Halogen-mercury

The popular approach to tetrahydrofurans involves an electrophilic process and the commonly used electrophiles for the cyclization are acids, oxygen, halogen, mercury (see Section 3.11.2.2.9) and selenium. The ionic hydrogenation of furans with excess triethyl-silane in trifluoroacetic acid affords high yields, e.g. 2-methylfuran is reduced to 2-methyl-tetrahydrofuran and 2-ethylfuran to 2-ethyltetrahydrofuran (see Section 3.11.2.5). The synthesis of several dihydro and tetrahydrofurans containing natural products by chirality transfer from carbohydrates has been used successfully for total synthesis, e.g. (-)-nonactic acid. A reasonable yield of 2-alkyltetrahydrofuran was prepared from 4-alkylbut-l-en-4-ol by hydroboration followed by cyclization with p-toluenesulfonic acid. 

In certain systems ascorbic acid was so effective in lowering the valence state of metals that it was used in analytical chemistry (8). Ascorbic acid was used with gold, lead, bismuth, tellurium, copper, phosphorus, uranium, halogens, mercury, and cobalt. 

Mercurous and mercuric chloride, known respectively as calomel and corrosive sublimate, are two of the most important salts of mercury. Other halogenated mercury salts include mercurous bromide, Hg2Br2, a yellowish-white powder insoluble in water mercuric bromide, HgBr2, comprised of white crystals sparingly soluble in cold water but readily soluble in hot water mercurous iodide, Hg2l2, a yellowish-green powder and mercuric iodide, which exists in two crystalline forms. Other mercuric and mercurous compounds include nitrates, nitrites, sulfides, sulfates, phosphides, phosphates, and ammonium salts. 

Light sources that have been applied to fluidized bed measurement are lamps (halogen, mercury, metal halide), LEDs (light emitting diodes), and lasers of... 

Oxidative Additions. Many covalent compounds (XY) such as hydrogen, halogens, mercury and silver halogenides can react with clusters resulting in an homolytic cleavage of the X-Y bond and in the oxidative addition of the two fragments to a metal-metal bond thus increasing the formal oxidation state of the metal atoms. 

Halogens can act as ligands and are commonly found in complex ions the ability of fluorine to form stable complex ions with elements in high oxidation states has already been discussed (p. 316). However, the chlorides of silver, lead(Il) and mercury(l) are worthy of note. These chlorides are insoluble in water and used as a test for the metal, but all dissolve in concentrated hydrochloric acid when the complex chlorides are produced, i.e. [AgCl2] , [PbC ] and [Hg Clj]", in the latter case the mercury(I) chloride having also disproportionated. 

The metal is slowly oxidised by air at its boiling point, to give red mercury(II) oxide it is attacked by the halogens (which cannoi therefore be collected over mercury) and by nitric acid. (The reactivity of mercury towards acids is further considered on pp. 436, 438.) It forms amalgams—liquid or solid—with many other metals these find uses as reducing agents (for example with sodium, zinc) and as dental fillings (for example with silver, tin or copper). 

Mercury(I) forms few complexes, one example is the linear [H2O-Hg Hg- H20] found in the mercury(I) nitrate dihydrate (above, p. 437), In contrast, mercury(II) forms a wide variety of complexes, with some peculiarities (a) octahedral complexes are rare, (b) complexes with nitrogen as the donor atom are common, (c) complexes are more readily formed with iodine than with other halogen ligands. 

Ammonia, anhydrous Mercury, halogens, hypochlorites, chlorites, chlorine(I) oxide, hydrofluoric acid (anhydrous), hydrogen peroxide, chromium(VI) oxide, nitrogen dioxide, chromyl(VI) chloride, sulflnyl chloride, magnesium perchlorate, peroxodisul-fates, phosphorus pentoxide, acetaldehyde, ethylene oxide, acrolein, gold(III) chloride... 

At ordinary temperatures, mercury is stable and does not react with air, ammonia (qv), carbon dioxide (qv), nitrous oxide, or oxygen (qv). It combines readily with the halogens and sulfur, but is Htde affected by hydrochloric acid, and is attacked only by concentrated sulfuric acid. Both dilute and concentrated nitric acid dissolve mercury, forming mercurous salts when the mercury is in excess or no heat is used, and mercuric salts when excess acid is present or heat is used. Mercury reacts with hydrogen sulfide in the air and thus should always be covered. 

Anthraquinone can be sulfonated, nitrated, or halogenated. Sulfonation is of the greatest technical importance because the sulfonic acid group can be readily replaced by an amino or chloro group. Sulfonation with 20—25% oleum at a temperature of 130—135°C produces predominandy anthraquinone-2-sulfonic acid [84-48-0]. By the use of a stronger oleum, disulfonic acids are produced. The second sulfonic acid substituent never enters the same ring a mixture of 2,6- and 2,7-disulfonic acids is formed (Wayne-Armstrong rule). In order to sulfonate in the 1-, 1,5-, or 1,8-positions, mercury or one of its salts must be used as a catalyst. 

Catalytic Oxidation. Catalytic oxidation is used only for gaseous streams because combustion reactions take place on the surface of the catalyst which otherwise would be covered by soHd material. Common catalysts are palladium [7440-05-3] and platinum [7440-06-4]. Because of the catalytic boost, operating temperatures and residence times are much lower which reduce operating costs. Catalysts in any treatment system are susceptible to poisoning (masking of or interference with the active sites). Catalysts can be poisoned or deactivated by sulfur, bismuth [7440-69-9] phosphoms [7723-14-0] arsenic, antimony, mercury, lead, zinc, tin [7440-31-5] or halogens (notably chlorine) platinum catalysts can tolerate sulfur compounds, but can be poisoned by chlorine. 

Metals in the platinum family are recognized for their ability to promote combustion at lowtemperatures. Other catalysts include various oxides of copper, chromium, vanadium, nickel, and cobalt. These catalysts are subject to poisoning, particularly from halogens, halogen and sulfur compounds, zinc, arsenic, lead, mercury, and particulates. It is therefore important that catalyst surfaces be clean and active to ensure optimum performance. 

Mercury can be used to dehalogenate acyl halides to ketenes when a halogen IS present next to the COCl group [67] (equation 35)... 

The reaction of Mc3SiNSO with HgE2 produces the covalent mercury(II) derivative Hg(NSO)2. Carefully controlled reactions of halogens with Mc3SiNSO or Hg(NSO)2 generate A-halosulfinylamines XNSO (X = E, Cl, Br) (Eq. 9.10). ... 

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