Amines unreacted excess

Unreacted excess amines, such as dicyandiamide (Dicy), were also a cause of corrosion in some early epoxy formulations. Dicy decomposes producing ammonia and other reactive amine compounds. The primary and secondary amines, being quite alkaline, react rapidly with aluminum. Analysis of sealed hybrid microcircuits that used Dicy-cured epoxies showed quantities of ammonia as high as 30,000-100,000 ppmv and extensive corrosion in the presence of moisture. Other... 

Titrations with dibutylamine [111-92-2] can also be used to determine the NCO content of isocyanates and prepolymers. Generally, an excess of amine in a suitable solvent such as chlorobenzene [108-90-7] is added to the sample. The resulting solution is allowed to react and the unreacted amine is back- titrated with dilute hydrochloric acid. For low NCO content levels, a colorimetric method is often used. The isocyanate-containing species is titrated with amine and the unreacted amine is deterrnined using malachite green [569-64-2]. 

An excess of crotonaldehyde or aUphatic, ahcyhc, and aromatic hydrocarbons and their derivatives is used as a solvent to produce compounds of molecular weights of 1000—5000 (25—28). After removal of unreacted components and solvent, the adduct referred to as polyester is decomposed in acidic media or by pyrolysis (29—36). Proper operation of acidic decomposition can give high yields of pure /n j ,/n7 j -2,4-hexadienoic acid, whereas the pyrolysis gives a mixture of isomers that must be converted to the pure trans,trans form. The thermal decomposition is carried out in the presence of alkaU or amine catalysts. A simultaneous codistillation of the sorbic acid as it forms and the component used as the solvent can simplify the process scheme. The catalyst remains in the reaction batch. Suitable solvents and entraining agents include most inert Hquids that bod at 200—300°C, eg, aUphatic hydrocarbons. When the polyester is spHt thermally at 170—180°C and the sorbic acid is distilled direcdy with the solvent, production and purification can be combined in a single step. The solvent can be reused after removal of the sorbic acid (34). The isomeric mixture can be converted to the thermodynamically more stable trans,trans form in the presence of iodine, alkaU, or sulfuric or hydrochloric acid (37,38). 

PAMAM dendrimers are synthesized in a multistep process. Starting from a multifunctional amine (for example ammonia, ethylenediamine, or tris(2-amino-ethyl)amine) repeated Michael addition of methylacrylate and reaction of the product with ethylenediamine leads to dendrimers of different generation numbers [1,9]. Two methylacrylate monomers are added to each bifunctional ethylenediamine generating a branch at each cycle. Unreacted ethylenediamine has to be completely removed at each step to prevent the initiation of additional dendrimers of lower generation number. Excess methylacrylate has also to be removed. Bridging between two branches of the same or of two different dendrimers by ethylenediamine can also be a problem, and has to be avoided by choosing appropriate reaction conditions. 

Among the most important indirect methods of analysis which employ redox reactions are the bromination procedures for the determination of aromatic amines, phenols, and other compounds which undergo stoichiometric bromine substitution or addition. Bromine may be liberated quantitatively by the acidification of a bromate-bromide solution mixed with the sample. The excess, unreacted bromine can then be determined by reaction with iodide ions to liberate iodine, followed by titration of the iodine with sodium thiosulphate. An interesting extension of the bromination method employs 8-hydroxyquinoline (oxine) to effect a separation of a metal by solvent extraction or precipitation. The metal-oxine complex can then be determined by bromine substitution. 

Reductive amination of an aldehyde with excess primary amine, using a support-bound borohy-dride, provides the desired secondary amine contaminated with the primary amine precursor. Covalent capture of the primary amine with a support-bound aldehyde provides the pure secondary amine. Treatment with excess isocyanate yields the final urea product, which is purified by reaction with a support-bound amine to remove unreacted isocyanate. For the full potential of this method to be realized, further development of support-bound reagents and scavengers for most of the important chemical transformations will be necessary. Al-... 

