Mercuric oxide-iodine

A-Nor-B-homo steroids with different substitution patterns than those described above may be prepared by acid catalyzed cyclization of 3)3-hydroxy-5(10)-seco-cholest-tra/w-l(l0)-en-5-one acetate (134a) formed in 30-40% yield by mercuric oxide-iodine sensitized irradiation of cholestane-3j3,5a-diol... 

Mercuric oxide-iodine. This combination has been used as a possibly superior alternative to the lead tetraacetate-iodine reagent for oxidative attack of angular methyl groups. Thus a 6j8-hydroxysteroid (1) reacts with mercuric oxide and iodine in a light-induced reaction to give the 6,19-oxide (2) through an intermediate hypoiodite. ... 

Saturated (and some unsaturated) long-chain hydroxy compounds can be converted to tetrahydrofurans by oxidation with reagents that convert the alcohol (ROH) to its alkoxide radical (RO ). These include lead tetra-acetate, silver oxide/bromine, mercuric oxide/iodine, sodium hypochlorite (domestic bleach), and A -iodosuccinimide (Scheme 12). 

Forbes, C.P., Goosen, A., and Laue, H.A.H., Hypoiodite reaction the reaction of mercuric oxide-iodine reagent with olefins, /. S. African Chem. Inst, 25, 144, 1972 Forbes, C.P., Goosen, A, and Laue, H.A.H, Hypoiodite reaction mechanism of the reaction of mercury(II) oxide-iodine with olefins, /. Chem. Soc., Perkin Trans. 1, 2346, 1974. 

The aHphatic iodine derivatives are usually prepared by reaction of an alcohol with hydroiodic acid or phosphoms trHodide by reaction of iodine, an alcohol, and red phosphoms addition of iodine monochloride, monobromide, or iodine to an olefin replacement reaction by heating the chlorine or bromine compound with an alkaH iodide ia a suitable solvent and the reaction of triphenyl phosphite with methyl iodide and an alcohol. The aromatic iodine derivatives are prepared by reacting iodine and the aromatic system with oxidising agents such as nitric acid, filming sulfuric acid, or mercuric oxide. 

Iodoveratrole has been prepared by iodination of veratrole in the presence of mercuric oxide and by methylation of 4-iodoguaiacol with methyl iodide in alcoholic sodium ethoxide solution. ... 

By Iodine Mercuric Oxide Photolysis of 5a.-Hydroxy Steroids... 

Styrene oxide has previously been prepared by the action of iodine, water and mercuric oxide on styrene.1 A description of Hibbert s method 2 using benzoylhydroperoxide has appeared... 

Iodination of 4 with molecular iodine in the presence of mercuric oxide formed the 3-iodo derivative (52JA4951 66CJC2283). Iodine in tetrahydro-furan oxidatively cyclized /3-(3-benzo[b]thienyl)-a-mercaptoacrylic acids rather than iodinating the thiophene ring [70JCS(C)2431]. 

When iodine is the reagent, the ratio between the reactants is very important and determines the products. A 1 1 ratio of salt to iodine gives the alkyl halide, as above. A 2 1 ratio, however, gives the ester RCOOR. This is called the Simonini reaction and is sometimes used to prepare carboxylic esters. The Simonini reaction can also be carried out with lead salts of acids." A more convenient way to perform the Hunsdiecker reaction is by use of a mixture of the acid and mercuric oxide instead of the salt, since the silver salt must be very pure and dry and such pure silver salts are often not easy to prepare. 

Advantage has been taken of the aforementioned observations in the synthesis of a terthiophene natural product, arctic acid (147) [123]. Pd-catalyzed carbonylation of bromobisthiophene 25, obtained from the Kumada coupling of 2-thienylmagnesium bromide and 2,5-dibromothiophene, gave bithiophene ester 144, which was converted to iodide 145 by reaction with iodine and yellow mercuric oxide. Subsequent propynylation of 145 was then realized using the Sonogashira reaction with prop-l-yne to give bisthienyl alkyne 146, which was subsequently hydrolyzed to 5 -(l-propynyl)-2,2 -bithienyl-5-carboxylic acid (147), a natural product isolated from the root of Arctium lappa. 

