M Y LIFE AND WORK* HEINRICH KILIANI,FREIRURG I. B.. GERMANY I, the son of Joseph Kiliani and his wife, Marie, nee Dietz, was born on October 30, 1855, a t Wiirzburg, Bavaria. After finishing the elementary school, I entered the humanistic gymnasium, and graduated in July, 1873. My father's modest income as police commissioner made i t necessary for me, even while in the gymnasium, t o earn money so I tutored other students. Part of this money enabled me to make an extensive trip on foot, August, 1S7:i, through and over the mountains of southern Bavaria and the Tyrol, as far as Mrran and Bozen. This trip definitely strengthened my purpose t o s t u d y s c i e n c e , and I chose chemistry because i t seemed to promise early self-support. Consequently, in October, 1873, I entered the Technische Hochschule in Munich. Professor E. Erlenmeyer. Sr., taught c h e m i s t r y there. He was an excellent teacher, but was prone to use rather drastic educational methods as I soon learned from personal experience. At the end of my first semester in the laboratory, I was standing a t the sink, , washing my apparatus, when I heard a v i s e behind me a t my desk. Turning I saw Professor Erlenmeyer pulling out one drawer after another, registering more and more diswst. I went to him and asked, rather nai'vely, as I know now, "Professor, what are you hunting? May I help you?" He glared a t me and roared, "I am looking for a mess," turned, and left the room. A t first I was so nonplussed that I could not comprehend what i t was all about. But when I opened the drawers, I was enlightened: blow-pipe charcoal, wire gauze, triangles, filter paper, all in hopeless confusion, half-dirty glassware covered with a filthy towel stained every color, etc. This incident converted me into a clean and orderly worker, and Erlenmeyer evidently was pleased with me, for within three years, January, 1877, he made me his assistant. When I conferred with him as to a research topic, he said, "I wish you would compete for the prize which is being offered for the best work on inulin." At
* This autobiographical sketch was written at the request of the translator, Ralph l?. Oesper, University of Cincinnati, Cincinnati, Ohio. 1908
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that time pure inulin could not be bought in the market, but had to be prepared from plants (dahlia or inula) or made from the commercial material. Experiments on a small scale soon showed me that the simplest method of separating and purifyinp. this compound was to prepare hot aqueous solutions from which the inulin could subsequently be frozen out. But the preparation of large quantities by this method led to a serious inconvenience. At that time there were no ice factories in Munich, and consequently ice was not available in the laboratory. Even the famous breweries of Munich had to secure their ice by cutting it in the winter and storing it. Fortunately there was a EMILERLENMEYER, SR. 182%1900 great deal of snow that winter and so, Professor, Trchnische Hochschule, armed with a large pan, I often took Munich. 1868-1883 the shortest route through a narrow A biography of him by Kiliani may be found in the Z. angnu. Chem.. 22, cellar window, into the courtyard of 48P (1909). the laboratory . to -gather the necessary cooling agent. A serious illness interrupted thilwork for several months so that i t was not completed until the summer of 1879. My essay was then awarded the prize, and in February, 1880, the University of Munich granted me the Ph.D. degree for this same work. The examining committee consisted of Baeyer (Chemistry), Jolly (Physics), and Kobell (Mineralogy). The latter had a reputation for his catch questions. His opening question was, "Mr. Candidate, how does water crystallize?" Although I had conscientiously prepared myself, I could not remember ever having heard or read anything about this, but fortunately I suddenly recollected the six-sided snow crystals and my answer, "hexagonal," was correct. At that time it was also obligatoty for the doctorate candidate to set up a number of theses and defend them in the public examination. When I went t o Baeyer for his approval of my proposed theses he said, ,,These are all well and good, but if we have to dispute with you on these for half an hour, it will be terribly boresome. Why don't you choose some controversial topics such as the constitutional formulas of complex minerals; that will imtate Kobell and we shall then have some entertainment." I therefore selected the formulas of dolomite and phosphorite for discussion and the results were all that Baeyer could desire. After a few minutes,
