Friedrich Konrad Beilstein’s Contributions to Organic Chemistry

Who was Friedrich Konrad Beilstein? We immediately think of the famous Beilstein Handbook, but what else? The chemist behind it was, as he himself called it, a “semi-mythological figure”.

Friedrich Konrad Beilstein was born in 1838 in St. Petersburg, Russia, to German parents. He was an elegant bachelor, fond of travel, full of life, sharp-witted, and an excellent pianist, reportedly owning the largest private music library in Russia. He was very organized, accurate, and incredibly hard-working. He spoke fluent German, Russian, French, and English.

A Journey From St. Petersburg to the Giants of Chemistry

At the age of 15, he left school and went to Germany to study chemistry under Robert Bunsen (1811–1899) and August Kekulé in Heidelberg and Justus Liebig in Munich, who was his relative. He earned his Ph.D. in 1858 at the age of 20 at Göttingen University, Germany, under Friedrich Wöhler (1800–1882), focusing on murexid.

Following studies at the Sorbonne in Paris, France, with Charles Friedel (1832–1899) and Charles Adolphe Wurtz (1817–1884), and in Breslau, today Poland, with Carl Löwig (1803–1890), Beilstein became a lecturer in 1860 and an assistant to Friedrich Wöhler, eventually assuming an extraordinary professorship in Göttingen in 1865.

In 1866 he succeeded Dmitri Ivanovich Mendeleev (1834–1907) at the Technological Institute in St. Petersburg, where he served until his retirement in 1896. The Technological Institute was a kind of technical college with a military-organized course system.

In addition, he taught at the Nicolai Military Academy and headed the chemical section of the Imperial Russian Technical Society. Beilstein also was regularly appointed by the Imperial government as Russia’s official representative at World Expositions, and he held many other positions and titles, including the right to be addressed as Privy Councillor and Excellency.

Beilstein passed away in October 1906 in St. Petersburg, Russia.

Aromatic Compound Research

Beilstein’s research primarily centered on aromatic compounds. In 1866, during the chlorination of toluene, he observed that halogenation of alkylbenzenes occurs at the side chain yielding benzyl chloride when subjected to heat and sunlight, while at the benzene core producing chlorotoluene under cold conditions or with a catalyst, such as iodine. This concept is summarized as follows: Heat and sunlight lead to side-chain chlorination, whereas cold and catalysts favor core chlorination.

However, in general he preferred the experimental result over the theory and did not contribute to the theory of the benzene ring. His publications are notable for using few formulas and expressing results mostly in words.

The Beilstein test is named after him. It is a nonspecific detection method for halogens in organic compounds. The halogen combines with copper to form a volatile copper halide that colors a flame green to green-blue.

Beilstein – The Handbook of Organic Chemistry

From 1865 to 1871 Beilstein published the “Zeitschrift für Chemie” together with Rudolph Fittig (1835–1910), the discoverer of the pinacol coupling reaction, mesitylene, diacetyl and biphenyl.

Beilstein was the founder and first editor of the “Handbuch der Organischen Chemie” (Handbook of Organic Chemistry, first edition 1881). The Handbook, a systematic catalog of organic compounds, was a milestone in the history of chemistry and is still considered a standard work today.

It was his life’s work, on which he worked for decades and whose first three editions he alone supervised and wrote. The first edition was immediately sold out; the second edition followed in 1885, the third in 1892. In 1896, due to the enormous growth of organic chemistry and related literature, the German Chemical Society (GDCh) under the leadership of its Vice-President Emil Fischer, took over the publication. Under its direction, the supplement volumes of the 3rd edition were published until 1906. From 1918 the so-called “main work” (the 4th edition) was published.

Since 1951 the handbook has been continued by the Beilstein-Institut für Literatur der organischen Chemie in Frankfurt a.M., Germany. The Beilstein-Institut was established in 1951 as a foundation by the Max Planck Society in honor of Friedrich Beilstein. “The purpose of the foundation is the exclusive and direct promotion of the chemical sciences, in particular by continuing the publication of the Beilstein-Handbuch der organischen Chemie and the scientific publications connected with it.”, it reads in the original statutes of 1951.

To update and modernize the Handbook, a database was developed and first published in 1988 as Beilstein-Online by STN International Systems. In 1999, the Beilstein-Institut foundation’s constitution was revised, and it was renamed to “Beilstein-Institut zur Förderung der Chemischen Wissenschaften.” The institute’s purpose is the advancement of chemical sciences, particularly by supporting information and communication. Since 2000, the Beilstein-Institut has continued to support chemistry and related fields through the publication of diamond open access journals, the development of data standards, hosting scientific events, and funding other community projects. In 2007, the database rights were sold to Elsevier, where it was combined with other data sources to become an integral part of Reaxys. The rights to the Handbook remain with the Beilstein-Institut to this day.

Beilstein’s Motivation

What made Beilstein so enthusiastic about his collection of all existing literature on organic chemistry?

Beilstein believed that summarizing all chemical facts could simplify and limit the field. In an 1865 letter to Alexander Butlerov (1828–1886), a Russian chemist who was one of the principal creators of the theory of chemical structure, he noted that structural formulas had vastly increased the range of possible compounds, making existing knowledge seem minimal. He questioned whether these countless compounds really existed and reflected on how this complexity made life difficult for chemists. This view was supported by the fact that at the time the physical properties of newly discovered compounds were often incorrectly observed due to impurities, leading to double descriptions of substances whose identities only became clear after several years.

Notably, the release of Beilstein’s Handbook in 1880 symbolized the final victory of Kekulé’s and Butlerov’s structural theory, as it became clear that chemical compounds could only be logically organized according to structural chemistry principles. Additionally, the vast number of described compounds, 15,000, highlighted the unprecedented growth of chemistry in the previous 20 years. On the other hand, this high number symbolizes Beilstein’s immense diligence and remarkable productivity.

“His contemporaries reported that he secretly carried proof sheets of his handbook hidden in a hymn book to church on Sundays. During his annual travels across half of Europe, he tirelessly worked on his handbook, using libraries along his route, whether in Moscow or Kiev in the east, Helsinki in the north, Paris in the west, or Naples in the south.”, Otto Krätz wrote [1].

Beilstein’s relentless pursuit of accuracy and correctness in his work is particularly noteworthy. He soon realized that his own efforts overshadowed all contemporary literature. In a letter to Emil Erlenmeyer (1825–1909), he humorously and vividly expressed his goals and the merits of his handbook, revealing his personality, his love for collecting precise facts, his pleasure in formulating, his passion for travel, but also a touch of vanity. He liked to compare his meticulous work to that of others and found great satisfaction in the frequent errors in newly published chemistry books, humorously comparing the abundance of mistakes to lice on a Russian’s head or fleas in Rome and Naples.