Urea Adducts

The history of iaclusion compounds (1,2) dates back to 1823 when Michael Faraday reported the preparation of the clathrate hydrate of chlorine. Other early observations iaclude the preparation of graphite iatercalates ia 1841, the P-hydroquiaone H2S clathrate ia 1849, the choleic acids ia 1885, the cyclodexthn iaclusion compounds ia 1891, and the Hofmann s clathrate ia 1897. Later milestones of the development of iaclusion compounds refer to the tri-(9-thymotide benzene iaclusion compound ia 1914, pheaol clathrates ia 1935, and urea adducts ia 1940. 

Various techniques have been proposed for the recovery of pure succinic acid, including extraction (141—145), selective crystalliza tion (146—151), heating to dehydrate the acid and subsequent recovery of succinic anhydride by distillation (152), esterification foUowed by fractionation of the mixture of the esters (65—69), and separation as urea adduct (118,119). 

Norma/andBranc/jedAlip/jatic Hydrocarbons. The urea-adduction method for separating normal and branched aHphatic hydrocarbons can be carried out in sulfolane (38,39). The process obviates the necessity of handling and washing the soHd urea—normal paraffin adduct formed when a solution of urea in sulfolane is contacted with the hydrocarbon mixture. OveraH recovery by this process is typicaHy 85% normal paraffin purity is 98%. 

Currently, there is continuing work on an iadustry standard method for the direct determination of monomer, dimer, and trimer acids. Urea adduction (of the methyl esters) has been suggested as a means of determining monomer ia distilled dimer (74). The method is tedious and the nonadductiag branched-chain monomer is recovered with the polymeric fraction. A micro sublimation procedure was developed as an improvement on urea adduction for estimation of the polymer fraction. Incomplete removal of monomer esters or loss of dimer duriag distillation can lead to error (75). 

Urea adduct Branched and cyclic alkanes, non-adduct V y Mono- aromatics Di- aromatics Tri- aromatics... 

FIGURE 3.6 Chiral helical hexagonal structure of urea and thiourea adducts. A chiral guest generates one helical form. (Straight chain alkyl guests fit in the urea adduct channel larger molecules such as trans-decalin fit in thiourea adduct channel.)... 

Further routes of cyclizations have been studied in parallel in the case of cis- and rra/J5-2-hydroxymethyl-l-cyclohexylamine (106) (880PP73). The preparation of thiourea or urea adducts 107 and 108 with phenyl isothiocyanate or phenyl isocyanate proceeds smoothly. The reaction of 107 with methyl iodide and subsequent alkali treatment, by elimination of methyl mercaptan, resulted in the iminooxazine 109 in high yields. The ring closures of both cis and trans thiourea adducts to 1,3-oxazines proceed with retention. Cyclodesulfuration of the adduct 107 by mercury(II) oxide or N,N -dicyclohexylcarbodiimide resulted in the iminooxazine 109, but the yield was low and the purification of the product was cumbersome. The ring closure of 108 with thionyl chloride led to the iminooxazine 109 in only moderate yield. 

F 0.1% H202-urea adduct (10.6 mM H2O2) in ddH20. Stable for several days in a refrigerator. 

H202-urea adduct (Mr 94,07) is used as a stable substance instead of H2O2 solution. The respective amounts of sodium percarbonate or sodium perborate are also suitable. 

Chemistry. Mabery showed early in this century that paraffin wax consists mainly of normal paraffins of C23H48 to C29HM (54) This work has been amply substantiated by combined fractional distillation and fractionations (11, 26, 62, 71) and recently by urea adducting (128). Most investigators also find that commercial products contain small amounts of naphthene-containing and possibly branched-paraffin molecules (65,69-71). These types of molecules melt lower than the normal paraffins for a given boiling point. They have been called soft waxes (11, 70). 

The microcrystalline or amorphous waxes separated from the crude fractions boiling above paraffin distillate are predominantly of the naphthene-containing paraffin structure (62, 70). Thus urea adducting of 149° to 165° F. melting point wax (Superla of Indiana) isolated but 15% of adductive material assumed to be normal or terminally branched paraffins. The microcrystalline waxes consist mostly of hydrocarbon with 34 to 60 carbon atoms (70) and have a melting range from 140° to 200° F. (16). 

Male Fischer 344 rats were exposed by inhalation to 1% 2-chloro-1,1,1 -trifluoroethane for 2 h and then urine was collected for 24 h. Urinary metabolites identified by 19F nuclear magnetic resonance and gas chromatography/mass spectrometry were 2,2,2-trifluoroethyl glucuronide (16%), trifluoroacetic acid (14%), trifluoroacetaldehyde hydrate (26%), trifluoroacetaldehyde-urea adduct (40%) and inorganic fluoride (3%). A minor, unidentified metabolite was also detected. No covalent binding of fluorine-containing metabolites was observed in the liver and kidney from the exposed rats (Yin et al., 1995). In-vitro incubation of 2-chloro-1,1,1-trifluoroethane with rat liver microsomes and an NADPH-generating system has been shown to involve a dechlorination reaction (Salmon et al., 1981) that produced trifluoroacetaldehyde hydrate as the only metabolite (Yin et al., 1995). 

Marine lipids with their diversity of unsaturated and branched chain acid moieties are a difficult class of materials to analyze. Ruminants (sheep, goats, cows, etc.) have a bacterial "factory" in the rumen which is able to produce branched-chain partially-hydrogenated lipids from ingested plant lipids. These lipids are incorporated into the milk and meat of the animals and eventually into animals which feed upon the ruminants. As a rule animal lipids are highly complex in comparison to plant materials. Although the branched chain materials are usually present in low concentration when compared to the common fatty acid moieties, complete description of these fats requires more sophisticated GC and thus long open tubular columns in tandem with mass spectrometry and computer analysis of the data has become an important approach. Even with a 100-m column, subcutaneous lipids of barley-fed lambs were so complex that prior fractionation with urea adducts was necessary (17). 

Chenite, A., and Brisse, F. (1992) Poly(tetrahydrofuran)-urea adduct a structural investigation, Macromolecules, 25, 776-782. 

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