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Kobe11 stood up, and said, "It is quite evident that you can defend even the most hopeless case," took his hat and departed. Meanwhile I had also passed an examination qualifying me to teach science in the Bavarian secondary schools. In October, 1879, I left the Technische Hochschule and went to the Industrieschule (Munich) with the same rank of assistant but a t an advanced salary because I also had to teach chemistty and physics in the Baugewerkschule. The laboratory a t this school was well equipped so that it was possible for me to continue my scientific investigations (on saccharins, etc.). Most of this work had to he done in the evening, hut its continuance was suddenly threatened by an edict of the Rector. "It is very strange that now, in summer, my residence uses more gas than the chemical laboratory, and so from now on, the gas will he turned off every day a t 6 o'clock." I a t once.inspected the arrangement of the gas pipes in the basement, and I found that the gas first went through a meter, part of it was then diverted to the house and the rest passed through a second meter, and thence to the chemical laboratory. I immediately suspected where the trouble lay, and called in the gas man and asked him to show me how he read and recorded the amount of gas used each month. At first he looked a t me as though I were committing an offenseagainst the sovereign, but eventually he told me what I wished to know. As I had suspected, he read the first meter only, and consequently the house was charged for all the gas, whereas the gas passing through the second meter should have been charged to the laboratory separately. Since this had been going on for so'me months the school had to pay the Rector a considerable refund. As a reward for my discovery, I asked that the two gas supplies be separated. This was done and I was then a t liberty to continue my researches. At this school I learned from the "Diener" who was an excellent fellow, though somewhat peculiar, that there can be two points of view concerning scientific work. On one occasion I gave him a large manuscript addressed to the "Berichte" and asked him to put it in the mail. When he learned that the postal charges were quite high, he said ingenuously, "Doctor, I certainly cannot understand you. You spend all of your time on this work and now you spend money on it besides." However, this work brought me the desired reward. In the spring of 1883 I became privatdozent a t the Technische Hochschule (Munich) and was advanced to extraordinary professor in 1884 and to professor in 1892. This is a fitting place to review my scientific work up to 1890. From my doctor's dissertation (1) the following results proved of permanent value: (1) the preparation and purification of inulin by the freezing-out process; (2) the proof that dextrose, CsHa06, is easily attacked in aqueous solution and a t room temperature by bromine, forming glumnic acid, CsHaOi, while levulose is broken down by this halogen very gradually and only
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after weeks of reaction, forming glycollic acid, CzH103, from which facts i t could be concluded that dextrose is an aldehyde and lewlose a ketone (this bromine oxidation later became of general significance in studying all the aldehyde sugars); (3) the knowledge that the oxidation of sugars and their derivatives by nitric acid is best carried out by warming the mixture in flasks in the water-bath a t a constant moderate temperature (60' a t most) instead of the usual procedure of heating in dishes on the waterbath. In contrast to these useful findings it is of historical interest to note that my first publication in the Berichte (2)contained a rather serious error; the fact that the various kinds of gum arabic have very diierent compositions and therefore yield different sugars in varying quantities when hydrolyzed was then only gradually beginning to be recognized. On the other hand, my studies of Peligot's saccharin, CoHmOs, isosaccharin, and the newly discovered metasaccharin proved of permanent value. Likewise, my investigations of the addition of hydrocyanic acid to the simple sugars lewlose, dextrose, and galactose, became of great importance to the whole chemistry of the sugars, and all the more so, because in the last experimentally tested case, arabinose (3),it was found that this compound has the composition CsHloOs,and not C6H120a,as had been believed formerly. By oxidation of arabinose carboxylic acid I obtained metasaccharic acid in the form of its beautifully 2H20, and this compound later acquired crystalline di-lactone, C6H606 special interest, first because it (together with arabinose carboxylic acid) was used by Emil Fischer as one of the key 'points in his fundamental work on the sugars ( 4 ) , and also because of