Reaction ethanolamines production

Although carbon dioxide must be generated on site for some processes, there is a trend toward carbon dioxide recovery where it is a major reaction by-product and, in the past, has been vented to the atmosphere. An absorption system, such as the use of ethanolamines (q.v.) or hot carbonate or bicarbonate solutions, is used for concentrating the carbon dioxide to over 99% purity. 

BBN reduces aldehydes and ketones rapidly and cleanly to the corresponding alcohols [1]. The reaction is carried out by the dropwise addition of an essentially stoichiometric quantity of 9-BBN solution in THF to the aldehyde or ketone in THF solution at 25 °C. After completion of the reaction, the product carbinol is isolated by either of the following procedures. After the reaction is over, the reaction mixture is treated with alkaline hydrogen peroxide to oxidize the 9-BBN moiety, and the alcohol is separated from the cA-l,5-cyclooctanediol by distillation. Alternatively and more conveniently, THF is removed and -pentane is added to the reaction mixture. The addition of 1 mol of ethanolamine precipitates the 9-BBN moiety as the adduct, displacing the carbinol to the pentane layer quantitatively. After removal of pentane, the desired alcohol is obtained in quantitative yields by distillation (Scheme 25.1). The process is an excellent neutral workup procedure for compounds having acid-and base- sensitive groups. In addition to pentane, ether and benzene also work quite satisfactorily. 

An example of mixed parallel and series reactions is the production of ethanolamines by reaction between ethylene oxide and ammonia ... 

Petroleum and Goal. The alkanolarnines have found wide use in the petroleum industry. The ethanolamines are used as lubricants and stabilizers in drilling muds. Reaction products of the ethan olamines and fatty acids are used as emulsion stabilizers, chemical washes, and bore cleaners (168). Oil recovery has been enhanced through the use of ethan olamine petroleum sulfonates (169—174). OH—water emulsions pumped from wells have been demulsifted through the addition of triethanolarnine derivatives. Alkanolarnines have been used in recovering coal in aqueous slurries and as coal—oil mix stabilizers (175—177). 

Ethanolamines. These are produced by the reaction of ethylene oxide and ammonia (see Alkanolamines). Approximately one-third of the production is used in detergents. Other appHcations include natural gas purification, cosmetics, metalworking, textiles, and chemical intermediates (282). 

Reaction of dibenzylamine with ethylene oxide affords the amino alcohol, 82. Treatment of that product with thionyl chloride gives the a-sympathetic blocking agent, dibenamine (83). (Condensation of phenol with propylene chlorohydrin (84) gives the alcohol, 85. Reaction with thionyl chloride affords the chloride (86). Use of the halide to alkylate ethanolamine affords the secondary amine (87). Alkylation of this last with benzyl chloride... 

Reaction of ciclopirox with ethanolamine gives the desired product. 

Ethanolamines are important absorbents of acid gases in natural gas treatment processes. Another major use of ethanolamines is the production of surfactants. The reaction between ethanolamines and fatty acids... 

Sheratte55 reported the decomposition of polyurethane foams by an initial reaction with ammonia or an amine such as diethylene triamine (at 200°C) or ethanolamine (at 120°C) and reacting the resulting product containing a mixture of polyols, ureas, and amines with an alkylene oxide such as ethylene or propylene oxide at temperatures in the range of 120-140°C to convert the amines to polyols. The polyols obtained could be converted to new rigid foams by reaction with the appropriate diisocyanates. 

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]. 

Recently, an environmentally benign and volume efficient process for enzymatic production of alkanolamides has been described where CALB catalyzes the amidation of lauric acid and ethanolamine in the absence of solvent, at 90 °C, to keep the reactants in a liquid state and to remove the water [18]. The enzyme was both very active and stable under the reaction conditions, with about half of the activity remaining after two weeks, obtaining the final amide with a 95% yield (Scheme 7.6). 

Whereas silylation-amination of 2-amino-5,8-dihydroxypyrimido[4,5-d]pyridazine 269 with 3-amino-l-propanol, HMDS 2, and TsOH affords, after 24 h at 120-140 °C, the mono-8-hydroxypropylamino derivative 270 in 50% yield [79], reaction of 269 with a shght excess of ethanolamine and HMDS 2 provides, after 30 h at 120-150°C, only 20% of the bis(amino) product 271 [79]. (Scheme 4.31) A larger excess of ethanolamine and longer reaction times wiU certainly increase the yield of 271. 

