Amines example: amine

This reaction can also be utili2ed to prepare functionali2ed initiators by reaction of butyUithium with a substituted 1,1-diphenylethylene derivative. For example, polymers end functionali2ed with primary amine, tertiary amine, phenol, and bis(phenol) groups have been prepared in essentiaUy quantitative yield by using the reaction of butyUithium with the corresponding substituted (or protected) 1,1-diphenylethylene (87). 

Coordination Compounds. Palladium forms numerous complexes with ammonia and with simple amines. Examples ate [Pd(NH2)4] ... 

Nonionic surfactants perform well in nonpolar polymers such as polyethylene and polypropylene. Examples of nonionic surfactants ate ethoxylated fatty amines, fatty diethanolamides, and mono- and diglycetides (see Amines, fatty amines Alkanolamines). Amphoteric surfactants find Httle use in plastics (134). 

Dyes with better wetfastness and better affinity in neutral or weakly acid bath have been developed by introducing more hydrophobic amines. Examples are Cl Acid Blue 129 [6397-02-0] (120) Cl 62058), Cl Acid Blue 126 [72152-61-5] (121) (130), and Cl Acid Blue 230 [12269-82-8] (122) Cl 62075). However, uniform leveling cannot be obtained with these dyes. 

Some authors use O] instead of cr as the substituent constant in such correlations.) An example is provided by the aminolysis of phenyl esters in dioxane the substrates RCOOPh were reacted with -butylamine, and the observed first-order rate constants were related to amine concentration by = k2 [amine] kj [amine]. The rate constants kz and k could be correlated by means of Eq. (7-54), the reaction constants being p = +2.14, b = + 1.03 (for A 2) and p = -1-3.03,8 = -1-1.08 (for ks). Thus, the two reactions are about equally sensitive to steric effects, whereas the amine-catalyzed reaction is more susceptible to electronic effects than is the uncatalyzed reaction. 

Distinguish between alcohols, ethers, aldehydes, ketones, carboxylic acids, esters, and amines. (Example 22.6 Problems 15-18) 16,18... 

Carbon dioxide released into the steam ultimately dissolves in condensate to produce carbonic acid. This acid is normally controlled by neutralization and beyond to provide a pH level of over 8.0, via the use of appropriate amines or amine blends. Examples of neutralization reactions for morpholine and cyclohexylamine (CHA) are shown here ... 

Nitrogen analogs are known for some of these phosphorus compounds, but they are less stable because the resonance is lacking. For example, amine oxides, analogs of... 

The donor-acceptor formation can be considered by transfer of electrons from the donor to the acceptor. In principle one can assume donor-acceptor interaction from A (donor) to B (acceptor) or alternatively, since B (A) has also occupied (unoccupied) orbitals, the opposite charge transfer, from B to A. Such a view refers to mutual electron transfer and has been commonly estabUshed for the analysis of charge transfer spectra of n-complexes [12]. A classical example for a donor-acceptor complex, 2, involving a cationic phosphorus species has been reported by Parry et al. [13]. It is considered that the triaminophosphines act as donor as well as an acceptor towards the phosphenium cation. While 2 refers to a P-donor, M-donors are in general more common, as for example amines, 3a, pyridines, 3b, or the very nucleophilic dimethylaminopyridine (DMAP) [ 14], 3c. It is even a strong donor towards phosphorus trichloride [15]. 

Several examples of the photoaddition of amines and amine derivatives to olefins have been reported/921 Butylamine adds to 1-octene upon ultraviolet irradiation to produce 4-aminoalkane ... 

Aminosilicas have been widely studied for use in catalysis, either as a base catalyst or as a support for metal complexes (12). For example, amine functionalized silica can be used to catalyze the Knoevenagel condensation, an important C-C bond forming reaction. Also, the amine sites on the silica can be further functionalized to form supported imines, guanidine, and other species... 

For example, amine 140 was treated with 1,5-dibromopentane 141 to give the azoniaspirocycle 142 <1999RCB1696>. Carrying the reaction out under similar conditions with 1,2-dibromoethane gave the bis-addition species 143 as the major product rather than a spirocycle (Equation 32). There is always the need to pick reactants and conditions carefully to favor cyclization over k-addition. 

Fig. 24. Example amines included in the proton affinity study (Eq. 6)...

These telomerization reactions of butadiene with nucleophiles are also catalyzed by nickel complexes. For example, amines (18-23), active methylene compounds (23, 24), alcohols (25, 26), and phenol (27) react with butadiene. However, the selectivity and catalytic activity of nickel catalysts are lower than those of palladium catalysts. In addition, a mixture of monomeric and dimeric telomers is usually formed with nickel catalysts ... 

Aromatic amination by replacement of halogens with amines (example... 

