Amines mixtures

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. 

Instmmental methods of analysis provide information about the specific composition and purity of the amines. QuaUtative information about the identity of the product (functional groups present) and quantitative analysis (amount of various components such as nitrile, amide, acid, and deterruination of unsaturation) can be obtained by infrared analysis. Gas chromatography (gc), with a Hquid phase of either Apiezon grease or Carbowax, and high performance Hquid chromatography (hplc), using siHca columns and solvent systems such as isooctane, methyl tert-huty ether, tetrahydrofuran, and methanol, are used for quantitative analysis of fatty amine mixtures. Nuclear magnetic resonance spectroscopy (nmr), both proton ( H) and carbon-13 ( C), which can be used for quaHtative and quantitative analysis, is an important method used to analyze fatty amines (8,81). 

Most of the inhibitors in use are organic nitrogen compounds and these have been classified by Bregman as (a) aliphatic fatty acid derivatives, b) imidazolines, (c) quaternaries, (d) rosin derivatives (complex amine mixtures based on abietic acid) all of these will tend to have long-chain hydrocarbons, e.g. CigH, as part of the structure, (e) petroleum sulphonic acid salts of long-chain diamines (preferred to the diamines), (/) other salts of diamines and (g) fatty amides of aliphatic diamines. Actual compounds in use in classes (a) to d) include oleic and naphthenic acid salts of n-tallowpropylenediamine diamines RNH(CH2) NH2 in which R is a carbon chain of 8-22 atoms and x = 2-10 and reaction products of diamines with acids from the partial oxidation of liquid hydrocarbons. Attention has also been drawn to polyethoxylated compounds in which the water solubility can be controlled by the amount of ethylene oxide added to the molecule. 

Sodium alkylamides can also be generated in situ by reacting the amine with sodium naphthalene in THF [207, 208]. This procedure has been used for the condensation of secondary amines with different 1,3-dienes to give high yields of monoalky-lated products without formation of 1 2 telomers. In the case of primary amines, mixtures of mono- and dialkylated products are obtained together with unidentified... 

Chapter Eight Binary Components ALCOHOL - AMINE MIXTURE... 

The reductive carbonylation has an advantage of low feedstock cost. A wide range of homogenous metal complexes have been tested for both reactions (1-16). The major drawback of the use of metal complex catalysts is the difficulty of catalyst recovery and purification of the reaction products (12). In addition, the gaseous reactants have to be dissolved in the alcohol/amine mixture in order to have an access to the catalyst. The reaction is limited by the solubility of the gaseous CO and 02 reactants in the liquid alcohol reactant (17). 

This encapsulation procedure gives the highest activity for the lipases. The lecithin/ amines mixture structuring the pore network leads to a suitable phospholipids bilayer-like environment, which avoids the necessity to create an interface by substrate assembly. Monduzzi and coworkers compared the activity of lipase that was immobilized on SBA-15 physically, or chemically with glutardialdehyde [200]. 

Aliphatic amines have been determined by a number of methods. Batley et al. [290] extracted the amines into chloroform as ion-association complexes with chromate, then determined the chromium in the complex colorimetri-cally with diphenylcarbazide. The chromium might also be determined, with fewer steps, by atomic absorption. With the colorimetric method, the limit of detection of a commercial tertiary amine mixture was 15ppb. The sensitivity was extended to 0.2 ppb by extracting into organic solvent the complex formed by the amine and Eosin Yellow. The concentration of the complex was measured fluorometrically. Gas chromatography, with the separations taking place on a modified carbon black column, was used by Di Corcia and Samperi [291] to measure aliphatic amines. 

The synergistic action of a phenol and aromatic amine mixture on hydrocarbon oxidation was found by Karpukhina et al. [16]. A synergistic effect of binary mixtures of some phenols and aromatic amines in oxidizing hydrocarbon is related to the interaction of inhibitors and their radicals [16-26]. In the case of a combined addition of phenyl-A-2-naphthylamine and 2,6-bis(l,l-dimethylethyl)phenol to oxidizing ethylbenzene (v, = const, 343 K), the consumption of amine begins only after the phenol has been exhausted [16], in spite of the fact that peroxyl radicals interact with amine more rapidly than with phenol (7c7 (amine) = 1.3 x 105 and /c7 (phenol) = 1.3 x 104 L mol 1 s respectively 333 K). This phenomenon can be explained in terms of the fast equilibrium reaction [27-30] ... 

When ammonia is used as the amine, mixtures of primary, secondary and tertiary amines are the products. The primary aliphatic amines give mixtures of secondary and tertiary amine. Best results are obtained with secondary amines which give tertiary amines. 

Suppliers of visible spectrophotometers are reviewed in Table 1.1. Spectroscopic methods are applicable to the determination of phenols, chlorophenols, amines, mixtures of organics, boron, halogens, total nitrogen and total phosphorus in soils, cationic surfactants, carbohydrates, total nitrogen, phosphorus and sulphur in non-saline sediments, boron, total organic carbon, total sulphur and arsenic in saline sediments, cationic surfactants, adenosine triphosphate and total organic carbon in sludges. 