Parallel Synthesis We start the reaction by using two sets of building blocks, amines (A) and carboxylic acids (B). The amines are first attached to solid supports, normally polystyrene beads coated with linking groups, in separate reaction vessels for each amine. After the amines have been attached, excess unreacted amines are washed off. Next, the carboxylic acids are added to the amines to form the desired amides. We illustrate these steps in Fig. 3.8. Assuming there are 8 amines to react with 12 carboxylic acids in a 96-well plate with 8 rows and 12 columns of tiny wells, the amines, A1 to A8, are added across the rows to each well containing the polystyrene beads. Different types of carboxylic acids, B1 to B12, are added to the wells in each column. 

The key to a controlled molecular weight build-up, which leads to the control of product properties such as glass transition temperature and melt viscosity, is the use of a molar excess of diisopropanolamine as a chain stopper. Thus, as a first step in the synthesis process, the cyclic anhydride is dosed slowly to an excess of amine to accommodate the exothermic reaction and prevent unwanted side reactions such as double acylation of diisopropanolamine. HPLC analysis has shown that the reaction mixture after the exothermic reaction is quite complex. Although the main component is the expected acid-diol, unreacted amine and amine salts are still present and small oligomers already formed. In the absence of any catalyst, a further increase of reaction temperature to 140-180°C leads to a rapid polycondensation. The expected amount of water is distilled (under vacuum, if required) from the hot polymer melt in approximately 2-6 h depending on the anhydride used. At the end of the synthesis the concentration of carboxylic acid groups value reaches the desired low level. 

The tertiary amine thus obtained was dissolved in absolute ethanol and was refluxed for two days with five molar percent excess of the appropriate bromoalkane (97% Humphrey Chemical, North Haven, Conn.). Solvent was removed and the residue in aqueous Na2C03 solution was extracted with hexane to remove any unreacted bromoalkane. Next, the N-alkyl N-benzyl N-methylglycine was extracted into chloroform from the aqueous layer. Solvent was stripped off and the crude material was recrystallized thrice from carbon tetrachloride and twice from THF/CHCl3 (60 40 v/v) mixture. The yields of the purified betaines were about 75% of the theoretical. 

Emmons and co-workers prepared a series of aliphatic secondary nitramines by treating amines with a solution of dinitrogen pentoxide in carbon tetrachloride at —30 C (Equation 5.9). The amine component needs to be in excess of two equivalents relative to the dinitrogen pentoxide if high yields of nitramine are to be attained. This is wasteful because at least half the amine remains unreacted. However, yields are high and there is no reason why the amine cannot be recovered as the nitrate salt. The method is particularly useful for the nitration of hindered secondary amines substrates such as those with branching on the a carbon. 

A minimum penetration of water to the interface. Silane coupling agents, themselves, may contribute hydrophilic properties to the interface. This is especially true when amino-functional silanes are used as primers for reactive polymers such as epoxies and urethanes. The primer may supply much more amine functionality than can possibly react with the resin at the interface. Excess unreacted amine at the interface is hydrophilic and is responsible for the poor water-resistance of such bonds. The amount of excess amine at the interface may be minimized by using very dilute solutions of silane in the primer, or by washing the primed surface with water or organic solvent to remove all but a very thin layer of chemically adsorbed silane. 

The reactions of esters of ,/i-unsatu rated acids with a 1.5 fold excess of amines were carried out without a solvent in a commercial microwave oven (Funai M0785VT) in a reaction vessel for several minutes. The power of microwave irradiation depends on the stability of the starting compound under microwave irradiation conditions. The Michael adduct was separated from the unreacted starting substances by column chromatography on silica gel with a hexane-ethyl acetate mixture (2 1) as the eluent. 

Schiff bases, Ar1-CH=N-Ar2, that are unreactive with triethylaluminium alone undergo ethylation in the presence of cerium(IV) the reaction site is the methine.36 The sterically sensitive reaction is favoured by electron-donating substituents. Excess Et3Al is required, or cleavage to aldehyde and amine results. 

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