An early example of this strategy is the palladium black catalyzed conversion of (Z)-2-buten-l,4-diol with primary amines (cyclohexyl amine, 2-aminoethanol, -hexyl amine, aniline) at 120 °C to give A-substituted pyrroles in 46-93% yield [119]. Trost extended this animation to the synthesis of a series of AT-benzyl amines 169 from the readily available a-acetoxy-a-vinylketones 168 [120]. This methodology allowed for the facile preparation of pyrrolo-fused steroids. 

Proton acceptor (Bronsted-Lowry base) example amine... 

If animal systems are chosen, preparations derived from fish (see, e.g., Kada, 1981) and birds (Parry et al., 1985) have been used. However, by far the most widely used and validated are those derived from rodents, in particular, the rat. Hamsters may be preferred as a source of metabolizing enzymes when particular chemical classes are being screened, for example, aromatic amines, heterocyclic amines, N-nitrosamines and azo dyes (Prival and Mitchell, 1982 Haworth et al., 1983). 

Compared with primary and secondary amines, tertiary amines are virtually unreac-tive towards carbenes and it has been demonstrated that they behave as phase-transfer catalysts for the generation of dichlorocarbene from chloroform. For example, tri-n-butylamine and its hydrochloride salt have the same catalytic effect as tetra-n-butylammonium chloride in the generation of dichlorocarbene and its subsequent insertion into the C=C bond of cyclohexene [20]. However, tertiary amines are generally insufficiently basic to deprotonate chloroform and the presence of sodium hydroxide is normally required. The initial reaction of the tertiary amine with chloroform, therefore, appears to be the formation of the A -ylid. This species does not partition between the two phases and cannot be responsible for the insertion reaction of the carbene in the C=C bond. Instead, it has been proposed that it acts as a lipophilic base for the deprotonation of chloroform (Scheme 7.26) to form a dichloromethylammonium ion-pair, which transfers into the organic phase where it decomposes to produce the carbene [21]. 

A few additional prodrug types are of interest in the present context. In common with the examples discussed earlier, these are prodrugs of active amines or amines that contain a carboxylate moiety, but would be difficult to classify with the prodrugs discussed in the above sections. 

There is no difference in the ability of photogeneration of radicals between systems that show photosubstitution and systems that do not, for example amines with 3,5-dinitroanisole and m-dinitro-benzene, respectively. This indicates that the formation of radicals from excited aromatic nitro-compounds in the presence of nucleophiles has no direct relation with the photosubstitution reaction. 

Interestingly, the reaction is clearly sensitive to substituent the absence of a carbonyl present in the reactant amide (95) above, with slight changes in electronic or conformational effects enough to perturb reaction outcome [84]. In the amine example below, the substituted pyrollidine (96) was not isolated, while a slight increase in chain length facilitated the desired cyclization to 97 (Scheme 37). 

In general, the reaction of unsaturated 5(4//)-oxazolones 497 with nitrogen nucleophiles effects ring opening to give the corresponding unsaturated acylamino amides 498 (Scheme 7.158). Depending on the nucleophile, for example, amines, hydrazines, oximes, and so on, the products obtained can be cyclized and this process allows the synthesis of a wide variety of new heterocyclic compounds. 

A similar mechanism was invoked by Ohshima and Kawabata (2) to account for their results in the nitrosation of tertiary amines and amine oxides. In applying these concepts to the nitrosative dealkylation of tetraalkyltetrazenes, Michejda al. 5) introduced an interesting variant by suggesting that immonium ions could be formed in two successive one-electron oxidation steps (for example by ferric ion oxidation of tertiary amine to the radical cation followed by radical abstraction of a hydrogen atom from the alpha position), rather than exclusively through the one-step removal of a hydride ion as nitroxyl. The resulting immonium ion was again considered to react directly with nitrite to produce the N-nitroso derivative. These reactions are summarized in Fig. 2b. 

Highly Lewis basic and nucleophilic functional groups are not compatible with zinc carbenoids. The methylation or ylide formation of heteroatoms is one of the most important side reactions of these reagents. For example, amines, thioethers and phosphines readily react with the zinc reagents to generate ammonium salts", sulfonium" and phosphonium ylides" ". Terminal alkynes generally lead to a large number of by-products". ... 

A wide variety of amines, including aryl alkyl amines, alkyl amines, and amino alcohols have been resolved on a multi-ton scale (Scheme 7.10) [7]. This method has been used with methyl ethers. For example the racemic (l-methoxy)-2-propylamine (R,S 19) can be separated to give the (S)-20 which is required for the synthesis of a corn herbicide (21) and produced at 2500 t/y [7, 30] (Scheme 7.11). 

Scheme 7.10 The resolution of chiral amines examples of the substrate range used by the BASF process demonstrated on a multi-ton scale.

---