Alkylamines, reaction with

Figure 22 5 shows what happens when a typical primary alkylamine reacts with nitrous acid Because nitrogen free products result from the formation and decomposition of diazonium ions these reactions are often referred to as deamination reactions Alkyl... 

The resihency and dyeabihty of poly(vinyl alcohol) fibers is improved by a process incorporating -hydroxybenzaldehyde to provide a site for the formation of a stable Mannich base. Hydroxyl groups on the fiber are converted to acetal groups by -hydroxybenzaldehyde. Subsequent reaction with formaldehyde and ammonia or an alkylamine is rapid and forms a stable Mannich base that is attached to the polymer backbone (94). 

Substituted Amides. Monosubstituted and disubstituted amides can be synthesized with or without solvents from fatty acids and aLkylamines. Fatty acids, their esters, and acid halides can be converted to substituted amides by reaction with primary or secondary aLkylamines, arylamines, polyamines, or hydroxyaLkylamines (30). Di- -butylamine reacts with oleic acid (2 1 mole ratio) at 200—230°C and 1380 kPa (200 psi) to produce di-A/-butyloleamide. Entrained water with excess -butylamine is separated for recycling later (31). 

In addition to being more basic than arylamines, alkylamines are also more nucleophilic. All the reactions in Table 22.4 take place faster with alkylamines than with arylanines. 

It is also possible to use salts of polyphosphoric acids, e.g., trimetaphosphate, as the phosphorylating agent in reaction with alkylamines, as is shown in Eq. (75). 

Copper phthalocyanine derivatives are well established as turquoise blue direct and reactive dyes for cellulosic fibres. Chlorosulphonation at the 3-position, followed by hydrolysis, yields sulphonated direct dyes such as Cl Direct Blue 86 (5.32 X = H) and Blue 87 (5.32 X = S03Na). Solubility and dyeing properties can be varied by introducing four chlorosulphonyl groups, some of which are hydrolysed and some converted to sulphonamide by reaction with ammonia or alkylamines. This approach is also the main route to reactive dyes of the copper phthalocyanine type. The reactive system Z is linked to a 3-sulphonyl site... 

For reaction of Ph3CS0C6H4N02-/> with a series of ArNH2 in 45% dioxan / Nu is +1.5 (Ciuffarin et al., 1971). For the step in (176) with rate constant kt, / Nu is also large, +1.25 (Senatore et ah, 1971). However, reaction of a series of alkylamines, RNH2, with Ph3CSOC6H4N02-/> has a / Nu value of only +0.6 (Ciuffarin et al., 1971). Whether this large difference in / Nu actually means that the transition state is reached much earlier in terms of degree of... 

Hindered di-t-alkylamines RNHBu1 (R = t-Bu, t-octyl or 1-adamantyl) have been synthesized from t-alkylamines as follows. Reaction with peracetic acid gave the nitrosoalkanes RNO, which were treated with t-butyl radicals, generated from t-butylhydrazine and lead(IV) oxide, to yield t-butyloxyhydroxylamines. Reduction with sodium naphthalide in THF gave the products (equation 12). The di-t-alkyl-amines are inert to methyl iodide and dimethyl sulphate but can be alkylated by methyl fluorosulphonate42. 

Reaction with all kinds of alkylamines and arylamines and with amino acid esters easily leads to replacement of the N-NO2 group. As can be expected, when chiral amino acid esters are used as reagents, the reaction occurs with retention of the configuration (Scheme III.30). See also the discussion on similar reactions with A-nitroimidazoles in Section III,A,5. 

This result is consistent with an equilibrium between an initially formed a-substituled allyl tellnroxide (resulting from the well-known regio-controlled electrophilic attack at the y-carbon) and the y-isomer (which is really the main product, as detected by NMR). In the snbseqnent reaction with amines, the more nucleophilic alkylamines attack the central carbon atom, giving rearranged products, whereas the less nucleophilic arylamines attack the terminal carbon, giving the thermodynamic y-product. 

The nitration of nitramine (153) with nitronium tetrafluoroborate, followed by neutralization of the resulting dinitraminic acid with ammonia, also generates ammonium dinitramide (152). Neutralization of this reaction with alkylamines, instead of ammonia, yields the corresponding alkylammonium salts of dinitramide. The nitration of ammonia with dinitrogen pentoxide (15 %) or nitronium salts like the tetrafluoroborate (25 %) yield ammonium dinitramide (152) through the initial formation of nitramine. 

Various alkylamino-artemisinins 155 were synthesized by the nucleophilic displacement of bromoartemisin 149, which was prepared in situ from 148 (Scheme 19), followed by reaction with alkylamines <2004AGE1381>. A more direct route involved treatment of 29a firstly with a mixture of NaBr and TMSCl and then with the amine <2006AGE2082>. HFIP can be used as an additive in the amination step to increase the yield <2005AGE2060>. Similar aminoartemisinins 155 (where NRR = NHAr) were prepared by reacting 29a with anilines, in the presence of a catalytic amount of pyridinium sulfate in pyridine, in good yields (e.g., Ar = Ph, 93% 72% ... 

Several chiral racemic alkylamines have been successfully resolved using hydrolase-catalyzed acylation reactions with esters as acyl donors. A few examples are described here (Table 4.2). 

Attachment of suitable linkers to the surface of silica can be achieved by transesterification with (3-aminopropyl)triethoxysilane, which leads to the support 2 (Figure 2.8) [198-200]. Alternatively, silica can be functionalized by reaction with alkyltri-chlorosilanes [201]. For the solid-phase synthesis of oligonucleotides, supports with a longer spacer, such as that in 3, have proven more convenient than 2 [202-206]. Supports 3, so-called LCAA-CPG (long chain alkylamine CPG [194,195]), are commercially available (typical loading 0.1 mmol/g) and are currently the most commonly used supports for the synthesis of oligonucleotides. For this purpose, protected nucleosides are converted into succinic acid monoesters, and then coupled to LCAA-CPG. CPG functionalized with a 3-mercaptopropyl linker has been used for the solid-phase synthesis of oligosaccharides [207]. 

All the reactions in Table 22.4 take place faster with alkylamines than with arylamines. 

Af-Alkylarylamines resemble secondary alkylamines in that they form (V-nitroso compounds on reaction with nitrous acid. 

This reduction can also be conducted in comparable yield with NaBH4 and BF3 etherate (ratio 1 1.5 equiv.) in THF.2 The hydroxylamines can be reduced completely to alkylamines on extended reaction with reagent generated in situ.3... 

---