Carbodiimides

Optically active thiazoline-5-ones (203) can be obtained when cycliza-tion of an optically active N-thiobenzoyl amino acid is brought about by the use of dicyclohexyl carbodiimide in pure chloroform, dich-loromethane (455), or tetrahydrofuran (453. 456) (Scheme 104). 

The selenoureas needed for condensation can usually be prepared by addition of hydrogen selenide to a solution of the corresponding cyanamides or carbodiimides. They can be less dangerously and quite... 

Carbodiimides (cyanamides) —N=C=N— 2140-2125 (s) 2150-2100 (vs) 1460 1150-1140 (vs) Asymmetric stretching of aliphatics Asymmetric stretching of aromatics two bands Symmetrical stretching of aliphatics Symmetric stretching of aryls... 

Bisa2iridine compounds and A/-(2-chloroethyl)carbodiimides have also been prepared using isocyanide dichlorides and ethyleneimine (178,179). The iodide-cataly2ed rearrangement of the formerly mentioned compounds provides a method for preparing the tetrahydroimida2oimida2ole system ... 

The available free carboxyl groups of the DAS—HMS can be linked via a peptide bond to available primary amine groups onto highly antigenic carriers using a carbodiimide (19). The carriers used in this case were bovine semm albumin (BSA) and poly-L-lysine (molecular weight 150,000 to 300,000). The... 

Carbodiimide formation is markedly accelerated when phosphine oxides (R PO) or phosphates are used as catalysts. Intermediates with P—NR bonds have been postulated as iatermediates ia these reactioas (59,60). 

Some of these isocyanates are commercially available in derivatized form, such as biurets and carbodiimides, to provide materials having improved handling or processing characteristics. 

Garbodiimide Formation. Carbodiimide formation has commercial significance in the manufacture of Hquid MDI. Heating of MDI in the presence of catalytic amounts of phosphine oxides or alkyl phosphates leads to partial conversion of isocyanate into carbodiimide (95). The carbodiimide (39) species reacts with excess isocyanate to form a 2 + 2cycloaddition product. The presence of this product in MDI leads to a melting point depression and thus a mixture which is Hquid at room temperature. 

Also, the presence of strong bases, even in trace amounts, can promote the formation of isocyanurates or carbodiimides. In the event of gross contamination, the exothermic reaction can sharply increase the temperature of the material. Normally, the trimerization reaction occurs first and furnishes heat for the carbodiimide reaction. The carbodiimide reaction Hberates carbon dioxide and forms a hard soHd. The Hberation of carbon dioxide in a sealed vessel could result in overpressurization and mpture. 

Other six-membered rings with two heteroatoms are also obtained from reaction of diketene with imidates, cyanamides, carbodiimides, isocyanates, oxa2olines, or other multiftmctional compounds. 

Anhydride Formation. The carboxyl group ia A/-protected amino acids is converted iato the symmetrical anhydride on treatment with the carbodiimide (84). 

Other Reactions. 2-Dioxolaniniines, 2-oxathiolaniniines, and 2-oxa2o1idinimines result from the reaction of propylene oxide with isocyanates, isothiocyanates, and carbodiimides, respectively (103,104). 

An intramolecular Diels-Alder cyclization produces excellent yields of 2-aminoquinoline-3-carboxylate esters (57). Equally fine yields of the requited carbodiimides have been reported, making this an attractive route to an unusual substitution type. 

By a suitable choice of activating reagents, primary and secondary alcohols can be selectively oxidi2ed to carbonyl compounds in good yields at room temperatures. Typical activating reagents are acetic anhydride, sulfur trioxide—pyridine, dicyclohexyl carbodiimide, and phosphoms pentoxide (40). 

Modification of cellular polymers by incorporating amide, imide, oxa2ohdinone, or carbodiimide groups has been attempted but only the urethane-modified isocyanurate foams are produced in the 1990s. PUIR foams often do not require added fire retardants to meet most regulatory requirements (34). A typical PUIR foam formulation is shown in Table 6. 

Ionic polymers are also formulated from TDI and MDI (43). Poly(urethane urea) and polyurea ionomers are obtained from divalent metal salts of /)-aminohen2oic acid, MPA, dialkylene glycol, and 2,4-TDI (44). In the case of polyureas, the glycol extender is omitted. If TDI is used in coatings apphcations, it is usually converted to a derivative to lower the vapor pressure. A typical TDI prepolymer is the adduct of TDI with trimethyl olpropane (Desmodur L). Carbodiimide-modified MDI offers advantages in polyester-based systems because of improved hydrolytic stabihty (45). Moisture cure systems based on aromatic isocyanates are also available. 

Gyanamides and Derivatives A/-Chloro-/-alkylcyanamides, RN(C1)CN, are oils that have medicinal and other appHcations (99). Primary and secondary alkyl-A/-chlorocyanamides add photochemically to olefins yielding 1 1 adducts. By contrast, A/-chloro-A/-/-butylcyanamide initially rearranges photochemically to A/-chloro-Af-/-butylcarbodiimide, (CH2)3CN=C=NC1, prior to addition to olefins giving carbodiimides (67,100). 

Olefin isomerization can be catalyzed by a number of catalysts such as molybdenum hexacarbonyl [13939-06-5] Mo(CO)g. This compound has also been found to catalyze the photopolymerization of vinyl monomers, the cyclization of olefins, the epoxidation of alkenes and peroxo species, the conversion of isocyanates to carbodiimides, etc. Rhodium carbonylhydrotris(triphenylphosphine) [17185-29-4] RhH(CO)(P(CgH )2)3, is a multifunctional catalyst which accelerates the isomerization and hydroformylation of alkenes. 

Dime thy laminopropy I )-3-ethylcarbodiimide hydrochloride [l-ethyl-3-(3-dimethyl-aminopropyl) carbodiimide hydrochloride] see entry on p. 212 in Chapter 4. 

One inherent weakness of Vulkollan-type materials is their susceptibility to hydrolysis. Life in a humid environment may, however, be doubled by the incorporation of 2 pphr (parts per hundred resin) of a carbodiimide. 

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