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With the successful synthesis and industrial production of vanillin, the chemist Dr. Wilhelm Haarmann founded the global fragrance and flavor industry. April 10, 2024, marks the 150th anniversary of filing the patent for synthetic vanillin, and the authorization to sell this soon-to-be-blockbuster exclusively.

Old image of Haarmann's house

Gustav Ludwig Friedrich Wilhelm Haarmann was born on May 24, 1847. His groundbreaking synthesis of vanillin wasn’t only the starting point for the company that would eventually become Symrise but also for an industry that has become an important part of the chemical industry over the last 150 years. Only 26 years old, he filed the patent for synthetic vanillin on April 10, 1874. Today, the F&F industry generates over €40 billion in revenue worldwide and has produced several Nobel laureates. It all began in a small shed in Altendorf am Holzmindebach, in what is now Lower Saxony.

After graduating from high school, Haarmann began his studies in Chemistry at the Clausthal University of Technology in 1866. In 1867, he decided to move to Göttingen to pursue his chemistry studies. Two years later, he moved to Berlin to join the most prominent chemist of his time, Professor August Wilhelm Hofmann (1818 – 1892), who had returned from England and established a new institute that was one of the most advanced chemical educational institutions.

In autumn 1871, Haarmann was searching for a topic for his dissertation. He received support from his friend and colleague Ferdinand Tiemann, who was heading a subgroup in the Hofmann provided him with a substance that his former classmate Wilhelm Kubel had noticed had a vanilla scent during its investigation. The idea of synthesizing a natural product intrigued Haarman. However, to do so, he first needed to isolate and characterize the active ingredient.

The patenting of vanillin synthesis on 10 April 1874 marks the birth of the global fragrance and flavor industry.Dr. Jean-Yves Parisot, CEO Symrise

Kubel had obtained the product from Theodor Hartig, a professor of forestry at Collegium Carolinum, who had discovered a crystallizing substance in the cambial sap of larch trees in 1861, later named coniferin. The cambial sap is “the fluid obtained when trees are felled and debarked during the time of wood formation, and the remaining cambium on the surface of the wood is scraped off using glass shards and the scraped mass is squeezed off.”

In 1866, Kubel had examined the substance and found that coniferin is a glucoside with a melting point of 185°C, which turned brownish and emitted a peculiar caramel odor at higher temperatures, eventually charring. He used dilute sulfuric acid to hydrolyze it and obtained a resinous substance that he couldn’t identify but noticed the vanilla scent during this reaction. He analyzed coniferin and determined its composition.

For his doctoral thesis, Haarmann obtained cambial sap from tree trunks of coniferous trees that had been felled during wood formation from May to July, resulting in 20 grams of coniferin. He repeated Kubel’s experiments. Due to the limited amount, he could only conduct a few experiments. Haarmann burned the substance and obtained the same result as Kubel. He then hydrolyzed the coniferin by heating with dilute sulfuric acid and obtained, in addition to glucose, a substance that Kubel had already named coniferetin, now referred to as coniferyl alcohol.

molecular formulas

In the next step, he oxidized coniferin with potassium dichromate in dilute sulfuric acid, triggering a vigorous reaction. After several weeks, colorless needles with an aromatic odor crystallized. He treated the crystals with a silver salt solution, resulting in the formation of elemental silver at the test tube. Reacting it with sodium bisulfite yielded a solid substance. Based on the results of these two reactions, he concluded that the resulting compound must be an aldehyde. The removal of the sugar with emulsin was simpler. After twelve hours, he obtained a white crystalline mass. He separated the sugar, and aromatic white crystals formed, which he named coniferogenin.

The small amount of coniferogenin obtained by Haarmann did not allow him to determine the structure of this new compound. Likewise, he did not know how to produce larger quantities of the aromatic substance. Haarmann and Tiemann joined forces. The results they had so far gave them hope that they could isolate the aromatic principle of vanilla and exploit it commercially. It took them another two years and countless experiments before they managed.

