Olamine

Ciclopirox olamine is available as a 1% cream and lotion applied topically for the treatment of cutaneous candidiasis and tinea corporis, cruris, pedis, and versicolor. 

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The nitro alcohols can be reduced to the corresponding alkan olamines (qv). Commercially, reduction is accompHshed by hydrogenation of the nitro alcohol in methanol in the presence of Raney nickel. Convenient operating conditions are 30°C and 6900 kPa (1000 psi). Production of alkan olamines constitutes the largest single use of nitro alcohols. 

In certain cases, alkanolamines function as reduciag agents. For example, monoethanolamine reduces anthraquiaone to anthranols, acetone to 2-propanol, and azobenzene to aniline (17). The reduction reaction depends on the decomposition of the alkan olamine iato ammonia and an aldehyde. Sinulady, diethan olamine converts o-chloronitrobenzene to 2,2 -dichloroazobenzene and y -dinitrobenzene to 3,3 -diamiQoazobenzene. 

Monoethan olamine can also be reduced catalyticaHy with hydrogen and ammonia over Raney nickel at 200°C and 20.7 MPa (3000 psig) to produce ethylenediamiue //(97-/NT/(18,19). 

ALkanolainines aie manufactuied fiom the coiiesponding oxide and ammonia. Anhydtous 01 aqueous ammonia may be used, although anhydtous ammonia is typically used to favor mono alkan olamine production and requires high temperature and pressure (20). Mono-, di-, and trialkanolamines are produced in the reactor and sent to downstream columns for separation (Fig. 2). 

Generally, alkan olamines are analyzed by gas chromatography or wet test methods. Details on gas chromatography conditions are available in the fiterature (1) for packed or glass capillary columns. 

Apparent equivalent weight can be deterrnined by titration with hydrochloric acid using a bromocresol green indicator. Calculations give the equivalent weight of total amines and are not specific for the mono-, di- or tri alkan olamines. 

Storage tanks, lines, and pumps should be heat traced and insulated to enable product handling. Temperature control is required to prevent product degradation because of color alkan olamines have poor heat transfer properties. Exposure to air will also cause product discoloration. Storage tanks should be nitrogen-padded if low color product is required. 

Reactions of monoethan olamine with mild steel are referenced in the Hterature (23). The complex formed, identified as triseth an o1 amin o—iron, can decompose in air to pyrophoric iron, with the potential to cause a fire, if contacted with combustible materials. 

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). 

Oral Toxicity. Alkan olamines generally have low acute oral toxicity, but swallowing substantial quantities could have serious toxic effects, including injury to mouth, throat, and digestive tract. 

Concentrated monoethan olamine and monoisopropan olamine can cause severe local irritation or even bums to the mouth, throat, and digestive tract. If monoethan olamine and monoisopropan olamine are swallowed, large volumes of milk or water should be administered immediately. If diethanolamine, triethanolamine, diisopropanolamine, or triisopropanolamine are swallowed, vomiting should be induced after drinking two glasses of water. 

Vapor Toxicity. Laboratory exposure data indicate that vapor inhalation of alkan olamines presents low hazards at ordinary temperatures (generally, alkan olamines have low vapor pressures). Heated material may cause generation of sufficient vapors to cause adverse effects, including eye and nose irritation. If inhalation exposure is likely, approved respirators are suggested. Monoethan olamine and diethanolamine have OSHA TLVs of 3 ppm. 

Eye Irritation. Exposure of the eye to undiluted alkan olamines can cause serious injury. Solutions as dilute as 1% of monoethan olamine and monoisopropan olamine can cause some eye irritation. 

Skin Irritation. Monoethan olamine and monoisopropan olamine, being strongly alkaline, are skin irritants, capable of producing serious injury in concentrations of 10% or higher upon repeated or prolonged contact. Occasional short contact, assurning the material is thoroughly washed off, should have httle adverse effect. 

Diethanolamine, diisopropanolamine, and isopropan olamine mixtures are less irritating to the skin than MEA and MIPA however, any one of them may produce severe skin irritation, even mild bums, if contact is prolonged or frequently repeated. Occasional short contact should not result in more than slight irritation. Undiluted triethanolamine and triisopropan olamine are slightly to moderately irritating to the skin. A bum may result from prolonged and repeated contact. Short occasional contact and solutions of less than 10% concentration are unlikely to cause more than very slight irritation, if any. 

Monoethan olamine and monoisopropan olamine may be moderately toxic by absorption through the skin. The other amines are low in toxicity by this route and are not likely to be absorbed in acutely toxic amounts. In the event of skin contact, clothing and shoes should be removed promptly, and the skin thoroughly washed with water. Contaminated clothing should be thoroughly cleaned before reuse shoes and leather products should be discarded. 

