Sulfamic acid derivatives

Preparation of polyamidic acid sulfamic acid derivatives... 

TABLE 1. Proton Conductivity and Open-Circuit Testing Results for Electrolytic Membranes Consisting of Selected Polyamidic Acid Sulfamic Acid Derivatives Conducted at 150oC ... 

Vinyl sulfamic acid derivatives were used to enhance the thermal stability of membranes. 

The isothiazole-1,1-dioxide 211 has been shown to react with 2 equiv of sodium azide affording the corresponding 4/7-1,2-thiazete carbonitrile 18 accompanied by the [l,2]thiazine carbonitrile 212 and the acyclic sulfamic acid derivative 213 (Equation 21). Prolonged heating of the mixture results only in the formation of the thermally stable 4/7-1,2-thiazete carbonitrile and the 1,2-thiazine carbonitrile <2002T5173>. 

Berglund showed that sulfamic acid derivatives are relatively stable under alkaline conditions which cause hydrolysis of A-acetamido groups. Jorpes, Bostrom and Mannson, utilizing these data, found that less than 10% of the total amino groups is liberated when a 0.2% solution of heparin in N sodium hydroxide is heated at 100° for 2 hours, whereas 55 % of that in chondroitinsulfate is released. 

In the food industry, sulfur dioxide and sulfites are extensively employed as preservatives to inhibit microbial spoilage and increase the storage life of foods. In addition, several sulfamic acid derivatives like saccharin (13) (1878), cydamate (14) (1937) and acesulfame potassium (15) (1973) are important artificial sweeteners (Figure 4). 

Many sulfamic acid derivatives are sweet and much work has been carried out on structure-taste relationships. For example, research showed that sodium exo-2-norbornylsulfamate (89) was some five times sweeter than sodium cyclamate (88), although the corresponding endo-isomer (90) was tasteless (Figure 3). 

Many organosulfur compounds have major industrial uses. For instance, carbon disulfide and DMSO are important commercial solvents and dithiocarbamates are used in the rubber industry as vulcanisation accelerators long chain alkanesulfonic or arenesulfonic acids are important synthetic detergents. Xanthates are used in the manufacture of rayon (see Chapter 8, p. 135) and cellophane, and many commercial dyes contain sulfonic acid groups (see Introduction, p. 5). Sulfamic acid derivatives such as saccharin (see Chapter 9, p. 162) acesulfame potassium (see Introduction, p. 5) and cydamates (see Chapter 9, p. 162) are valuable artificial sweeteners. 

The sulfur derivative (87) is 1000 times as sweet as sugar and without the bitter after-taste of saccharin however, it was discovered that N-alkylation of (87) removed the sweetness. On the other hand, in the saccharins (88a)-(88e) containing substituents in the 4-position and 6-position, sweetness was retained after N-alkylation. Many sulfamic acid derivatives are sweet, and there have been numerous studies of structure-taste relationships which have highlighted the importance of molecular shape and stereochemistry (see Chapter 9, p. 162). Two sulfamates which are commercial, non-nutritive sweeteners are cyclamate (85) and acesulfame potassium (86) (Figure 11). Cyclamate (85) is manufactured by refluixing cyclohexylamine either with triethylamine-sulfur trioxide in dichloromethane or with sulfamic acid (see Chapter 9, p. 162). 

Sulfamic acid derivatives in synthesis of heterocycles 80CRV151. Sulfamides in synthesis of heterocycles 840PP49. 

A. Scozzafava, M. D. Banciu, A. Popescu, C. T. Supuran, J. Enzym. Inhib. 2000,15,443-453. Carbonic anhydrase inhibitors Inhibihon of isozymes 1,11 and IV by sulfamide and sulfamic acid derivatives 85. 

The sulfamic acid derivative cyclamate 27, discovered in 1937, is some 30 times sweeter than sucrose and may be obtained by the action of chlorosulfonic acid on cyclohexylamine (two equivalents) in hot trichloroethene as solvent (see Chapter 5, p 175) as shown in Scheme 8 (Chapter 6, ref 33). 

Before a 1/1 /70 FDA ban (rescission proposed in early 1990), cyclamate noncaloric sweeteners were the major derivatives driving cycloliexylamine production. The cyclohexylsulfamic acid sodium salt (39) [139-05-9J and mote thermally stable calcium cyclohexylsulfamic acid (40) [139-06-1] salts were prepared from high purity cyclohexylamine by, among other routes, a reaction cycle with sulfamic acid. 

Aldehydes form addition products with sulfamic acid salts. These are stable ia neutral or slightly alkaline solutions but are hydroly2ed ia acid and strongly alkaline solutions. With formaldehyde, the calcium salt of the methylol (hydroxymethyl) derivative [82770-57-8], Ca(02SNHCH20H)2, is obtained as a crystalline soHd. 

The A/-alkyl and W-cyclohexyl derivatives of sulfamic acid are comparatively stable. The A/-aryl derivatives are very unstable and can only be isolated ia the salt form. A series of thia2olylsulfamic acids has been prepared. 

Imidodisulfuric acid derivatives can be prepared from urea by using less sulfuric acid than required for sulfamic acid (p. 741) warm... 

HN(S02F)2 melts at 17°, boils at 170° and can be further fluorinated with elemental F2 at room temperature to give FN(S02F)2, mp —79.9°, bp 60°. The chloro derivative HN(S02C1)2 is a white crystalline compound, mp 37° it is made in better yield from sulfamic acid by the following reaction sequence ... 

More recently, Carreira and coworkers reported the reactions of sulfamic acid with branched allylic alcohols to form branched primary allylic amines [106]. One enantioselective reaction was disclosed, and the product was isolated in 70% ee when using a 5//-dibenzo[h, / jazepine-derived phosphoramidite with [lr(COE)2Cl]2 (Scheme 33). This reaction occurs under acidic conditions, which is incompatible with the metalacyclic catalysts. 

Didemnum rodriguesi from New Caledonia contained the unusual peptidyl alkaloid caledonin (76), that formed a complex with Zn2+ and Cu+ ions between thiol and primary amine groups [100], The minalemines D-F (77-79) are peptide guanidine derivatives isolated from a Caribbean collection of D. rodriguesi and contain a sulfamic acid group [101]. The stereochemistry of cyclodidemniserinol trisulfate (80) from a Palauan specimen of Didemnum guttatum was partially determined [102]. 

While esters of sulfuric acid do not play as central a role in metabolism as do phosphate esters, they occur widely. Both oxygen esters (R-0-S03 , often referred to as O-sulfates) and derivatives of sulfamic acid (R-NH-SOg, N-suIfates) are found, the latter occurring in mucopolysaccharides such as heparin. Sulfate esters of mucopolysaccharides and of steroids are ubiquitous and sulfation is the most abundant known modification of tyrosine side chains. Choline sulfate and ascorbic acid 2-sulfate are also found in cells. Sulfate esters of phenols and many other organic sulfates are present in urine. 

The peptide guanidine derivatives minalemines D-F (459-461), isolated from the New Caledonian tunicate Didemnum rodriguesi, were the first marine metabolites containing a sulfamic acid functional group [354]. Their structures were elucidated through their spectral data and by chemical transformations. 

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