The synthesis of ethylenediamine (EDA) from ethanolamine (EA) with ammonia over acidic t3pes of zeolite catalyst was investigated. Among the zeolites tested in this study, the protonic form of mordenite catalyst that was treated with EDTA (H-EDTA-MOR) showed the highest activity and selectivity for the formation of EA at 603 K, W/F=200 g h mol, and NH3/ =50. The reaction proved to be highly selective for EA over H-EDTA-MOR, with small amounts of ethyleneimine (El) and piperazine (PA) derivatives as the side products. IR spectroscopic data provide evidence that the protonated El is the chemical intermediate for the reaction. The reaction for Uie formation of EDA from EA and ammonia required stronger acidic sites in the mordenite channels for hi er yield and selectivity. 

Allylic boranes such as 9-allyl-9-BBN react with aldehydes and ketones to give allylic carbinols. The reaction begins by Lewis acid-base coordination at the carbonyl oxygen, which both increases the electrophilicity of the carbonyl group and weakens the C-B bond to the allyl group. The dipolar adduct then reacts through a cyclic TS. Bond formation takes place at the 7-carbon of the allyl group and the double bond shifts.36 After the reaction is complete, the carbinol product is liberated from the borinate ester by displacement with ethanolamine. Yields for a series of aldehydes and ketones were usually above 90% for 9-allyl-9-BBN. 

From a separation-process point of view, a fluid-fluid reaction is intended to enhance separation (e.g., preparation of feed for a subsequent process step, product purification, or effluent control for environmental protection). Examples include the use of ethanolamines for the removal of H2S and C02 (reactions (A) and (B) in Section 9.2), the removal of SO, by an aqueous stream of a hydroxide, and absorption of 02 by blood or desorption of C02 from blood. A solid catalyst may be involved as a third phase, as in hydrodesulfurization in a trickle-bed reactor. 

To the reaction flask is added 200 ml. of ethanolamine, and it is heated to 140° with stirring. The slurry above is added in moderate portions over a 40- to 50-minute period (Note 7). When the heating bath is maintained at 230-240°, the addition of the slurry should provide an inner temperature at 120-140° as the water and oily product distill. After the addition is complete, the dropping funnel is rinsed with 100-150 ml. of water. As soon as the inner temperature has reached 160°, 50 ml. of ethanolamine is added and the temperature is maintained at 160-170° for 20 minutes. Water (50 ml.) is added through the dropping funnel to initiate a rapid steam distillation. Steam distillation is continued by the addition of 50-ml. portions of water at an inner temperature of 120-140° and a bath temperature of 230-240° until no more oil appears in the distillate (Note 8). 

Dillard, C. J., and A. L. Tappel. Fluorescent products from reaction of peroxidiz-ing polyunsaturated fatty acids with phosphatidyl ethanolamine and phenylalanine. Upids 8 183-189, 1973. 

A mixture of concentrated sulfuric and nitric acids has been used for the A-nitration of amides and ureas. A, A -Dinitro-A,A -bis(2-hydroxyethyl)oxamide dinitrate (NENO) (11) is prepared from the action of mixed acid on A, A -bis(2-hydroxyethyl)oxamide (61), itself prepared from the condensation of diethyloxalate with two equivalents of ethanolamine. Niuo-sylsulfuric acid is an inhibitor of A-nitration and so nitrous acid should be rigorously excluded. The reaction of (61) with absolute nitric acid results in 6>-nitration of the hydroxy groups but no A-nitration, and consequently, (62) is isolated as the sole product. 

Introduction of a halogen atom into the amine component is not possible, but an alternative solution is represented by the use of ethanolamines 26, performing the cyclization under Mitsunobu or Mitsunobu-like conditions to give ketopiperazines. These compounds have been observed as side products in reactions promoted by... 

Ethanolamines are made by reacting ethylene oxide and excess ammonia, followed by separation of unreacted ammonia and the three ethanolamines. The proportion of the three products depends on reaction conditions. 

In contrast to NjPjCle, N4P4Q8 is extremely reactive towards difunctional reagents. This has led to the isolation of several decomposition products. Reactions with Af-methyl ethanolamine [87], 1,3-propane diol and 1,3-diamino propane afford mainly spiro products [138]. A detailed investigation on the reactions of N4P4CI8 with HO- CH2) -OH (n = 3, 4) has revealed that... 

Ethanolamines became available commercially in the early 1930s they assumed steadily growing commercial importance as intermediates after 1945, because of the large-scale production of ethylene oxide. Since the mid-1970s, economical production of very pure, colourless ethanolamines has been possible. Ethanolamines are produced on an industrial scale exclusively by reaction of ethylene oxide (see lARC, 1994) with excess ammonia. This reaction takes place slowly but is accelerated by water. An... 

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