CRAFTS, JAMES MASON

(b. Boston, Massachusetts, 8 March 1839, d. Ridgefield, Connecticut, 20 June 1917), organic chemistry, thermometry.

Crafts was one of the most prominent American chemists of the late nineteenth century, teaching at Cornell University and the Massachusetts Institute of Technology (MIT). He is most famous for discovering, with the French chemist Charles Friedel, a series of chemical reactions of aromatic compounds with organic halides in the presence of aluminum trichloride that proved extremely useful in the preparation of new organic compounds.

Early Years . Crafts was born in Boston to Royal Altemont Crafts, a prosperous textile merchant, and Marian Mason, daughter of Jeremiah Mason, a prominent lawyer and senator from New Hampshire. During his childhood he was acquainted with members of the academic community in Boston, and he received a bachelor of science degree from Harvard in 1858. After an additional year of study at Harvard, he studied in Europe for short periods at both the Freiberg school of mines and in Heidelberg with Robert Bunsen, before spending four years in Paris with Charles-Adolphe Wurtz at the École de médicine. During this period, Crafts met Charles Friedel (1832–1899), a prominent student of Wurtz and after 1856 curator of the mineral collection at the School of Mines. Crafts would share an extremely fruitful collaboration with Friedel that resulted in seventy-five coauthored papers published between 1863 and 1889.

Upon returning to the United States in 1865, Crafts became an inspector of mines in Mexico, and in 1867 he was chosen as professor of chemistry at the recently formed Cornell University. In 1868, he married Clémence Haggerty, with whom he would have four daughters. His experience in creating a new course in analytical chemistry led him to write a full textbook on qualitative analysis, integrating practical and theoretical chemistry and dedicated to Wurtz, which appeared in 1869. In 1870, Crafts accepted the chair of general and analytical chemistry at MIT, where, following the model of Bunsen’s laboratory in Heidelberg, he modernized the teaching laboratories by installing ventilation systems and steam tables. He taught organic chemistry at an advanced level using the research literature; the choice of text was left to the students, and the majority chose August Kekulé’s large and comprehensive German textbook. In his 1872 annual report, Crafts wrote that in his course he emphasized the details of theory in organic chemistry because that would serve better to ground students in general chemical theory.

Research and Academic Success . Because of health problems, in 1874 Crafts became a nonresident professor at MIT and returned to Paris to pursue research once again with Wurtz and Friedel. He intended his stay in Paris to be only one or two years, but the success of the collaboration with Friedel compelled him to stay. In 1880, he resigned his position with MIT, and he remained in Paris until 1891.

This period was the most productive of his scientific life. In 1877 with Friedel, Crafts reported in a series of three papers the discovery a new class of chemical reactions of aromatic compounds with aluminum trichloride and organic halides. As Crafts would later remember, the general reaction was discovered by the accidental observation of the reaction of amyl chloride with metallic aluminum. Among the products were hydrochloric acid, aluminum trichloride, and a mixture of various hydrocarbons. Friedel and Crafts noticed that the hydrogen and chlorine atoms in the hydrochloric acid formed must come from different hydrocarbons, and the hydrocarbon residues were combining with each other to yield the mixture of hydrocarbons in the presence of the aluminum trichloride.

This reaction led them to suspect that aluminum trichloride would work as a general reagent to couple organic chlorides with other organic compounds. In their first attempt, they combined amyl chloride with benzene and succeeded in substituting a hydrogen atom on benzene with an amyl group to give amyl benzene as the principal product:

Friedel and Crafts quickly expanded on the general implications of this reaction and found that any organic chlo-ride would add to the aromatic ring in the presence of aluminum trichloride, and that other halogens and nonaluminum metal chlorides would work equally well. In the second paper, they reported that acid chlorides would also react with aromatic compounds to give aromatic ketones:

Crafts later reported that these reactions were very easy to execute and that the reactions described in the first three papers of 1877 took only five or six weeks to complete, despite what he regarded as insufficient laboratory conditions. Between 1877 and 1889, Friedel and Crafts published over sixty papers describing the scope and power of this new synthetic technique.

While in Paris, Crafts also began an independent project on measurement of the relationship between the vapor pressure of iodine and temperature. He was soon led into research on establishing fixed reference points for high temperature thermometry. Crafts returned to the United States and MIT in 1892, where he resumed teaching organic chemistry. In 1895, he became head of the Chemistry Department. Two years later he was elected president of MIT.

As a teacher, Crafts was highly regarded by his students, who eagerly sought him out for advice on both laboratory and personal matters. In his 1899 MIT graduation address, Crafts emphasized the importance of a close relationship between teacher and student. Good students, Crafts said, “find [themselves] trying to pass beyond the boundaries marked out by routine and textbooks, and, in companionship with your teachers, trying to discover something new. This is the chief end of education; not so much to make you learned as to make you original and able to stand on your own feet” (Ashdown, 1928, p. 916).

In 1900, after a successful term as president, he resigned to return to full-time research in thermometry. Designing his own apparatus, Crafts determined the relationship between temperature and the vapor pressure of various substances water, naphthalene, and benzophe-none, and found that naphthalene was nearly equivalent to water for establishing fixed points of reference for a temperature scale. His work on thermometry served to correct earlier attempts at constructing a fixed temperature scale. After 1911, he abandoned laboratory work because of ill health and wrote his final comprehensive articles on thermometry near the time of his death in 1917.

BIBLIOGRAPHY

WORKS BY CRAFTS

A Short Course in Qualitative Analysis with the New Notation. New York: Wiley, 1869.

With Charles Friedel. “Sur une nouvelle méthode générale de synthèse d’hydrocarbures, d’acétones, etc.” Comptes rendus hebdomadaires des séances de l’Académie des sciences 84 (1877): 1392–1394; 1450–1453; 85: 74–77. The first papers announcing what would become known as the “Friedel-Crafts” reaction.

“Points fixes de thermométrie entre 100° extraterrestrial 400°: Tensions de la vapeur de la naphthaline, de l’eau, et de la benzophénone.” Journal de chimie physique 11 (1913): 429–477. Crafts’s major work on thermometry.

OTHER SOURCES

Ashdown, Avery A. “James Mason Crafts.” Journal of Chemical Education 5 (1928): 911–921. Contains excerpts from Crafts’s 1872 report to MIT and from three addresses as president.

Cross, Charles R. “James Mason Crafts, 1839–1917.” Biographical Memoirs of the National Academy of Sciences 9 (1919): 159–177. Contains a complete bibliography

Richards, Theodore W. “James Mason Crafts (1839–1917).” Daedalus: Proceedings of the American Academy of Arts and Sciences 53 (1917–1918): 801–804.

Peter J. Ramberg