Sulfamic acid amines

Primary, secondary, and tertiary amines react with sulfamic acid to form ammonium salts (28) ... 

In sulfamation, also termed A/-sulfonation, compounds of the general stmcture R2NSO2H are formed as well as their corresponding salts, acid hahdes, and esters. The reagents are sulfamic acid (amido—sulfuric acid), SO —pyridine complex, SO —tertiary amine complexes, ahphatic amine—SO. adducts, and chlorine isocyanate—SO complexes (3). 

Sulfamation is the formation (245) of a nitrogen sulfur(VI) bond by the reaction of an amine and sulfur trioxide, or one of the many adduct forms of SO. Heating an amine with sulfamic acid is an alternative method. A practical example of sulfamation is the artificial sweetener sodium cyclohexylsulfamate [139-05-9] produced from the reaction of cyclohexylamine and sulfur trioxide (246,247) (see Sweeteners). Sulfamic acid is prepared from urea and oleum (248). Whereas sulfamation is not gready used commercially, sulfamic acid has various appHcations (see SuLFAMiC ACID AND SULFAMATES) (249—253). 

Determination of Hydroxy-Nitrosamines. The column extraction procedure has proven flexible and convenient for isolating NDELA and BHP from a variety of matrices. No artifactual formation of these nitrosamines has been observed when sulfamic acid was incorporated with the sample. Addition of excess acid prevents elution of amines from the Celite column, minimizing nitrosation reactions at later stages. The triisopro-panolamine sample examined contained approximately 250 mg/kg BHP (Table IV). 

Acetate, (C6H5)4AsC1, citrate, 2,3-dimercaptopropanol, EDTA, I-, Na5P3O10, SO)-, S20)-, tartrate, tiron, tetraphenylarsonium chloride, triethanolamine, thioglycolic acid Acetylacetone, citrate, CN-, EDTA, I-, NH3, N02, SCN-, S20)-, tartrate, triethanol amine Citrate, CN-, EDTA, I-, NH3, N02, SCN-, S20 -, tartrate, urea Reduction to Pu(IV) with sulfamic acid C20)-, citrate, EDTA, F-, tartrate Oxidation to perrhenate Citrate, tartrate, thiourea CN-, thiourea... 

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. 

An entirely different approach has been developed by Carreira and coworkers [57], who used sulfamic acid as the ammonia source. In conjunction with dimethyl formamide (DMF), amination occurred via an imidate, which was formed in situ. Although only those examples with branched allyUc alcohols as substrates were reported, a promising enantiomeric excess was achieved with the novel phosphora-midite L9 (Scheme 9.24). 

Primary amines react with 1,3,2-benzodioxathiole 2,2-dioxide affording sulfonylamines (72), which themselves are readily hydrolyzed to sulfamic acid salts (Equation (13)) <80JOC5371> this two-step procedure represents a mild, high yielding method for the sulfamoylation of primary... 

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]. 

PIRIA REACTION. Formation of arylsulfamic acids or sulfonation pioducts oi both by refluxing aromatic nitro compounds with a metal sulfite and boiling the mixture with dilute add to yield the amines and sulfamic acids. 

The above mentioned hydroxy and epoxy functional silanes represent reactive intermediates which can be transformed into ionic trimethyl silane derivatives. To give an example, hydroxyhexyltrimethylsilane can be reacted with sulfamic acid in the presence of a polar aprotic solvent such as f -methyl pyrrolidone or dimethyl formamide. The transformation of the ammonium salt into the appropriate alkyl ammonium derivative is readily achieved by addition of amine under generation of ammonia gas. 

Salts of primary aromatic amines react with nitrous acid to produce diazonium salts. The reaction is usually performed by adding a cold solution of sodium nitrite to a cold solution of the arylamine in aqueous mineral acid. The end point of the reaction is conveniently determined by the detection of excess nitrous acid with potassium iodide-starch paper. Sulfamic acid has long been used both in industry and in the laboratory to remove excess nitrous acid. It has been found to react with the more active diazo compounds. In most cases, high temperatures are avoided to prevent the formation of phenols and the decomposition of the unstable nitrous acid. An excess of mineral acid is necessary to prevent coupling between the diazonium salt and unreacted amine (cf. method 494). If the amine salt is somewhat insoluble, a fine crystalline form, which is produced by rapid crystallization from a warm aqueous solution, may be employed. ... 

Keywords A-Boc protection, amine, sulfamic acid, sonication... 

Sulfonation was carried out by heating the asphalt with sulfur trioxide-trimethyl amine complex or sulfur trioxide-pyridine complex at temperatures near 135°C. Sulfamic acid treatment was also included in this series. Many other reagents were evaluated such as methyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, 2-dimethyl-aminoethyl methacrylate, 2-vinylpyridine, 4-vinylpyridine, tetrahydro-phthalic anhydride, norbomene dicarboxylic anhydride, and phthalic anhydride. 

Substitution. Secondary aUyUc alcohols ate converted to amines by reaction with sulfamic acid, which forms the internal salt [Me2N=CH0S03] and NH3 to provide both activator and nucleophile. ... 

Chiral Al-salen complexes enable pyranoquinolines to be obtained with high diastereoselectivity by an inverse electron demand DA reaction between dihydropyran and benzylidene aniline <04BMCL2035>. Sulfamic acid effects the one-pot reaction between benzaldehyde, an aromatic amine and dihydropyran which leads to the same products (Scheme 3). An intramolecular version of the latter variant involves the imines derived from O-prenylsalicylaldehyde and gives isochromanoquinolines <04S69> and sulfamic acid is also a suitable catalyst for the Pechmaim synthesis of coumarins <04SL1909>. 

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