Primary and secondary amine functions

Cyclization can also occur between primary and secondary amine functions that are adjacent on a ring. Thus, the following reaction has been used to prepare a bactericide [2] ... 

All excipient chemical reactions should be incorporated into the experimental design. For example, drugs that contain primary and secondary amines functionality undergo Maillard reactions with lactose and other reducing carbohydrates such as glucose and maltose under pharmaceutically reasonable conditions.This reaction should be considered during formulation development. Alternative excipients such as mannitol, sucrose, and trahalose, which are not subject to the Maillard reaction, should be used in place of lactose in such cases. 

Lu and Macosko (2004) and Lu et al. (2003) have prepared compatibilized blends of polyurethane with functionalized PP characterizing the blends by rheology, DMA, tensile properties, and morphology. Primary and secondary amine-functionalized PP were more efficient compatibilizers than was PP-g-MA. A degradative mechanism for copolymer formation involving polyurethane chain cleavage was postulated. See also Kobayashi et al. (2011) for related PE/TPU blends. 

Table 2.6 Reactive Polymers with Primary and Secondary Amine Functionalities...

Primary and secondary amine functional systems require a phenolic catalyst to react at ambient temperature and are characterised by a relatively slow cure. Tertiary amines are also used to crosslink qwxy functional acrylics. However, the reaction will only occur in the presence of a protonating agent, such as an acid or moisture. The slow cure of this system can be compensated for by using relatively hard polymers to give good physical drying. 

Based on this information, Lu and Macosko studied the compatibility of blends composed of functionalized PPs and TPU [107]. In this work, maleated PP (PP-g-MA), primary and secondary amine-functionalized PPs (PP-g-NH2 and PP-g-NHR, respectively) were blended with TPU. The compatibility of... 

Some materials such as water, alcohols, carboxylic acids and primary and secondary amines may be able to act simultaneously as proton donors and acceptors. Cellulose and poly(vinyl alcohol) are two polymers which also function in this way. 

Nearly every substitution of the aromatic ring has been tolerated for the cyclization step using thermal conditions, while acid-promoted conditions limited the functionality utilized. Substituents included halogens, esters, nitriles, nitro, thio-ethers, tertiary amines, alkyl, ethers, acetates, ketals, and amides. Primary and secondary amines are not well tolerated and poor yield resulted in the cyclization containing a free phenol. The Gould-Jacobs reaction has been applied to heterocycles attached and fused to the aniline. 

RAFT polymerization can be performed simply by adding a chosen quantity of an appropriate RAFT agent to an otherwise conventional radical polymerization. Generally, the same monomers, initiators, solvents and temperatures are used. The only commonly encountered functionalities that appear incompatible with RAFT agents are primary and secondary amines and thiols. 

N-hydroxylation is not restricted to primary and secondary amines. For example, nitrogen-based functional groups such as amides, amidino, guanidino, hydrazino, etc. that have at least one nitrogen-hydrogen bond are susceptible to N-hydroxylation. 

The next series of four preparations describe the synthesis and/or use of recently introduced reagents for functional group protection. The first in this series describes the preparation of 2-TRIMETHYLSILYLETHANE-SULFONYL CHLORIDE (SEC-C1), an effective reagent for protection of primary and secondary amines as the corresponding sulfonamide. The SES-protected amines are stable intermediates which can be readily purified treatment with CsF in DMF or TBAF in acetonitrile liberates the parent amine. The preparation of (l/S,2,S)-METHYL-30,40-(l, 2 -DIMETHOX YCYCLOHEXANE -l, 2 - DIYL) - a -d -M ANNOPYRANO-... 

Rovis and Vora sought to expand the utility in alpha redox reactions to include the formation of amides [116]. While aniline was previously demonstrated as an efficient nucleophile in this reaction (Scheme 29), attempts to develop the scope to include non-aryl amines as various primary and secondary amines resulted in low yields. The discovery of a co-catalyst was the key to effecting amide formation (Table 15). Various co-catalysts, including HOBt, HOAt, DMAP, imidazole, and pentafluorophenol, are efficient and result in high yields of a variety of amides including those involving primary and secondary amines with additional functionality. 

Figure 2.8, is generated, presenting peaks correspondent to functional groups, such as epoxide, primary and secondary amines, and hydroxyl. The values of the absorption bands for these groups can be found in the papers referenced earlier. The basic principle of all these methods is the comparison between the spectrum of reference substances and spectra of the reactants and products of a curing reaction subjected to radiation. A qualitative and quantitative identification of the components is then possible. 

Schultz and co-workers31 also described the preparation of a 2,6,9-trisubstituted purine library. A preformed 2-fluoro-6-(4-aminobenzylamino) purine was reductively aminated onto the BAL linker 12. Mitsunobu chemistry was employed to alkylate the C9 position on the support-bound intermediate (Scheme 4). Subsequently, SNAr chemistry was used to incorporate amines at C6. The newly introduced primary and secondary amines bear diverse functional groups and the Mitsunobu reaction allows for incorporation of primary and secondary alcohols lacking acidic hydrogens. The support-bound product 13 was cleaved with 90% TFA/10% H20 to give a library with HPLC purities ranging between 51 and 85%. 

An adequate set of kinetic equations must describe the rate at which functional groups (epoxides, primary and secondary amines, hydroxy groups), rather than individual species (monomers, dimers, i-mers), evolve during reaction. This assumes that the rate at which a functional group reacts does not depend on the size (finite or infinite) of the molecule to which it is attached. The implication of this hypothesis may be understood if we write Eqs (5.6) and (5.7) in terms of the formation of an activated complex. 

The differential reactivity of the sterically hindered and unhindered isocyanate groups of tolylene-2,4-diisocyanate facilitates the stepwise conjugation of hapten (R) and protein (P) amino groups (Fig. 3, Rn 7). jd.jj -Difluoro-m,m -dinitrobenzene (DFDNB) reacts with numerous functionalities including primary and secondary amines, imidazoles, and phenols to yield mixtures of conjugated materials (Fig. 3, Rn 8). This reaction is apparently harder to control than the diisocyanate reactions, but it is much more versatile. 

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