Urazole

Submitted by Paul G. Gordon and Ludwig F. Audrieth Checked by P. LENsif 

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These compounds generally exist in carbonyl forms. The oxygen function can be converted into halogen by phosphorus halides. Reactions with electrophiles are quite complex. Thus urazole (511) reacts with diazomethane quickly to yield (512), which is more slowly converted into (513). 1-Phenylurazole gives (514) however, 4-phenylurazole yields (515). Oxadiazolinones of type (516) can be alkylated at both O- and N-atoms. 

Triazole has been prepared by the oxidation of substituted 1,2,4-triazoles, by the treatment of urazole with phosphorus pentasulfide, by heating equimolar quantities of formyl-hydrazine and formamide, by removal of the amino function of 4-amino-l,2,4-triazole, by oxidation of l,2,4-triazole-3(5)-thiol with hydrogen peroxide, by decarboxylation of 1,2,4-triazole-3(5)-carboxylic acid, by heating hydrazine salts with form-amide,by rapidly distilling hydrazine hydrate mixed with two molar equivalents of formamide, i by heating N,N -diformyl-hydrazine with excess ammonia in an autoclave at 200° for 24 hours, and by the reaction of 1,3,5-triazine and hydrazine monohydrochloride. ... 

Certain facts in the urazole series can also be interpreted in this way. Urazole (17) itself reacts with diazomethane quickly to yield 4-methyl-3-methoxy-l,2,4-triazolin-5-onc (18), which is more slowly converted to l,4-dimethyl-3-methoxy-l,2,4-triazolin-5-one (19). 1-Phenylurazolc gives 4-methyI-3-mcthoxy-l-plicnyl-l,2,4-triazolin-5-one (20) however, 4-phenylurazole yields the 1,2-dimethyl derivative (21). In the case of 4-methylurazole both O- and A"-methylation... 

The low temperature ene reaction of triazolinediones with polydienes occur under heterogeneous conditions to yield hydrophilic surfaces, especially after neutralization of the resulting pendant urazole groups. Permanent hydrophilic surfaces can be obtained when (TD)2DPM is used. The use of the other RTDs tested results in surfaces that lose their hydrophilicity within 5-20 days. In applications such as improving the adhesion of rubber to other substrates, these reagents are probably sufficient (18). However, when more permanent hydrophilic surfaces are desired a bis-triazolinedione such as (TD)2DPM would be required. 

Analogous reactions are reported for the synthesis of urazoles (1,2,4-triazacyclo-pentandione-3,5), monothiouracoles, and dithiouracoles.11491... 

Electron spin resonance (ESR) studies of the urazole-bridged 1,3 diradicals 64 derived from the azoalkanes 63 confirm a triplet ground state for these species. The nearly zero symmetry parameter, that is, Elhc= 0.0004 0.0001 cm-1, for the triplet diradical 64 of the diphenyl azoalkane 63 establishes a planar conformation <1995JOC308, 1997JA10673>. 

The radical cations of urazole-annelated azoalkanes 65 were generated by pulse radiolysis and the transients characterized spectrally and kinetically by time-resolved optical monitoring. The initial distonic 1,3 radical cations 66 were detected, and the methyl-substituted 66 further deprotonates to radical 67 (Scheme 1) <1997JA10673>. 

PTAD reacts with cyclopropanaphthalene 352 to give 77% yield of 353 (Equation 49). Attempts to hydrolyze the urazole ring failed <1995T10979>. 

Reaction of urazoles 359 with carbon suboxide in dilute solutions (dioxane-MeCN 1 1, acetone, MeCN) provides 360, while in more concentrated solutions small yields (<25%) of 361 are also obtained (Scheme 54) <1995H(41)303>. 

Treatment of urazole 381 with ethyl isocyanatoformate gives a quantitative yield of ethyl ester 382 and its cyclization at 160 °C affords 383 in only 35% yield but a yield of 85% is obtained only if the ethanol formed is trapped with tetrachlorosilane (Scheme 58) <1999M327>. 

Substituted (5R,6A,)-6-(dimethyl(phenyl)silyl)-2-phenyldihydropyrazolo[l,2- ][l,2,4]triazole-l,3(2//,5//)-dione 716, synthesized via the [3+2] annulation of a-substituted allylic silanes 715 with PTAD, were oxidized to the corresponding hydroxy substituted urazoles 717. This work shows that allylsilanes with a single substituent at the allylic carbon undergo exclusive stereoselective [3+2] annulation (Scheme 114) <2007TL6671>. 

In contrast to thermal uncatalyzed reactions of /V-acylsulfinylamines with aryl isocyanates which give rise to azoarenes,188 the cobalt or iron carbonyl-catalyzed process gives additionally 3,5-dioxo-l,2,4-triphenyl-1,2,4-triazolidine (Scheme 124).189 The only possible restriction on this simple urazole synthesis would be the expectation that the substituents on the reactants must be the same to prohibit exchange. 

Triazoline-3,5-dione 184 underwent an ene reaction with olefins 183 to yield trialkylated allylic urazoles 185, which were further elaborated into allylic amines 186 . DBU has been found to be a mild and convenient base for the alkylation of 1,2,4-triazole with various alkyl halides in the high yielding syntheses of 1-substituted-1,2,4-triazoles <00TL1297>. 

A novel route to synthesize l,3 -triazine-2,4(l//,3//)-diones through the desulfurization of thiocarboamides, such as 1,3-disubstituted 2-thioureas, trisubstituted thioureas and N-substituted thioamides by silver cyanate has been reported <00H(53)929>. Treatment of urazole 23 with one equivalent of sodium hydride under anhydrous conditions, followed by addition of dimethyl sulfate, leads to l,3,5-triazine-2,4-dione 24 in 80% yield . 

Table 3 Photoreactions of urazole 80 with /3-ketoesters in the presence of triethylamine...

The extraction procedure increases the yield of 4-phenyl-urazole by about 6%. This step is unnecessary when preparing... 

Substituted urazoles have also been made by heating the corresponding N,N -disubstituted diamides of hydrazodicar-boxylic acid,9 but the results are difficult to reproduce. 

Phenyl-l,2,4-triazoline-3,5-dione has been prepared by oxidizing 4-phenylurazole with lead dioxide,7 and with ammoni-acal silver nitrate followed by an ethereal solution of iodine.8 The yields are low for both methods. 4-Substituted triazoline-diones can also be made by oxidation of the corresponding urazole with fuming nitric acid9 or dinitrogen tetroxide.10 Oxidation by <-butyl hypochlorite in acetone solution has also been described 1112 it, however, yields an unstable product, even after sublimation. Either dioxane12 or ethyl acetate are preferred as solvents for the reaction, since the product is obtained in a stable form. The latter solvent is superior since... 

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