Strange Salts

These apparent strange results are to be contrasted with the results at high salt concentrations (v 3/5),... 

Herman Boerhaave stated that the salt mines of Wieliczka, near Cracow, Poland, were discovered in the year 1251. He described them as a subterraneous republic, which has its polity, laws, families, and even high-ways and common carriers.. . . When a traveller is arrived at the bottom of this strange abyss,. . . he is surpriz d with a long series of lofty vaults. . . which. . . appear by the light of flambeaux. . . as so many crystals. . . casting a lustre which the eye can scarce bear (35). 

A seemingly minor technical problem, the ability of triphenylmethyl to pick up virtually any solvent as solvent of crystallization, occupied Gomberg for some time and led him into consideration of then fashionable structures involving tetravalent oxygen, which were later abandoned. Another sidetrack, more serious in view of the absence of a useful theory, was caused by experiments based on the known fact that triphenylchloromethane showed salt-like conductivity in solution in liquid SO2 It was thus definitively established that there are carbonium salts in the true sense of the definition applied to salts. When triphenylmethyl was dissolved in liquid SO2, it was found that it too conducted the electric current quite well. " How should one explain this strange phenomenon, a hydrocarbon behaving like an electrolyte ... 

Strange to say, but we could move almost as much natural gas with a dirty compressor rotor as we could with a clean compressor rotor. Of course, the amount of fuel we needed to run the turbine increased substantially as the rotor salted up. But our fuel in Laredo was self-produced, and therefore more or less free natural gas, so we did not care. 

For the preparation of MIPM, the above phenol, 2,5-dimethoxyphenol was isopropylated with isopropyl bromide in methanolic KOH giving 2,5-dimethoxy-l-(i)-propoxybenzene as an oil. This formed the benzaldehyde with the standard Vilsmeier conditions, which melted at 77-78 °C from hexane and which gave a yellow malononitrile derivative melting at 171.5-173 °C. The nitrostyrene, from nitroethane in acetic acid was orange colored and melted at 100-101 °C from either methanol or hexane. This was reduced with lithium aluminum hydride in ether to give 2,5-dimethoxy-4-(i)-propoxyamphetamine hydrochloride (MIPM). The properties of the isolated salt were strange (soluble in acetone but not in water) and the microanalysis was low in the carbon value. The molecular structure had a pleasant appeal to it, with a complete reflection symmetry shown by the atoms of the amphetamine side chain and the isopropoxy side chain. But the nature of the actual product in hand had no appeal at all, and no assay was ever started. 

At low salt concentrations, the share of the co-ions in the conductivity is negligible and thus equation (68) is obtained. As was said before, it was found by P. Meares and H. H. Ussing (95) that, strangely enough, this formula does not hold true. 

As far as we are aware, the number of luminescent extended systems with gold-platinum interactions is reduced to only one report. This is a puzzling situation since the situation of platinum in the periodic table suggests considerable relativistic effects for this atom and extended chains of squared-planar Pt(II) cation-anion complexes built by metal-metal interactions are not strange. In fact, salts such as [Pt(CNR)4][Pt(CN)4] ,67 which are luminescent and display vapochromic behavior, and the modified form of the Magnus salt [Pt(NH3)4][Pt(CN)4] ,68 which shows semiconducting properties, are examples of this type of supramolecular systems. Therefore, the stable combination of gold and platinum in cation/anion-acid/base systems should be anticipated. 

The ugly name of the Skraup reaction appropriately applies to the worst witch s brew of all the heterocyclic syntheses. Some workers have added strange oxidizing agents such as arsenic acid, iron (III) salts, tin (IV) salts, nitrobenzenes of various substitution patterns, or iodine to make it go better . 

Sulfides are nucleophiles even when not deprotonated—the sulfur atom will attack alkyl halides to form sulfonium salts. This may look strange in comparison with ethers, but it is, of course, a familiar pattern of reactivity for amines, and you have seen phosphonium salts formed in a similar way (Chapters 14 and 31). 

He transported his laboratory to the shores of the Baltic Sea where he joined forces with a magistrate of the city of Treves, who also belonged to that band of erring men impelled by an almost insane force to the strange search. I am convinced/ said this magistrate, that the secret of the philosopher s stone lies in the salt of the sea. Let us rectify it day and night until it is as clear as crystal. This is the dark secret of the stone. So for more than a year they labored, but the opus majus still remained concealed. 

Paracelsus abandoned all this witchcraft and superstition. He started the search for the potent drugs which the alchemist was to prepare or purify. Even the many herbs and extracts in common medical use were placed secondary to the value of these chemicals. There were many who gave ear to his instructions They went back to their laboratories, threw away the crucibles filled with the strange concoctions that would not change to gold, and sought medicines to relieve human suffering. Paracelsus himself showed the way. He experimented in his laboratory, and introduced into medicine salves made from the salts of mercury. He was the first to use tincture of opium, named by him laudanum, in the treatment of disease. The present pharmacopoeia includes much that Paracelsus employed —lead compounds, iron and zinc salts, arsenic preparations for skin diseases, milk of sulfur, blue vitriol, and other chemicals. 

Nomenclature before Werner (to 1897)- The Lavoisierian system of nomenclature, even with the Berzelius modifications, provided no suitable names for that class of compounds which later was designated coordination compounds. Names based on the patterns for double salts and addition compounds were not satisfactory because the properties of these materials were not those consistent with the patterns provided. Consequently, names based on properties, especially color (Table I), or the names of prominent investigators became popular (2) because they, at least, did not commit the user to any theory of their structure. The developments in organic chemistry after 1860 did not contribute to the understanding of these strange compounds, so there was no carry-over to them of the nomenclature developments in organic chemistry. 

The second possibility considered by Werner comes more closely to what is understood today by second-sphere coordinsJtion. As an example of this kind of outer-sphere coordination, Werner 43) mentions the addition compounds of tris(acetylacetonato) complexes of trivalent metals with various amines. Strangely enough Werner also considers double salts... 

Thus while isomeric derivatives are known corresponding to two isomeric acids only one acid is known and this one has the structure of the iso-cyanic acid. When we study the salts obtained from this iso-cyanic acid we find, unlike the alkyl derivatives, that they are known in only one form but strangely enough in the form of the cyanic acid, e.g, K—O—C=N, potassium cyanate. 

---