Medicines and Poisons
In the delicate balance of these processes, disturbances may occur which can be remedied by specific phosphate-containing medicines. Thus, adenosine phosphate has been recommended in cases of angina pectoris and marketed under trade names like sarkolyt, or in compounds named angiolysine. A considerable number of physiologically active organic phosphates can be found in the patent literature.39 Yeast itself is considered to be a valuable food additive.
On the other hand, there are phosphate compounds that act as poisons. One group of such compounds was discovered in 1929 by W. Lange, who wrote: “Of interest is the strong action of mono-fluorophosphate esters on the human body—the effect is produced by very small quantities.”40 Diisopropyl fluorophosphate has since become a potential agent for chemical warfare. It inactivates an enzyme which controls the transmission of nerve impulses to muscle, acetylcholine esterase.
Organic esters of phosphoric acids are used as insecticides. The hexa-ethylester of tetraphosphoric acid, prepared by Gerhard Schrader by heating triethylphosphate with phosphorus oxychloride,41 actually contains tetraethylpyrophosphate (TEPP) among others. Bayer’s Dipterex, the dimethyl ester of 2,2,2-trichloro-1-hydroxyethyl-phosphonate, has been modified to dimethyl-2,2-dichlorovinyl-phosphate and is especially active against the oriental fruit fly.42
Bayer’s L 13/59
(Dipterex)
Schradan
Octamethylpyrophosphoramide
The story of phosphorus, which began 300 years ago, has acquired new importance in this century. Many scientists have contributed to it: 13 of them have received Nobel Prizes for work directly bearing on the chemical and biological importance of phosphorus compounds. In chronological order, they are: Eduard Buchner, Albrecht Kossel, Otto Meyerhof, Arthur Harden, Hans von Euler-Chelpin, George de Hevesy, Carl F. Cori, Gerty T. Cori, Fritz Lipmann, Lord Alexander Todd, Arthur Kornberg, Severo Ochoa, and Melvin Calvin. The developers of industrial production and commercial utilization of phosphate compounds have had other rewards.
Some impression of the continuing growth in this field43 can be gained from the following data.
Phosphate Rock
annually “sold or used by producer” in the United States in million long tons (2,240 lbs.)
| 1880 | 0.2 |
| 1890 | 0.5 |
| 1900 | 1.5 |
| 1910 | 2.655 |
| 1920 | 4.104 |
| 1930 | 3.926 |
| 1940 | 4.003 |
| 1945 | 5.807 |
| 1950 | 11.114 |
| 1955 | 12.265 |
| 1955 | (world: about 56) |
| 1960 | 17.202 |
| 1962 | 19.060 |
Sources: U.S. Bureau of the Census. Historical Statistics of the United States 1789-1945 (1949); Statistical Abstract of the United States.
Elemental Phosphorus
annually produced in the United States in short tons (2,000 lbs.)
| 1939 | 43,000 |
| 1944 | 85,679 |
| 1950 | 153,233 |
| 1956 | 312,200 |
| 1958 | 335,750 |
| 1959 | 366,350 |
| 1960 | 409,096 |
| 1961 | 430,617 |
| 1962 | 451,970 |
Source: U.S. Department of Commerce.
Footnotes
1 Wilhelm Homberg, Mémoires Académie, 1666-1699 (Paris, 1730), vol. 10, under date of April 30, 1692, pp. 57-61.
2 Fortunio Licetus, Lithiophosphorus sive de lapide Bononiensi (Venice, 1640).
3 Cited in Peter Joseph Macquer Chymisches Wörterbuch, 2nd ed. (Leipzig: Weidmann, 1789), vol. 4, p. 508, footnote “c” as “Kletwich (de phosph. liqu. et solid. 1689, Thes. II).”
4 Ferdinand Hoefer, Histoire de la Chimie (Paris, 1843), vol. 1, p. 339.
5 G. W. von Leibniz, Mémoires Académie (Paris, 1682); Akademie der Wissenschaften, Miscellanea Berolinensia (Berlin, 1710), vol. 1, p. 91.
6 Jean Hellot, Mémoires Académie 1737 (Paris, 1766), under date of November 13, 1737, pp. 342-378.
7 Macquer, op. cit. (footnote 3), p. 551.
8 A. S. Marggraf, Akademie der Wissenschaften, Miscellanea Berolinensia (Berlin, 1743), vol. 7, 342 ff.; see also Wilhelm Ostwald Klassiker der Exakten Naturwissenschaften (Leipzig: Engelmann, 1913), no. 187.
9 G. Hanckewitz, [Hankwitz], Philosophical Transactions of the Royal Society of London, 1724-1734, abridged (London, 1809), vol. 7, pp. 596-602.
10 Antoine Laurent Lavoisier, “Sur la Combustion du Phosphore de Kunckel, Et sur la nature de l’acide qui resulte de cette Combustion,” Mémoires Académie 1777, (Paris, 1780), pp. 65-78.
11 Guyton de Morveau and others, Méthode de Nomenclature Chimique, Proposée par MM. de Morveau, Lavoisier, Bertholet, & de Fourcroy (Paris, 1787), plate 9.
