Tertiary amine functionality

In 159 and 163-166 the tertiary amine function is coordinated to the boron atom and transmits the electronic change due to the ester formation to the chromophore. In 160-162 the boron atom is directly connected to the chromophore. After the complexation of the saccharide, the change of the charge transfer, e.g., for 159 [249-251], or the fluorescence bands, e.g., for 160-166 [252-255], can be measured and interpreted. The most selective binding of n-glucose has been achieved with host 164 that forms a 1 1 complex with a macrocyclic structure (Scheme 1). 

In summary, the preparation of polyimidazolinones from polyamides containing a-aminoacid units (3, X = NH) can now be considered to be a general reaction provided that Rz and/or R3 are not hydrogen. When the polyamide has additional secondary or tertiary amine functionality in the backbone, cyclodehydration appears to be exceptionally facile. In the absence of amine functionality however, a catalyst is necessary to promote cyclization. Further studies of this new heterocyclic polymer system are ongoing in our laboratories. 

NADH, containing a tertiary amine functional group, has been readily determined by Ru(bpy)32+ ECL. However the oxidized form, NAD+, containing an aromatic secondary amine group produces virtually no ECL signal. This had led to a variety of indirect enzymic methods of analysis, where the activity of the enzyme results in the conversions between NAD+ and NADH. These are discussed in Sec. 8. 

Since the order of increasing CL intensity for alkyl amines reacted with Ru(bpy)32+ is tertiary amines > secondary amines > primary amines, pharmaceutical compounds bearing a tertiary amine function (e.g., antihistamine drugs [99], anticholinergic drugs [100], erythromycin [101], and its derivatives [102]) have been sensitively determined after HPLC separation (Table 3). The method was applied to the detection of d- and L-tryptophan (Trp) after separation by a ligand-exchange HPLC [103], The detection limits for d- and L-Trp were both 0.2 pmol per injection. Oxalate in urine and blood plasma samples has also been determined by a reversed-phase ion-pair HPLC (Fig. 18) [104], Direct addition of... 

Peripentadenia is a monotypic genus of the family Elaeocarpaceae represented by Peripentadenia mearsii (C. T. White) L. S. Smith, a tree growing in rain forests of northern Queensland. Besides unidentified minor alkaloids, the species yields one major alkaloid, peripentadenine (49) (87). Its molecular formula, C22H34N203, was established by high-resolution mass spectroscopy the presence of phenol, ketone, secondary amide, and tertiary amine functionalities was deduced from examination of spectroscopic data. 

From the first transition state (TSl, Fig. 1), the reaction path leads to the tetrahedral intermediate 1 (INTI). In the latter, the proton transfer from methanol to the tertiary amine function is completed (from 1.183 to 1.059 A), and the negative charge at the former carbonyl oxygen atom reaches its maximum. This charge is compensated by a further shortening of the bifurcated hydrogen bonds to 2.040 A (-0.103 A) and 1.765 A (-0.096 A) (Fig. 1). The thiourea moiety thus forms an oxyanion hole similar to the amide groups of the serine protease backbone [41]. 

Chen and co-workers utilized the chiral bifunctional catalysts to directly access vinylogous carbon-carbon bonds via the asymmetric Michael addition of a,a-dicy-ano-olefms to nitro-olefms [102]. The scope of the reaction was explored with a variety of substituted a,a-dicyano-olefins and P-substituted nitro-olefms (Scheme 50). The authors propose the catalysf s tertiary amine functionality depro-tonates the cyano-olefm, activating the nucleophile to add to the -face of the pre-coordinated nitro-olefm. 

With Secondaiy and Tertiary Amine Functions in Chiral Macrocyclic Polyether Rings. 264... 

Scheme 6.38 Ring-opening polymerization of L-lactide catalyzed by tertiary amine-functionalized thiourea rac-12.

