A,co-Diamines

Primary ( ) amines e.g. alkyl amines [1—3] lipid amines [4] a, co-diamines [5, 6] polyamines [6] alkanol amines [7] subst. anilines [8] aminoglycoside antibiotics [9, 10] biogenic amines [11] hydrazines... 

Bis-4-arylidene-5(4//)-oxazolones are easily obtained from aromatic dialdehydes by the Erlenmeyer synthesis. Such bis(oxazolones) react with a,co-diamines to provide a convenient approach to macrolactams.Tandem Erlenmeyer condensation-macrolactamization (TECM) has been used to prepare analogues of naturally occurring, biologically active cyclic peptides such as bastadin-5. 

In the 1980s Ogino first applied this interaction in rotaxane synthesis, i.e., threading CD on to an a,co-diamine [38—40]. Almost at the same time, Yamanari et al. reported the preparation of very similar rotaxanes by the same approach [41,42]. Lawrence and coworkers prepared a stable rotaxane by threading / -CD... 

Careful inspection of the reported photocatalytic reactions may demonstrate that reaction products can not be classified, in many cases, into the two above categories, oxidation and reduction of starting materials. For example, photoirradiation onto an aqueous suspension of platinum-loaded Ti02 converts primary alkylamines into secondary amines and ammonia, both of which are not redox products.34) ln.a similar manner, cyclic secondary amines, e.g., piperidine, are produced from a,co-diamines.34) Along this line, trials of synthesis of cyclic imino acids such as proline or pipecolinic acid (PCA) from a-amino acids, ornithine or lysine (Lys), have beer. successfuL35) Since optically pure L-isomer of a-amino acids are available in low cost, their conversion into optically active products is one of the most important and practical chemical routes for the synthesis of chiral compounds. It should be noted that l- and racemic PCA s are obtained from L-Lys by Ti02 and CdS photocatalyst, respectively. This will be discussed later in relation to the reaction mechanism. 

The favourable intra-molecular hydrogen-bonding between the oxime proton and the phenol oxygen atom will reduce or overcome liganddigand repulsion enthalpy terms normally involved in the formation of bis-chelate complexes. The integrity of this head-to-tail macrocyclic assembly is preserved in c/.v-octahcdral complexes which are formed in the presence of a, co-diamines. [66, 67]... 

Dorr, Lewis, and co-workers found evidence through quenching experiments and flash spectroscopy for a triplex in the system trans-stilbene — amine — benzene — [105]. They quenched singlet excited trans-stilbene with various mono- and diamines and found a steric effect on the quenching constant The a, co-diamines (dabco, diaminoethane, -propane and -butane) quenched the stilbene fluorescence more efficiently than the monoamines, depending on the chain length between the amino groups. This was ascribed to the formation of cyclic radical cations, with a N-N three electron a-bond. In this case, an exciplex between diamine and stilbene is formed. 

The original procedure as reported by Goubeau and Zappel in their pioneering work B involves the pyrolysis of a mixture of trialkylborane and aliphatic a, co-diamines. It was shown that the reaction proceeds through various intermediates and it can be illustrated by the following Eqs. (1)—(3). 

A third basic procedure of synthesizing 1,3,2-diazaboracyloalkanes involves the interaction of aliphatic a, co-diamines with boron trihalides in the presence of a tertiary amine as hydrogen halide acceptor as is illustrated by Eq. 5 15>17). 

Upon reacting SWCNT-acyl chlorides with a,co-diamines such as tripropylene-tetramine as molecular linker and subsequent diamide formation with another SWCNT, Roth and coworkers [109, 110] and Kiricsi et al. [Ill] succeeded in the interconnection of tubes and the formation of carbon nanotube junctions. End-to-end (Scheme 1.6a) and end-to-side nanotube interconnections (Scheme 1.6b) were formed and observed by AFM. Statistical analyses of the AFM images showed around 30% junctions in functionalized material [42],... 

Scheme 5.14 Modular one-pot, three-component synthesis of poly(squaraines) from terminal a,co-diamines.

Pyrrole-substituted a,co-diamines 517 varying in length and number of heteroatoms between the amine functionalities were obtained from the corresponding acid and appropriate diamine under standard amide-forming conditions in yields of 18-70%. The amines 517 were reacted with l,l -ferrocenedimethanol 518 under pseudo high-dilution conditions to form 7 r 7-ferrocenes 519, the macrocyclic anion receptors, in 20-35% yields (Equation 122) <2001JOM(637)343>. 

