Synthesis of 6-methyl-2-[2-phenyl-2-(arylhydrazono)ethyl]-3<Emphasis Type="Italic">Н</Emphasis>-pyrimidine-4-ones and their oxidation by hydrogen peroxide and selenium dioxide

The reaction of 6-methyl-2-(2-oxo-2-phenylethylidene)-2,3-dihydropyrimidine-4(1H)-one with arylhydrazines leads in high yields to the corresponding hydrazones, in which the ethylidene fragment of the starting compound is transformed to the ethylene fragment. By oxidation of the hydrazones with hydrogen peroxide or selenium dioxide the corresponding 6-methyl-2-[2-phenyl-2-(arylhydrazono)acetyl]-3H-pyrimidine-4-ones were synthesized.     

Synthesis and study of 2-(1-pyrazolyl)pyrimidine derivatives

Alkyl derivatives of 2-(1-pyrazolyl)-4(3H)-pyrimidinone were synthesized and converted to 4-chloro-, 4-arylamino-, and 4-hydrazino-2-(1-pyrazolyl)pyrimidines. The corresponding hydrazones were obtained by reaction of 5-ethyl-2-hydrazino-6-methyl-2-(4-ethyl-3,5-di-n-propylpyrazolyl) pyrimidine with isatin and salicylaldehyde. The UV and IR spectra of the synthesized compounds were studied. It was established that the hydrazones contain intra-molecular hydrogen bonds.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1255–1257, September, 1977.     

Two New Anti-Tobacco Mosaic Virus Isoindolin-1-Ones from the Leaves of Nicotiana tabacum

Chemistry of Natural Compounds - Two new isoindolin-1-ones, 6-(3-hydroxypropyl)-2,4-dimethylisoindolin-1-one (1) and 4-(hydroxymethyl)-6-(3-hydroxypropyl)-2-methylisoindolin-1-one (2), were...     

Anthraquinone pigments from the crinoid Comanthus bennetti

From the crinoid Comanthus bennetti we isolated and characterized five pigments. One is the known 3-(1′-hydroxypropyl)-1,6,8-trihydroxy-9,10-anthraquinone (rhodoptilometrin). The remaining four had not previously been isolated from a natural source: 3-propyl-1,6,8-trihydroxy- 9,10-anthraquinone; 3-propionyl-1,6,8-trihydroxy-9,10-anthraquinone; 3(2′-hydroxypentyl)-1,6,8- trihydroxy-9,10-anthraquinone; and 2-(1′-hydroxypropyl)-1,4,5,7-tetrahydroxy-9,10-anthraquinone.     

Pyrimidine acyclo-C-nucleosides by ring transformations of 2-formyl-L-arabinal

The protected 2-formyl-L-arabinal 2 reacted with thiourea and cyanamide in the presence of sodium hydride to afford via ring transformations the 5-[1R,2S-1,2- bis(benzyloxy)-3-hydroxypropyl]-1,2-dihydropyrimidines 3 and 4, respectively. Similarly, treatment of 2 with 3-amino-2H-1,2,4-triazole yielded 6-[1R,2S-1,2- bis(benzyloxy)-3-hydroxypropyl][1,2,4]-triazolo[1,5-a]pyrimidine (5).     

Synthesis of N-Substituted 3-Aminothiazolidin-4-ones Containing Hetaryl Fragments

Condensation of the N-(3,5-dichloropyridyl-2)- and N-(benzothiazolyl-2-thioacetyl)hydrazones of carbonyl compounds with thioglycolic acid gave the 3-(3,5-dichloropyridyl-2)amino- and 3-[N-(benzothiazolyl-2-thioacetyl)amino]-2-R¹-2-R²-thiazolidin-4-ones. Reaction of 1-(benzothiazolyl-2-thioacetyl)-4-R-thiosemicarbazides with chloroacetic acid in the presence of sodium acetate gave the 2-[N-(benzothiazolyl-2-thioacetyl)hydrazono]-3-R-thiazolidin-4-ones. It was found that the N-(benzothiazolyl-2-thioacetyl)hydrazones, both in the solid state and in solution, exist in the form of an equilibrium mixture of the EZ'- and EE'-isomers as a result of hindered rotation around the amide N-CO bond.     