12 Macquer, op. cit. (footnote 3), p. 513.
13 Marie Boas, Robert Boyle and Seventeenth Century Chemistry (New York: Cambridge University Press, 1958), p. 226; see also Wyndham Miles, “The History of Dr. Brand’s Phosphorus Elementarus,” Armed Forces Chemical Journal (November-December 1958), p. 25.
14 Archibald Clow and Nan L. Clow, The Chemical Revolution (London: Batchworth Press, 1952), p. 451.
15 Émile Kopp, Comptes-rendus hebdomadaires des Séances de l’Académie des Sciences, Paris (1844), vol. 18, p. 871; Wilhelm Hittorf, Annalen der Chemie und Pharmazie, suppl. to vol. 4, p. 37; Anton Schrötter, Annales de Chimie et de Physique, series 3, vol. 24 (1848), p. 406; see also Schrötter’s report on “Phosphor und Zündwaaren” in A. W. von Hofmann, Bericht über die Entwicklung der Chemischen Industrie (Braunschweig: Vieweg, 1875), pp. 219-246.
16 R. Glauber, Furni Novi Philosphici (Amsterdam, 1649), vol. 2, pp. 12 ff.
17 Hermann Schelenz, Geschichte der Pharmazie (Berlin: Springer, 1904), p. 598.
18 J. Personne, Comptes-rendus..., Paris (1869), vol. 68, pp. 543-546.
19 A. Wurtz, Dictionnaire de Chimie (Paris, 1876), vol. 2, part 2, p. 951.
20 Karl W. Scheele, Nachgelassene Briefe und Aufzeichnungen, edit. A. E. Nordenskiöld (Stockholm: Norstedt, 1892), pp. 38, 144.
21 J. J. Berzelius, Lehrbuch, transl. F. Wöhler (Dresden, 1827), vol. 3, part 1, p. 96.
22 Thomas Graham, Philosophical Transactions of the Royal Society of London (1833), pp. 253-284.
23 Justus Liebig’s Annalen der Pharmacie (1838), vol. 26, p. 113 ff.
24 A. Wurtz, Annales de Chimie et de Physique, series 3, vol. 16 (1846), p. 190.
25 Carroll D. Wright, The Phosphate Industry in the United States, sixth special report of the Commissioner of Labor (Washington, 1893).
26 J. Stoklasa, Biochemischer Kreislauf des Phosphat-Ions im Boden, Centralblatt für Bakteriologie... (Jena: Fischer, March 22, 1911), vol. 29, nos. 15-19.
27 N. T. Gobley, Comptes-rendus..., Paris (1845), vol. 21, p. 718.
28 A. Wurtz, Comptes-rendus..., Paris (1868), vol. 66, p. 772.
29 L. Thudichum, Die chemische Constitution des Gehirns des Menschen und der Tiere (1901); see also H. Wittcoff, The Phosphatides (New York: Reinhold, 1951).
30 William Crookes, British Association for the Advancement of Science, Reports (1887), sec. B, p. 573.
31 J. E. Courtois and A. Lino, Progress in the Chemistry of Organic Natural Products, edit. L. Zechmeister (Vienna: Springer Verlag, 1961), vol. 19, p. 316-373.
32 A. Wurt, Dictionnaire de Chimie, supp. part 2, [n.d.] p. 1087; A. Kossel, Zeitschrift für physiologische Chemie, series 3 (1879), p. 284.
33 Alexander Todd, Les Prix Nobel en 1957 (Stockholm).
34 Hans von Euler-Chelpin, Les Prix Nobel en 1929 (Stockholm).
35 O. Meyerhof and E. Lundsgaard, Naturwissenschaften (Berlin, 1930), vol. 18, pp. 330, 787.
36 K. Lohmann, Naturwissenschaften (Berlin, 1929), vol. 17, p. 624; C. H. Fiske and Y. Subbarow, Science (Washington, 1929), vol. 70, p. 381 f.
37 J. Brachet, Scientia, Revista di Scienza (1960), vol. 95, p. 119.
38 George de Hevesy, Les Prix Nobel en 1940 (Stockholm). See also Eduard Farber, Nobel Prize Winners in Chemistry, 2nd ed. (New York: Schuman, 1963), p. 179.
39 See, e.g., Chemical Week, vol. 77 (September 3, 1955), p. 79 f.; J. Bolle, Chimie et Industrie (1960), vol. 83, p. 252.
40 W. Lange, Berichte der Deutschen Chemischen Gesellschaft (Berlin, 1929), vol. 62, p. 793; vol. 65 (1932), p. 1598.
41 Gerhard Schrader, U.S. patent 2,336,302 of 1943 (priority in Germany, 1938); S. A. Hall and M. Jacobson, Industrial and Engineering Chemistry (1943), vol. 40, p. 694.
42 A. M. Mattsen and others, Journal of Agriculture and Food Chemistry (1955), vol. 3, p. 319.
43 John B. Van Wazer, Phosphorus and its Compounds, 2 vols. (vol. 1, Chemistry; vol. 2 Technology, Biological Functions and Applications), New York: Interscience, 1958, 1961.
U.S. GOVERNMENT PRINTING OFFICE: 1965
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