Aliphatic amines structure

Greim, H., H. J. Klimisch, M. Deben-Negele, and K. Ziegler-Skylakakis. 1998. Toxicity of aliphatic amines structure-activity relationship. Chemosphere 36(2) 271-95... 

Two substituents on two N atoms increase the number of diaziridine structures as compared with oxaziridines, while some limitations as to the nature of substituents on N and C decrease it. Favored starting materials are formaldehyde, aliphatic aldehydes and ketones, together with ammonia and simple aliphatic amines. Aromatic amines do not react. Suitable aminating agents are chloramine, N-chloroalkylamines, hydroxylamine-O-sulfonic acid and their simple alkyl derivatives, but also oxaziridines unsubstituted at nitrogen. Combination of a carbonyl compound, an amine and an aminating agent leads to the standard procedures of diaziridine synthesis. 

A number of aromatic amines also function as cross-linking agents. By incorporating the rigid benzene ring structure into the cross-linked network, products are obtained with significantly higher heat distortion temperatures than are obtainable with the aliphatic amines. 

These Br nsted-type plots often seem to be scatter diagrams until the points are collated into groups related by specific structural features. Thus, p-nitrophenyl acetate gives four separate, but parallel, lines for reactions with pyridines, anilines, imidazoles, and oxygen nucleophiles.Figure 7-4 shows such a plot for the reaction of trans-cmmm c anhydride with primary and secondary aliphatic amines to give substituted cinnamamides.All of the primary amines without substituents on the a carbon (R-CHi-NHi) fall on a line of slope 0.62 cyclopentylamine also lies on this line. If this line is characteristic of normal behavior, most of the deviations become qualitatively explicable. The line drawn through the secondary amines (slope 1.98) connects amines with the structure R-CHi-NH-CHi-R. The different steric requirements in the acylation reaction and in the model process... 

The schematic model of the film deposited by the technique is shown in Figure 45. A single-stranded DNA layer is sandwiched between two aliphatic amine monolayers. Thus, the technique can be useful for our objectives, for it allows depisition of single-stranded DNA on practically any substrate and does not demand a large quantity of DNA, since only one monolayer will be deposited. Nevertheless, there is a question of whether DNA in such a structure will hybridize. In fact, the film contains a single-stfanded DNA monolayer between two amine monolayers, and it is questionable whether the upper amine monolayer will prevent hybridization with complementary DNA stfands. 

Inspired by the results of aromatic-ring hydroxylation from the laboratory of Karlin and co-workers, a few groups provided further examples of such reactivity, including some structurally characterized complexes of modified m-xylyl-based pyridine-donor ligands (Schiff base and non-Schiff base acyclic ligands), as well as aliphatic amine donor ligands (179) (Cu-Cu 2.990 A),169 (180) (Cu-Cu 3.015 A),170 and (181) (Cu-Cu 2.999 A).171 172 A m-xylyl-based ligand system that was used by Mukherjee and co-workers in the formation of complex (181) also resulted in the isolation of a bis(/i-hydroxo)dicopper(II) complex (182) (Cu-Cu 3.004 A).171,172 Casella and co-workers demonstrated that when their dicopper(I) complex... 

A list of structurally characterized copper(I) complexes of tripodal aliphatic amines is provided in Table 4 (cf. Section 6.6.3.1.1 for corresponding mononuclear or dinuclear copper(II) complexes). Copper(II) complexes [(L)CuCl]Cl (664) and [(L)Cu(MeCN)][C104]2 (665) with the ligand that is present in complex (662) were also structurally characterized.522... 

Oxidative attack on a carbon-hydrogen bond of an alkyl group a to a nitrogen atom is not restricted to saturated aliphatic amines. In fact X in an X-N-CH- structural subunit can be virtually any common atomic grouping that can be found in stable organic molecules. For example, w-carbon hydrogens of Aralkyl-substituted aromatic cyclic amines (119), aryl amines (120), amides (121), amidines (122), A-nitrosodialkylamines (123), etc. are all subject to oxidative attack, carbinolamine formation, and in most cases release of an aldehyde or ketone depending on the substitution pattern (1° or 2°)... 