Reaction of 2-acyl-3-aminobenzofurans with hydrazines

While 2-acetyl and 2-benzoyl-3-aminobenzofurans did not react with hydrazine, monomethyl- and N,N-dimethylhydrazine to give the related hydrazones, their 3-N-(p-toluenesulfonyl) derivatives afforded them smoothly in good yields. Depending upon reaction conditions, products arising from hydrazone cyclization to benzofuropyrazoles and/or from furan ring cleavage at the C2 O bond to give 5-(2-hydroxyphenyl)pyrazoles were also formed. The formation of these products depends upon hydrazones configuration and is discussed. Only (E)-isomers appear to undergo furan ring opening. In acidic media at room temprature either the hydrazones or the monomethylhydrazones gave the same related α-azines. Microanalyses, ir, uv, ¹H-nmr and ms spectra are in agreement with the proposed structures.     

Synthesis of 2-(1,5,9-Triazabicyclo[7.3.1]tridec-10-en-5-yl)-4-methylthiobutanoic Acid Derivatives

Reactions of 1,3-bis(3-chloro-2-hydroxypropyl)uracil, 1,3-bis(3-chloro-2-hydroxypropyl)-6-methyluracil, 1,3-bis(3-chloro-2-hydroxypropyl)-5-hydroxy-6-methyluracil, and 1,3-bis(3-chloro-2-hydroxypropyl)-5-fluorouracil with 2-amino-4-methylthiobutanoic acid (methionine) were studied for the first time.     

Hydroxy-containing ionic liquids as catalysts in the synthesis of organic carbonates from epoxides and CO2

Russian Chemical Bulletin - Hydroxy-containing ionic liquids such as triethyl(3-hydroxypropyl)ammonium, 1-(3-hydroxypropyl)-3-methylimidazolium, 3-(2-hydroxyethyl)-1-methylimidazolium, and...     

微波辐射下2-[4-二-(4-氟苯)甲基]哌嗪乙酰腙化合物的合成

微波辐射条件下, 以丙酮作溶剂, 1-[二-(4-氟苯)甲基]哌嗪与氯乙酸乙酯反应得到2-[二-(4-氟苯)甲基]哌嗪乙酸乙酯(1), 1与水合肼在微波辐射条件下反应得到2-[二-(4-氟苯)甲基]哌嗪乙酰肼(2), 进一步在微波辐射条件下由2-[二- (4-氟苯)甲基]哌嗪乙酰肼(2)与取代芳香醛反应制得目标化合物3a～3f. 合成的6个目标化合物通过熔点测定和质谱、红外光谱、核磁共振氢谱分析、元素分析对其结构进行确证.     

About the synthesis of [1,2]diazepinoindole derivatives from ethyl 2-(1-methylindole)acetate, 2-indole and 3-indoleacetohydrazones

The Vilsmeier-Haack reaction with ethyl 2-(1-methylindole)acetate and N,N-Dimethylamides/phosphorus oxychloride gave (65–85%) of ethyl 2-(3-acyl-1-methylindole)acetates 2 , which when boiled with hydrazine yielded about 90% of 4,5-dihydro-6-methyl-4-oxo-3H[1,2]diazepino[5,6-b]indoles 3. The attempted cyclization of 2-(1-methylindole)acetohydrazones 6 with acyl (acetyl and benzoyl) chlorides/triethylamine, to [1,2]diazepino[5,6-b]indole derivatives was fruitless and the bis(acyl)hydrazones 9 were obtained. Several transformations of 9 are reported. Similarly, the attempted cyclization of 3-indoleacetohydrazones 14 with acetyl chloride/triethylamine to [1,2]diazepino[4,5-b]indole derivatives was also fruitless and the bis(acyl)hydrazones 16 were again obtained.     

