Amines sulfonate complexes

Ligno sulfonate—metal complexes are weaker complexes than those formed from amine-based complexing agents such as ethylenediaminetetracetic acid (EDTA). They are compatible with most pesticides /herbicides, but thek use in phosphate fertilisers is not recommended. 

Sulfonates react with a variety of nucleophiles. Synthesis of M A -bis(trifluoro-methyl)aminotnfluoromethanesulfonate and its reactions with nucleophiles were investigated [33] (equation 31) (Table 13). Nucleophilic attack occurs at either nitrogen or sulfur amines give complex mixtures [33]. Polyfluoroalkyl fluorosul-fates react with amines, alcohols, or alkoxides to yield polyfluoroalkyl sulfamates and dialkyl sulfates, respectively [34] (equation 32) (Table 13). In these reactions. 

With primary and secondary amines the reaction is more complex, leading eventually to the respective aminal and the amine sulfonate salt. Benzene reacts to give diphenylmethane in 94% yield. Toluene gives an isomeric mixture of ditolyl-methanes. The sulfonate cleaves a number of ethers. 

W-Functionalization. Pyridazine can be functionalized at the nitrogen position to form N-0, N-N, and N-C bonds. The resulting products enhance the reactivity at the Cs-position and provide a handle toward the formation of more complex heterocycles. For instance, pyridazine dissolved in an aqueous mixture of hydroxyl amine sulfonic acid (HOS A), potassium iodide, and potassium hydrogen carbonate affords the corresponding aminated pyridazine (eq 2). ... 

Primary nitroparaffins react with two moles of formaldehyde and two moles of amines to yield 2-nitro-l,3-propanediamines. With excess formaldehyde, Mannich bases from primary nitroparaffins and primary amines can react further to give nitro-substituted cycHc derivatives, such as tetrahydro-l,3-oxa2iaes or hexahydropyrimidines (38,39). Pyrolysis of salts of Mannich bases, particularly of the boron trifluoride complex (40), yields nitro olefins by loss of the amine moiety. Closely related to the Mannich reaction is the formation of sodium 2-nitrobutane-1-sulfonate [76794-27-9] by warming 1-nitropropane with formaldehyde and sodium sulfite (41). 

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). 

Sulfur trioxide reactivity can also be moderated through the use of SO adducts. The reactivity of such complexes is inversely proportional to their stabihty, and consequentiy they can be selected for a wide variety of conditions. Whereas moderating SO reactivity by adducting agents is generally beneficial, the agents add cost and may contribute to odor and possible toxicity problems in derived products. CeUulosic material has been sulfated with SO.—trimethyl amine adduct in aqueous media at 0 to 5°C (16). Sulfur trioxide—triethyl phosphate has been used to sulfonate alkenes to the corresponding alkene sulfonate (17). Sulfur trioxide—pyridine adduct sulfates oleyl alcohol with no attack of the double bond (18). 

Because phenoHc compounds are easily sulfonated, their sulfation must be accompHshed with mil der sulfating agents, eg, complexes of sulfur thoxide or chlorosulfonic acid with trimethyl amine, dimethylform amide, pyhdine, or dim ethyl a n i1 in e, in anhydrous or aqueous medium below 100°C (86-89). 

The major problem of these diazotizations is oxidation of the initial aminophenols by nitrous acid to the corresponding quinones. Easily oxidized amines, in particular aminonaphthols, are therefore commonly diazotized in a weakly acidic medium (pH 3, so-called neutral diazotization) or in the presence of zinc or copper salts. This process, which is due to Sandmeyer, is important in the manufacture of diazo components for metal complex dyes, in particular those derived from l-amino-2-naphthol-4-sulfonic acid. Kozlov and Volodarskii (1969) measured the rates of diazotization of l-amino-2-naphthol-4-sulfonic acid in the presence of one equivalent of 13 different sulfates, chlorides, and nitrates of di- and trivalent metal ions (Cu2+, Sn2+, Zn2+, Mg2+, Fe2 +, Fe3+, Al3+, etc.). The rates are first-order with respect to the added salts. The highest rate is that in the presence of Cu2+. The anions also have a catalytic effect (CuCl2 > Cu(N03)2 > CuS04). The mechanistic basis of this metal ion catalysis is not yet clear. 

Sulfonic acid strong acids Carboxylic acid weak acids Tertiary amine weak bases Quaternary amine strong bases Aminediacetic acid complex formers... 

SFC-FID is widely used for the analysis of (nonvolatile) textile finish components. An application of SFC in fuel product analysis is the determination of lubricating oil additives, which consist of complex mixtures of compounds such as zinc dialkylthiophosphates, organic sulfur compounds (e.g. nonylphenyl sulfides), hindered phenols (e.g. 2,6-di-f-butyl-4-methylphenol), hindered amines (e.g. dioctyldiphenylamines) and surfactants (sulfonic acid salts). Classical TLC, SEC and LC analysis are not satisfactory here because of the complexity of such mixtures of compounds, while their lability precludes GC determination. Both cSFC and pSFC enable analysis of most of these chemical classes [305]. Rather few examples have been reported of thermally unstable compounds analysed by SFC an example of thermally labile polymer additives are fire retardants [360]. pSFC has been used for the separation of a mixture of methylvinylsilicones and peroxides (thermally labile analytes) [361]. 

In the tris-pentafluorophenyl analog (TFPC), in contrast to other Co corroles, aromatic amines can substitute PPh3 to form six-coordinate trivalent bis(amine) complexes.788 Bis-chlorosulfon-ation of TFPC occurs regioselectively to give the 2,17-(pyrrole)-bis-chlorosulfonated derivative fully characterized as its triphenylphosphinecobalt(III) complex.789 The amphiphilic bis-sulfonic acid was also obtained. 

Prochiral imines can be hydrogenated to the corresponding amines with extremely high enan-tioselectivities in H20/ethyl ethanoate biphasic systems, using Rh1 complexes of sulfonated phosphines 342 The cationic rhodium complex [Rh(NBD)(131)]+ was an active catalyst for hydrogenation of 2-ethanamido-propenoic acid in aqueous solution.343... 

The reaction of alcohols with CO was catalyzed by Pd compounds, iodides and/or bromides, and amides (or thioamides). Thus, MeOH was carbonylated in the presence of Pd acetate, NiCl2, tV-methylpyrrolidone, Mel, and Lil to give HOAc. AcOH is prepared by the reaction of MeOH with CO in the presence of a catalyst system comprising a Pd compound, an ionic Br or I compound other than HBr or HI, a sulfone or sulfoxide, and, in some cases, a Ni compound and a phosphine oxide or a phosphinic acid.60 Palladium(II) salts catalyze the carbonylation of methyl iodide in methanol to methyl acetate in the presence of an excess of iodide, even without amine or phosphine co-ligands platinum(II) salts are less effective.61 A novel Pd11 complex (13) is a highly efficient catalyst for the carbonylation of organic alcohols and alkenes to carboxylic acids/esters.62... 

Apart from complex formation involving metal ions (as discussed in Chapter 4), crown ethers have been shown to associate with a variety of both charged and uncharged guest molecules. Typical guests include ammonium salts, the guanidinium ion, diazonium salts, water, alcohols, amines, molecular halogens, substituted hydrazines, p-toluene sulfonic acid, phenols, thiols and nitriles. 

Ionically bound complexes on sulfonated or aminated ion-exchange resins have been used, as have complexes adsorbed (van der Waals forces) onto silica gel and other supports. 

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