Diethanolamine reaction

In the context of mechanism, substrates with two or more OH groups are of particular interest since the question arises as to whether the groups will react in sequence or in parallel. If the reaction is wholly or partially sequential then an intermediate containing both OH and COO groups will be present at partial conversion. In order to determine if this happens, a method for analysis of the intermediate(s) at different stages of reaction is needed. In the present work we have developed H NMR spectroscopy for this purpose and made use of it to follow the reaction of diethanolamine, reaction [3]. 

The best known phosphorus polyol of significant commercial importance is diethyl-N,N-bis (2-hydroxyethyl) aminomethyl phosphonate, which is obtained by a Mannich reaction between diethylphosphite, formaldehyde and diethanolamine (reaction 18.11) [5, 34] ... 

The synthetic route to iV-aryl [3.2.2] cryptands 5a and 5b is shown in the Scheme. Starting from the A-aryl diethanolamine, reaction with two equivalents of chloro-acetic and /-BuOK in t-BuOH followed by conversion of the diacid to the diester for purification gave la and lb in yields of 49 and 25%, respectively. Subsequent acid-catalyzed hydrolysis produced the dicarboxylic acid amine hydrochlorides 2a and 2b quantitatively. Attempts to form the diacid chloride of 2a resulted in an unreactive deep blue-colored substance of unknown identity. Ring closure was effected by adaptation of a method from peptide synthesis [8]. Mixed anhydrides 3a and 3b formed by reaction with two equivalents of isobutyl chloroformate in the presence of triethylamine were cyclized with l,10-diaza-18-crown-6 in toluene to produce the corresponding cryptand diamides 4a and 4b in 36 and 32% yields, respectively. Reduction with borane-dimethyl sulfide in THF provided 74% yields of 5a and 5b. 

Poly (isobutene)/maleic anhydride adduct, diethanolamine reaction prod. 

Here the ethylene oxide undergoes parallel reactions, whereas the monoethanolamine undergoes a series reaction to diethanolamine and triethanolamine. 

Two principal secondary reactions occur, to diethanolamine and triethanolamine ... 

An excess of ammonia in the reactor decreases the concentrations of monoetha-nolamine, diethanolamine, and ethylene oxide and decreases the rates of reaction for both secondary reactions. 

The use of an excess of ammonia is home out in practice. A mole ratio of ammonia to ethylene oxide of 10 1 3delds 75 percent monoethanolamine, 21 percent diethanolamine, and 4 percent triethanolamine. Using equimolar proportions under the same reaction conditions, the respective proportions become 12, 23, and 65 percent. 

Reaction with Acids. Under anliydrous conditions, mono- and diethanolamines and isopropanolaniines fomi carbamates with carbon dioxide (2,3). 

Sulfurization of unsaturated compounds and meicaptans is normally carried out at atmospheric pressure, in a mild or stainless steel, batch-reaction vessel equipped with an overhead condenser, nitrogen atmosphere, an agitator, heating media capable of 120—215°C temperatures and a scmbber (typically caustic bleach or diethanolamine) capable of handling hydrogen sulfide. If the reaction iavolves the use of H2S as a reactant or the olefin or mercaptan is a low boiling material, a stainless steel pressurized vessel is recommended. 

The second type of diethanolamide is the 1 1 or superamide which contains components of the reaction of one mole fatty acid and one mole diethanolamine. A typical superamide composition is >90% diethanolamide, 7% unreacted diethanolamine, and 2.5% amine and amide ester. 

P-Ghloroalkoxy Titanates. The reaction of TiCl with epoxides, such as ethylene or propylene oxide (qv), gives P-chloroalkyl titanates (8,9). One example is Ti(OCH2CH2Cl)4 [19600-95-5]. The P-chloroalkoxy titanates can be used to biad refractory powders and ia admixture with diethanolamine to impart thixotropy to emulsion paints (10). 

The addition of an alkanolamine, such as diethanolamine, to TYZOR TBT, as well as the use of a less moisture-sensitive alkanolamine titanate complex such as TYZOR TE, has been reported to prolong catalyst life and minimi2e ha2e formation in the polymer (475—476). Several excellent papers are available that discuss the kinetics and mechanism of titanate-cataly2ed esterification and polycondensation reactions (477—484). 

In the manufacture of highly resident flexible foams and thermoset RIM elastomers, graft or polymer polyols are used. Graft polyols are dispersions of free-radical-polymerized mixtures of acrylonitrile and styrene partially grafted to a polyol. Polymer polyols are available from BASF, Dow, and Union Carbide. In situ polyaddition reaction of isocyanates with amines in a polyol substrate produces PHD (polyhamstoff dispersion) polyols, which are marketed by Bayer (21). In addition, blending of polyether polyols with diethanolamine, followed by reaction with TDI, also affords a urethane/urea dispersion. The polymer or PHD-type polyols increase the load bearing properties and stiffness of flexible foams. Interreactive dispersion polyols are also used in RIM appHcations where elastomers of high modulus, low thermal coefficient of expansion, and improved paintabiUty are needed. 

Ammonium acetate and sodium methoxide are effective catalysts for the ammonolysis of soybean oil (49). Polyfunctional amines and amino alcohols such as ethylenediamine, ethanolamine, and diethanolamine react to give useful intermediates. Ethylenediamine can form either a monoamide or a diamide depending on the mole ratio of reactants. With an equimolar ratio of reactants and a temperature of >250° C, a cyclization reaction occurs to give imidazolines with ethylenediamine (48) ... 

