Tris sulfur

F. 1,4,7,10,13,16-Hexaazacyclooctadecane (6). A 3-1., threenecked, round-bottomed flask is equipped with mechanical stirrer, nitrogen inlet, and addition funnel. In the flask are placed 200 g. (0.169 mole) of cyclic hexamine 5 and 500 ml. of concentrated (97%) sulfuric acid. The stirred mixture is held at 100° for 70 hours and then cooled in ice as 1300 ml. of anhydrous ethyl ether is slowly added. The precipitated polyhydrosulfate salt is filtered under nitrogen and washed with anhydrous ethyl ether (Note 7). The salt is then stirred in 200 ml. of water and cooled in ice as 71 ml. of aqueous 50% NaOH is added to neutralize the solution. Three grams of activated carbon are added, and the solution is heated to 80° and filtered through Celite. The filtrate is cooled in ice and reacidified to pH 1 by adding 42 ml. of concentrated sulfuric acid. The white, non hygroscopic tris(sulfuric acid) salt of 6 that precipitates is collected and washed with 95% ethanol. 

In binding thermite with sodium silicate, it is very essential that all the water be driven out, and, because of the difficulty of completely drying the silicate-bound thermite, a number of other binders w ere tried. Sulfur W as highly recommended as a binder, since a unit of weight of mixture made up according to the equation... 

Sample preparation Filter (0.45 jim) urine or plasma. Mix plasma filtrate with an equal volume of 50 mM pH 8.0 Tris-sulfuric acid buffer containing 0.1 mM zinc acetate and 40 mM sodium dodecyl sulfate. Inject a 50 p,L aliquot of the urine filtrate or the diluted plasma onto column A with mobile phase A, elute to waste with mobile phase A, after 5 min backflush the contents of column A onto column B with mobile phase B, after 3 min remove column A from the circuit, elute column B with mobile phase B, monitor the effluent from column B. Re-equilibrate column A with mobile phase A for 5 min before next injection. 

Mobile phase A 50 mM pH 8.0 Tris-sulfuric acid buffer containing 0.1 mM zinc acetate B Gradient. MeCN 100 mM pH 5.2 acetate buffer 10 90 containing 500 mM NaCl for 3 min then MeCN 100 mM pH 5.2 acetate buffer 23 77 containing 500 mM NaCl (step gradient). (Increase in gradient occurs at the same time as column A is removed from the circuit.)... 

The name of the parent six membered sulfur containing heterocycle is thiane It is num bered beginning at sulfur Multiple incorporation of sulfur in the ring is indicated by the prefixes di tri and so on... 

Replacement of Oxygen by Other Chalcogens. Acids derived from oxoacids by replacement of oxygen by sulfur are called thioacids, and the number of replacements are given by prefixes di-, tri-, and so on. The affixes seleno- and telluro- are used analogously. 

Sulfonation. Sulfonation of naphthalene with sulfuric acid produces mono-, di-, tri-, and tetranaphthalenesulfonic acids (see Naphthalene derivatives), ah of the naphthalenesulfonic acids form salts with most bases. Naphthalenesulfonic acids are important starting materials in the manufacture of organic dyes (15) (see Azo dyes). They also are intermediates used in reactions, eg, caustic fusion to yield naphthols, nitration to yield nitronaphthalenesulfonic acids, etc. 

Sulfur reacts with mercaptans ia the presences of basic catalysts at temperatures of 75—105°C, forming sulfides. These sulfides are usually light ia color and are formed without cross-linking. The sulfurization of mercaptans leads to di-, tri-, or higher polysulfides, depending on the mole ratio used (eqs. 5 and 6). An extensive Hst of references to the sulfurization of mercaptans is available (8). 

Uses ndReactions. Dihydromyrcene is used primarily for manufacture of dihydromyrcenol (25), but there are no known uses for the pseudocitroneUene. Dihydromyrcene can be catalyticaUy hydrated to dihydromyrcenol by a variety of methods (103). Reaction takes place at the more reactive tri-substituted double bond. Reaction of dihydromyrcene with formic acid gives a mixture of the alcohol and the formate ester and hydrolysis of the mixture with base yields dihydromyrcenol (104). The mixture of the alcohol and its formate ester is also a commercially avaUable product known as Dimyrcetol. Sulfuric acid is reported to have advantages over formic acid and hydrogen chloride in that it is less compUcated and gives a higher yield of dihydromyrcenol (105). 

Other methods of preparing tertiary bismuthines have been used only to a limited extent. These methods iaclude the electrolysis of organometaUic compounds at a sacrificial bismuth anode (54), the reaction between a sodium—bismuth or potassium—bismuth alloy and an alkyl or aryl haUde (55), the thermal elimination of sulfur dioxide from tris(arenesulfiaato)bismuthines (56), and the iateraction of ketene and a ttis(dialkylainino)bismuthine (57). 

The replacement of rhodium from a wide range of rhodacycles to form condensed furans, thiophenes, selenophenes, tellurophenes and pyrroles has been widely explored and a range of examples is shown in Scheme 97. The rhodacycles are readily generated from the appropriate dialkyne and tris(triphenylphosphine)rhodium chloride. Replacement of the rhodium by sulfur, selenium or tellurium is effected by direct treatment with the element, replacement by oxygen using m-chloroperbenzoic acid and by nitrogen using nitrosobenzene. 

Chloroethyldisulfides are obtained by electrophilic attack on the sulfur atom of thiiranes by sulfenyl halides (Scheme 39). Sulfur dichloride and disulfur dichloride react similarly to give more sulfur-rich derivatives di- and tri-sulfenyl halides, and tri- and tetra-sulfides (Scheme 42). A 1 1 ratio of sulfur halide to thiirane gives the di- or tri-sulfenyl halide a 2 1 ratio the tri- or tetra-sulfide. Thiirane 1-oxides are cleaved by sulfenyl halides to thiolsulfinates (Scheme 43) (74JAP7440461). 

---