Amine potentials

Following acute exposure to cyclodiene organochlorine pesticides, seizures and respiratory depression may occur (Ellenhom 1988 Proctor et al. 1988). Benzodiazepines (e.g., diazepam or lorazepam) or other anticonvulsant medications (e.g., phenobarbital) have been commonly used to control seizures (Ford 1993). Organochlorines may sensitize the myocardium to the proarrhythmic effects of adrenergic amines, potentially resulting in initiation of ventricular fibrillation (TOMES 1994). 

It is believed that tricyclic antidepressants inhibit the (neuronal) reuptake of norepinephrine (noradrenaline) and/or serotonin by presynaptic nerve endings, thus blocking one of the leading mechanisms of their inactivation, and thereby increasing the concentration of the indicated amines potentiating their effects. It should be noted that, as a rule, secondary amines, which are representatives of tricyclic antidepressants, exhibit high activity, blocking the neuronal reuptake of norepinephrine, while tertiary amines act more on the neuronal reuptake of serotonin. 

Kozerski, L. et al., Solution and solid state 13C NMR and x-ray studies of genistein complexes with amines. Potential biological function of the C-7, C-5, and C-4 -OH groups, Org. Biomol. Chem., 1, 3578, 2003. 

SCHEME 8.8 Ti(IV) mediated reductive amination - potential reaction pathways. 

Low reactivity in general Reversible reactivity with weak nucleophiles (e.g. amines) Potential for product processing applications supercritical anti solvents, SAS rapid expansion of supercritical solution, RESS super fluid chromotography, SEC Reacts with strong nucleophiles... 

Schneider CH, Pfeuti C, de Week AL (1973) Aspects of formation of the D-penicillamine-antigenic determinant from penicilloyl compounds. Helv Chim Acta 56 1235-1243 Schwartz MA (1969) Chemical aspects of penicillin allergy. J Pharm Sci 58 643-661 Schwartz MA, Amidon GL (1966) Reaction of aspirin with amines. Potential mechanism for aspirin allergy. J Pharm Sci 55 1464-1465 Schwartz MA, Wu G-M (1966) Kinetics of reactions involved in penicillin allergy. I. Mechanism of reaction of penicillins and 6-aminophenicillanic acid with glycine in alkaline solutions. J Pharm Sci 55 550-555... 

Reactions of mustard with amines potentially can form products of special value to industry even if not needed in large quantities. Because weapons-grade mustard is a complex mixture of chloroalkyl sulfides [6], the materials formed in reactions with amines may be mixtures. For some purposes, they may nevertheless be quite suitable. 

Quats made from reaction of benzyl chloride with tertiary amines potentially contain residual benzyl chloride. However, it has been demonstrated by HPLC analysis that benzyl chloride is unstable in the reaction product and is undetectable in a matter of hours (23). Benzyl alcohol and benzaldehyde may be determined in this same HPLC analysis, but the preferred method for these substances is gas chromatography, following the recommendations of GC column manufacturers. 

Because of the charged nature of many Langmuir films, fairly marked effects of changing the pH of the substrate phase are often observed. An obvious case is that of the fatty-acid monolayers these will be ionized on alkaline substrates, and as a result of the repulsion between the charged polar groups, the film reverts to a gaseous or liquid expanded state at a much lower temperature than does the acid form [121]. Also, the surface potential drops since, as illustrated in Fig. XV-13, the presence of nearby counterions introduces a dipole opposite in orientation to that previously present. A similar situation is found with long-chain amines on acid substrates [122]. 

Now the easy part -isolating your product. One of the most attractive features of this new synthesis is that the standard Ai/(Hg) amination mixture must be tediously filtered to separate the product from the spent aluminum hydroxide sludge at this point. The following remedies this most frustrating step and will probably give many a new outlook on the potential of the AI(Hg) reduction. 

The next method Strike has for semi-direct amination is really weird, Strike is really exposing Strike s ignorance of chemistry with this dog. But if one looks hard at the articles cited, the potential is there. The authors came up with this little procedure that produced vicinal diamines out of alkenes [83]. Later they found that if they did a couple of things different, they would end up with a monoamine with the majority product being at the beta carbon. The following is a conjoining of the two paper s experimentals ... 

You can examine the structure of methyl amine including its electrostatic potential map in more detail on Learning By Modeling... 

An orbital hybridization description of bonding m methylamme is shown m Figure 22 2 Nitrogen and carbon are both sp hybridized and are joined by a ct bond The unshared electron pair on nitrogen occupies an sp hybridized orbital This lone parr IS involved m reactions m which amines act as bases or nucleophiles The graphic that opened this chapter is an electrostatic potential map that clearly shows the concentration of electron density at nitrogen m methylamme... 

Controlled-potential coulometry also can be applied to the quantitative analysis of organic compounds, although the number of applications is significantly less than that for inorganic analytes. One example is the six-electron reduction of a nitro group, -NO2, to a primary amine, -NH2, at a mercury electrode. Solutions of picric acid, for instance, can be analyzed by reducing to triaminophenol. 

Hbls Process. Chemische Werke Huls AG has developed a process to produce soda ash and hydrochloric acid from salt via an amine—solvent system (12). A potential advantage of the Huls process is that, under some market conditions, hydrochloric acid may be more easily sold than either ammonium or calcium chloride. 

The cellulose dissolving potential of the amine oxide family was first realized (79) in 1939, but it was not until 1969 that Eastman Kodak described the use of cycHc mono(/V-methy1amine-/V-oxide) compounds, eg, /V-methylmorpho1ine-/V-oxide [7529-22-8] (NMMO), as a solvent size for strengthening paper (80) by partially dissolving the cellulose fibers. 

