Two-step α-ureidoalkylation of ureas with 4,5-dihydroxyimidazolidin-2-ones

Two-step α-ureidoalkylation of ureas with various 4,5-dihydroxyimidazolidin-2-ones gave novel 1,3-dialkyl-4,5-bis(3-alkylureido)-, 1,3-dialkyl-4,5-bis[3-(2-pyrimidyl)ureido]-, or 1,3-dialkyl-4,5-bis(3,3-dialkylureido)imidazolidin-2-ones and ensembles of three imidazolidine rings. The structure of 4,5-bis(2-oxoimidazolidin-1-yl)imidazolidin-2-one was confirmed by X-ray diffraction data. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 140–145, January, 2007.     

Synthesis and structure of 1,3-dialkyl-4-(sulfonylimino)imidazolidin-2-ones

The reactions of 1,3-dialkyl-4,5-dihydroxyimidazolidin-2-ones with alkyl sulfamides have been studied and previously undescribed 1,3-dialkyl-4-(alkylaminosulfonylimino)imidazolidin-2-ones have been obtained. The structure of 1,3-dimethyl-4-(benzenesulfonylimino)imidazolidin-2-one was investigated by X-ray structural analysis. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1159–1166, August, 2007.     

4,5-Dihydroxyimidazolidin-2-ones in an α-ureidoalkylation reaction of N-(carboxyalkyl)-, N-(hydroxyalkyl)-, and N-(aminoalkyl)ureas 3. α-Ureidoalkylation of N-[2-(dimethylamino)ethyl]urea

α-Ureidoalkylation of N-[2-(dimethylamino)ethyl]urea with 1,3-unsubstituted, 1,3-dialkyl-, and 1,3-dimethyl-4,5-diphenyl-4,5-dihydroxyimidazolidin-2-ones(thiones) was systematically studied. Hitherto unknown N-[2-(dimethylamino)ethyl]glycolurils and their hydrochlorides were synthesized. The yields of the target glycoluril hydrochlorides decreased on going from 1,3-H₂- to 1,3-dialkyl-4,5-dihydroxyimidazolidin-2-ones and increased with the introduction of phenyl groups at the positions 4 and 5 of the starting 4,5-dihydroxyimidazolidin-2-one. X-ray diffraction study showed that 2-[2-(dimethylamino)ethyl]glycoluril crystallizes in the form of a conglomerate.     

α-Ureidoalkylation of thiosemicarbazide and aminoguanidine

azo[4,5-e][1,2,4]triazin-6-ones, 4,5-bis(3-thiosemicarbazido(guanidinoamino))imidazolidin-2-ones, and 1,3-dialkyl-4-(guanidinoimino)imidazolidin-2-ones by α-ureidoalkylation of thiosemicarbazide or aminoguanidine were found. A novel conglomerate in the series of imidazolidin-2-one derivatives was detected: 4,5-bis(guanidinoamino)-1,3-dimethylimid-azolidin-2-one dihydrochloride dihydrate. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 836–843, May, 2006.     

Diastereoselective synthesis of 4,5-dihydroxyimidazolidin-2-ones (-thiones) and their structure

Studies on the synthesis of 4,5-dihydroxyimidazolidin-2-ones (-thiones) based on the condensation of ureas or thioureas with glyoxal or 1,2-dioxo-1,2-diphenylethane showed high diastereoselectivity in the formation of racemates (trans-diastereomers) of 4,5-dihydroxyimidazolidin-2-ones (-thiones) and meso-forms (cis-diastereomers) of 4,5-dihydroxy-4,5-diphenyl-1,3-dialkylimidazolidine-2-thiones; plausible mechanisms of their formation were suggested. X-ray diffraction studies confirmed structures of diastereomers for separate examples of racemates and meso-forms of 4,5-dihydroxyimidazolidin-2-ones (-thiones).     

Synthesis and structures of 5(3H)-oxotetrahydro-1H-imidazo[4,5-c][1,2,5]thiadiazole 2,2-dioxides

The reactions of sulfamides with 4,5-dihydroxyimidazolidin-2-ones were studied at ambient and high pressure. The previously unknown derivatives of 5(3H)-oxotetrahydro-1H-imidazo-[4,5-c][1,2,5]thiadiazole 2,2-dioxide, viz., sulfo analogs of tetrahydroimidazo[4,5-d]imidazole-2,5-(1H,3H) diones (glycolurils), were synthesized. The structures of some of these compounds were established by X-ray diffraction. The high-pressure reactions performed under conditions of solvent phase transitions afforded also N-(1,3-diethyl-5-hydroxy-2-oxoimidazolidin-4-yl)-N,N′-dialkylsulfamides. Among these compounds, a new conglomerate was found. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1711–1719, May, 2008.     