Strong oxidizers and strong acids are incompatible with nikanolamines. Reactions, generating temperature and/or pressure increases, may occur with halogenated organic compounds. Alkan olamines are corrosive to copper and brass and may react. Contact with aluminum by alkan olamines, particularly when wet or at elevated temperatures (60°C), should be avoided. 

Gleaners. Properties, such as foaming and detergency (qv), make alkanolamines useflil in cleaning formulations. Monoetbanolamine is particularly effective in wax removal formulations because of its ability to penetrate films. Cleanets that involve skin contact use triethanolamine because of its mildness. Derivatives of the amines (49,50) as well as the free alkan olamines (51—53), may be formulated into cleaning products. 

Alkan olamines ate used in urethane coatings for glass shatter proofing (68) and have been utilized as amides, salts, or free amines in providing antifrosting, antifogging, and dirt-resistant films on glass and plastics (69—72). 

Cosmetics and Personal Care Products. Alkanolamines ate important taw materials in the manufacture of creams (95—97), lotions, shampoos, soaps, and cosmetics. Soaps (98) formed from triethanolamine and fatty acids ate mild, with low alkalinity and excellent detergency. Triethanolamine lauryl sulfate is a common base for shampoos (99—101) and offers significant mildness over sodiumlauryl sulfate. Diethanolamine lauryl sulfate and fatty acid soaps of mono- and trietban olamine can also be used in shampoos and bubble bath formulations. Chemistry similar to that used in soluble oils and other emulsifiers is appUcable to cleansing creams and lotions (102,103). Alkanolamides or salts ate added to the shampoo base to give a smooth, dense foam (104). 

The new Uquid laundry detergents, with no phosphates, have developed a use for alkan olamines. In nonenzyme formulations, they contribute alkalinity, pH control, and enhanced product stabiUty. In enzyme products, alkan olamines contribute to the stabiUty of the enzyme in water solutions (107). 

Alkan olamines ate also used in formulations for removing photoresists (114,115) and cleaning printed-ckcuit boards (116). Formulations containing diethanolamine ate used for electrodip coating of substrates (117). 

Various documents relate to the use of formulations containing trietban olamine as flux for a variety of metals (118,119), for solders (120), for soldering pastes (121,122), and for low corrosion solder pastes (123). 

Work continues on improving the efficiency of this process, such as for freeing the alkan olamine from heat-stable salts that can form (125). Formulations have been developed which inhibit degradation of mono- and diethanolamine in processing (126). Models (127), computer programs (128), and kinetics and enthalpies (129—136) have been developed to help determine equiUbria of the acid gas—alkanolamine—water system. Additional references relate to the use of tertiary alkan olamines, such as triethanolamine, for gas conditioning (137—139). 

Extensive work has been done on corrosion inhibitors (140), activated carbon use (141—144), multiple absorption zones and packed columns (145,146), and selective absorption and desorption of gas components (147,148). Alkan olamines can also be used for acid gas removal in ammonia plants (149). 

Methyl dietb an olamine (MDEA) and solutions of MDEA have increased in use for gas treating (150,151). Additional gas treating capacity can often be obtained with the same working equipment, because of the higher amine concentrations that can be used. 

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). 

Triisopropan olamine is used in natural mbber cross-linking and as a color stabilizer for polyethylene formulations. Chain termination of polybutadiene with triisopropan olamine gives improved cold-flow properties. 

Pigment Dispersion. The alkan olamines and thek derivatives are useful in dispersing titanium dioxide and other pigments (209). Monoisopropanolamine and triethanolamine are particularly effective in aiding titanium dioxide dispersion in the production of Ti02 and in water-based paints (210). The alkan olamines are also an aid in the grinding of titanium dioxide (211). 

Alkan olamines are used in the manufacture of a variety of pharmaceutical compounds. Some of these products include antitumor agents, anti-inflammatory and allergy agents, and anticonvulsants. The Hterature reports ethan olamine derivatives in the treatment of Alzheimer s disease (216), the treatment of cerebral psychoorganic syndromes (217), and veterinary dmgs (218). 

The major use of alkan olamines in agricultural products is as a neutralizer for acidic herbicides. They also contribute increased water solubiUty, reduced volatility, and more uniform solutions. Various ethan olamines are reported in formulations to improve potato tuber size (219) and enhance the resistance to salt of some crops (220). 

A variety of appHcations, including photography, employ alkan olamines for pH control. Reports have described formulations including mon oeth an olamine and triethanolamine in films and processing (221—224). 

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