A facile route to 1,5‐benzodiazepin‐2‐yl‐phosphonates via ytterbium chloride‐catalyzed three‐component reaction

1,5‐Benzodiazepin‐2‐yl‐phosphonates were facilely synthesized via a one‐pot three‐component condensation of o‐diaminobenzene, 1,3‐diketone and diethyl phosphite in the presence of a catalytic amount of ytterbium chloride under mild reaction conditions. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:89–95, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20573     

Microwave‐assisted synthesis of novel 4‐N,N‐dimethylamino‐ and 4‐cycloamino‐ substituted 1,2,4‐triazole‐3‐thiones

4‐N,N‐Dimethylamino‐ and 4‐cycloamino‐5‐phenyl‐1,2,4‐triazole‐3‐thiones 1–13 have been synthesized from benzhydrazides and substituted methyl dithiocarbazates under various conditions including short microwave irradiations. The last method seemed faster than the classical refluxing one. The influence of base and solvent types on the reaction direction has been also examined. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:188–195, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20594     

Synthesis,structure, and antibacterial evaluation of new N‐substituted‐3‐amino‐ 5‐oxo‐4‐phenyl‐2,5‐dihydro‐1H‐pyrazole‐1‐carbothioamides

Novel N‐substituted‐3‐amino‐5‐oxo‐4‐phenyl‐2,5‐dihydro‐1H‐pyrazole‐1‐carbothioamide derivatives were synthesized by means of two methods. First is the cyclization reaction of 1‐(cyanophenyl)acetyl‐4‐substituted thiosemicarbazide, and the second one is reaction of cyanophenyl acetic acid hydrazide with isothiocyanate. Structures of new compounds were confirmed by elemental analysis, ¹H NMR, and X‐ray diffraction analysis. Biological evaluation showed that some of them possess promising antibacterial activities. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:215–221, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20598     

Synthesis of [1,2‐a] benzimidazolo‐1,3,5‐triazin‐2‐thione, [1,2‐a] benzimidazolo‐1,3,5‐thiadiazin‐2‐thione, [1,2‐a] benzimidazolo‐1,3,5‐triazin‐2‐amine,and [1,2‐a] benzimidazol‐2‐yl amidrazone

N‐benzimidazol‐2‐yl imidate type 1 reacts with thiourea, carbon disulfide, cyanamide, and hydrazide to give, respectively, [1,2‐a] benzimidazolo‐1,3,5‐triazin‐2‐thione 2 , [1,2‐a] benzimidazolo‐1,3,5‐thiadiazin‐2‐thione 3 , [1,2‐a] benzimidazolo‐1,3,5‐triazin‐2‐amine 4 , and [1,2‐a] benzimidazol‐2‐yl amidrazone 5 with good yields. Structures elucidation of all newly synthesized heterocyclic compounds was based on the data of IR, ¹H NMR, ¹³C NMR, elemental analysis, and MS of some products. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:279–283, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20618     

4‐Phosphorylated 1,2‐disubstituted imidazoles

4‐Selenophosphoryl‐1,2‐disubstituted imidazoles have been obtained by thermal decomposition of methyl 5‐(diamidoselenophosphoryl)imidazolium chlorides. The position of selenophosphoryl group in the imidazole ring was proved by ¹H, ¹³C NMR spectroscopy, and X‐ray analysis. Previously unknown diamido‐ and dichloro(imidazol‐4‐yl)‐ phosphonites were synthesized, and differences in their reactivity compared to analogous 5‐phosphorylated imidazoles are shown. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:103–118, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20584     

Highly selective synthesis of 1‐phenylpentane‐1, 4‐diones,and (E)‐5‐hydroxy‐5‐phenylpent‐3‐en‐2‐ones catalyzed by organophosphorus compounds

1‐Phenylpentane‐1, 4‐diones, and (E)‐5‐hydroxy‐5‐phenylpent‐3‐en‐2‐ones were synthesized via organophosphine‐catalyzed addition reaction of but‐3‐en‐2‐one with aldehydes. The features of the present protocols include high selectivity, operational simplicity, atom economy, and mild reaction conditions without transition metals. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 20:425–430, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20568     

Mild and efficient synthesis of aryliodonium ylides of 2,6‐dimethylpyrimidin‐4‐ol

