Sulphamic acids reactions

Sulphamic acid reaction with nitrous acid is examined in section 4.4 (p. 304). 

In the second method of homogeneous precipitation, the precipitant itself is generated by a chemical reaction. For example, Ba + can be homogeneously precipitated as BaS04 by hydrolyzing sulphamic acid to produce S04 . 

No satisfactory direct gravimetric procedure is available but nitrite can be oxidised to nitrate by permanganate or cerium(IV) and then determined in that form. The determination of total nitrate + nitrite is an important analysis, e.g. for soil samples. Nitrite may be destroyed using urea, sulphamic acid or hydrazine sulphate the reaction with the former is ... 

Nitrites react similarly to nitrates. They are best removed by adding a little sulphamic acid (compare Section IV.7, reaction 10). The following reaction takes place in the cold ... 

Nitrites give a similar reaction and may be removed most simply with the aid of sulphamic acid (see reaction 3). Another, but more expensive, procedure involves the addition of sodium azide to the acid solution the solution is allowed to stand for a short time and then boiled in order to complete the reaction and to expel the readily volatile hydrogen azide ... 

Reduction to nitrite test Nitrates are reduced to nitrites by metallic zinc in acetic acid solution the nitrite can be readily detected by means of the sulphanilic acid-a-naphthylamine reagent (see under Nitrites, Section IV.7, reaction 11). Nitrites, of course, interfere and are best removed with sulphamic acid (see reaction 3 above). 

The reaction of sulphur dioxide (or of sulphurous acid) with hydroxylamine forms sulphamic acid (2) and smaller quantities of ammonia and sulphite (3)... 

Singh, P. R., Singh, D. U., Samant, S. D. Sulphamic acid - an efficient and cost-effective solid acid catalyst for the pechmann reaction. Syn/eff 2004, 1909-1912. 

Further phenylation can be accomplished by reaction with phenylmagnesium bromide to give products only previously obtained by the potentially hazardous azide route. Sulphamic acid also reacts with phenylchlorophosphoranes in a similar way ... 

SULPHAMIC ACID (5329-14-6) Violent reaction with chlorine, nitric acid. Violent reaction with strong bases, chlorine, fuming nitric acid. Aqueous solution is a strong acid in elevated temperatures, it hydrolyzes to ammonium bisulfate. Incompatible with alkylene oxides, aliphatic amines, alkanolamines, amides, ammonia, epichlorohydrin, organic anhydrides, isocyanates, metal nitrates/nitrites, oxidizers, vinyl acetate, water. 

The application of CFD methods also makes it possible to carry out the analysis of such inorganic substances as anions and metals. As an example let us consider the analysis of trace amounts of nitrates in water. Tan [44] proposed a simple and sensitive method for determining nitrates in aqueous solutions using GC—mass spectrometry (MS) with an ionic detector-multiplier. The method is based on the nitration of 1,3,5-trimethoxy-benzene (TMB) in sulphuric acid. In this medium the nitration follows the hydrolysis of the ether groups of TMB, and nitrobenzene is formed as the final product [44]. The reaction mixture is analysed by GC and detected with a mass spectrometer. Hexamethyl-benzene (HMB) is used as an internal standard. To avoid interference from nitrates and chlorides, sulphamic acid and mercury(ll) sulphate are used. 

The coprecipitation of barium and lead sulphates from homogeneous solutions using sulphamic acid has been studied using electron microscopy and diffraction methods56. The reaction crystallization of sulphamic acid from urea and fuming sulphuric acid has been investigated57. 

In another sulphation study the kinetics of the reaction of sulphamic acid with 2-octanol to give sec-octylsulphate were found to be first order in sulphamic acid with energies and entropies of activation of 3.1 + 0.6 kcal mol-1 and 15 2 e.u. (in DMF) and 33.7 + 1.0 kcal mol -1 and 17 + 3 e.u. (in dimethyl sulphoxide)64. In dimethylformamide the mechanism involves the slow formation of DMF SO 3 followed by its rapid reaction with the alcohol to give R0S020NH4. 

Photolysis at 254 nm of sodium N-phenylsulphamate (39) gives three isomeric anilinesulphonic acids, viz. orthanilic, methanilic and sulphanilic acids and aniline65. The involvement of an intramolecular radical cage mechanism is supported by the absence of a substrate concentration effect and a considerable lowering of sulphamic acid yields in the presence of a radical scavenger. Stern-Volmer plots have provided evidence for involvement of two triplets in the reaction. 

The sulphamic acids 61 have been prepared by an unusual route for example, reaction of 2-HO-5-(CH3)3CC6H3CHO with ammonium sulphamate gave, after reduction with sodium borohydride and treatment with HC1, the compound 61, R = R2 = R3 = H, R1 = (CH3)3C111. 

Reaction of aniline with sulphamic acid at 160 to 170 °C for 1 hour gave a mixture of orthanilic, sulphanilic and 2,4-anilinedisulphonic acids and a little 2,4,6-anilinetrisul-phonic and phenylsulphamic acids138. The reaction of formaldehyde with potassium sulphamate at 25-30 °C and subsequent reaction of the product with glyoxal at 35-45 °C gave dipotassium 4,5-dihydroxyimidazoline-l,3 disulphonate (111)139. 

The metal sulphamates of Co, Ni and Cu have been prepared by reaction of sulphamic acid with the metal in the presence of H202144. 

The preparation of the tributyltin sulphamate 114 has been reported146. It undergoes slow hydrolysis to tributyltin sulphamate 115, which can be prepared under controlled conditions from the reaction of sulphamic acid with (Bu3Sn)20. In the same reaction at higher temperatures tributylstannylation of both the hydroxyl and amino groups occurs146. 

Some crystallochemical characteristics of complex iridium sulphamates have been reported152. A series of lanthanide sulphamates (122) have been prepared153, by reaction of the lanthanide carbonate and sulphamic acid, isolated as solids and examined by infrared, X-ray diffraction and thermography. The sulphamates have a higher solubility in water than other alkali or alkaline earth sulphamates. 

A convenient synthesis of the triethylamine-sulphur trioxide complex Et3NS03 (129) has been reported by Nair and Bernstein177. A 75% yield of 129 was obtained by the reaction of triethylamine with chlorosulphonic acid. Reaction of quinuclidine N-oxide with SO2 yield a stable colourless, non-hygroscopic material which was identified by X-ray and elemental analysis to be the quinuclidine-sulphur trioxide complex 130178. The complex was exceedingly stable and its hydrolysis in water even at 86 °C was very slow, 280 times slower than the analogous rate for triethylamine-sulphur trioxide (129). A single X-ray structure determination of the complex showed a sulphamic acid type coordination of SO3 to the quinuclidine nucleus [N-S =1.831 (6) A]. 

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