Nesper and co-workers [219, 248] synthesized nanotubules of alkylammonium intercalated VO by hydrothermal means. The vanadium alkoxide precursor was hydrolyzed in the presence of hexadecylamine and the hydrolysis product (lamellar structured composite of the surfactant and the vanadium oxide) yielded VO, nanotubes along with the intercalated amine under hydrothermal conditions (Figure 8.27(a) and (b)). The interesting feature of this vanadium oxide nanotube is the presence of vanadium in the mixed valent state, thereby rendering it redox-active. The template could not be removed by calcination as the structural stability was lost above 250 °C. Nevertheless, it was possible to partially extract the surfactant under mildly acidic conditions. These workers have later shown that the alkylamine intercalated in the intertubular space could be exchanged with other alkylamines of varying chain lengths as well as a,co-diamines [248]. The distance... 

As the name suggests, diamine oxidase catalyzes the oxidative deamination of diamines. Preferably a,co-diamines such as putrescine (1,4-diaminobutane) or cadaverine (1,5-diaminopentane) (the names already suggest their smell), but also various derivatives are readily converted. Quite often cyclic imines are obtained via internal nucleophilic attack by the unreacted amino function (Fig. 16.7-16) l38 40l. 

A similar, but less pronounced chain length vs chemical shift dependence is observed for a series of nylon-6,6 type polyamides based on aliphatic or aromatic a,co-diamines and aliphatic or aromatic diacids in trifluoroacetic acid. However, the downfield chemical shift caused by increasing the chain length of aliphatic diacid residues is less pronounced relative to that of aliphatic diamines [12]. 

Figure 5.21 Change in transport number of nitrate ions relative to chloride ions with the number of methylene groups of a, co-diamines. ( ) Concentration of Na+, 0.01 N (A) concentration of Na+, 0.04 N. The transport number of nitrate ions relative to chloride ions was measured using a 1 1 mixed salt solution of sodium nitrate and sodium chloride (concentration of sodium ions 0.01 or 0.04 N) at a 0.10 mA cm 2 for 60 min at 25.0 °C under vigorous agitation.

Other compounds such as benzoic acid and pyrazole, which can effect similar concerted proton transfer and avoid charged species, also catalyze this and related reactions Another type of bifunctional catalysis has been noted with a, co-diamines in which one of the amino groups is primary and the other tertiary. These substituted diamines are from several times to as much as 1000 times more reactive toward imine formation than monofunctional amines. This is attributed to a catalytic intramolecular proton transfer. 

As a proof-of-concept, the Lavigne group has investigated the sensor response for simple a,co-diamines with a chain lengths between two and six methylene groups. In addition, histamine was used as an analyte. The analysis was performed with the UV-Vis data obtained for a constant polymer concentration of 0.4mM, and for five different analyte concentrations between 0.5 and 5.0mM. The normalized absorption values at nine wavelengths were subjected to a LDA (see Glossary in Box 7.1). A jack-knifed classification matrix showed that the analyte can be identified with an accuracy of over 99% [23]. 

Polymers containing pyridine can be converted into polyaldehydes, by the action of cyanogen bromide, which can then be converted back to pyridines by the amino-groups of proteins." Relatively delicate and expensive enzymes may be immobilized by condensation copolymerization of a water-soluble functionalized prepolymer, a low molecular weight a, co-diamine and the enzyme. Inclusion of substrates, cofactors, products, or reversible inhibitors during the immobilization procedure protects the enzyme active site against deactivating acylation." ... 

Compounds containing both an isocyanate and a carbamoyl chloride group (for example, 179) have been prepared by reacting monoalkyl a,co-diamines (for example, 178) with phosgene [111, 112]. 

R. Yamdagni and P. Kebarle, Gas-phase basicities of amines. Hydrogen bonding in proton-bound amine dimers and proton-induced cyclization of a,co-diamines, J. Am. Chem. Soc., 95 (1973) 3504. 

A conformational analysis of the homologous series of the linear a,co-diamines (H2N(CH2)nNH2) (n=2 - 10, n=12) and the tri- and tetramines spermidine and spermine was undertaken (40-48). These molecules display a high conformational freedom, as well as an interdependence of the particular effects due to the nitrogens electronegativity and electron lone-pairs. 

By this chemistry, polymers with one amine end group as well as a,co-diamine-functionalized polymers can be used to prepare AB or ABA copolymers, respectively. The method gives copolymers with well-controlled polypeptide segments. Furthermore, no unreacted homopolymers or homopolypeptides could be detected. Several examples of the polymer B block have been reported poly(octenamer) prepared by acylic diene metathesis polymerization [67], poly(methyl acrylate) prepared by atom transfer radical polymerization (ATRP) [70], poly(ethylene glykol) PEG, and PDMS [68]. The method was expanded for the synthesis of... 

Nishimoto S, Ohtani B, Yoshikawa T, Kagiya T (1983) Photocatalytic conversion of primary amines to secondary amines and cyclization of polymethylene-a, co-diamines by an aqueous suspension of titanium (IV) oxide/platinum. J Am Chem Soc 105(24) 7180-7182... 

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