Tertiary’ amines, neutralization

TABLE 16.1 Structures of tertiary amines, melting points, and ionic conductivities for tertiary amines neutralized with an equimolar amount of HTFSI... 

Derivatives with 3-nitrophthalic anhydride. 3-Nitrophthalic anhydride reacts with primary and secondary amines to yield nitro-phthalamic acids it does not react with tertiary amines. The phthalamic acid derived from a primary amine undergoes dehydration when heated to 145° to give a neutral A -substituted 3-nitrophthalimide. The phthalamic acid from a secondary amine is stable to heat and is, of course, soluble in alkali. The reagent therefore provides a method for distinguishing and separating a mixture of primary and secondary amines. 

Amines are powerful nucleophiles which react under neutral or slightly basic conditions with several electron-accepting carbon reagents. The reaction of alkyl halides with amines is useful for the preparation of tertiary amines or quaternary ammonium salts. The conversion of primary amines into secondary amines is usually not feasible since the secondary amine tends towards further alkylation. 

The oxidation of higher alkenes in organic solvents proceeds under almost neutral conditions, and hence many functional groups such as ester or lac-tone[26,56-59], sulfonate[60], aldehyde[61-63], acetal[60], MOM ether[64], car-bobenzoxy[65], /-allylic alcohol[66], bromide[67,68], tertiary amine[69], and phenylselenide[70] can be tolerated. Partial hydrolysis of THP ether[71] and silyl ethers under certain conditions was reported. Alcohols are oxidized with Pd(II)[72-74] but the oxidation is slower than the oxidation of terminal alkenes and gives no problem when alcohols are used as solvents[75,76]. 

Allylation under basic conditions. Allylation can be carried out under basic conditions with allylic acetates and phosphates, and under neutral conditions with carbonates and vinyloxiranes. The allylations under neutral conditions are treated separately in Section 2.2.2.1 from those under basic conditions. However, in some cases, allylations of the same substrates are carried out under both basic and neutral conditions to give similar results. These reactions are treated together in this section for convenience. Allylic acetates are widely used for Pd-catalyzed allylation in the presence of bases tertiary amines or NaH are commonly used[6,7,4l]. As a base, basic alumina or ICF on alumina is conveniently used, because it is easy to remove by filtration after the reaction[42]. Allyl phosphates are more reactive than acetates. The allylation with 40 proceeds stepwise. At first allylic phosphate reacts with malonate and then allylic acetate reacts with amine to give 41(43]. 

Reductive amination has been successfully applied to the preparation of tertiary amines from carbonyl compounds and secondary amines even though a neutral mine is not possible m this case... 

To analy2e fatty amines, both wet and instmmental methods of analysis are used. Wet methods routinely used are total amine value (ASTM Method D2073) combining weight or neutralization equivalent primary, secondary, and tertiary amine content (ASTM Method D2083) moisture, Kad-Fischer (ASTM Method D2072) and iodine value, measure of unsaturation (ASTM Method D2075). These provide important information on physical and chemical characteristics of the amine products used in various appHcation areas (8,76,81). In addition to the ASTM methods available, the American Oil Chemists Society has developed methods of analysis for fatty amines (82). 

The majority of U(V1) coordination chemistry has been explored with the trans-ddo s.o uranyl cation, UO " 2- The simplest complexes are ammonia adducts, of importance because of the ease of their synthesis and their versatihty as starting materials for other complexes. In addition to ammonia, many of the ligand types mentioned ia the iatroduction have been complexed with U(V1) and usually have coordination numbers of either 6 or 8. As a result of these coordination environments a majority of the complexes have an octahedral or hexagonal bipyramidal coordination environment. Examples iuclude U02X2L (X = hahde, OR, NO3, RCO2, L = NH3, primary, secondary, and tertiary amines, py n = 2-4), U02(N03)2L (L = en, diamiaobenzene n = 1, 2). The use of thiocyanates has lead to the isolation of typically 6 or 8 coordinate neutral and anionic species, ie, [U02(NCS)J j)/H20 (x = 2-5). 

For more selective hydrogenations, supported 5—10 wt % palladium on activated carbon is preferred for reductions in which ring hydrogenation is not wanted. Mild conditions, a neutral solvent, and a stoichiometric amount of hydrogen are used to avoid ring hydrogenation. There are also appHcations for 35—40 wt % cobalt on kieselguhr, copper chromite (nonpromoted or promoted with barium), 5—10 wt % platinum on activated carbon, platinum (IV) oxide (Adams catalyst), and rhenium heptasulfide. Alcohol yields can sometimes be increased by the use of nonpolar (nonacidic) solvents and small amounts of bases, such as tertiary amines, which act as catalyst inhibitors. 

