Sulfur diamides

Figure 2-31. Sample SOfile for sulfamide (sulfuric diamide).

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). 

Sulfur diamides (diaminosulfanes) are obtained by the action of sulfur chlorides with an aliphatic secondary amine (Eq. 10.10). ° The monoselanes Se(NR2)2 (R = Me, Et) have also been prepared. Polyselanes Scx(NR2)2 (x = 2 - 4, NR2 = morpholinyl x = 4, NR2 = piperidinyl) are formed in the reaction of elemental selenium with the boiling amine in the presence of Pb304. ... 

A few examples of other functional nomenclature are also included in Table IR-8.2 e.g. phosphoryl chloride, sulfuric diamide). These particular names are well entrenched and can still be used, but this type of nomenclature is not recommended for compounds other than those shown. Again, additive and substitutive names may always be constructed, as exemplified in the Table. 

AgN OAg mw 523.64 dark red crysts. Insol in acet, ethanol, eth, carbontetra-chloride, chlf, w, etc. Prepn is by addn of 100ml of coned aq ammonia to 4.8g of sulfuric diamide and 17g of Ag nitrate under red light. After conen of the resultant mixt to 10ml by means of a rotary evaporator, N, N -diargentosulfuric diamide is pptd. This salt is filtered off and w washed. The disilver salt is then converted to the trisilver salt by addn of an excess of 5% ammonia. The desired tetrasilver salt is subsequent-... 

Two methylations of levan by means of dimethyl sulfate and potassium hydroxide (not sodium hydroxide) followed by one inethylation with methyl iodide and silver oxide yielded trimethyllevan in 88% yield. This was purified by solvent fractionation over-all yield 75%, m. p. 145-146°, OCHs 45.9%. Trimethyllevan, hydrolyzed by heating at 95° for twenty-four hours with a dilute solution of sulfuric acid gave a 98.5% yield of a crystalline trimethyl-D-fructose. The trimethyl-D-fructose was proved940 to be 1,3,4-trimethyl-D-fructofuranose since oxidation with nitric acid gave a 97% yield of a dimethyl-2-keto-D-gluco-saccharic acid which was identified as the crystalline diamide (95% yield). 

A new class of sulfurated heterocycles - dithiadiazaphospholidine S-oxides 170 - was obtained by treatment of phosphonic diamide 168 with sulfur monochloride its precursor heterocycle 169 was detected in the mixture. However, it was found to be susceptible to oxidation and only S-oxide 170 was isolated (1995CC1449 Scheme 88). 

Tris(dialkyl)stibines react with sulfur dioxide (equation 33), affording tetraalkylsulfurous diamides and an unidentified antimony/nitrogen compound.101... 

One of the possibilities to convert the amino nitrile (R,S)-3 to (5)-terMeucine (7) is shown in the reaction sequence of Scheme 25.3. Hydrolysis of the aminonitrile (R,S)-3 to the diamide 5 was performed in concentrated sulfuric acid. Removal of the phenylacetamide group using H2 and Pd-C gave (S)-tert-leucine amide (6). Acidic hydrolysis of the amide 6 yielded (S)-tert-leucine (7) in 73% overall yield for the 3 steps and an enantiomeric excess of >98%. The overall yield for this nonoptimized protocol is 66% based on pivaldehyde. Obviously, other routes to convert the amino nitrile to the amino acid can be envisaged. As an example, by heating the diamide in sulfuric acid, after dilution with water, the diacid can be obtained that, after hydrogenolysis, affords the amino acid in 2 steps from the amino nitrile 3. 

The large group of inhibitors of free radical chain reactions are frequently used in combination with metal salts or organometallic stabilizers. They are amines, sulfur- or phosphorus-containing compounds, phenols, alcohols, or chelates. Aromatic phosphites at about 1 p.p.r. chelate have undesirable metal impurities and inhibit oxidative free radical reactions. Some of the more popular are pentaerythritol, sorbitol, melamine, dicyan-diamide, and benzoguanamine. Their synergistic effect is utilized in vinyl floors where low cost is imperative. 

Thio analogs of these compounds, for example, PhP(S)(NHR)2 can also be prepared similarly, from the corresponding thiophosphonic halides and amines or by oxidative addition of sulfur to diaminophosphines, RP(NR92 Phenylphosphonic acid diamides, PhP(Q)(NHBu )2 (Q = S, Se) were prepared from PhP(NHBfr)2 by oxidative addition of sulfur or selenium and the 0x0 derivative PhP(0)(NHBu )2 by oxidation with tert-butyl peroxide. Their lithiation produces unusual cyclic or polycyclic dUithium salts of the phosphonate dianions [PhP(Q)(NBfr)2] (Q = O, S, Se). The dimethylaluminum derivatives PhP(Q)(NBu )2AlMe2 (Q = S, Se) obtained from PhP(Q)(NHBu )2 with AlMes are fom-membered chelate rings. ... 

Similarly the Diels-Alder adduct of bis(methoxycarbonyl)sulfur diimide (R = COOCII3) is transformed to the vicinal dicarbamate. The (E)-anti vicinal tosyl diamide can be obtained by starting from ( ,Z)-2,4-hexadiene92. Similar results, with respect to selectivity, are found in the rearrangement ot Diels-Alder adducts of sulfur diimides and 1-substituted dienes93. 

This is a new reaction for the preparation of N-alkyl amides. Nitriles and various substituted cyano compounds are treated with active olefins in the presence of sulfuric acid. Reaction occurs at room temperature in glacial acetic acid or dibutyl ether solution. The use of hydrogen cyanide in the reaction leads to the formation of N-alkylformamides. /-Butyl alcohol and sodium cyanide are used in place of the olefin and hydrogen cyanide in the preparation of N-/-butylfotmamide (50%). The reaction has been extended to the synthesis of N-alkyl diamides from dinitriles and olefins or alcohols. ... 

Coordination of the diamide with the metal ion can occur in both a bidentate mode through both carbonyl oxygens or one carbonyl oxygen and the bridging oxygen/sulfur, or in a tridentate mode via both carbonyl oxygens and the bridging atom. ... 

Additional catalysts have also been proposed for the reaction of Et2Zn with aromatic aldehydes, including (proline derivative 2.13 (R = CPh2OH) [110] and a four-membered analog [646], (1S,2R)-1.61 (R = S02Tol), 2.47, and pyridine-derived aminoalcohols [110, 644, 651, 1173]. Other catalysts include sulfur derivatives of ephedra alkaloids [645, 728], the Li diamide of piperazine 2.46, diamines 1.64 (R = 2-Py) and other related 2-aminopyridines [367, 648, 649, 1174], p-Hydroxysulfoximines have also been used as catalysts in these reactions [1175], as has an oxazaborolidine derived from ephedrine [1176],... 

With iV-chloro compounds, sulfur in the valence states two or four is oxidized into the next highest level. Hence, sulfides or sulfanylbis(amines) are converted into sulfoxides or sulfurous acid diamides by known methods.47... 

A series of macrocycles containing two sulfur and two nitrogen atoms was prepared in yields of 37-64% from the appropriate diacid dichlorides and diamines (method Z-5) (Siegfried and Kaden, 1984). The cyclic diamides were reduced by borane in yields of 34-64%. The reaction of dimethylmalonyl... 

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