Activators amines

Acetophenone similarly gives an oxime, CHjCCgHjlCtNOH, of m.p. 59° owing to its lower m.p. and its greater solubility in most liquids, it is not as suitable as the phenylhydrazone for characterising the ketone. Its chief use is for the preparation of 1-phenyl-ethylamine, CHjCCgHslCHNHj, which can be readily obtained by the reduction of the oxime or by the Leuckart reaction (p. 223), and which can then be resolved by d-tartaric acid and /-malic acid into optically active forms. The optically active amine is frequently used in turn for the resolution of racemic acids. 

Two important pathways for catecholamine metaboHsm are 0-methylation by COMT, which is cytoplasmicaHy localized, and oxidative deamination by the mitochondrial localized enzyme MAO. There are large amounts of MAO in tissues such as the fiver and the heart which are responsible for the removal of most of the circulating monoamine, including some taken in from the diet. Tyramine is found in high concentrations in certain foods such as cheese, and in wine. Normally, this tyramine is deaminated in the fiver. However, if MAO is inhibited, the tyramine may then be converted into octopamine [104-14-37] which may indirecdy cause release of NE from nerve terminals to cause hypertensive crisis. Thus MAO, which is relatively nonspecific, plays an important role in the detoxification of pharmacologically active amines ingested from the diet. 

ION-SELECTIVE ELECTRODES REVERSIBLE TO PHYSIOLOGICALLY ACTIVE AMINE CATIONS THE MAIN WAYS FOR CONTROLLING POTENTIOMETRIC SELECTIVITY... 

Despite the fact that a great lot of ion-selective electrodes (ISEs) with liquid and film polymeric membranes for the determination of physiologically active amines (PhAA) has been described, the factors responsible for their selectivity have not yet been studied sufficiently. In this work, the influence of plasticizer and ion-exchanger nature on the selectivity of ISEs reversible to PhAA cations of various stmctures has been discussed. 

During the 1990s concern increased about the odour and volatility of amino catalysts, particularly in enclosed spaces such as automobiles. Odourless low volatility (and hence low-fogging) catalysts based on salt-like or ionic carboxylates containing active amine centres became available. Another approach was to incorporate amine groups into the polymer to provide a built-in rather than a free-standing catalyst. 

Denniatk and co-wotkets teporied tlie brst example in 1990 [16], using substrates 1, s7ntliesized Grom adiital allylic alcohols and tead dy ava dable optically active amine auxdiaries. Substrates 1 were tlien employed in coppet-niediaied allylic substitution reactions, as shown in Sdienie 8.4. 

Since these adducts undergo reductive desulfuration with Raney nickel, optically active aryl methyl sulfoxides are versatile reagents for the conversion of imines to optically active amines. 

In Ugi four-component reactions (for mechanism, see Section 1.4.4.1.) all four components may potentially serve as the stereodifferentiating tool65. However, neither the isocyanide component nor the carboxylic acid have pronounced effects on the overall stereodiscrimination60 66. As a consequence, the factors influencing the stereochemical course of Ugi reactions arc similar to those in Strecker syntheses. The use of chiral aldehydes is commonly found in substrate-controlled syntheses whereas the asymmetric synthesis of new enantiomerically pure compounds via Ugi s method is restricted to the application of optically active amines as the chiral auxiliary group. 

Because of their surfactant and filming properties fatty amines such as coco-alkylamine acetate (and more especially diamines, such as tallow propylenediamine) are also occasionally employed in other types of water treatment programs. For example, they may be used as corrosion inhibitors for steel cooling systems, especially those smaller units where minimal operational control is provided. The amines must be continuously dosed to ensure good film formation (and thus corrosion protection), typically at 5 to 10 ppm active amine. They also tend to have good biostatic control properties, which provide a benefit of algal and bacterial control at no extra cost. 

A typical feed rate is 1 to 3 ppm of active amine. Most filmer products contain between 3 and 10% amine (3-5% being the norm), so that product feed rates are around 10 to 30 ppm, dosed continuously to achieve 0.1 to 0.5 ppm amine (as ODA) in the returned condensate. However, products generally are diluted to 2 to 20% strength before application. Solutions are best prepared by using warm to hot condensate (150-160 °F/66-71 °C maximum) and agitated with a mechanical mixer until a uniform solution is reached. The solution should always be kept over 60 °F/16 °C. 

The procedure herein presented allows the preparation of the same optically active amine in approximately 70% yield by the use of a... 

Considerably less is known about the chemistry of palladium and platinum 1,1-dithio complexes. Of late, there has been only one report that dealt with the synthesis of a large number of palladium dithiocar-bamates 392). Twenty-five yellow palladium dithiocarbamate complexes were obtained by reaction of PdCla with NaR2dtc in methanol solution. Several other reports have appeared in which a few dithiocarbamate complexes of palladium were synthesized. Thus, the novel [Pd (OH)2dtc 2], which is soluble in water, was isolated 393). The synthesis of optically active palladium(II) complexes of AT-alkyl-a-phen-ethyldithiocarbamates, similar to (XXIV), via the reaction between the optically active amine, CS2, and PdCl2, has been described. From ORD and CD spectra, it has been established that the vicinal contribution of a remote, asymmetric carbon center could give rise to optical activity of the d—d transitions of palladium 394). Carbon disulfide has been shown to insert into the Pt-F bond of [PtF(PPh3)3]HF2, and X-ray studies indicated the structure (XXIX). 

Addition to alkenes of the form RCH=CH2 has been made enantioselective, and addition to RCH=CHR both diastereoselective enantioselective, by using optically active amines, such as 81,82 (derivatives of the naturally occurring quinine... 