For larger cryptands [6] (Cox et al., 1978), the protonation/deprotonation kinetics have also been measured. Table 4 lists the kinetic and the equilibrium data for such cryptands. When compared to the neutralization of protonated tertiary amines by OH, the reaction of the second smallest protonated cryptand [2.1.1] H is 10 to 10 times slower (Cox et al., 1978), indicating a strong shielding and possibly an i -orientation of the proton. For the [2.2.1] cryptand, no k and k-i values could be calculated, probably due to a fast pre-equilibrium between in,in- and m,OMt-conformations. 

An alternative approach to increase the oxidation rate is the use of alkaline solutions, because bases enhance the reactivity of L-sorbose and weaken the adsorption strength of 2-KLG. Unfortunately, the rate enhancement at higher pH is accompanied by a drop in selectivity due to the poor stability of 2-KLG in alkaline solutions. To circumvent this problem, we have modified the platinum catalysts by adsorbed tertiary amines and carried out the oxidation in neutral aqueous solution [57], This allowed to enhance the rate without increasing the pH of the bulk liquid, which leads to detrimental product decomposition. Small quantities of amines (molar ratio of amine sorbose = 1 1700, and amine Pts = 0.1) are sufficient for modification. Using amines of pKa a 10 for modification, resulted in a considerable rate enhancement (up to a factor of 4.6) with only a moderate loss of selectivity to 2-KLG. The rate enhancement caused by the adsorbed amines is mainly determined by their basicity (pKa). In contrast, the selectivity of the oxidation was found to depend strongly on the structure of the amine. 

Summary New lyophilic cationic silicone surfactants have been synthesized by direct quatemization of halogenated siloxanyl precursors or by transformation of these precursors into tertiary amines with a subsequent quatemization step. After transformation of the precursors into secondary amines, reaction with maleic anhydride and neutralization, new anionic products were obtained. 

To synthesize new surfactants, having incorporated both structural elements, the known siloxanyl modified halogenated esters and ethers of dicyclopentadiene [5] were treated with different amines according to the reaction scheme. Triethylamine yielded quaternary ammonium salts directly. Alternatively, after reaction with diethylamine or morpholine, the isolated siloxanyl-modified tertiary amines were also converted to quaternary species. To obtain anionic surfactants, the halogenated precursors were initially reacted with n-propylamine. In subsequent reaction steps the secondary amines formed were converted with maleic anhydride into amides, and the remaining acid functions neutralized. Course and rate of each single reaction strongly depended on the structure of the initial ester or ether compound and the amine applied. The basicity of the latter played a less important role [6]. 

Interestingly, bases and water have different effect on stability of BENA and intermediate SENA. Additives of tertiary amines stabilize SENAs (191), whereas bases cause spontaneous decomposition of BENAs. SENAs are hydrolytically unstable, whereas BENAs are inert toward water under neutral conditions. 

The TEAF system can be used to reduce ketones, certain alkenes and imines. With regard to the latter substrate, during our studies it was realized that 5 2 TEAF in some solvents was sufficiently acidic to protonate the imine (p K, ca. 6 in water). Iminium salts are much more reactive than imines due to inductive effects (cf. the Stacker reaction), and it was thus considered likely that an iminium salt was being reduced to an ammonium salt [54]. This explains why imines are not reduced in the IPA system which is neutral, and not acidic. When an iminium salt was pre-prepared by mixing equal amounts of an imine and acid, and used in the IPA system, the iminium was reduced, albeit with lower rate and moderate enantioselectivity. Quaternary iminium salts were also reduced to tertiary amines. Nevertheless, as other kinetic studies have indicated a pre-equilibrium with imine, it is possible that the proton formally sits on the catalyst and the iminium is formed during the catalytic cycle. It is, of course, possible that the mechanism of imine transfer hydrogenation is different to that of ketone reduction, and a metal-coordinated imine may be involved [55]. 

The electrophiles in such reactions can be either aryl halides or triflates, possessing electron-rich, neutral or electron-poor ring systems, whereas amines can range from aliphatic to aromatic and primary to tertiary amines. The Pd-catalyzed C—N bond formation works both inter- and intramolecularly. 

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