First, they painstakingly collected cambial sap during the spring and summer of 1873, and were able to obtain approximately 2.5 kilograms of coniferin from it. With this material, they could continue the previous work. They repeated the experiment of oxidizing coniferin for cleaving off coniferyl alcohol, and obtained after 6 to 8 days, a white, fluffy crystalline mass. They identified glucose and a compound whose composition, based on elemental analysis, would give the molecular formula C8H8Ow.

Bottle of Jicky perfume

They were convinced that the pleasant-smelling substance obtained from coniferin was a known compound, previously only produced by nature, which had been described by the French chemist Pierre-Paulin Carles in 1872 and referred to by him as “vanilline”. They believed that they had synthesized the principal odor- and flavor-imparting component of vanilla pods and claimed that only this compound was responsible for the pleasant aroma of vanilla. Today, we know that vanillin is the dominant flavor component in vanilla beans, but its complex aroma comes from several hundred components, of which approximately 35 contribute significantly to the typical aroma, even in small quantities.

Haarmann had no intention of pursuing an academic career. He wanted to commercially exploit the results of his dissertation and follow in his father’s footsteps. It was a bold idea that Haarmann pursued, as who needed a synthetic replica of a luxury spice that only the wealthy used at the time.

Some investors, including his father, provided him with the necessary starting capital, and in 1874, he founded a start-up company in his hometown. The factory was intended for the production of vanillin from the wood of coniferous trees. Haarmann’s Vanillin Factory in Holzminden was the first factory worldwide to produce a synthetic fragrance or flavor substance on an industrial scale. Haarmann’s business acumen was evident early on, as he applied for a patent for his invention, which was granted on April 10, 1874, for a period of five years from the ducal Brunswick-Lüneburg district directorate.

Haarmann’s idea was to sell the product to large-scale entrepreneurs, such as chocolate industry, as well as other sectors of the food industry, bakeries, ice cream manufacturers, and housewives. However, the acceptance of vanillin was low. To gain acceptancefor his synthetic product, Haarmann had to demonstrate that his vanillin was identical to natural vanillin and, furthermore, cheaper. Therefore, they had to develop a method to determine the vanillin content in the vanilla pods, as it was assumed to vary greatly among different varieties. In 1875 they successfully developed a method to determine the vanillin content, depending on the harvest year and quality. It was now possible to calculate the price of natural vanillin. The resulting values ranged from 6.60 to 25.60 Reichsmark (ca. 33 to 128 Euro) per gram. Thus, the “outrageous” price of 7 to 9 Reichsmark per gram for vanillin were justified.

Haarmann & Reimer particularly targeted chocolate manufacturers. According to their calculations, in 1879, these manufacturers consumed approximately 3,000 to 4,000 kg of vanilla in Germany, which cost them between 180,000 and 240,000 Reichsmark. In contrast, the substitute, synthetic vanillin, would only cost 84,000 to 112, 000 Reichsmark. This meant potential savings of roughly 100,000 Marks in Germany alone. Globally, the entrepreneurs estimated a consumption of 50,000 kg of vanilla, equivalent to 1,000 kg of vanillin, and saving of 1,400,000 Reichsmark. After successfully synthesizing vanillin in 1874, Haarmann founded Haarmann’s Vanillin Factory in Holzminden. It is considered the first factory worldwide to produce a synthetic fragrance or flavor substance on an industrial scale. In collaboration with Ferdinand Tiemann and Karl Reimer, both of whom, like Haarmann, were trained in the laboratory of August Wilhelm Hofmann, the company, renamed Haarmann & Reimer, became one of the largest and leading manufacturers of flavors and fragrances. An industry emerged that systematically searched for aroma compounds that could be produced by chemical means. The aromatic principle of the corresponding plant had to be identified in order to synthetically reproduce it. Haarmann demonstrated a willingness to take risks, as he expanded his activities to France early on, a country with which relations were strained due to the political context of the time. The company constantly sought new inventions and successfully brought them to the market. Together with his friend and academic supervisor Ferdinand Tiemann, Haarmann also disovered the ionones and methyl ionones, and improved the access to coumarin which previously had been synthesized by William Henry Perkin. Haarmann proved to be an influential and visionary entrepreneur.