Amines, 738 table

Tertiary Aliphatic and Aromatic Amines, Table IV, lOOC. 

Trace Amines. Table 1 The trace amine-associated receptor (TAAR) family... 

Tacticity of VIA A is influenced by solvent,90 9 the presence of amines (Table 8.3)90 and complcxation. PYIAA appears more isotactic when formed in a nonhydrogen-bonding solvent,90 95 Polymerization of MAA in CHCh in the presence of 14 or 15 also yields a more isotactic polymer90 Polymerization of zinc complexes of MAA also yields more isotaclic polymers,9 >... 

The strong electronegativity of the fluorinated substituents is reflected in the effect that this group has upon the acidity of alcohols and carboxylic acids, as well as the effect it has on the basicity of amines (Tables 1.3-1.5). 

If the more activated alkene 2-vinylpyridine is used in place of styrene with the same catalysts and the same range of substrates, anti-Markovnikoff hydroamination is also found. Thus, N-[2-(2 -pyridyl)ethyl]piperidine was isolated in 53% yield from reaction of 2-vinylpyridine with piperidine in the presence of [Rh(COD)2]+/2PPh3 under reflux. N H addition was observed with other amines, the remaining product in all cases being primarily that from oxidative amination (Table 12). When the catalytic reaction was run in the absence of phosphine, the yield of hydroamination product increased dramatically.171... 

Despite the vivid 27 kcal mol-1 variation in TB splitting (Ae , dashed line) in Fig. 3.72(a), the total energy (Eioi, solid line) exhibits only the typical 2 kcal mol-1 variations of an ordinary alkyl amine (Table 3.23). Thus, the variations in Ae do not seem to reflect significant variations in stability or localization of the parent neutral species. 

In 2001, the preparation of allylytterbium bromide and the synthesis of homoallylic alcohols using allylytterbium bromide were reported.39 393 Ytterbium metal was found to be activated by a catalytic amount of Mel at 0 °C in THF to produce allylytterbium bromide 66 (Equation (11)). The allylation reaction of a wide range of aromatic aldehydes and ketones proceeded at ambient temperature or less in good to high yields (Table 2). Imines also reacted with allylytterbium bromide to afford homoallyl amines (Table 3). 

In summary, the reaction of osmium tetroxide with alkenes is a reliable and selective transformation. Chiral diamines and cinchona alkakoid are most frequently used as chiral auxiliaries. Complexes derived from osmium tetroxide with diamines do not undergo catalytic turnover, whereas dihydroquinidine and dihydroquinine derivatives have been found to be very effective catalysts for the oxidation of a variety of alkenes. OsC>4 can be used catalytically in the presence of a secondary oxygen donor (e.g., H202, TBHP, A -methylmorpholine-/V-oxide, sodium periodate, 02, sodium hypochlorite, potassium ferricyanide). Furthermore, a remarkable rate enhancement occurs with the addition of a nucleophilic ligand such as pyridine or a tertiary amine. Table 4-11 lists the preferred chiral ligands for the dihydroxylation of a variety of olefins.61 Table 4-12 lists the recommended ligands for each class of olefins. 

Carboxylic acids were introduced by the reaction of the polysilane(II) with carboxylic acid anhydrides in the presence of an amine. Table 2 shows the results. In order to examine the effect of unsaturated bonds and halides in the side chain on photolysis, double bonds or chloride groups were introduced with the carboxylic acid. Polysilanes(III) were also soluble in polar solvents and basic aqueous solution. The solubility in tetramethyl ammonium hydroxide aqueous solution(TMAH) depended strongly... 

Comparison of IP( n) values of cyclic secondary amines (Table 6) with those of the respective 1-methyl derivatives (Table 7) reveals that the effect of the additional methyl group decreases from 0.6 eV in aziridine to 0.1 eV in hexahydroazepine (hexa-methyleneimine). 

The mn ionizations of tertiary aliphatic amines (Table 5) are mostly lower than 9 eV and thus small enough for an electron donor in charge-transfer (CT) interactions. Mutai and collaborators64 have studied intramolecular CT interaction in a series of 1 -( >-dimethylaminoalkyl)-4-nitrobenzenes. 

Ten years ago Rorabacher (13) observed the substitution rate constants for aquonickel(II) ion with different amines (Table II). There is a decrease in the rate constants by a factor of 14 in going from ammonia to dimethylamine. If nickel-(II) substitution reactions are dissociative, then why is the effect this large Is this a steric effect with some associative contribution or is it an outer-sphere effect There has been surprisingly little investigation of the nature of the entering ligand so far as its bulk or its nucleophilicity is concerned even for what have been generally considered as simple substitution reactions. 

This highly stereoselective procedure where four stereocenters are fixed in one pot can be applied to other nitroaldehydes. Thus, the nitrocychtols are easily isolated in good yields. The reduction of the nitro group provides the corresponding amines. Tables 6.1 and 6.2 give details of some other examples, in particular the condensation of (3/f)-3-hydroxy-4-nitrobutyraldehyde. 

Protected primary allylic amines were generated from allylic carbonates and ammonia equivalents. Iridium-catalyzed allylic substitution has now been reported with sulfonamides [90, 91], imides [89, 91-93], and trifluoroacetamide [89] to form branched, protected, primary allylic amines (Table 5). When tested, yields and selectivities were highest from reactions catalyzed by complexes derived from L2. Reactions of potassium trifluoroacetamide and lithium di-tert-butyhminodi-carboxylate were conducted with catalysts derived from the simplified ligand L7. Reactions of nosylamide and trifluoroacetamide form singly-protected amine products. The other ammonia equivalents lead to the formation of doubly protected allylic amine products, but one protecting group can be removed selectively, except when the product is derived from phthalimide. 

Dipole moments from 6-31G and 6-311+G calculations are nearly identical both for the amines (Table 10-3) and for the full set of molecules found in Appendix AlO. Comparison of Figures 10-3 and 10-4 further drives home the point. It is difficult to justify use of the larger basis set for this purpose. On the other hand, dipole moments resulting from all density functional models (including local density models) and from MP2 models, display some sensitivity to basis set. In most (but not all) cases, agreement with experiment improves, as generally reflected by the mean absolute errors in Table 10-4, and by... 

Fluorescence of PDC is also quenched by amines. The ordering of reactivity is tertiary > secondary > primary, which follows inversely the ionization potential (Table 9.13). The results are explained as indicating that PDC undergoes photoreduction by amines, thereby forming triplet charge-transfer intermediates as the primary step in quenching. Therefore, the mechanism of the PDC reaction is not the same as the proposed mode of reaction of PDC, which involves direct formation of an yhde intermediate by electrophilic attack on the lone-pair electrons of the amine (Table 9.13). ... 

Most local anesthetic agents consist of a lipophilic group (eg, an aromatic ring) connected by an intermediate chain via an ester or amide to an ionizable group (eg, a tertiary amine) (Table 26-1). In addition to the general physical properties of the molecules, specific stereochemical configurations are associated with differences in the potency of stereoisomers (eg, levobupivacaine, ropivacaine). Because ester links are more prone to hydrolysis than amide links, esters usually have a shorter duration of action. 

Boc) and 7V-(benzyloxycarbonyl) (Z) protective groups are stable under these conditions. In contrast to that, the jV-(4-methoxybenzyloxycarbonyI) (Moz) protecting group can readily be cleaved by the cation radical of tris(2,4-dibromophenyl)amine (Table 11, No. 13) ° >. 

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