Ethanolamines, and

A brief summary of safety and health hazards follows detailed health hazards, however, should be obtained from producers by requesting Material Safety Data Sheets. Proper protective equipment and exposure hazards should be noted before handling any alkan olamine. Detailed toxicological testing is found in the CTEA Chemical Ingredient Review Board Reports on ethanolamines and isopropanolamines (24). 

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) ... 

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. 

Corti and Manfrida [2] have also done detailed calculations of the performance of plant A2. They drew attention to the need to optimise the amines blend (including species such as di-ethanolamine and mono-ethanolamine) in the absorption process, if a removal efficiency of 80% is to be achieved and in order to reduce the heat required for regenerating the scrubbing solution. Their initial estimates of the penalty on efficiency are comparable to those of Chiesa and Consonni (about 6% compared with the basic CCGT plant) but they emphasise that recirculation of water from... 

Plasmalogens are ether glycerophospholipids in which the alkyl moiety is d5-a,/3-unsaturated (Figure 8.10). Common plasmalogen head groups include choline, ethanolamine, and serine. These lipids are referred to as phosphati-dal choline, phosphatidal ethanolamine, and phosphatidal serine. 

Phosphatidylethanolamine synthesis begins with phosphorylation of ethanol-amine to form phosphoethanolamine (Figure 25.19). The next reaction involves transfer of a cytidylyl group from CTP to form CDP-ethanolamine and pyrophosphate. As always, PP, hydrolysis drives this reaction forward. A specific phosphoethanolamine transferase then links phosphoethanolamine to the diacylglycerol backbone. Biosynthesis of phosphatidylcholine is entirely analogous because animals synthesize it directly. All of the choline utilized in this pathway must be acquired from the diet. Yeast, certain bacteria, and animal livers, however, can convert phosphatidylethanolamine to phosphatidylcholine by methylation reactions involving S-adenosylmethionine (see Chapter 26). 

Due to the convenience of the Wenker aziridine formation from P-aminoethyl sulfate ester (4) and base, many improvements ensued. Leighton et al. improved the yield of the first step for the formation of sulfate ester 4. First of all, both ethanolamine and 95% sulfuric acid were diluted with half of their weight of water and then slowly mixed together at 0 C. Finally, by keeping the temperature below 145 C, sulfate ester 4 was obtained in 90-95% yield. 

A variety of inorganic (31,87) and organic bases have been added to the catalyst to improve selectivity. The effectiveness of organic bases is very sensitive to structure. Morpholine is an effective inhibitor, more so than /Si-melhylmorphollne > N-elhylmorpholine > 3,5-dimethylmorpholine (55). Piperazine is effective, but ethanolamine and ethylenediamine are poisons. 

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... 

Neutralization agents may be caustic soda (predominantly), ammonia, mono-ethanolamine, and triethanolamine. Examples of reaction equations are as follows ... 

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]. 

Hauser, H., Pascher, I., Pearson, R.H. Sundell, S. (1981). Preferred conformation and molecular packing of phosphatidyl ethanolamine and phosphatidylcholine. Biochimica Biophysica Acta, 650, 21-51. 

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. 

WENG x c and Gordon m h (1993) Antioxidant synergy between phosphatidyl ethanolamine and oc-tocopherylquinone . Food Chem, 48 (2) 165-8. 

Ethanolamines and polyphosphates slow the reaction down as a whole. Both tetrahydrofurantetracarboxylic acid and polyphosphates are sometimes to be found in commercial examples. 

Ferromagnetic starch 1-50 Extracorporeal maneuvering to tumor tissue after IV injection Ethanolamine and albumin as model compounds... 

Azaacetals Oxazolidines are formed from ethanolamines and aldehydes or ketones. The C-O bond in oxazolidines can be cleaved selectively by catalytic hydrogenolysis (Scheme 4.15). 

More complex hydrophilic moieties are sometimes encountered, however, such as mono-, di- and tri-ethanolamine and the corresponding isopropanolamines in anionic surfactants. Morpholine, once employed, is now obsolete owing to its toxicity. 

This process probably occurs in vivo because the adduct of ethanolamine and p-hydroxyphe-nylacetaldehyde is abundant in the phospholipids of LDL exposed to activated neutrophils and tyrosine. 

AMISOL A process for removing sulfur compounds and carbon dioxide from refinery streams by absorption in methanol containing mono- or di-ethanolamine and a proprietary additive. Developed by Lurgi, Germany, in the 1960s and first commercialized in the early 1970s. 

Figure 12.12 Sphingomyelins. Sphingomyelins are esters of a ceramide and phospho-ryl choline. However, similar compounds are ceramide-1-phosphoryl ethanolamines and phosphono forms of sphingolipids. Ceramides W-acyl-sphingosines) are amides of a long chain di- or trihydroxy base containing 12 to 22 carbon atoms, of which sphingosine (4-sphingenine) is the commonest, and a long chain fatty acid whose acyl chain is shown by R1. This may contain up to 26 carbon atoms.

Ninhydrin 2 g 1 1 in acetone Containing free amino groups Purple spots appear with phosphatidyl ethanolamine and phosphatidyl serine, for instance, after heating at 100°C... 

The majority of PC is synthesized in mammalian cells by the CDP-choline or Kennedy pathway in the endoplasmic reticulum (Eigiue 1). In this pathway, choline taken up from the external medium or released in the cytosol by breakdown of choline containing compoimds, is first converted to phosphocholine by the enzyme choline kinase (CK) (Ishidate, 1997). There are two isoforms of CK cloned which both can convert also ethanolamine to phosphoethanolamine, albeit with a lesser affinity (Aoyama et al 2000). Alternatively phosphocholine can be generated by enzymes that preferentially phosphorylate ethanolamine and are therefore designated ethanolamine kinases (EK). As yet also two different EKs are known (EKI 1 and 2 Lykidis etal., 2001). 

Finally PC is made by releasing the CMP group in the process of fusing phosphocholine to diacylglycerol (DAG) by the enzyme CDP-choline 1,2-diacylglycerol choUnephosphotransferase (CPT McMaster and Bell, 1997). One cloned isoform of CPT seems specific for CDP-choUne, whereas another CPT also can synthesize PE from CDP-ethanolamine and DAG (Henneberry and McMaster, 1999 Heimeberry et al., 2000). 

ET), which catalyzes the formation of CDP-ethanolamine, and (iii) an ethanolaminephosphotransferase (EPT), which finally synthesizes PE from DAG and CDP-ethanolamine. As discussed rmder PC synthesis, four enzymes have been cloned that can phosphorylate ethanolamine, two of which preferentially use ethanolamine as a substrate, and two which are more specific for choline. Only one isoform of ET has been cloned, which contains two active sites, but seems to be not as strictly regulated compared to its counterpart CT (Bladergroen et al, 1999a). 

Maulik, N., Kagan, M.V., Tyuiin, V., and Das, O.K., 1998 Redistribution of phosphahdyl-ethanolamine and phosphatidyseiine precedes reperfusion-induced apoptosis. Am. J, Physiol. 274 H242-H248... 

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. 

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