its very reharkable solubility which is still being investigated by myself and others. The further study of this di-lactone showed me that i t could be reduced by sodium amalgam to mannite and I here allowed an important discovery to slip through my hands, because I did not immediately see that this reduction pointed to the formation of a sugar as an intermediate product, and that I was dealing with a general reaction common to the most varied lactones. Emil Fischer recognized these facts and used them experimentally, to great advantage (5). The trend of my scientific work changed in the summer of 1888. Dr. Engelhorn of the Fabrik E. F. Boehringer u. Siihne (Mannheim-Waldhof) came to my laboratory and said, "I have just had a conversation with von Baeyer, to whom I went in search of a pure scientist whom he could recommend as qualified to work on the digitalis problem. He told me that he thought that you could carry out this investigation. Our factory will furnish you the necessary raw materials in any desired quantity." This commission greatly surprised and perplexed me. At that time I was teaching analytical chemistry, fuels and heating devices, as well as technical gas analysis, including laboratory; that is, subjects entirely unrelated to
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medical chemistry. I had no idea of the great medicinal value of digitalis, and just as little comprehension of the standing of the Boehringer firm. Consequently I asked Dr. Engelhorn if I might be allowed time for consideration. I immediately went to Baeyer to get his reaction, and he urged me to accept the offer, both because of the importance of the topic and because there was a possibility of considerable financial return. My monetary reward was vanishingly small, but the scientific aspect of the problem soon fascinated me, and resulted, in the course of decades, in my long series of articles on digitalis. The especially important results of my studies are: the crystalkability of digitonin (from seeds) (6) ; the preparation of digitalinurn verum (7) on a factory scale; the inclusion of digitoxin (from leaves) among the glucosides (8). and the discovery of two specific digitalis sugars, digitalose, CsH140s,and digitoxose, GH1204. A number of derivatives of the accompanying "aglucones" (i. e., digitogenin, digitaligenin, and digitoxigenin) were prepared, but their preparation in the pure state was often extremely difficult, as was that of the original glucosides and so the later revisions of my original formulas for these compounds are not at all surprising. These corrections have been made in excellent fashion by my pupil, Professor A. Windaus, Gijttingen, and his co-workers. In 1895, at the suggestion of the pharmacologist, Professor Rudolf Boehm (Leipzig), I began to study the sap of Antiark toxicaria (upas tree). I found that antiarin has the formula GHa010 4Ha0 and may be split into antiarigenin, C21H3006, and antiarose, CBHIZO~, and that the sap contained antiarol which was found to be a p?eviously known benzene derivative, C9H12041, i. e., 1,2,3-trimethoxy-5-hydmxybenzene (9). Undoubtedly, it was these studies of digitalis and antiaris that were primarily responsible for my being called to the University of Freiburg i. B. in the spring of 1897, as successor to Professor Baumann and as director of the chemical laboratory of the Medical School. The reorganization of the management of the laboratory and the erection of a large new auditorium and additions to the laboratory made such demands on my time that I accomplished comparatively little research. When I was again a t liberty, I had a serious accident, resulting from the explosion of a fire extinguisher. A rather curious chain of circumstances was involved in this. A fire broke out in the Anatomical Institute in the room in which the alcohol was stored and the "Diener" who wished to save as much as possible, was so badly burned that he died a few days later. My colleague, the anatomist, then asked if I could recommend a fire extinguisher. Several years before I had bought for my laboratory an "Excelsior" after witnessing a practical test of this apparatus. When I now attempted to demonstrate the action of this device which had been kept charged for two years with sodium bicarbonate and hydrochloric acid, it exploded violently and I fell back on a
