Synthesis of novel methoxy and hydroxy derivatives of 2-phenyl-1H-benz[g]indoles

The synthesis of novel methoxy-derivatives of 2-phenyl-1H-benz[g]indole 3 by condensation of α-naphthyl-amines 1 with N-phenacyl-pyridinium salts 2 is described, as well as their conversion into the corresponding hydroxy-derivatives 5 . Unexpected quinoxaline derivatives 4 were obtained when in the condensation reaction the N-nitrophenacylpyridinium salts 2d,e have been used.     

Condensation of Trifluoromethanesulfonamide with Paraformaldehyde and Oxamide

Depending on the conditions, three-component condensation of trifluoromethanesulfonamide with paraformaldehyde and oxamide led to the formation of linear products, N-mono- and N,N’-bis[(trifluoromethylsulfonyl)aminomethyl]oxamide, bis[(trifluoromethylsulfonyl)aminomethyl] ethanedioate, as well as of hydrolysis and cyclization product, N-(4,5-dioxo-1,3-oxazolidin-3-ylmethyl)trifluoromethanesulfonamide.     

Synthesis of some new N,N′-diarylsubstituted methylene-bis-dihydro-2H-1,3-benzoxazines

The synthesis of a new series of six-membered N,N′-diarylsubstituted methylene-bis-dihydro-2H-1,3-benzoxazines （5a-e） was achieved in excellent yields by Mannich-type condensation of N,N′-diarylsubstituted methylene-bis-o-hydroxybenzyl amines （4a- e） with formaldehyde in chloroform at reflux. These amines （4a-e） were obtained by the reduction of N, Nr-diarylsubstituted methylene-bis-o-hydroxybenzyl imines （3a-e） with NaBH4, which inturn were obtained by the condensation of methylene-bissalicylaldehyde （2） with various substituted arylamines.     

Ionic Liquid Promoted One-Pot Synthesis of Furo[2,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidine-2,4(1<Emphasis Type="Italic">H</Emphasis>,3<Emphasis Type="Italic">H</Emphasis>)-diones

Summary. The three-component condensation of aldehyde, N,N′-dimethylbarbituric acid and alkyl or aryl isocyanide afforded the corresponding furo[2,3-d]pyrimidine-2,4(1H,3H)-diones in 1-butyl-3-methylimidazolium bromide as an ionic liquid in high yields at room temperature within several minutes.     

Alkylgermasesquioxide derivatives of tert‐butyl‐diacylhydrazines

N‐tert‐Butyl‐N‐benzoylhydrazine was synthesized by a new method. Its condensation and the condensation of its N,N′‐isomer with 3‐(trichlorogermyl)propionyl chloride provided N‐tert‐butyl‐N′‐(3‐trichlorogermyl)propionyl‐N‐benzoylhydrazine or its N,N,N′‐isomer, respectively, in good yields. Subsequent hydrolysis of the trichlorogermyl compounds using saturated sodium carbonate yielded the corresponding germasesquioxide derivatives that have good solubility in organic solvents. The structures of these compounds were confirmed by ¹H NMR, IR, MS, and elemental analysis. The hydrolysis of organogermanium trichloride was studied, and the elimination of HGeCl₃ was observed when the basicity was too high (pH > 10). © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:293–297, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10174     

New Synthetic Approach to 4-N-Arylaminoazuleno[2,1-d]pyrimides

1-Cyano-2-N,N-dimethylformamidinylazulenes as new synthons directed to heterocycle-fused azulenes were obtained by the condensation of 2-amino-1-cyanoazulenes and N,N-dimethylformamide dimethyl acetal (DMFDMA). 1-Cyano-2-N,N-dimethylformamidinylazulene (2a) and 1-bromo-3-cyano-2-N,N-dimethylformamidinylazulene (2b) reacted with anilines (3a–h) to give 4-N-arylaminoazuleno-[2,1-d]pyrimidines in moderate yields. This reaction provides a new procedure for synthesis of pyrimidine-fused azulenes.     

