 1866 to a Polish girl, Alexandrine Caroline Mollwo, who survived him. He had two sons, both of whom became distinguished professors of chemistry, from his first marriage and one son, Frederick, and four daughters from his second. Perkin was of a retiring disposition and chose to avoid publicity; although colleagues in pure chemistry accorded him considerable recognition for his work, he was less honored by his co-workers in the field of commercial dyestuffs manufacture. In 1906, however, jubilee celebrations were held in England and the United States in commemoration of Perkin’s discovery of mauve; distinguished scientists and industrialists from all over the world attended them, and Perkin was knighted upon this occasion. He died of pneumonia, perhaps weadened by the strain attendant upon celebrity, shortly thereafter.

BIBLIOGRAPHY

A complete list of Perkin’s work is in Sidney M. Edelstein, “Sir William Henry Perkin,” in American Dyestuff Reporter, 45 (1956), 598–608.

For further information on Perkin’s life and work, see B. Harrow, Eminent Chemists of Our Times (New York, 1927); R. Meldola, Jubilee of the Discovery of Mauve and of the Foundation of Coal-Tar Industry by Sir W. H. Perkin (London, 1906), and “Obituary Notice,” in Journal of the Chemical Society, 93 (1908), 2214; and M. Reiman, “On Aniline and Its Derivatives,” a treatise on the manufacture of aniline colors, to which is added an appendix, “The Report on the Colouring Matters Derived from Coal Tar,” shown at the French Ex hibition (1867) by A. W. von Hofmann, Mme G. DeLair, and C. Girard; William Crookes revised and edited the whole work (London, 1868).

Sidney Edelstein