Other patents (81,82) coveted the preparation of cellulose solutions using NMMO and speculated about their use as dialysis membranes, food casings (sausage skins), fibers, films, paper coatings, and nonwoven binders. NMMO emerged as the best of the amine oxides, and its commercial potential was demonstrated by American Enka (83,84). Others (85) have studied the cellulose-NMMO system in depth one paper indicates that further strength increases can be obtained by adding ammonium chloride or calcium chloride to the dope (86). 

Perfluorinated ethers and perfluorinated tertiary amines do not contribute to the formation of ground level ozone and are exempt from VOC regulations (32). The commercial compounds discussed above have an ozone depletion potential of zero because they do not contain either chlorine or bromine which take part in catalytic cycles that destroy stratospheric ozone (33). 

The single-step -duoroaruline [31-40-4] process based on duorodeoxygenation of nitrobenzene (via in situ generation of /V-phenylhydroxyl amine) in anhydrous hydrogen duoride (94—96) has not been commercialized primarily due to concurrent formation of aniline, as well as limited catalyst life. The potential attractiveness of this approach is evidenced by numerous patents (97—101). Concurrent interest has been shown in the two-step process based on /V-phenylhydroxylamine (HF-Bamberger reaction) (102—104). 

Detergent Additives. Diesel engine deposits ate most troublesome in the fuel dehvery system, ie, the fuel pump and both fuel side and combustion side of the injectors. Small clearances and high pressures mean that even small amounts of deposits have the potential to cause maldistribution and poor atomization in the combustion chamber. The same types of additives used in gasoline ate used in diesel fuel. Low molecular weight amines can also provide some corrosion inhibition as well as some color stabilization. Whereas detergents have been shown to be effective in certain tests, the benefit in widespread use is not fully agreed upon (77). 

Many different types of foaming agents are used, but nonionic surfactants are the most common, eg, ethoxylated fatty alcohols, fatty acid alkanolamides, fatty amine oxides, nonylphenol ethoxylates, and octylphenol ethoxylates, to name a few (see Alkylphenols). Anionic surfactants can be used, but with caution, due to potential complexing with cationic polymers commonly used in mousses. 

Divalent copper, cobalt, nickel, and vanadyl ions promote chemiluminescence from the luminol—hydrogen peroxide reaction, which can be used to determine these metals to concentrations of 1—10 ppb (272,273). The light intensity is generally linear with metal concentration of 10 to 10 M range (272). Manganese(II) can also be determined when an amine is added to increase its reduction potential by stabili2ing Mn (ITT) (272). Since all of these ions are active, ion exchange must be used for deterrnination of a particular metal in mixtures (274). 

The nitro alcohols available in commercial quantities are manufactured by the condensation of nitroparaffins with formaldehyde [50-00-0]. These condensations are equiUbrium reactions, and potential exists for the formation of polymeric materials. Therefore, reaction conditions, eg, reaction time, temperature, mole ratio of the reactants, catalyst level, and catalyst removal, must be carefully controlled in order to obtain the desired nitro alcohol in good yield (6). Paraformaldehyde can be used in place of aqueous formaldehyde. A wide variety of basic catalysts, including amines, quaternary ammonium hydroxides, and inorganic hydroxides and carbonates, can be used. After completion of the reaction, the reaction mixture must be made acidic, either by addition of mineral acid or by removal of base by an ion-exchange resin in order to prevent reversal of the reaction during the isolation of the nitro alcohol (see Ion exchange). 

Reactions of monoethan olamine with mild steel are referenced in the Hterature (23). The complex formed, identified as triseth an o1 amin o—iron, can decompose in air to pyrophoric iron, with the potential to cause a fire, if contacted with combustible materials. 

Alkylamiaes are toxic. Both the Hquids and vapors can cause severe irritations to mucous membranes, eyes, and skin. Protective butyl mbber gloves, aprons, chemical face shields, and self-contained breathing apparatus should be used by aH personnel handling alkylamiaes. Amines are flammable and the lower mol wt alkylamiaes with high vapor pressures at ordiaary temperatures have low flash poiats. Amines should be handled ia weH-veatilated areas only after eliminating potential sources of ignition. 

The 1,4-isomer has been similarly generated from terephthalonitdle [623-26-7] (56) using a mixed Pd/Ru catalyst and ammonia plus solvent at 125 °C and 10 MPa (100 atm). It is also potentially derived (57) from terephthaUc acid [100-21-0] by amination of 1,4-cyclohexanedimethanol (30) [105-08-8], Endocyclization, however, competes favorably and results in formation of the secondary amine (31) 3-a2abicyclo[3.2.2]nonane [283-24-9] upon diol reaction with ammonia over dehydration and dehydrogenation catalysts (58) ... 

Alkylamines and diamines are generally classified as corrosive to the skin based on results from laboratory animal (rabbit) studies performed in accordance with the Department of Transportation (DOT) test method (84) rabbits are considered to be especially sensitive to alkylamines which even at low concentrations can induce skin redness and swelling. Oleylamine has been shown to induce mild to moderate skin irritation in laboratory rats when appHed at a concentration of 0.3% in mineral oil (Chemical Manufacturer s Association, 1985). Fatty amines which contain alkyl chains of 10—14 carbons are considered more irritating than related products which contain alkyl chains of 14—18 carbon atoms. Ethoxylation generally decreases the irritation potential of alkylamines. 

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