Sulfur displacements

In a similar way, oxygen displaces sulfur from many compounds on long-continued exposure to air. 

The enamine product of decarboxylation reacts with lipoamide, displacing sulfur and opening the lipoamide ring. 

Occurrence, — Selenium must be considered a rare element, although it is found widely distributed in nature. The distinctive selenium minerals are rare, and they are usually selenides, of such metals as lead, mercury, copper, bismuth, and silver. The element is also found in the free state associated with sulfur and as a selenite. The most common occurrence of selenium is in ores in which the element has partially displaced sulfur. Generally the selenium is present in very small proportions, but on account of the fact that enormous quantities of sulfide ores are used, this represents a considerable amount of selenium. It occurs also in small amounts in meteoric iron, in volcanic lavas, and in certain deposits of coal. Traces of selenium have been detected in rain and snow. Even though present in mineral ores in mere traces, it is readily concentrated either in the flue dusts or in the anode mud of the electrolytic refineries. Considerable quantities are known to exist in Hawaii, Japan,... 

Hydrochloric add displaces sulfuric acid at 75°C to produce nitrosyl chloride HNOSO + HCI - NOD + H2SO ... 

This conversion of 101 to 102 is a substitution, but the intermediacy of 104 leads to an intramolecular transfer of chlorine to displace sulfur dioxide. Reactions such as this are classified as internal nucleophilic substitution, which is abbreviated by the symbol SnI. 

An unusual system where the carbene carbon is part of a six-membered ring, but with two adjacent nitrogens, has been the subject of a short series of papers.Reactions of hypervalent sulfur-containing precursors with a platinum(O) complex take place under mild conditions, yielding new complexes 145 and 146 (Scheme 36). Little detail is given, but it is believed the displaced sulfur ends up as Ph3P=S. 

Molten selenium mixed whith metals will produce either metal selenides for alloys, most of which are highly insoluble, particularly those of the heavy metals. Mercury selenide, for example, has a Kgp of 10 [33]. Most of the organic and inorganic complexation chemistry involve the 2-oxidation state, and many of the compounds are sulfur analogs, where selenium has displaced sulfur. An exhaustive treatment of the selenium complexation chemistry is found in Nazarenka and Ermakov [53]. 

The ionic radii of Se and are similar, and selenium often displaces sulfur... 

Displacement Reactions with Carbon, O.xygen. and Sulfur Nucleophiles... 

It is estimated that mote than 25 x 10 different potentially toxic OP esters can be made using Schrader s classic (27) formula for effective phosphorylating agents, (39), where R and are short-chain alkyl, alkoxy, alkylthio, or alkylamino groups, and X is a displaceable moiety with a high energy P-bond such as E or acyl anhydride, and the pentavalent phosphoms atom is bonded to oxygen or sulfur. 

Dinitrochlorobenzene can be manufactured by either dinitration of chlorobenzene in filming sulfuric acid or nitration ofy -nitrochlorobenzene with mixed acids. Further substitution on the aromatic ring is difficult because of the deactivating effect of the chlorine atom, but the chlorine is very reactive and is displaced even more readily than in the mononitrochlorobenzenes. 

Sulfur Substituents. Acetylation and alkylation of pyridinethiones usually take place on sulfur (39). An exception to this is 4-pyridinethione [19829-29-9] which is acetylated on nitrogen. Displacement of thioethers can be achieved with hydroxide or amines (eq. 13) (40). Thioether functional groups can also be removed by reduction (39). 

Tiichloiomethanesulfenyl chloiide can be reduced to thiophosgene by metals in the presence of acid and by various other reducing agents. The sulfur-bonded chlorine of trichloromethanesulfenyl chloride is most easily displaced by nucleophilic reagents, but under some conditions, the carbon-bound chlorines are also reactive (54). 

Using sulfur trioxide plus chlorine, or sulfur dioxide plus chlorine, sulfur monochloride yields thionyl chloride [7719-09-7] SOCI2. Various nucleophilic reactions can displace the chlorine atoms of sulfur monochloride ... 

In the olivanic acid series of carbapenems the ( )-acetamidoethenyl grouping can be isomerised to the (Z)-isomer (19) (22) and reaction with hypobromous acid provides a bromohydrin that fragments to give a thiol of type (20) when R = H, SO H, or COCH. The thiol is not isolated but can react to provide new alkyl or alkenyl C-2 substituents (28). In the case of the nonsulfated olivanic acids, inversion of the stereochemistry at the 8(3)-hydroxyl group by way of a Mitsunobu reaction affords an entry to the 8(R)-thienamycin series (29). An alternative method for introducing new sulfur substituents makes use of a displacement reaction of a carbapenem (3)-oxide with a thiol (30). Microbial deacylation of the acylamino group in PS-5 (5) has... 

Nitrogen nucleophiles used to diplace the 3 -acetoxy group include substituted pyridines, quinolines, pyrimidines, triazoles, pyrazoles, azide, and even aniline and methylaniline if the pH is controlled at 7.5. Sulfur nucleophiles include aLkylthiols, thiosulfate, thio and dithio acids, carbamates and carbonates, thioureas, thioamides, and most importandy, from a biological viewpoint, heterocycHc thiols. The yields of the displacement reactions vary widely. Two general approaches for improving 3 -acetoxy displacement have been reported. One approach involves initial, or in situ conversion of the acetoxy moiety to a more facile leaving group. The other approach utilizes Lewis or Brmnsted acid activation (87). 

Conversion to a more facile, sulfur-derived, leaving group can be achieved by treatment with sodium thiosulfate or salts of thio and dithio acids (75,87). Under anhydrous conditions, boron tribromide converts the 3 -acetoxy group to a bromide whereas trimethyl silyl iodide gives good yields of the 3 -iodide (87,171,172). These 3 -halides are much more reactive, even when the carboxyl group is esterified, and can be displaced readily by cyano and by oxygen nucleophiles (127). 

Iron Precipitation. Rich sulfide ore or Hquated antimony sulfide (cmde antimony) is reduced to metal by iron precipitation. This process, consisting essentially of heating molten antimony sulfide ia cmcibles with slightly more than the theoretical amount of fine iron scrap, depends on the abihty of iron to displace antimony from molten antimony sulfide. Sodium sulfate and carbon are added to produce sodium sulfide, or salt is added to form a light fusible matte with iron sulfide and to faciHtate separation of the metal. Because the metal so formed contains considerable iron and some sulfur, a second fusion with some Hquated antimony sulfide and salt foHows for purification. 

Cellulose valerates have been synthesized by conventional methods using valeric anhydride and sulfuric acid catalyst (25,26). Alternatively, the cellulose is activated by soaking in water, which is then displaced by methylene chloride or valeric acid the temperature is maintained at <38° C to minimize degradation. 

It resembles tetracyanoethylene in that it adds reagents such as hydrogen (31), sulfurous acid (31), and tetrahydrofuran (32) to the ends of the conjugated system of carbon atoms suffers displacement of one or two cyano groups by nucleophilic reagents such as amines (33) or sodiomalononittile (34) forms TT-complexes with aromatic compounds (35) and takes an electron from iodide ion, copper, or tertiary amines to form an anion radical (35,36). The anion radical has been isolated as salts of the formula (TCNQ) where is a metal or ammonium cation, and n = 1, 1.5, or 2. Some of these salts have... 

Besides displacement reactions, oxidations, rearrangements and cleavage of the sulfide linkage, the most important reactions take place at the sulfur atom. 

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