Derive an equilibrium expression for the reactive absorption of HiS in diethanolamine DEA . The molarity of DEA is 2 kmol/m. The following reaction takes place ... 

Functionalization may be accomplished before cyclization by preparing the appropriate diethanolamine derivative first . An alternative and more straightforward approach is simply to prepare 9 by any of the typical methods and then substitute the secondary nitrogens afterward. Reaction between 9 and chloroacetamide and acrylonitrile yielded compounds 10 and 11 in 61% and 100% yields respectively. 

Urea maybe reacted with acetoacetic ester and that product nitrated to give 5-nitro-orotec acid That is hydrogenated, then reacted with urea and potassium cyanate to give tetrahydroxypy-imidopyrimidine. The tetrahydroxy compound Is converted to the tetrachloro compound POCI3. Reaction with diethanolamine and then with piperidine gives dipyridamole. 

Formulated products tend to use a 10 to 20% neutralized erythorbate, buffered to pH of 5 to 6 with ammonia, morpholine, cyclohexy-lamine, diethanolamine (DEA), or triethanolamine (TEA) to reduce the acidity of erythorbic acid. Similarly, amines are used with sodium erythorbate to improve the reaction rate. 

Example 4. Glycolysis of Polyurethanes with Propylene Oxide after Pretreatment with a Mixture of Diethanolamine and Potassium Hydroxide.57 Polyurethane scrap was treated with a mixture of diethanolamine and potassium hydroxide at a temperature between about 80 and 140° C with stirring to form an intermediate product. The weight ratio of the scrap PUR polymer to the mixture of diethanolamine and potassium hydroxide was from about 15 1 to 30 1. The intermediate product was reacted with propylene oxide at a temperature of from about 100 to 120°C in a closed reaction vessel to form a polyol. The propylene oxide was added at a rate to maintain a pressure of from about 2 to 5 atm (29-73 psi). The progress of the reaction was followed by following the change of pressure with time. When the pressure remained constant, the reaction of the intermediate product with propylene oxide was considered to be complete. The crude polyol obtained was treated with 10 mol % excess of dodecylbenzene sulfonic acid to remove the potassium hydroxide. 

A cooling, lubricating, and cleaning agent for use by the metalworking industry has been patented. It is produced by the condensation reaction of an excess diethanolamine or monoethanolamine with boric acid and an ether carboxylic acid or mixtures of ether carboxylic acids and fatty acids [46]. An advantage of these products is that they prevent the deposition of lime soaps. 

The preparation of purine derivatives substituted at the C-2 position via amine displacement of a halogen is known as a difficult reaction step requiring several days of reaction time. However, Al-Obeidi and coworkers have recently prepared 2,6,9-trisubstituted purines on soUd-phase by employing a synthetic route in which the critical step was performed with microwave irradiation (Fig. 37) [62]. PS resin-bound 2-iodosubstituted purine was treated with diethanolamine or propanolamine in NMP with microwave irradiation at 200 °C for 30 min. Trifluoroacetic acid-mediated cleavage resulted in the 2-amino substituted purines in 45-59% yields and 77-89% purities. 

Also the impact of various reaction parameters on enzymatic synthesis of amide surfactants from ethanolamine and diethanolamine has been studied, although the possibilities of acyl migration are not investigated. However, it was found that the selectivity of the reaction depended on the solubility of the product in the solvent used, and that the choice of solvent was critical to obtain an efficient process [17]. 

Davidow (19), of the Food and Drug Administration, has described a colorimetric method applicable to technical chlordan. The method is based on the observation that when technical chlordan is heated with a mixture of diethanolamine and methanolic potassium hydroxide, a purple color is produced. When known amounts of this insecticide were added to cabbage, pears, and fresh and rancid rat fat, recoveries of 74 to 104% of the insecticide were obtained. However, because two crystalline isomers of chlordan isolated from the technical product do not give a colored reaction product with the reagent, further investigation of the method is being made. The red color obtained when technical chlordan is heated with pyridine, alcoholic alkali, and ethylene glycol monoethyl ether, as described by Ard (2), likewise fails with the crystalline isomers of this insecticide. 

AP isoenzymes can cleave associated phosphomonoester groups from a wide variety of substrates. The exact biological function of these enzymes is not well understood. They can behave in vivo in their classic phosphohydrolase role at alkaline pH, but at neutral pH AP isoenzymes can act as phosphotransferases. In this sense, suitable phosphate acceptor molecules can be utilized in solution to increase the reaction rates of AP on selected substrates. Typical phosphate acceptor additives include diethanolamine, Tris, and 2-amino-2-methyl-lpropanol. The presence of these additives in substrate buffers can dramatically increase the sensitivity of AP ELISA determinations, even when the substrate reaction is done in alkaline conditions. 

Absorbents based on a variety of amines are by far the most common. Amines that have been used include monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), diisopropanolamine (DIPA), methyl diethanolamine (MDEA), and digly-colamine (DGA). C02 is typically absorbed at 80-140°F temperature and up to 1000 psig pressure by chemically reacting with the basic amine functional group in the absorbent, for example, primary amine, MEA, reacts with C02 by the following reaction forming a carbamate salt ... 

In case (1), the reaction is used for the removal of an undesirable substance from a gas stream. In this sense, the process is commonly referred to as gas absorption with reaction. Examples are removal of H2S or CO, from a gas stream by contact with an ethanolamine (e g., monoethanolamine (MEA) or diethanolamine (DEA)) in aqueous... 

---