Sulfamidic Acid

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). 

DOT UN 2967 mf H3NO3S mw 97.10 PROP White crystals nonhygroscopic solid. Mp 200° (decomp), bp decomp, d 203 12°. Very sol in H2O, liq NH3, formamide. SYNS AMIDOSULFONIC ACID AMIDOSULFURIC ACID AMINOSULFONIC ACID KYSELINA AMIDOSULFONOVA (CZECH) KYSELINA SULFAMINOVA (CZECH) SULFAMIDIC ACID SULPHAMIC ACID pOT)... 

Synonyms Amidosulfonic acid Amidosulfuric acid Aminosulfonic acid Sulfamidic acid Sulphamic acid... 

Sulfamic acid, dimethyl-, 5-butyl-2-(ethylamino)-6-methyl-4-pyrimidinyl ester. See Bupirimate Sulfamic acid, monoammonium salt. See Ammonium sulfamate Sulfamidic acid. See Sulfamic acid p-Sulfamidoaniline Sulfamidyl. See Sulfanilamide... 

Sulfamic acid, also known as amidosulfonic acid, amidosulfuric acid, aminosulfonic acid, and sulfamidic acid, is a molecular compound with the formula H3NSO3. This colorless, water-soluble compound finds many applications. 

Figure 15.50 The structures of (a) sulfamic acid, (b) the sulfamate ion, and (c) sulfamide.

In the solid state sulfamic acid forms a strongly H-bonded network which is best described in terms of zwitterion units +H3NSO3" rather than the more obvious formulation as aminosulfuric acid, H2NS02(0H). The zwitterion has the staggered configuration shown in Fig. 15.50a and the S-N distance is notably longer than in the sulfamate ion or sulfamide. 

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). 

Ref 10) and by fluorination of 1) cyanuric acid (Ref 5) 2) sulfamide, yield 45% (Ref 14) [Kelly and Sukornick found that sulfamic acid, w, and F will react continuously in a flow re-... 

Other types of HIV-1 protease inhibitors have also been prepared using microwave-promoted Suzuki reaction [37]. The symmetric cyclic sulfamide (3K,4S,5S,6it)-3,6-bis(phenoxymethyl)-2,7-bis[4-(2-thienyl)benzyl]-l,2,7-thi-adiazepane-4,5-diol 1,1-dioxide, for instance, was synthesized via cross-couphng of (3aS,4R,8it,8aS) - 5,7 - bis(4 - bromobenzyl) - 2,2 - dimethyl - 4,8 - bis-(phenoxymethyl) hexahydro [1,3] dioxolo [4,5 - d] [ 1,2,7 ] - thiadiazepine 6,6 - dioxide with 2-thienylboronic acid for 3 min at 45 W (Scheme 19). 

Paquin in 1948 found that a strongly exothermic reaction occurred when 40% formaldehyde was added to a solution of sulfamide in 25% aqueous ammonia. At once beautiful crystals precipitated they were recrystallized from 96% alcohol to give a compound, C5H10N4SO2, mp 224-225 "C, in 88% yield.245 From the similar character to hexamethylenetetramine, he named this product pentamethylenetetramine sulfone it is 225. One year later, in 1949, Hecht and Henecka at Bayer research laboratory reported that a condensation product from one mole of sulfamide in strong mineral acid and two moles of formaldehyde showed very strong toxicity and was five times more toxic than strychnine. They called this product (226) tetra-methylenedisulfotetramine. 246... 

Treatment of the 2,5-dihydro-l,2,5-thiadiazole 1,1-dioxide 69 with/>-toluenesulfonic acid monohydrate affords the ring-opened phenylethyl sulfamide 70 (Equation 9) <2004BMC6249>. 

Glutarimide has been prepared from glutaric acid and sulfamide 3 or formamide,4 by distillation of ammonium glutarate,6 by hydrolysis of pentanedinitrile with acetic acid,6 and by oxidation of piperidine with hydrogen peroxide.7... 