Iododurene has been prepared by treatment of durene either with iodine and mercuric oxide,4 or with sulphur iodide and nitric acid.5... 

The iodine atom in the monoiodide may be replaced by other groups and, by reaction with silver salts, for example, As(CF3)2CN (b.p. 89 5°) and As(CFg)2SCN (b.p. 116—118°) are readily prepared. Reaction of the monoiodide with mercury gives the cacodyl As2(CF3)4 (b.p. 106 to 107°), while with mercuric oxide the oxide As2(CF3)40 (b.p. 95—97°) is formed. The chemistry of these substances has not yet been studied in detail, but it is noteworthy that hydrolysis of the perfluorocacodyl gives both fluoroform and fluoride, which parallels the observations made on the diphosphine. 

The following reactions with inorganic substances are taken from the book of Clark, Hydrazine (1953), pp 4 to 18 Potassium reacts with N2H4 expl violently (p 4) Mercuric oxide reacts with N2H4.H2O with expl violence (p 5) Chlorine, bromine and iodine react violently (p 8) with N 2H4 and spontaneous ignition of N2H) takes place in a chlorine atm. 

Among the oxidative procedures for preparing azo compounds are oxidation of aromatic amines with activated manganese dioxide oxidation of fluorinated aromatic amines with sodium hypochlorite oxidation of aromatic amines with peracids in the presence of cupric ions oxidation of hindered aliphatic amines with iodine pentafluoride oxidation of both aromatic and aliphatic hydrazine derivatives with a variety of reagents such as hydrogen peroxide, halogens or hypochlorites, mercuric oxide, A-bromosuccinimide, nitric acid, and oxides of nitrogen. 

Azoalkanes have also been produced by oxidation with mercuric oxide. This reagent is considered the reagent of choice for azoalkanes [76, 87, 93], as well as for the preparation of cyclic azo compounds [94], and 1-pyrazolines [95a]. When used in the preparation of a-carbonyl azo compounds, evidently mercury complexes are formed with the diacylhydrazine starting materials. These complexes are then treated with halogens (iodine or chlorine) to produce the azo compounds [92]. 

Silver foil is transformed by an aq. soln. of the trichloride into silver chloride and iodide silver oxide with an excess of the trichloride is transformed into the chloride and iodic acid with more silver oxide, silver iodate is formed and with an excess of the oxide and a boiling soln. some silver periodate is formed. Mercuric oxide is slowly transformed into mercuric chloride and oxide chlorine, oxygen, and possibly chlorine monoxide are evolved. Aq. soln. of the trichloride give a precipitate of iodine with a little stannous chloride with more stannous chloride, some stannous iodide is formed. Consequently, although chloroform extracts no iodine from the aq. soln., it will do so after the addition of stannous chloride. Sulphur dioxide and ferrous sulphate are oxidized. 

A. J. Balard found mercury immediately decomposes hypochlorous acid without the disengagement of any gas, but mercury oxychloride is formed. P. Grouvelle reported previously that when chlorine acts on mercuric oxide suspended in water, mercury oxychloride, very slightly soluble in cold water, is formed. L. J. Thenard found that the liquid contained both chloride and chlorate of mercury, also in soln. A. J. Balard, however, believed that these bodies are formed consecutively, and that their existence was preceded by that of a mercuric hypochlorite, as takes place with the salts of silver, and, as previously indicated, he prepared hypochlorous acid by the action of chlorine on mercuric oxide suspended in water. No mercury hypobromite has yet been isolated. There is a possible formation of mercury hypoiodite, or more probably of hypoiodous acid, when iodine is shaken up with... 

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