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cement pavement and sulked a fracture at the base of the skull. My subsequent study of this type of extinguisher disclosed several fundamental errors in its construction, as well as in the directions for charging it (10). I was bedfast for several months and suffered a permanent impairment of my hearing. As part of my duties I conducted a laboratory course for medical students, and this gave rise to a most amusing incident. My assistant noticed that one of the students was carefully noting the contents of each of the bottles in a large reagent rack. He repeated this at a second rack and was starting on a third when the assistant went to him and said, "Doctor, the text pre"What are you looking for? Can I help you!" scribes the addition of 'excess' hydrochloric acid, and I can't find it." My scientific work from 1903-20 was predominately on the further investigation of digitalis and antiaris. The details are of no consequence here.* In October, 1920, I reached the retiring age, 65, and because of my deafness I gave up my position. On this occasion the medical faculty honored me with the degree "Dr. Med. honoris causa." I was permitted to keep a laboratory in the Chemical Institute where I still work. In the last eleven years I have devoted myself chiefly to the study of sugars and of the results that I have obtained I believe the most important is the observation that most oxidations of sugars and their derivatives by nitric acid can be carried out at room temperature provided that, in the individual cases, the proper concentration of nitric acid is chosen and suitable cooling is provided for. The most important point, however, is to use that most vital reagent, c "patience" (11). "Gutta sae$e cadendo cauat lapidem" (constant dripping wears away a stone), I wrote as a motto a t the head of my prize essay on inulii and this precept I have found to be invaluable in many of my later investigations (especially on digitalis) and in these nitric acid oxidations, which in some cases require hours and hours before they seem to get under way. I expressed this as follows in a lecture before the Chemical Society of Freiburg. "Nitric acid apparently nuzzles around the organic molecules until it secures a response from several of them, gradually more of them take part in the dance, and finally the whole company dances to the melody piped by the nitric acid; but the result is not the wild orgy, which formerly ensued, but a very stately minuet which it is a real pleasure to witness." I am firmly convinced that this mode of oxidation will serve admirably in many other cases, and with compounds which do not belong to the sugar group, provided that it is properly applied.
* During this perid I published: "Kurzes Lehrbuch der analytischen Chemie." von Miller n. Kiliani. 6th edition. 1909. This was translated 1906 into Frenchby Defoin and Winniwarter, at the suggestion of de Koninc!-"Chemisches Practicum fur Mediziner9'-which has passed through three editions.
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As to my private life, little needs to be told. In 1883 I married Magdalena von Widmann: our only son died at the age of 26. My brother, Martin Kiliani (b. 1858), also studied chemistry and while in the employ of the General Electric Company of Berlin discovered a practical method of preparing aluminum and was therefore made technical director of the Aluminum Fabrik Neuhansen (am Rhein, Switzerland). He died in 1595. Long-continued and intensive working in a chemical laboratory damages one's health if occasional vacations are not taken. During my younger years I took these in the form of extended trips through the mountains of Bavaria, the Tyrol, and Switzerland,and later, up to 1914, I made numerous sea voyages: southward to Tripoli and Tunis, eastward to Smyrna and Constantinople, westward to Southampton and Gibraltar, northward to Spitzbergen. During a stay at Rapallo on the Italian Riviera, my deafness led to a comical situation. While walking with my wife, a man approached us, whom we had already recognized as English. I t is customary with the English when in foreign countries to immediately ask every one from whom they wish information, "Do you speak English?" Assuming that this was what he had said I replied, "A little." My wife then told him what he wished to know and when he had left us, said, "He asked you. 'Are yon an Englishman?' " Since the Great War, most Germans do not have the means for long trips. I seek my recreation now in the nearby mountains of the Schwarzwald, which, though they lack the splendor'of the Alps and the beauty of the sea, are nevertheless quite lovely and refresh the body and the spirit. Literature Cited Abstract in Liebig's Annahn. 205, 145 (1880). Bn., 13, 2304 (1880). The identity of arabinose and lactose (now galactose). Ibid.. 20, 339 (1887). Ibid., 23; 2116,2130,2131 (1890). IKd., 22,2204 (1889); 23,930 (1809). Ibid., 24,339 (1891). Arch. Pharm., 230,250 (1892); 233,299 (1895). Ibid.,233,311 (1895); 234, 481 (1896). Ibid., 234,439 (1896). C h m . Zeit.. 26, 421 (1902). Bn., 54, 456 (1921); 55, 75, 2817 (1922).