Mild and efficient synthesis of new synthetically useful aryliodonium ylides of 2,6‐dimethyl‐ pyrimidin‐4‐ol ( 3a–d ) using (dichloroiodo)arenes in aqueous medium is reported. Antibacterial activity of these ylides 3a–d against Escherichia coli and Bacillus Licheniformis is also described. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:339–342, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20608     

Influence of colloid suspensions of humic acids on the alkaline hydrolysis of N‐methyl‐N‐nitroso‐p‐toluene sulfonamide

The influence of humic substances (HSs) upon the alkaline hydrolysis of N‐methyl‐N‐nitroso‐p‐toluene sulfonamide has been studied. Important inhibition of hydrolysis reaction has been reported. This inhibition has been explained in terms of association of reactants to the humic substances. Kinetic results have been modeled using the micellar pseudophase model. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 316–322, 2010     

Diastereoselective addition of Di‐(trimethylsilyl)phosphite to chiral N‐(R)‐α‐methylbenzyl and N‐(1‐methoxycarbonyl‐iso‐pentyl) Schiff bases of various aldehydes

The addition of bis‐(trimethylsilyl) phosphite to chiral imines of several aldehydes was diastereoselective. The separation of predominant diastereoisomers of a majority of formed aminophosphonic acids has been observed. Moreover, the ferrocene‐derived acid 5d occurred in diastereoselectivity up to 100%. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:326–331, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20624     

Stereoselective synthesis of pyrano[3,2‐c]‐ and furano[3,2‐c]quinolines: Gadolinium chloride catalyzed one‐pot aza–Diels–Alder reactions

A simple and efficient method for the cis‐selective synthesis of pyrano‐ and furano[3,2‐c]quinolines via gadolinium chloride catalyzed one‐pot aza–Diels–Alder reaction is described. Solvent conditions played a major role in affecting the diastereoselectivity of the products. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:351–354, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20612     

Formation of long‐range stripe patterns with sub‐10‐nm half‐pitch from directed self‐assembly of block copolymer

We have demonstrated directed self‐assembly of poly(styrene‐b‐dimethylsiloxiane) (PS‐b‐PDMS) down to sub‐10‐nm half‐pitch by using grating Si substrate coated with PDMS. The strong segregation between PS and PDMS enables us to direct the self‐assembly in wide grooves of the grating substrate up to 500 nm in width. This process can be applied to form various type of sub‐10‐nm stripe pattern along variety of grating shape. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Synthesis and in vitro antibacterial evaluation of 1‐substituted‐4‐ethoxycarbonylmethylthiosemicarbazides and products of their dehydrocyclization

A series of s‐triazoles and thiohydantoines were synthesized by dehydrocyclization of 1‐substituted‐4‐ethoxycarbonylmethylthiosemicarbazides. The molecular structure proposed for s‐triazoles was confirmed by the X‐ray crystal structure analysis of one compound that was prone to crystallization. All compounds were tested in vitro for their antibacterial activity. Some of them showed low levels of activity against Gram‐positive species, MIC range 100–400 μg/mL or higher. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:131–138, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20597     

Intramolecular cyclization of N‐hetarylphosphinimidic isocyanates in the synthesis of 1,7‐dihydro‐4H‐imidazo[4,5‐d][1,3,2]diazaphosphinin‐4‐one (2‐phosphapurine)

It has been found that N‐(4‐imidazolyl)phosphinimidic isocyanates obtained by the reaction of the corresponding chlorophosphine N‐hetarylimide with alkali metal cyanates can undergo intramolecular heterocyclization to yield previously unknown phosphapurine derivatives containing an endocyclic PN double bond. This radically novel approach to building the 2‐phosphapurine system shows promise for the synthesis of related phosphorus‐containing fused heterocycles. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:453–455, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20617     

Synthesis of novel 1,3‐substituted 1H‐[1,2,4]‐triazole‐3‐thiol derivatives

By means of regioselective S‐alkylation of 1H‐1,2,4‐triazole‐3‐thiol ( 1 ), a series of S‐substituted derivatives 2a‐j were synthesized. In certain conditions, the reaction of 2 with arylsulfochlorides, arylisocyanates, and quaternary ammonium salts of azines corresponding compounds were obtained 1‐arylsulfonyl‐ (3a‐d) , 1‐arylcarbonamido‐ ( 4a,b ), and 1‐azinyl‐1,2,4‐ ( 6a‐p ) triazoles. Structures of compounds were confirmed by ¹H NMR and elemental analyses. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 20:405–410, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20565     

