More on the discovery of phosphorus

In his History of the match industry m tire Journal of Chemical Education, M. F. Crass, Jr., quoted Paracelsus s recipe for the separation of the elements from watery substances (28, 29). Paracelsus s icicles which are the element of fire, which he apparently obtained by distillation of urine, may possibly have been elemental phosphorus. If that be the case, it is difficult to understand why they aroused so little interest 

Most authorities agree that the original discoverer of elemental phosphorus was tire seventeenth-century alchemist and physician Hennig (or Henning) Brand of Hamburg. Gottfried Wilhelm Leibniz (1646- 

EditOH s noxe- Readers who prefer a shorter, yet connected, account of the discovery ot the elements may find it convenient to omit the supplementary information provided in chapters 2, 4, 6, 8, 10,12, 14, 15, 17, and 19. 

Gottfried Wilhelm Leibniz, 1646-1716 German mathematician, philosopher, historian, and scientist. Independent discoverer of the differential calculus He was personally acquainted widi Brand and Krafft, and wrote a detailed account of the discovery of phosphorus, including biographical sketches of Brand, Krafft, Kunckel, and Becher. 

On December 24, 1678, Dr. Krafft sent diis letter to Leibniz, saying, Since you mention having received an angry letter from him [Brand], I am sending you mine herewidi. You may compare them and see which is die prettier (1). Nevertheless, Leibniz advised the Duke to deal more liberally witii Dr. Brand, pardy out of sympadiy, and pardy to prevent him from selling his secrets to others. 

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It is important to know that the inhibition of acetylcholinesterase by OPs is through an attack on the relatively positive phosphorus atom by the hydroxyl group of a serine residue at the enzyme s site of action. Electron withdrawing substitutions within the OP tend to make the phosphorus more positive and, therefore, more reactive. Unfortunately, this type of substitution also makes the compound less stable hydrolytically. The discovery and development of OP insecticides has always been a balance between activity against the enzyme of the insect, selectivity in comparison with mammalian systems and stability within the insect. The binding of OPs to acetylcholinesterase is often irreversible. Typical OP insecticides are shown in Figure 3.3. 

A review entitled thiophenes from Viktor Meyer to Poly (thiophene) some reactions and synthesis was published in a special issue of Phosphorus, Sulfur and the related elements (13PS287). Over 80 reaction schemes are presented outlining important discoveries in the chemistry of thiophenes. Another review generalized published data on the reactions of 4-(2-R-aryl)-1,2,3-thia- and selenadiazoles (13RJOC479). Special emphasis on the use of these selenadiazole for the synthesis of 1-benzothiophenes, 1-benzosele-ophenes, and their more complex derivatives was presented. A recent review on recent advances in the use of the Wfllgerodt-Kindler reaction in thiophene syntheses appeared this year (13CSV7870). Extensive reviews on selenium and tellurium chemistry from small molecules to biomolecules and materials (B-13M001) as well as data on the synthesis, reactions, crystal structures, and spectral characteristics of benzo[b]tellurophene, dibenzo[b,d]... 

The discovery that the keto chelates (especially the p ones) are the species controlling the strict alternation of the monomers and the intrinsic copolymerisation rate in ethene/CO propagation has stimulated much research aimed at designing catalytic systems where the keto chelates can be readily opened by CO. These studies have allowed the development of a new generation of more efficient Pd" copolymerisation catalysts based on diphosphines with o-methoxyphenyl groups on the phosphorus atoms [13b, 31-34]. 

Since the red modification can be handled much more safely than white phosphorus this discovery has been extremely beneficent to workers in the match industry. As early as 1851 von Schrotter prepared matches with it, but they were not easily ignited. H. Hochstatter of Langen, near Frankfort-on-the Main, exhibited successful red phosphorus matches at the London Exhibition of 1872 ( 54). The Hochstatter matches, according to von Schrotter, can be struck even upon cloth, they burn quietly,. . . almost without smoke and smell.. . . What is still more important, the workmen during their production are not... 

Recently some bicyclo and cage structures based on P—P bonds have been obtained by reacting a mixture of RPCl and PCI3 with magnesium. Only the phosphorus skeletons are shown (Fig. 4.12). These discoveries show that the chemistry of catenated phosphorus derivatives, like that of catenated silicon compounds, is much more diverse than was imagined even ten years ago. 

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