Facile Synthesis of Benzotriazines and Indoles by Ring-Scissions of α-Benzotriazol-1-yl Hydrazones

Abstract: α-(Benzotriazol-1-yl)hydrazones 2a-d and 13a-c were prepared by refluxing the corresponding α-(benzotriazol-1-yl)ketones with p-tosyl hydrazide or benzenesulfonyl hydrazide. Treatment of 2a-b with n-butyllithium in the presence of TMEDA gave benzotriazines 6a-b, while lithiation of 13a-c resulted in indole derivatives 16a-c, depending on the structure of the hydrazones.     

Transition metal complexes of novel tridentate S,N,O donor ligands

Summary Complexes of chromium(III), iron(III), cobalt(III), nickel(II) and copper(II) with salicylaldehyde N(1-piperidyl) thiocarbonyl hydrazone (spthH₂), salicylaldehyde N-(1-morpholyl) thiocarbonyl hydrazone (smthH₂), 2-hydroxy 4-methyl acetophenone N-(1-piperidyl) thiocarbonyl hydrazone (apthH₂) and 2-hydroxy 4-methyl acetophenone N-(1-morpholyl) thiocarbonyl hydrazone (amthH₂) have been prepared and characterized by analytical, spectral and magnetic measurements. Mixed ligand complexes of Cu^II-thiocarbonyl hydrazones and heterocyclic bases have been isolated. Depending on the nature of the metal salts used and the reaction conditions the thiocarbonyl hydrazones act as neutral or dibasic tridentate ligands.     

Reactivity of N-(omega-haloalkyl)-beta-lactams with regard to lithium aluminium hydride: novel synthesis of 1-(1-aryl-3-hydroxypropyl)aziridines and 3-aryl-3-(N-propylamino)propan-1-ols

The reactivity of 4-aryl-1-(2-chloroethyl)azetidin-2-ones and 4-aryl-1-(3-bromopropyl)azetidin-2-ones with regard to lithium aluminium hydride has been evaluated for the first time. 4-Aryl-1-(2-chloroethyl)azetidin-2-ones were transformed into novel 1-(1-aryl-3-hydroxypropyl)aziridines through an unprecedented conversion of beta-lactams into 2,3-unsubstituted aziridine derivatives. Unexpectedly, 4-aryl-1-(3-bromopropyl)azetidin-2-ones underwent dehalogenation towards 3-aryl-3-(N-propylamino)propan-1-ols upon treatment with LiAlH(4). 1-(1-Aryl-3-hydroxypropyl)aziridines were further elaborated by means of ring opening reactions using benzyl bromide in acetonitrile towards 3-aryl-3-[N-benzyl-N-(2-bromoethyl)amino]propan-1-ols and using aluminium(iii) chloride in diethyl ether, affording 3-aryl-3-[N-(2-chloroethyl)amino]propan-1-ols.     

Studies on biologically active heterocycles. Part I. Synthesis and antifungal activity of some new aroyl hydrazones and 2,5-disubstituted-1,3,4-oxadiazoles

A series of new 1-(2,4-dichlorobenzoyl) hydrazones and 2-aryl/aralkyl-5-(2,4-dichlorophenyl)-1,3,4-oxadiazoles have been synthesized from 2,4-dichlorobenzoylhydrazine and different aldehydes. Subsequent ring closure of the substituted aroyl hydrazones yielded the 1,3,4-oxadiazoles. All the compounds were characterized by their sharp melting point, microanalysis, ir, ¹H nmr and mass spectra and screened for their fungitoxic properties against Alternaria tenuis and Curvularia verruciformis. A few of the compounds showed good activity.     

