Amines described

A.mina.tlon. Amination describes the introduction of amino groups into aromatic molecules by reaction of ammonia or an amine with suitably substituted halogeno, hydroxy, or sulfonated derivatives by nucleophilic displacement. Although reaction and operational conditions vary, the process always involves the heating of the appropriate precursor with excess aqueous ammonia or amine under pressure. 

MeNENA. Designation for N-ffl-nitroxyethyl) me thy blit r amine, described under N-(/Miy dr oxy-ethyl) me thy Ini tr amine in Vol 7, H241-R... 

Bu-NENA. Designation for N-(2-Nitroxyethyl) -butylnitr amine described here as [l (N -Butylnitramino)-ethan-2-ol] Nitrate under Butylaminoethanol and Derivatives... 

IV) Amines 0.20% calcd as methylamine when detd using the proced IV for secondary amines described under Centr 1 but calcg % methyl-aniline from the formula [l0.7(Vt-V2)N] /W Ax 1.78, where V ml of NaOH soln required to titrate blank Vz=ml of NaOH soln required to titrate sample N=normality of NaOH soln W=wt of sample and A=% acidity as AcOH Note This method is not specific for amines but will detect other groups such as OH... 

Either (S)-specific aminopeptidase catalyzed hydrolysis of racemic PGA11 or crystallization-induced asymmetric transformation of racemic PGA with (.S l-mandelic acid as resolving agent12 can be used to prepare (R)-PGA. As a result of its ready availability on large scale within DSM, we envisaged the application of (R)-PGA for the production of enantiomerically pure amine functionalized compounds using the chirality transfer concept. Obviously, (S)-phenylglycine amide is also available and can be used for the preparation of the opposite enantiomer of the amines described. 

Amin described a simple and sensitive spectrophotometric method for the determination of three gyrase inhibitors, including ciprofloxacin, in pharmaceutical formulations [10]. This method is based on the formation of an ion pair with Sudan III in 40% v/ v aqueous acetone. The color of the dye changes at 566 nm in the presence of ciprofloxacin. Beer s law is obeyed over the range of 0.4-10.4 pg/mL, and the results showed good recovery (100 1.7%) with a RSD of 1.08%. 

In ihe method for acetylating aromatic amines described in Chapter 8, p. 000 (the Lumiere-Barbier method) the amine was dissolved in aqueous HCl. Using 1M amine, p.fCa 4.6, and 1M HC1, piCj -7, what will be the approximate equilibrium constant in the reaction ... 

Macrocyclic diether derivatives, (IV), prepared by Chen (5) were also effective as NS3 serine protease inhibitors of the hepatitis C virus after conversion into amide derivatives using Intermediate Amines described in Table 3. 

TABLE 3. Results of water and methylene/iodine repellency testing of polyimide films obtained by reacting 1,2,3,4-cyclobutane tetracarboxylic dianhydride with amines described in Table 1. 

The oxidation of amines, acylhydrazines, and alkoxy amines described in this section involves the formation of nitrenes or other intermediates, depending on the nature of the nitrogen substituent and the oxidant, although lead tetraacetate is commonly employed. For example, a nitrenium ion or an amino lead derivative was proposed as the intermediate in the oxidation of alkoxyamines with lead tetraacetate 2. However, evidence has been provided that the jV-acetoxy species is the intermediate in the aziridination of alkenes with V-aminophthal-imide and /V-aminoquinazolinone, where a mechanism analogous to the Bartlett mechanism for the peracid epoxidation of alkenes should be operating3,4. 

In Problem 11, calculations proved to be a good way of assigning structures to the spectra of some aromatic amines. Describe an experimental way of differentiating between the following amines. 

Secondary and tertiary amines. Tertiary amines can be used as sole curing agents but in adhesive formulations they are more normally found in blends, for example as accelerators with polyamide systems(4) and as an essential part of polysulphide systems. The cured resins tend to be less temperature and chemical resistant than the amines described above. Secondary amines react first like primary then as tertiary amines. 

One of the most common methods employed for the generation of allylpalladium complexes involves oxidative addition of allylic electrophiles to Pd . This transformation has been explored by several groups, and has been the topic of recent reviews [69]. A representative example of this process was demonstrated in a recent total synthesis of (+ )-Biotin [70]. The key step in the synthesis was an intramolecular amination of 89, which provided bicydic urea derivative 90 in 77% yield (Eq. (1.40)). In contrast to the Pd"-catalyzed reactions of allylic acetates bearing pendant amines described above (Eq. (1.10)), which proceed via alkene aminopalladation, Pd -catalyzed reactions of these substrates occur via initial oxidative addition of the allylic acetate to provide an intermediate Jt-allylpalladium complex (e.g., 91). This intermediate is then captured by the pendant nudeophile (e.g., 91 to 90) in a formal reductive elimination process to generate the product and regenerate the Pd catalyst. Both the oxidative addition and the reductive elimination steps occur with inversion... 

The condensations of amines described so far are possible only for primary derivatives, because the nitrogen of the amine has to supply both of the hydrogens necessary to form water. Reaction with a secondary amine, such as azacyclopentane (pyrrolidine), therefore takes a different course. After the initial addition, water is eliminated by deprotonation at carbon to produce an enamine. This functional group incorporates both the ene function of an alkene and the amino group of an amine. 

This chapter deals with the use of hydrolases for enantioselective transformations of alcohols and amines, describing acylation reactions as synthetic challenges. Initially, general comments regarding the action and use of hydrolases in different media will be discussed. Special attention will be paid to the selection of reactants... 

The membranes synthesized contained both AIBA-K and KHCO3-K2CO3 (converted from KOH) as the mobile carriers and poly(allylamine) as the fixed carrier for CO2 transport. 2-Aminoisobutyric acid is a sterically hindered amine, and its reaction with CO2 is depicted in Eq. (28.4) (Sartori et al., 1987). Poly(allylamine) contains unhindered, primary amino groups, and the reaction of these groups is shown in Eq. (28.5) (Sartori et al., 1987). The reaction mechanism of the CO2 with KHCO3-K2CO3 was presumably similar to that of potassium carbonate promoted by hindered amine described in Eq. (28.6) (Sartori and Savage, 1983 Shulik et al., 1996) ... 

Camphorsulfonic acid (0.11 g, 0.46 mmol) and paraformaldehyde (16 mg, 0.54 mmol) were added to a solution of the secondary amine described in the preceding paragraph (0.27 g) in 12 mL of benzene. The reaction mixture was stirred at 70°C for 16 hours before it was diluted with 20 mL of a 1-N aqueous solution of NaOH. The layers were separated, and the aqueous layer was extracted with dichloromethane (3 x 20 mL). The combined organic layers were dried with MgS04 and concentrated in vacuo to afford 0.29 g of a yellow solid. This material was used in the next step without further purification. 

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