Synthesis and antifungal activity of novel 5‐substituted 4‐(1,3,4‐thiadiazol‐2‐yl)benzene‐1,3‐diols

5‐Substituted (amine, alkyl, aryl, heterocyclic) 4‐(1,3,4‐thiadiazol‐2‐yl)benzene‐1,3‐ diols were synthesized, and their antifungal properties were examined. The compounds were obtained by the one‐pot reaction of sulfinylbis((2,4‐dihydroxyphenyl)methanethione) with hydrazides or thiosemicarbazides. Their structures were identified from elemental, IR, ¹H NMR, and MS spectra analyses. The activities of the derivatives against five phytopathogenic fungi in vitro were measured. Moderate fungicidal effect of the compounds under consideration was found. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:533–540, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20645     

Gas‐phase tautomerism in hydroxy azo dyes – from 4‐phenylazo‐1‐phenol to 4‐phenylazo‐anthracen‐1‐ol

The tautomeric constants of a series of azo dyes were estimated in the gas phase by using electron ionization mass spectrometry. It was shown that the relative amount of the keto tautomer increases from 4‐phenylazo‐1‐phenol to 4‐phenylazo‐anthracen‐1‐ol, thus confirming the quantum‐chemical predictions. The existence of the enol tautomer of 4‐phenylazo‐anthracen‐1‐ol is shown for the first time by mass spectrometry in the gas phase. This finding is supported by flash photolysis measurements in solution. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis,characterization, and field‐effect transistor performance of poly[2,6‐bis(3‐tridecanoxythiophen‐2‐yl)benzo[1,2‐b;4,5‐b′]dithiophene]

A new copolymer of benzo[1,2‐b:4,5‐b′]dithiophene and 3,3′‐bis(tridecanoxy)‐5,5′‐bithiophene was synthesized through Stille copolymerization. The bis‐(3‐alkoxythiophene) monomer was synthesized through a silver fluoride mediated, palladium‐catalyzed cross‐coupling, in which bromide functional groups were preserved instead of consumed. The copolymer has been characterized and applied in field‐effect transistors, giving a hole mobility of 2 × 10^?3 cm²/Vs and an on/off ratio >10⁶, with negligible hysteresis, on standard silicon substrates. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1973–1978, 2010     

Preparation of remarkably tough polyHIPE materials via polymerization of oil‐in‐water HIPEs involving 1‐vinyl‐5‐aminotetrazole

Interconnected microcellular polymeric monoliths having unexpected high mechanical strength have been prepared using the high internal phase emulsion (HIPE) methodology. Oil‐in water concentrated emulsions of aqueous 1‐vinyl‐5‐amino [1,2,3,4]tetrazole (1‐VAT) mixed with a low molar ratio (7%) of N,N′‐methylenebisacrylamide as crosslinking agent were prepared using dodecane as dispersed phase and a mixture of hydrophilic surfactants. “Reverse” polyHIPE materials were obtained after radical copolymerization, solvent extraction, and drying. Their morphology, chemical composition, and physicochemical behavior are discussed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2942–2947, 2010     

Addition of di‐(trimethylsilyl)phosphite to N,N′‐dialkyl terephthalic schiff bases: Synthesis of 1,4‐phenylene‐bis‐ (aminomethyl)‐phosphonic acids

The addition of di‐(trimethylsilyl)phosphite to N,N′‐terephthalylidene‐alkyl‐(or aryl‐)amines resulted in 1,4‐phenylene‐bis‐(N‐alkylamino‐ methyl)‐phosphonic acids in moderate yields. The stereochemical behavior of such reactions was studied, and NMR studies demonstrated that, for several examples, this reaction led to the exclusive formation of only one diastereomeric form. The investigation of the chiral salt of the acid identified the pair of enantiomers. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 20:431–435, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20569     

Synthesis and NMR spectral assignments of indol‐3‐yl pyridines through one‐pot multi‐component reaction

Asimple protocol for the efficient preparation of 6‐(ferrocene‐1‐yl)‐2‐(indol‐3‐yl)pyridine and 2‐(1H‐indol‐3‐yl)‐6‐(2‐thienyl)pyridine derivatives has been achieved through multi‐component reaction, and these compounds were thoroughly characterised by 2D NMR spectral techniques. Copyright © 2010 John Wiley & Sons, Ltd.