The Takemoto group synthesized a series ofdiaminocyclohexane-based thiourea derivatives (e.g., 12, 40, 57, and 58) for catalysis of the Michael addition [149-152] ofmalonates to trons-j3-nitrostyrenes (Figure 6.18) [129, 207]. In the model, Michael addition of diethyl malonate to trons-]3-nitrostyrene at room temperature and in toluene as the solvent tertiary amine-functionalized thiourea 12 (10mol% loading) was identified to be the most efficient catalyst in terms of catalytic activity (86%... 

Berkessel and co-workers synthesized a library of structurally diverse tertiary amine-functionalized catalyst candidates incorporating a chiral 1,2- or 1,4-diamine chiral backbone [231, 232, 246]. Structure-efficiency studies through sequential modification of the diamine backbone, the tertiary amine functionality, the (thio) urea N-substituents as well as of the amide substituent pattern, exemplarily illustrated a Jacobsen-type 1,2-diamine-based structure (figure 6.24), identified... 

Chen et al. identified (R,R)-l,2-diphenylethylenediamine-derived tertiary amine-functionalized thiourea 79 (20mol% loading), an analog of Takemoto s bifunc-... 

Figure 6.26 Multiple hydrogen-bonding tertiary amine-functionalized thioureas screened in the asymmetric Michael reaction between trans-P-nitrostyrene and acetylacetone at 10mol% loading.

Figure 6.49 Binaphthyl-derived tertiary amine-functionalized bifunctional thiourea derivatives screened in the MBH reaction between 2-cyclohexen-l-one and 3-phenylpropionaldehyde at rt in dichloromethane.

In 2008, Tang and co-workers reported the utilization of tertiary amine-functionalized saccharide-thiourea 211 as a bifunctional hydrogen-bonding catalyst for the enantioselective aza-Henry [224] (nitro-Mannich) addition [72] of... 

Murugan E, Sherman RL Jr, Spivey HO, Ford WT. Catalysis by hydrophobically modified poly(propylenimine) dendrimers having quaternary ammonium and tertiary amine functionality. Langmuir 2004 20 8307-8312. 

Mercaptopropionic acid has been used as a scavenger in detritylation of protected imidazoles. In the purification, A-21 tertiary amine-functionalized resin 23 sequestered excess of this acidic reagent, the tritylated byproduct formed from it, and TFA (reaction 6).32... 

Elguero and Espada29S have used this dealkylation reaction with quaternary salts of heterocyclic compounds. Another application is the preparation of tertiary amines functionalized in the <5 position.296 In these reactions, the ammonium salt 196 is both the catalyst and the reagent. 

The structures of some of the better known plant alkaloids are shown in Figure 23-1. You will recognize some of them by name even if you have never seen their structures before. Many of the alkaloids are polycyclic structures and have other functional groups in addition to basic nitrogen. You will see that the nitrogens of alkaloids frequently are tertiary amine functions. 

Weak-base resins have primary, secondary or tertiary amine functional groups and, in neutral or alkaline solution, the amines are in the free-base (un-ionized) form and have no ion-exchange properties. In acidic solution, the amine groups are protonated and extract anions according to the following equations ... 

On the modem plants employing the Bufflex flowsheet, uranyl sulfate is stripped from the resins with the bisulfate anion. The eluate contains about 1 M sulfuric acid since this is the optimum concentration for the subsequent solvent-extraction process at lower acid concentrations, the tertiary amine in solvent extraction is only partially ionized, which reduces its capacity for uranyl sulfate, whereas at higher acid concentrations the bisulfate anion begins to compete with the uranyl sulfate anion for tertiary amine functional groups. 

The acrylic weak base resins are synthesized from copolymers similar to those used for the manufacture of weak acid cation-exchange resins. For example, under appropriate temperature and pressure conditions, a weak acid resin reacts with a polyfunctional amine, such as dimethylaminopropylamine [109-55-7] (7) to give a weak base resin with a tertiary amine functionality. 

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