The dioxolanones 33 <95JAP07291959> and 34 <95JAP07285960> are both reported to be useful as solvents, while 35 has been used as an X-ray contrast medium <96MIP19487>. Carboxydioxolanes such as 36 are useful for controlled release of volatile aldehyde pheromones <96JCR(S)274> and pharmaceutically active amines R2NH can be administered in... 

Mikolajczyk and coworkers have summarized other methods which lead to the desired sulfmate esters These are asymmetric oxidation of sulfenamides, kinetic resolution of racemic sulfmates in transesterification with chiral alcohols, kinetic resolution of racemic sulfinates upon treatment with chiral Grignard reagents, optical resolution via cyclodextrin complexes, and esterification of sulfinyl chlorides with chiral alcohols in the presence of optically active amines. None of these methods is very satisfactory since the esters produced are of low enantiomeric purity. However, the reaction of dialkyl sulfites (33) with t-butylmagnesium chloride in the presence of quinine gave the corresponding methyl, ethyl, n-propyl, isopropyl and n-butyl 2,2-dimethylpropane-l-yl sulfinates (34) of 43 to 73% enantiomeric purity in 50 to 84% yield. This made available sulfinate esters for the synthesis of t-butyl sulfoxides (35). 

Attempts to prepare optically active amines by replacing dppe with optically active diphosphines such as DIOP or DIPAMP in the Pd/dppe system [183] or by replacing PhP(Oi-Pr)2 with dimenthyl phenylphosphinite in the Ni/PhP(Oi-Pr)2 system [184] have met with little success. 

Analogously, the chirality of optically active amines or alcohols can also be determined t49]... 

DIBENZOCYCLOHEPTANES AND DIBENZOCYCLOHEPTENES Drugs in this structural class have effected a revolution in the treatment of severely depressed patients such that deinstitutionalization is a feasible public policy. The compounds often show other CNS activities which depend on the length of the side chain. One-carbon chains generally lead to anticonvulsant activity amines separated from the nucleus by three carbons usually donvey antidepressant activity. Selected examples possess significant anticholinergic activity. 

Optically active amine-thioether ligands (492) have been investigated in nickel-catalyzed asymmetric cross-coupling reactions of Grigard reagents.1338... 

Scheme 26 Synthesis of optically active amines 91 using the chiral amination reagent 89...

The 1,2-diol is liberated easily from cyclic osmate ester by either reductive or oxidative hydrolysis.213 Importantly, the ligand acceleration has been utilized extensively for the production of chiral 1,2-diols from (achiral) olefins using optically active amine bases (such as L = dihydroquinidine, dihydroquinine and various chiral diamine ligands).215... 

In situ rhodium(I) complexes containing both triphenylphosphine and optically active amines are said to effect asymmetric hydrogenation of the amino acid precursors (265). 

The most efficient way to produce optically active amines, at least with a rhodium-DIOP catalyst, is via the hydrosilylation-hydrolysis process (229, 284, Chapter 9 in this volume) for example ... 

Cyanoaminecobaltate(II) catalysts (/, p. 150) were initially studied in relation to the well-known activity of Co(CN)53 (/, p. 106). Use of such catalysts with optically active amines (1,2-propanediamine and N.N-dimethyl-1,2-propanediamine), thought to be bridged in complexes such as [(CN4)Co-amine-Co(CN4)]4 , led to asymmetric hydrogenation of atro-pate [Eq. (55)] to a 7% ee (309). 

The use of optically active amines in bis(dimethylglyoximato)co-baltate(Il)amine systems (Section II,C) has led to asymmetric reduction... 

Mechanisms involving axial coordination of the optically active amine have also been invoked, and crystal structure data on RCo(DMG)2B complexes, where R is alkyl or (R)-l-(methoxycarbonyl)ethyl, and B is (R )-a-methylbenzylamine, were obtained (316, 317). Because deuteration of the (R)-methoxycarbonyl complex gave (5)-methylpropionate-2-d, it was concluded that Co—C bond cleavage occurred with inversion of configuration at the carbon (317). It would be useful to know the mechanistic details of this step, which could involve attack by D+, DCo(III), or coordinated D, as well as D2, for it is an unusual, if not unique, observation [contrast with the usual retention mechanism outlined in Eq. (39)]. 

The preparation of optically active analogues of the natural amino acids has proven reasonable using the reaction of tris(trimethylsilyl) phosphite with chiral aldimines prepared from optically active amines.225 The asymmetric induction has been observed to be as high as 80%, a significant competitive process compared to the multistep approaches available.226227 An alternative one-step approach involving asymmetric induction upon addition to an aldimine derived from a chiral N-substituted urea provided a product with less desirable optical purity.228... 

Paper chromatography has been used to separate and detect pseudoephedrine hydrochloride from other pharmacologically active amines. Whatman No. 1 paper developed in n-butanol water 95% acetic acid (4 5 1), n-butanol toluene water 95% acetic acid (10 10 5 5), ethyl acetate water 95% acetic acid (3 3 1), or chloroform water 95% acetic acid (10 5 4) gave Rf values of 0.73, 0.35, 0.57, and 0.52 for pseudoephedrine hydrochloride respectively. Visualization of pseudoephedrine hydrochloride was done by spraying the chromatogram with 0.5% bromcresol green in methanol or 0.2% nin-hydrin in acetic acid butanol 5 95.30... 

Pfaltz and Leitner found that some imines are hydrogenated enantioselectively at a partial H2 pressure of 30 atm and 40 °C in scC02 (d = 0.75 g mL 1) containing a chiral phosphinodihydrooxazole-Ir complex to give optically active amines in up to 81 %... 

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