4,5-Dihydroxyimidazolidin-2-ones in α-ureidoalkylation of N-carboxy-, N-hydroxy-, and N-aminoalkylureas 2. α-Ureidoalkylation of N-(hydroxyalkyl)ureas

Russian Chemical Bulletin - The α-ureidoalkylation of N-(hydroxyalkyl)ureas (ureido alcohols) with 1,3-H2- and 1,3-Me2-4,5-dihydroxyimidazolidin-2-ones was systematically studied. The yields...     

4,5-Dihydroxyimidazolidin-2-ones in the α-ureidoalkylation reaction of N-(carboxyalkyl)-, N-(hydroxyalkyl)-, and N-(aminoalkyl)ureas 1. α-Ureidoalkylation of N-(carboxyalkyl)ureas

Russian Chemical Bulletin - The α-ureidoalkylation of N-(carboxyalkyl)ureas (ureido acids) with 1,3-H2 s-, 1,3-Me 2 s-, and 1,3-Et2 s-4,5-dihydroxyimidazolidin-2-ones was systematically...     

Reactions of N,N-Disubstituted 5-Arylmethylidene-2-amino-thiazol-4(5H)-ones with CH Acids

Summary.  N,N-Disubstituted 5-arylmethylidene-2-aminothiazol-4(5H)-ones reacted with diethyl malonate, ethyl benzoylacetate, acetylacetone, or cyclopentadiene in refluxing toluene and in presence of powdered sodium to give the respective 5-arylmethylidene-2′-amino-2,5′-bithiazolylidene-4,4′-dione derivatives in moderate yields. 5-Benzylidene-2-morpholin-4-yl-2-thiazol-4(5H)-one reacted with malononitrile in toluene and in presence of powdered sodium under mild conditions to afford the 1:1 adduct, benzylmalononitrile, and 2-morpholin-4-yl-2-thiazol-4(5H)-one. However, similar treatment of 5-(4-methoxyphenylmethylidene)-2-morpholin-4-yl-2-thiazol-4(5H)-one with malononitrile yielded the 2,5′-bithiazolylidene-4,4′-dione derivative together with 4-methoxyphenylmethylidene malononitrile. Treatment of 5-benzylidene- and 5-(4-methoxyphenylmethylidene)-2-morpholin-4-yl-2-thiazol-4(5H)-ones with 3-phenyl-4-oxo-2-thioxo-1,3-thiazolidine in refluxing toluene and in presence of powdered sodium produced 5-arylmethylidene-3-phenyl-4-oxo-2-thioxo-1,3-thiazolidines in good yields. The structures of all products were deduced from microanalytical and spectroscopic data, mechanistic details are discussed. Corresponding author. E-mail: kamalkandeel@hotmail.com Received November 5, 2001. Accepted (revised) December 17, 2001     

4,5-Dihydroxyimidazolidin-2-ones in α-ureidoalkylation of N-carboxyalkyl-, N-hydroxyalkyl-, and N-(aminoalkyl)ureas 4.* α-Ureidoalkylation of N-(2-acetylaminoethyl)ureas

α-Ureidoalkylation of N-(2-acetylammoethyl)ureas with various 4,5-dihydroxyimidazoli-din-2-ones was systematically studied. Novel N-(2-acetylaminoethyl)glycolurils were obtained. Their yields were found to decrease both when moving from l,3-H₂-to l,3-Alk₂-4,5-dihydroxy-imidazolidin-2-ones and when increasing the size of the substituent at the second N atom in the starting acetylaminoethylurea. The higher yields were achieved with 4,5-diphenyl-4,5-dihydroxyimidazolidin-2-one as the starting compound. 2-(2-Acetylaminoethyl)-4-methylgly-coluril exhibits nootropic activity.     

Novel Domino Reactions of (Z,Z)-2,2′-Thiobis(1,3-diarylprop-2-en-1-ones) with Acetylacetone and Ethyl Acetoacetate: Stereoselective Synthesis of Highly Functionalized Dihydrofurans

The domino reactions of (Z,Z)-2,2′-thiobis(1,3-diarylprop-2-en-1-ones) with acetylacetone and ethyl acetoacetate in the presence of sodium ethoxide afforded the corresponding 4,5-dihydrofurans stereoselectively in moderate yields presumably via a Michael addition–enolization–displacement sequence.     

α-Ureidoalkylation of 1,3-bis(hydroxymethyl)-imidazolidin-2-one

The α-ureidoalkylation of imidazolidine-2,4-dione, urea, carboxylic acid amides, and sulfonamides has been studied using 1,3-bis(hydroxymethyl)-imidazolidin-2-one as ureidoalkylating agent. Methods have been developed for the synthesis of 1,3-bis(2,4-dioxoimidazolidin-1-ylmethyl)-, 1,3-bis(acetylaminomethyl)-, 1,3-bis(benzoylaminomethyl)-, 1,3-bis(phenylsulfonylaminomethyl)-, and 1,3-bis(p-toluenesulfonylaminomethyl)imidazolidin-2-ones. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1655–1659, November, 2007.     