When sulfamate esters 114 are used as substrates, six-membered-ring formation is favored, and results in the selective formation of 1,2,3-oxathiazinane-2,2-dioxide heterocycles 115.251 Nevertheless, five-membered cyclic sulfamidates could be obtained when no alternative cyclization was possible. 1,3-Amino alcohols and related /2-amino acids are thus readily accessible from the same simple alcohols 113 by converting them into sulfamates 114 (Equation (90)). Furthermore, in comparison to the carbamate reaction (Scheme 9), the sulfamate substrates have... 

The sulfamate ester variant of this chemistry has already been shown to be a very powerful protocol for the syntheses of 1,3-amino alcohols and related /3-amino acids (Equation (90)), as well as iminium ion equivalents (Equation (91)). The further showcases of this chemistry are the total syntheses of the bromopyrrole alkaloids, manzacidins A and C (Scheme 13).234 The cyclic sulfamidate 129 was obtained diastereospecifically from sulfamate 128 using intramolecular rhodium-catalyzed G-H insertion. It was then found to react with sodium azide in NfN-dimethylformamide at room temperature after introduction of the Boc-activating group to afford the 1,3-diamino precursor 130 in 78% yield over 3 steps. Four subsequent manipulations afford the target structure 131. 

Partial sulfonation or sulfamide formation may stabilize a pigment toward flocculation. Combining partial sulfonation and chlorination will further improve the effect of each individual type of modification. Similar results are observed if carboxylic acid groups are introduced into the pigment molecule. 

The kinetics of the hydrolysis reactions of 4-amino-2-phenethyl- (354 R = PhCH2CH2) and 4-amino-2-cyclohexyl-2,3-dihydro-3-oxo-l,2,5-thiadiazole 1,1-dioxide (354 R = CeHii) have been investigated in the pH range 1-10 at 24-73 °C. The products are the corresponding new compounds 2-anuno-2-[(A -substituted-sulfamoyl)imino]acetic acid salts (355 R = PhCH2CH2 or CeHn) which hydrolyse further, in a slow reaction, to the sulfamide and oxalic acid derivatives. ... 

For sulfamides with larger alkyl groups (C3 to Cg) the following j)rocedure is preferred. To a stirred mixture of 135 g. (1.00 mol( ) of sulfuryl chloride and 500 ml. of chloroform is added, dropwise and with cooling to —10° to —5°, a solution of 316 g. ( (.00 moles) of pyridine in 400 ml. of chloroform followed by, with cooling to —5° to 0°, a solution of 2.5 moles of alkylamine in 600 ml. of chloroform. After addition is complete the mixture is stirred for 30 minutes at room temperature and then evap-ora(,( d under reduced pressure to a thick brown liquid, to wbic li aqueous 2M hydrochloric acid is added until the pyridine dissolves. On cooling of the acidic solution the crystalline MiiHaiMidc precipitates and is filtered. Any dissolved sulfamide limy be recovered by extraction of the filtrate with ether. Tb( crude product may be purified by recrystallization from bd )), cf.hanol. 

A number of other secondary nitramide explosives have been prepared from the action of mixed acid on the parent amide. Treatment of sulfuryl chloride with two equivalents of ethanolamine, followed by nitration of the resulting sulfamide (64) with mixed acid, yields the nitramide explosive A, A -dinitro-A, A -bis(2-hydroxyethyl)sulfamide dinitrate (65). " ... 

Intermolecular reactions of hydroxylamines with secondary alkyl halides and mesylates proceed slower than with alkyl triflates and may not provide sufficiently good yield and/or stereoselectivity. A nseful alternative for these reactions is application of more reactive anions of 0-alkylhydroxamic acids or 0-alkoxysulfonamides ° like 12 (equation 8) as nucleophiles. The resulting Af,0-disubstituted hydroxamic acids or their sulfamide analogs of type 13 can be readily hydrolyzed to the corresponding hydroxylamines. The same strategy is also helpful for synthesis of hydroxylamines from sterically hindered triflates and from chiral alcohols (e.g. 14) through a Mitsunobu reaction (equation 9). 

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>. 

In the case of the thiazolidinedioxides (38), the increased acidity of the cyclic sulfamide determines the reactivity. Metallation (NaH) occurs at N—H producing an anion which is readily alkylated <93TL4705>. Treatment with triphenylphosphine produces a stable betaine which can be used to couple alcohols and acids in a variant of the Mitsunobu reaction <94JOC2289>. 

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