The precursor model of FAB applies well to ionic analytes and samples that are easily converted to ionic species within the liquid matrix, e.g., by protonation or deprotonation or due to cationization. Those preformed ions would simply have to be desorbed into the gas phase (Fig. 9.6). The promoting effect of decreasing pH (added acid) on [M+H] ion yield of porphyrins and other analytes supports the precursor ion model. [55,56] The relative intensities of [Mh-H] ions in FAB spectra of aliphatic amine mixtures also do not depend on the partial pressure of the amines in the gas phase, but are sensitive on the acidity of the matrix. [57] Furthermore, incomplete desolvation of preformed ions nicely explains the observation of matrix (Ma) adducts such as [M+Ma+H] ions. The precursor model bears some similarities to ion evaporation in field desorption (Chap. 8.5.1). 

Belaribi, B.F., Belaribi-Boukais, G., Ait Kaci, A., and Jose, J. Isothermal vapor-liquid equilibria ofbinary-r amine mixtures,/... 

About one-half of the product-weiglit could not be recovered in chromatograpliy of the reductive-amination mixture, and more work is clearly needed to unravel the complexity of the process. Thus far, 4 minor byproducts were isolated crystalline in yields of 1.5—3%. All possessed one 3-acetamido-3-deoxy-X-D-altro residue, in common with 91, but were not aminated in the second residue. Two of them were epi-meric 3 -carbinols resulting from nonaminative reduction, and the other two were epimeric 3 -cyanohydrins. 

Two other refining processes are also frequently employed. One involves hydrometallurgical refining in which sulfide concentrates are leached with ammonia solution to convert the copper, nickel, and cobalt sulfides into their complex amines. Copper is precipitated from this solution upon heating. Under such conditions, the sulfide-amine mixture of nickel and cobalt are oxidized to their sulfates. The sulfates then are reduced to metalhc nickel and cobalt by heating with hydrogen at elevated temperatures under pressure. The metals are obtained in their powder form. 

A samarium iodide-water-amine mixture has been shown to be effective for cyclizations of 0-cyclohexenyliodo-phenols and pyridines into heterocycles <2003OBC2423>. 

The introduction of TA into the epoxide-primary amine system should lead to the inhibition of polycondensation due to a decrease in the concentration of the free proton-donor molecules due to their bonding to give nonreactive complexes with TA. Therefore, in the general case the curing rate in the presence of amine mixtures can be both" higher (as in the above case) and lower as compared with the primary... 

The widely used reduction of thiopyrylium salts to thiopyrans has been accomplished with complex hydrides. Alternative reductions with ethanol-amine mixtures or with trichlorosilane are rarely used. 

Water-soluble transition metal complexes, which are effective catalysts in other hydrogenation processes, were found to be effective catalysts in C02 hydrogenation. The first report disclosed the application of Rh complexes with water-soluble phosphine ligands in water-amine mixtures to afford formic acid.122 Water-soluble Ru-phosphine121,123,124 and Rh-phosphine123 124 complexes were used in aqueous solution to hydrogenate C02 or HCO3 to formic acid or HCOO-, respectively. 

The nature of the cure reactions in these epoxies can be confirmed by monitoring the epoxide consumption via near infra-red spectroscopy for a series of epoxide-amine mixtures containing a range of amine contents. A plot of % epoxide consumption vs. amine concentration for DGEBA-T403 epoxies is illustrated in Fig. 2. This plot confirms that the DGEBA-T403 epoxy system forms exclusively from epoxide-amine addition reactions, because (i) 100% epoxide consumption is attained at the stoichiometric amine concentration associated with exclusive epoxide-amine addition cure reactions and (ii) extrapolation of this plot to zero amine content indicates there is no epoxide consumption i.e. there are no epoxide homopolymerization reactions. 

Commercial chlorotrimethylsllane was used without purification. When it was added to the acetone/triethyl amine mixture, only a very mild exothermic reaction occurred (ca. 2°C). Dense white fumes formed, and a turbid solution was obtained. 

C. tert-Butyl-tert-ootylamine. In a dry 500-nL, three-necked flask equipped with a mechanical stirrer, addition funnel, and nitrogen Inlet are placed 25.6 g (0.20 mol) of naphthalene, 250 nt of dry tetrahydrofuran (THF), and 10.8 g (0.47 mol) of sodium pieces. The mixture is stirred at room temperature for 30 min. To the blue-green sodium naphthalenide solution is added the hydroxyl amine mixture (Note 10) in 50 iri. of THF over 20 m1n (Caution exothermic reaction). The mixture is stirred for 2.5 hr at room... 

An interesting example for the type C reaction is the simultaneous reaction of I with alcohol/amine mixtures. In the case of Ic the reaction can be controlled in such a way, that practically exclusively the esteramide of the dithiophosphoric acid is formed (8) ... 

The phosphorus pentoxide-amine mixtures, which can readily be prepared in an exothermic reaction, were found to react analogously to phosphoramides. 

Aliphatic Amines. Mixtures of amines with fuming HN03 may ignite.15... 

Reductive Silylation of Amides Using Trichlorosilane/Tertiary Amine Mixture... 

A trichlorosilane/tertiary amine mixture has been shown to reduce the carbonyl moiety of aromatic amides to give ASMAs. This constitutes an alternative to the reductive silylation described in Section III.B.2.f.194 This work has been reviewed195 and extended to aliphatic amides to give RSMA. 

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