Synthesis and study of new 2-aryl-1-(4-nitrophenyl)-1,1a-dihydroazireno[1,2-a]quinoxaline derivatives

New derivatives of photochromic 2-aryl-1-(4-nitrophenyl)-1,1a-dihydroazireno[1,2-a]quinoxalines were synthesized by condensation of 4-methyl-and 4,5-dimethyl-1,2-phenylenediamine with 1,3-diaryl-2,3-dibromopropan-1-ones. The reactions of 4-methyl-1,2-phenylenediamine produce mixtures of regioisomers. The chemical properties of the reaction products were studied. The structure of one of the latter was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 350–356, February, 2006.     

Synthesis of 4,5-bifunctionally substituted imidazolidin-2-ones

It is shown that the reaction of readily available 4,5-dihydroxyimidazolidin-2-ones with hydrazoic or p-toluenesulfinic acid takes place stereo- and regioselectively and leads to the formation of 4,5-diazido- or 4,5-di(p-tolylsulfonyl)imidazolidin-2-ones. The example of 4,5-diazidoimidazolidin-2-one is used to demonstrate the possibility of using compounds of this type for stereoselective introduction of substituents into the 4 and 5 positions of the imidazole ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1645–1649, December, 1993.     

2-R-5-Ar(Het)-5,6-dihydro-7H-[1,2,4]triazolo[5,1-b][1,3]thiazin-7-ones

A novel method for synthesis of 2-R-5-Ar(Het)-5,6-dihydro-7H-[1,2,4]triazolo[5,1-b][1,3]thiazin-7-ones by condensation of 3-R-4,5-dihydro-1H-1,2,4-triazole-5-thiones with 3-aryl(heteryl)-2-propenoyl chlorides is proposed.     

Heterophase N-aminomethylation of 5-arylidenepseudothiohydantoins by arylamines and aqueous formaldehyde in aromatic solvents: Effect of substituents in the heterocyclic substrate and the aryl amine on the efficiency of the process

We have obtained a series of 3-aryl-7-arylidene-3,4-dihydro-2H-[1,3]thiazolo[3,2-a][1,3,5]triazin-6(7H)-ones by means of heterophase aminomethylation of 2-amino-5-arylidene-1,3-thiazol-4(5H)-ones with aqueous formaldehyde and aromatic amines in benzene or toluene. We explain the effect of substituents in the heterocyclic substrate and the aryl amine on the efficiency of the process within a detailed scheme for one of the possible aminomethylation reaction routes. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1095–1104, July, 2006.     

Synthesis of isomeric 2-oxazolidinones from (1<Emphasis Type="Italic">R</Emphasis>,2<Emphasis Type="Italic">R</Emphasis>)-and (1<Emphasis Type="Italic">S</Emphasis>,2<Emphasis Type="Italic">S</Emphasis>)-2-amino-1-(4-nitrophenyl)-1,3-propanediols

A synthesis is reported for (4R,5R)-and (4S,5S)-4-hydroxymethyl-5-(4-nitrophenyl)oxazolidin-2-ones and (1′R,4R)-and (1′S,4S)-4-[hydroxy(4-nitrophenyl)methyl]oxazolidin-2-ones from (1R,2R)-and (1S,2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediols. The effect of the experimental conditions on the formation of these compounds was studied. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1562–1570, October, 2007.     

Facile Synthesis of Dihydro-1,2,4-benzotriazepin-5-ones

Summary. Direct interaction between model anilines and an 1,3-dipolar nitrile imine, derived from 2-[N′-(1-chloro-2-oxopropylidine)hydrazine]benzoic acid, yielded the respective acyclic amidrazones. The latter adducts underwent CDI-induced cyclocondensation involving the hydrazone–NH terminus and the activated carboxy group to produce the corresponding dihydro-1,2,4-benzotriazepin-5-ones.     

Oxidation of nitrogen-containing heterocycles using biocatalysts

A method for stereospecific hydroxylation of 1,2-dihydro-3H-1,4-benzodiazepin-2-ones using free and immobilized cells of actinomycetes as biocatalysts was developed. The hydroxylation under the action of yeast results in the formation of racemates. Actinomyces do not hydroxylate quinazolinones, quinoxalinones, and tetrahydro-1,5-benzodiazepin-2-ones; derivatives of 1,2,3,4-tetrahydro-1,5-benzodiazocin-2-ones are transformed into 2-[N-(3-acetylaminopropionyl)amino]benzophenones. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1608–1613, August, 1998.     

1-Oxa-3-azapentalen-2-ones as Precursors of cis-2-Amino Alcohols: Synthesis from Propargyl Alcohols, CO2, and Amines Using an Intramolecular Amidoalkylation Reaction of Oxazolidin-2-ones

The reaction of 5-methyl-5-(4-methyl-3-pentenyl)-4-methylene-1,3-dioxolan-2-one with primary amines gives the corresponding 4-hydroxy-4-methyloxazolidin-2-ones. These undergo an intramolecular amidoalkylation reaction to form 1-oxa-3-azapentalen-2-ones which are potential precursors of cyclopentanyl cis-2-amino alcohols.