Ethanolamine production

Fig. 2. Flow sheet for ethanolamine production. EO = ethylene oxide MEA, DEA, and TEA ate defined in Table 1.

The ability of pyruvate decarboxylase from many microbial sources to produce phenylacetylcarbinol has been exploited for many years in the synthesis of ephedrine, a natural adrenergic compound (92). The acyloin is reductively aminated to produce the ethanolamine product, (1R,2S)-ephediine, with two chiral centers. 

Figure 11.1 Representative product-ion mass spectrometric analyses of protonated acylcar-nitine, protonated acyl CoA, deprotonated acyl CoA, and protonated Al-acyl ethanolamine. Product-ion ESI-MS analyses of protonated palmitoylcarnitine (a), protonated palinitoyl CoA (b), deprotonated palmitoyl CoA (c), and protonated Al-palmitoyl ethanolamine (d) were performed at collision energy of 23, 57, 43, and 18 eV, respectively, by using a QqQ mass spectrometer (Thermo Fisher TSQ Vantage). Gas pressure of 1 mTorr was employed in the collision activation.

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

Lecithin. Lecithin [8002-43-5] (qv) is a mixture of fat-like compounds that includes phosphatidyl choline, phosphatidyl ethanolamines, inositol phosphatides, and other compounds (37). Commercial lecithin was originally obtained from egg yolks, but is now extracted from soybean oil. Lecithin is used in many products, including margarine, chocolate, ice cream, cake batter, and bread. 

U.S. capacity of the etbanolamines ia 1989, almost one-half of global capacity, was estimated to be 379,000 t. Global capacity for 1989 was estimated at 692,000 t. Estimated annual U.S. production figures are Hsted in Table 3 (21). U.S. consumption of ethanolamines for various appHcations is shown in Table 4. 

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). 

In a typical gas oil design, the lighter products overhead from the quench tower/primary fractionator are compressed to 210 psi, and cooled to about 100°F. Some Q plus material is recovered from the compressor knockout drums. The gases are ethanolamine and caustic washed to remove acid gases sulfur compounds and carbon dioxide, and then desiccant dried to remove last traces of water. This is to prevent ice and hydrate formation in the low temperamre section downstream. 

An explosion and fire (March 13, 1991) occurred at an ethylene oxide unit at Union Carbide Chemicals Plastics Co. s Seadrift plant in Port Lavaca, TX, 125 miles southwest of Houston. The blast killed one, injured 19, and idled the facility, that also produces ethylene, ethylene glycol, glycol ether ethanolamines, and polyethylene. Twenty-five residents were evacuated for several hours as a safety precaution. The plant lost all electrical power, for a few days, because its cogeneration unit was damaged. The Seadrift plant, with 1,600 workers, is capable of making 820 million lb per year of ethylene oxide which is one-third of Carbide s worldwide production of antifreeze, polyester fibers, and surfactants Seadrift produces two thirds of Carbide s worldwide production of polyethylene. 

The simplification of the local anesthetic phaimacophore of cocaine to an aryl substituted ester of ethanolamine has been described previously. Atropine (S2) is a structurally closely related natural product whose main biologic action depends on inhibition of the parasympathetic nervous system. Among its many other actions, the compound exerts useful spasmolytic effects. 

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. 

Ethylene oxide is a precursor for many chemicals of great commercial importance, including ethylene glycols, ethanolamines, and alcohol ethoxylates. Ethylene glycol is one of the monomers for polyesters, the most widely-used synthetic fiber polymers. The current US production of EO is approximately 8.1 hillion pounds. 

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... 

Monoethanolamine (MEA), ethanolamine (ETA) 2-aminoethanol 2-hydroxyethylamine Nt CPLjCHjOH. MW = 61.1. Sp. gr. = 1.012. Flash point 93 °C. Also used as an absorbent for acidic gases in petrochemical operations. A breakdown product of morpholine and so is often found in secondary steam cycles systems. Thought to be superior to morpholine. Available as a 99+% alkylamine, commodity product, from several international manufacturers, including BP Chemicals PLC, Union Carbide, and Texaco Corporation. Commonly available through chemical distributors. 

Cocamide ethanolamines are used as foaming agents in shampoos and bath products and as emulsifying agents in cosmetics. 

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. 

Example 5. Glycolysis of Polyurethanes with Propylene Oxide after Pretreatment with Ethanolamine.55 A rigid polyurethane foam (ca. 100 g) was dissolved in 30 g ethanolamine by heating. Excess ethanolamine was stripped, leaving a clear solution. Infrared and GPC analysis indicated that the clear solution obtained contained some residual polyurethane, aromatic polyurea, aliphatic polyols, aromatic amines, and N,N -bis(f -hydroxyethyljurea. Next the mixture was dissolved in 45 g propylene oxide and heated at 120°C in an autoclave for 2 h. The pressure increased to 40 psi and then fell to 30 psi at the end of the 2-h heating period. The product was a brown oil with a hydroxyl number of485. 

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. 

Soya lecithin is a natural product which contains about 34% glycerides (soya oil), 5% sugars, and 61% phosphatides. The phosphatides in turn are comprised of phosphatidyl choline, i.e., chemical lecithin (20%), phosphatidyl ethanolamine (20%), and phosphatidyl inositol (21%). 

This strategy has resulted in entirely new formulations with remarkable benefits. Sustainable Earth (SE) cleaning products combine reagents determined to be safer for human and environmental health with a positively characterized hybrid surfactant system containing a stabilized oxidizing compound. This system eliminates conventional ingredients such as alkyl glycol ethers, alkali builders, alkylphenol ethoxylates, EDTA and ethanolamine. 

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. 

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