PET-5, PET-6 and PET-7 are examples of macrobicydic structures (cryptands) (Figure 10.12). The cavity of PET-6 and PET-7 fits well the size of K+. PET-6 has been successfully used for monitoring levels of potassium in blood and across biological membranes, but pH must be controlled because of pH sensitivity of this compound via protonation of the nitrogen atoms. This difficulty has been elegantly overcome in benzannelated cryptand PET-7, in which the aromatic nitrogens have lower pKa than those of aliphatic amines. 

In Table 1 we report structural parameters for some aliphatic amines. 

In Tables 1-8 the first IP values of various amines are summarized. These values refer to the removal of an electron from the n orbital of the amines. The other ionizations of simple saturated aliphatic amines are of no particular interest. They are associated with the orbitals of the a framework of the molecules. More interesting are the effects of substituents and other structural factors on the energy of the n ionization or—in the limits of Koopmans theorem17, IP,- = —efCF—on the energy of the orbital. 

The observed ya-SCS(X) values in 7-exo-substituted norcaranes 97 (225) and those of M(CH3)3 (M = Si, Ge, Sn, or Pb) in cyclohexyl and bicy-clo[2.2. l]heptane derivatives (133) were later interpreted on the same basis. The back-lobe-overlap treatment was further supported by interpretations of H and 13C contact shifts of aliphatic amine signals in the presence of nickel acetyl-acetonate and by INDO calculations (226,227). Additional support came from extensive investigations of the structure dependence of three-bond coupling constants 3JCX (X = H, C, or F) (228,229), although the interpretation of these data has been subjected to criticism (230). 

Demjanov rearrangement org chem A structural rearrangement that accompanies treatment of certain primary aliphatic amines with nitrous acid the amine will undergo a ring contraction or expansion. dem ya-nof re-3 ran -m3nt) denaturant chem An inert, bad-tasting, or poisonous chemical substance added to a product such as ethyl alcohol to make it unfit for human consumption. de na-chs rsnt ... 

Takayama, C., Akamatsu, M., and Fujita, T. Effects of structure on 1-octanol/water partitioning behavior of aliphatic amines and ammonium ions, Quant. Struct.-Act. Relat., 4 (4) 149-160, 1985. 

We found 192 unique structures, with 252 recorded activities on 46 targets (see also Figure 2.3). A vast majority of them (176 structures) are likely to be charged at pH 7.4, as they are aliphatic amines, amidines or guanidines, and sometimes carboxylic acids. This indicates that low MW compounds are likely to require salt bridge interactions... 

Diamines of varying structure show rate enhancements of 20-200 fold, compared to monofunctional aliphatic amines, in nucleophilic reactions with N-acetylimidazole (Page and Jencks, 1972). These were attributed to intramolecular general base catalysis of proton removal from the attacking nitrogen, viz.. 

This process has many benefits in the context of green chemistry it involves two enzymatic steps, in a one-pot procedure, in water as solvent at ambient temperature. It has one shortcoming, however-penicillin acylase generally works well only with amines containing an aromatic moiety and poor enantioselectivities are often observed with simple aliphatic amines. Hence, for the easy-on/easy-off resolution of aliphatic amines a hybrid form was developed in which a hpase [Candida antarctica hpase B (CALB)] was used for the acylation step and peniciUin acylase for the deacylahon step [22]. The structure of the acyl donor was also optimized to combine a high enanhoselectivity in the first step with facile deacylation in the second step. It was found that pyridyl-3-acetic acid esters gave optimum results (see Scheme 6.8). 

Shinkai s 38 is also a PET system whose fluorescence is controlled by Na" binding to a coordinatively active spacer which is a calix[4]aiene tetraester in this case. However, the through-space distance between the photoactive termini is expanded by Na complexation, thus reducing the PET efficiency. Kuhn s 39 is not dissimilar in that a PET-type quencher (a nitroaromatic unit) is held away from the lumophore by Ca binding. However a conventional lumophore-spacer-receptor is also contained within 39 as found in 24. At this point it would not be out of place to mention several important studies on the control of PET/EET by ion binding to a coordinatively active spacer between photoactive terminii." " System 36 is structurally related to Verhoewen s 40 since they both contain an aromatic lumophore and an aromatic amine with one or more interposed aliphatic amines. System 40 also displays the functional similarities that PET processes were... 

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