Homochiral (R)- and (S)-1-heteroaryl- and 1-aryl-2-propanols via microbial redox

Preparation of various heteroaryl propanols 2a–g and of the corresponding propanones 3a–g as starting materials for microbial redox is described. The kinetic resolution of the racemic propanols 2a–g is obtained via oxidation with Pseudomonas paucimobilis and Bacillus stearothermophilus [(R)-alcohols, ee 74–100%]. Similar results are achieved with 3-(2-hydroxypropyl)trifluoromethylbenzene 7 (44%, ee 100% of the (R)-alcohol 6). The reduction of the propanones 3a–d and 3g with baker's yeast and other fungi gives the (S)-alcohols (ee 100%). The pure (S)-alcohols are also obtained by reduction of 1-[3-(trifluoromethyl)phenyl]-2-propanone 7. 1-[(4,4-Dimethyl)-2-(Δ²)oxazolinyl]-2-propanone 3e and 1[2-(Δ²)-thiazolinyl)-2-propanone 3f are not reduced. The heterocyclic rings of (S)-5-(2-hydroxypropyl)-3-methylisoxazole 2d and of (S)-2-(2-hydroxypropyl)-4-methylthiazole 2g are deblocked to the homochiral enamino ketone 8 (78%) and to the protected β-hydroxy aldehyde 9 (73%), respectively. The (R)-3-(2-hydroxypropyl)trifluoromethylbenzene 6 is transfomed into the homochiral precursor of (S)-fenfluramine 10 (overall yield 65%).     

Reaction of 2-{[2-(ethenyloxy)ethoxy]methyl}oxirane with oxazolidin-2-ones

Reactions of 2-{[2-(ethenyloxy)ethoxy]methyl}oxirane with N-unsubstituted oxazolidin-2-ones give mixtures of isomeric 3-{3-[2-(ethenyloxy)ethoxy]-2-hydroxypropyl}- and 5-{[2-(ethenyloxy)ethoxy]- methyl}-3-(2-hydroxyalkyl)oxazolidin-2-ones. If the initial oxazolidin-2-one contains two alkyl groups on C⁴, 3-{3-[2-(ethenyloxy)ethoxy]-2-hydroxypropyl}oxazolidin-2-ones are selectively formed.     

Synthesis of Macrocyclic Pyrimidine Derivatives

A reaction was studied of previously unknown 1,3-bis(2-hydroxy-3-chloropropyl)uracil, 1,3-bis(2- hydroxy-3-chloropropyl)-6-methyluracil, and 1,3-bis(2-hydroxy-3-chloropropyl)-5-fluorouracil with 1,3-bis[3-(3-methyl-2H-5-pyrazolon-1-yl)-2-hydroxypropyl]-6-methyluracil.     

Regioselective synthesis of (E)-3-[2-(arylmethylene)-1-(arylsulfonyl)hydrazino]-2-propenoates via the reaction of arylsulfonyl hydrazones and alkyl propiolates in the presence of triphenylphosphine

A regioselective method for the synthesis of (E)-3-[2-(arylmethylene)-1-(arylsulfonyl)hydrazino]-2-propenoates is described. The reaction takes place between arylsulfonyl hydrazones and alkyl propiolates in the presence of triphenylphosphine as the catalyst.     

The ligational behavior of a phenolic quinolyl hydrazone towards copper(II)- ions

Background  

The heterocyclic hydrazones constitute an important class of biologically active drug molecules. The hydrazones have also been used as herbicides, insecticides, nematocides, redenticides, and plant growth regulators as well as plasticizers and stabilizers for polymers. The importance of the phenolic quinolyl hydrazones arises from incorporating the quinoline ring with the phenolic compound; 2,4-dihydroxy benzaldehyde. Quinoline ring has therapeutic and biological activities whereas, phenols have antiseptic and disinfectants activities and are used in the preparation of dyes, bakelite and drugs. The present study is planned to check the effect of the counter anions on the type and geometry of the isolated copper(II)- complexes as well as the ligational behavior of the phenolic hydrazone; 4-[(2-(4,8-dimethylquinolin-2-yl)hydrazono)methyl] benzene-1,3-diol; (H₂L).