Tertiary amines, derivatives

Use has been made of the C-N cleavage in the conversion of the bicyclic tertiary amines, derived from the 4tc + 2tc cycloaddition of pyrroles and isoindoles with benzynes, into aromatic systems, e.g. naphthalen-l,4-imines and anthracen-9,10-imines yield naphthalenes and anthracenes with the extrusion of the nitrogen bridge [24] in yields which are higher than those obtained by standard oxidation procedures. 

Kinetics studies carried out in acetonitrile solutions provided a similar picture for the mechanism of peroxidation. Studies were carried out for three related tertiary amine-derived ligands /V,/V-bis(2-pyridylmcthyl)glycinc, /V-(2-pyridylmcthyl)imin-odiacetic acid, and AK2-amidomethyl [iminodiacetic acid [14], The kinetics studies... 

The same rule obtains for the secondary and tertiary amines derived from the three nitranilines. 

Pilocarpine is unique among the cholinergic agents in that it is a tertiary amine derivative, whereas the majority of the members of this class are quaternary ammonium compounds. It has been demonstrated (104,105) that pilocarpine loses its activity when it is measured at pH 9, whereas acetylcholine does not, suggesting that pilocarpine acts in its ionized form, i.e., its activity decreases with increasing pH. 

In other investigations by the author [2,3] additional positive resists compositions were prepared containing either imidazole, (11), or tertiary amine derivatives, (III), respectively, and then blended with the select copolymer, (IV), as illustrated. 

Preparative Methods the title reagent is prepared by the treatment of (IR, 25)-(—)-norephedrine with 1,4-dibromo-butane and NaHCOs in toluene. This approach can be modified to form a wide variety of cyclic and acyclic tertiary amine derivatives. The enantiomeric reagent has also been formed from (+)-norephedrine. 

Recently Betrand et al. have reported the sensitized intermolecular addition of tertiary amines derived from pyrrolidines to (5R)-5-menthyloxy-2[5//]-furanone (328) using ketonic sensitizers (Scheme 73, Table 13) [329]. 

Planar chiral compounds should also be accessible from the chiral pool. An example (with limited stereoselectivity) of such an approach is the formation of a ferrocene derivative from a -pinene-derived cyclopentadiene (see Sect. 4.3.1.3 [81]). A Cj-symmetric binuclear compound (although not strictly from the chiral pool, but obtained by resolution) has also been mentioned [86]. Another possibility should be to use the central chiral tertiary amines derived from menthone or pinene (see Sect. 4.3.1.3 [75, 76]) as starting materials for the lithiation reaction. In these compounds, the methyl group at the chiral carbon of iV,iV-dimethyl-l-ferrocenyl-ethylamine is replaced by bulky terpene moieties, e.g., the menthane system (Fig. 4-2 le). It was expected that the increase in steric bulk would also increase the enantioselectivity over the 96 4 ratio, as indicated by the results with the isopropyl substituent [118]. However, the opposite was observed almost all selectivity was lost, and lithiation also occurred in the position 3 and in the other ring [134]. Obviously, there exists a limit in bulkiness, where blocking of the 2-position prevents the chelate stabilization of the lithium by the lone pair of the nitrogen. 

Many surfactants are made from petroleum with hazardous reagents. Sulfur trioxide was used with the carcinogen benzene to make the alkylbenzenesulfonates described earlier. The carcinogen ethylene oxide is used to make many nonionic surfactants from phenols and long-chain alcohols. A common surfactant, sodium dodecyl sulfate, is made from an alcohol derived from coconut oil by reduction followed by treatment with sulfur trioxide. Long-chain tertiary amines derived from natural fats and oils are quat-ernized with methyl chloride. Perhaps this can be done with... 

Feng and Wilson (243) prepared some tertiary amines derived from ephedrine the quaternary ammonium halides of ephedrine have been described by Feng (244). 

In 2008, the Bode group documented a convenient solution to the synthesis of stereochemically defined tertiary amine derivatives via NHC-catalyzed formal homoenolate additions to ketimines derived from saccharin with low catalyst loading (0.5 mol%). ° This methodology features high activity of the catalyst, cfs-selectivity, and superiority of aprotic solvents. Based on detailed... 

Figure 2.2 Tertiary amines derived from cinchona alkaloids.

The workhorse amphoteric surfactants are the alkyl- and alkylamidopropyl betaines, containing C8-C18 linear chain distributions that are derived from coconut or palm kernel oil, or ethylene-based alpha olefins. The alkyl betaines are prepared from ADMA feedstocks that are typically derived from alpha olefins and dimethyl amine throngh hydrohalogenation and alkylation reaction steps. The alkylamidopropyl betaines are based on tertiary amines derived from whole triglycerides or their fractionated derivative fatty acids or methyl esters reacted with DMAPA. 

Hlavka and Bitha have reported a photochemical reduction of a tertiary amine derivative of a tetracyclene (equation 103) ° . 

The first amino substituted boronic esters were tertiary amines derived from dibutyl (iodomethyl)boronate and secondary amines [58]. Mysteriously, ammonia did not yield the simple (aminomethyl)boronic ester, but ilure of a reaction does not prove anything. Subsequent rechecking with primary, secondary, and tertiary amines as reactants showed that primary amines with dibutyl (iodomethyl)boronate did not yield isolable primary (aminomethyl)boronic esters [59]. The tertiary amines and quaternary ammonium salts derived from secondary and tertiary amines were stable and easily isolable. 

As an extension of this work, the same authors have used polystyrene-supported proline as a recyclable catalyst in the Morita-Baylis-Hillman reaction of a range of aryl aldehydes with methyl or ethyl vinyl ketone. These reactions were performed in the presence of imidazole and provided a series of Morita-Baylis-Hillman adducts in moderate to high yields (17 88%) combined with high enantioselectivities of up to 95% ee (Scheme 2.55). This study represented the first example of supported proline as heterogeneous catalyst for the Morita-Baylis-Hillman reaction. In addition, Zhou et al. reported that these reactions could be eatalysed by combinations of L-proline with chiral tertiary amines derived from various readily available chiral sources, such as L-proline or (5)-a-phenylethylamine. In these conditions, the Morita-Baylis-Hillman adducts were obtained in reasonable chemical yields (34-97%) and low to good enantioselectivities (12 83% ee). In this study, it was demonstrated that the proline stereochemistry was the sole factor to determine the eonfiguration of the newly formed chiral centre. 

Isoindoles and isoindolines have been prepared from tertiary amines derived from 2-chlorobenzylamine, via aryne intermediates. ... 

The catalytic asymmetric dihydroxylation reaction developed by Sharpless (Sharpless asymmetric dihydroxylation [SAD]) allows the straightforward oxidation of alkenes 76 to the corresponding cw-diols 77 with good to excellent yields and enantioselectivities without suffering from the presence of oxygen and moisture. The core of the catalytic system is based on an Os(VIII) metal center that coordinates the alkenes and transfers an oxygen atom to it using KsFe (CN)6 as terminal oxidant in the presence of enantiopure tertiary amines derived by dihydroquinidine 78 or... 

The present invention relates to novel tertiary amines derived from bisphenols, diepoxides and aromatic secondary amines, to a process for their preparation and to their use as hardening accelerators for ethylenically unsaturated cold hardenable acrylic and polyester resins. 

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