Sulfuric acid sulfamides

Sulfamide, (H2N)2S02, can be made by ammonolysis of SO3 or O2SCI2. It is a colourless crystalline material, mp 93°, which begins to decompose above this temperature. It is soluble in water to give a neutral non-electrolytic solution but in boiling water it decomposes to ammonia and sulfuric acid. The structure (Fig. 15.50c)... 

This class of aziridine-forming reaction includes the first reaction reported to afford aziridines. In 1888 Gabriel reported that aziridines could be prepared in a two-step process, by chlorination of ethanolamines with thionyl chloride, followed by alkali-induced cyclization [75]. Wenker subsequently reported that heating of 600 g of ethanolamine with more than 1 kg of 96 % sulfuric acid at high temperature produced P-aminoethyl sulphuric acid 282 g of it was distilled from aqueous base to give 23 g of aziridine itself, the first preparation of the parent compound in a pure condition [76]. Though there is no evidence to substantiate the hypothesis, the intermediate in these reactions is perhaps a cyclic sulfamidate (Scheme 4.51). 

Bis(trichlorophosphoranylidene)sulfamide is best preserved in sealed glass ampuls, although it can be stored in a vacuum desiccator over concentrated sulfuric acid or phosphorus(V) oxide. 

Hydrolysis of this substance leads by intermediate steps to sulfamide (Scheme 1). Ammonolysis, on the other hand, yields a cyclic mixed derivative of sulfuric acid and carbonic acid (LXXXIII). Sulfuryl amide gives salts and also numerous organic derivatives. A silver salt (AgNH)2S02... 

Sodium nitrite/hydrogen chloride Sulfuric acid amide esters and mixed sulf amides from sym. sulfamides... 

Sulfamide, (H2N)2S02, has a structure similar to that of sulfuric acid. Draw Lewis and VSEPR diagrams of this molecule. 

Amides. Names for amides are derived from the names of the acid radicals (or from the names of acids by replacing acid by amide) for example, S02(NH2)2, sulfonyl diamide (or sulfuric diamide) NH2SO3H, sulfamidic acid (or amidosulfuric acid). 

Cyclic sulfamides (14) exhibit enhanced acidity versus their acyclic counterparts by about 4 pA units. The sulfur d-orbitals and/or the added ring strain may be responsible <84JCS(P2)l85l>. 

All the recorded derivatives of these systems have the sulfur atom in the fully oxidized state, the N—S02—N grouping being introduced by the use of sulfamide or a substituted derivative. The 3-unsubstituted 2,2-dioxopyrazolo[3,4-c][l,2,6]triazines (176) and (177 R = H) are formed by heating with sulfamide. With the substituted sulfamides, cyclization of the intermediate is achieved with either alcoholic sodium hydroxide or trifluoracetic acid in moderate yields (Scheme 17) <85S190>. In a similar synthesis (Equation (25)) the tetrahydro-2,2-dioxopyrazolo[4,3-c][l,2,6]thiadiazine (179) is formed from the aminopyrazole (178) <76IJC(B)766>. 

The S—N compounds containing sulfur in higher oxidation states are also important. Thus, there are cyclic compounds of the types shown in Fig. 12-7, and there are N—S bonds in sulfamic acid (H3N+S03 ), the sulfamate anion (H2NS03 ), and sulfamides, (R2N)2S02. There are also some Se-N and S-Se-N compounds.24... 

Of the various possible types of -substituted sulfamoyl (sulfamyl) chlorides, the dialkyl compounds are of particular interest because they serve as intermediates in the syntheses of substituted sulfamides (synthesis 28) and of certain of their derivatives (synthesis 29). The dialkyIsul-famoyl chlorides have been prepared by the reaction of sulfuryl chloride with an appropriate amine or its hydrochloride, " by the treatment of secondary 7V-chloroamines with liquid sulfur dioxide, and by the reaction of dialkyl-aminosulfinic acids with chlorine in carbon tetrachloride. Although either of the first two procedures can be recommended in terms of convenience and yield, the availability of starting materials normally dictates that the first be used. It is of interest that treatment of sulfuryl chloride with either ammonia or ammonium chloride in terms of this procedure does not give the parent sulfamoyl chloride, H2NSO2CI. This compound is obtained in an altogether different way. ... 

HAF carbon black 40, zinc oxide 5, N-cyclohexyl-2-benzothiazole sulfamide 1, diphenyl guanidine 1, stearic acid 1 and sulfur 1.5. After 40 mins, of milling, the homogeneous stock was cured for 30 minutes at 160°. Extraction was carried out witii n-hexane at 65° for 24 hours. 

The explanation for the increased acidity of the six-membered rings could lie in the sulfur J-orbital overlap of the nitrogen pair. This acid-strengthening effect is greater for sulfamides in a five-membered ring (84JCS(P2)1851). 

Acid-catalyzed condensation of 2-acetyl-l-tetralone with sulfamide affords 83 (76IJC(B)66). The sulfur dioxide isoester of norlumiflavine (84) can be obtained from quinoxaline-2-carboxylic esters and sulfamide (86AP79) (Scheme 33). 

The 5,6-dihydro-477-l,2,6-thiadiazine 1,1,2-trioxides (162) described in Section 6.16.9.2.3.1 are susceptible to nucleophilic attack at sulfur, which promotes heterolytic cleavage of the heterocyclic ring and formation of )S-hydroxyaminosulfamic acid derivatives (163) as outlined in Scheme 15 <90LA775>. However, with a primary amine as the attacking nucleophile the sulfamides (163) so formed undergo base-catalysed ring closure to the 4,5-dihydropyrazoles (164) in yields of 72-90%. 

One method to reduce the volatility of sulfur dioxide is to complex it with imidazole and then add the complex to the adhesive. Chelates of boric acid derivatives with polyhydroxy compounds have also been prepared as anionic polymerization inhibitors. The chelates can be preformed or prepared in situ by adding the boric acid compound and the polyhydroxy compound to the adhesive. Sulfamides have been used to stabilize cyanoacrylates. The sulfamides (24) in question are prepared by reacting sulfuryl diisocyanate (23) with active hydrogen compounds such as carboxylic acids, as shown in Eq. (7). ... 

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