A facile synthesis of unsymmetrical heterocyclic azines by cyclodesulfurization: Reaction of methyl arylalkylidenehydrazinecarbodithioates with diamines

A new and facile synthesis of unsymmetrical heterocyclic azines is described. Methyl arylalkylidenehydraz-inecarbodithioates, prepared by the condensation of ketones or aldehydes with methyl hydrazinecarbodithioate, were heated under reflux with various diamines in ethanol. Secondary diamines, such as N,N′-dimethyl-ethylenediamine, N,N′-dimethyl-1,3-diaminopropane or N,N′-dimethyl-o-phenylenediamine, reacted smoothly with loss of hydrogen sulfide to give good yields of unsymmetrical azines. However, primary diamines, such as ethylenediamine or o-phenylenediamine, and primary/secondary diamines, such as N-methylethyl-enediamine and N-methyl-1,3-diaminopropane gave, instead, only the corresponding uncyclized thiosemi-carbazones. A cyclodesulfurization mechanism for azine formation is discussed.     

Synthesis and biological activity of novel N‐benzoyl‐N‐tert‐butyl‐N′‐(β‐triphenylgermyl)propionylhydrazines

A series of new N‐benzoyl‐N‐tert‐butyl‐N′‐(β‐triphenylgermyl)propionylhydrazines were synthesized by the condensation reaction of β‐triphenylgermyl propanoic acid with N‐benzoyl‐N‐tert‐butylhydrazines in good yields by using N,N′‐dicyclohexylcorbodiimide as dehydrating agent. These title compounds were evaluated for molting hormone mimicking activity. The results of bioassay showed that the compounds exhibit moderate larvicidal activity, and toxicity assays indicated that the title compounds can induce a premature, abnormal and lethal larval molt. We found that the title compounds possess potential anticancer activities in vitro. Copyright © 2002 John Wiley & Sons, Ltd.     

NEW DERIVATIVES OF 4,5-BENZO-1,3,2-OXAZA (OR D1AZA)-PHOSPHOLANE FROM CONVENIENT CONDENSATION OF SUBSTITUTED UREA WITH TRIS(DIALKYLAMINO)PHOSPHINE

Abstract

The condensation of N-phenyl-N′-(2-hydroxylphenyl)urea or N-phenyl-N′-(2-aminophenyl)urea with tris(dia1kylamino)phosphine afforded derivatives of 4,5-benzo-1,3,2-oxaza (or diaza)-phospholane which formed intramolecular hydrogen bond. The cleavage of the amide bond to give N,N-dialky1-N′-phenylurea together with polymers of 1,3,2-benzodiazaphosphole was observed in the latter reaction.     

Catalyst-free one-pot synthesis of 1,4,5-trisubstituted pyrazoles in 2,2,2-trifluoroethanol

A simple, efficient and three component one-pot synthesis of 1,4,5-trisubstituted pyrazoles by condensation of β-dicarbonyls, N,N-dimethylformamide dimethyl acetal (DMFDMA) and hydrazine derivatives in 2,2,2-trifluoroethanol without using any catalyst and activation, is described.     

Synthesis of 4-(N,N-Dialkylamino)benzyltriphenylphosphonium Iodides from Hydroxymethyltriphenylphosphonium Iodide and N,N-Dialkylaniline

Reinvestigation of the one-pot synthesis of 4-(N,N-dialkylamino)benzyltriphenylphosphonium iodides has shown that the product forms after the initial condensation of triphenylphosphine upon formaldehyde.     

Pyrimidine derivatives. IV. Synthesis of N1 -(2-methoxy-4-pyrimidyl)sulfaniiamide

N¹-(2-Methoxy-4-pyrimidyl)sulfanilamide was successfully prepared through three alternative routes. Namely, the above compound was obtained by condensation of 4-amino-2-methoxy-pyrimidine (III) with p-acetaminobenzenesulfonyl chloride and p-nitrobenzenesulfonyl chloride and by direct condensation with sulfanilamide.     

Supramolecular dimeric structures of pyrazole-containing meso-oxo carbaphlorin analogues

Synthesis and properties of a novel meso-oxo carbaphlorin analogue embedded with an N-free pyrazole moiety are described. The N-benzyl precursor was prepared by a [3 + 1]-MacDonald condensation of N-benzyl pyrazole dialdehyde and β-alkyl-substituted tripyrrane dicarboxylic acid and subsequent oxidation by ferric chloride. Upon deprotection of the benzyl group, the resulting N-free oxophlorin analogue formed a unique supramolecular dimer through mutual hydrogen bonding interactions between the pyrazole NH and meso-carbonyl group. The assembled behaviour was characterised by various spectroscopies, X-ray crystallographic analysis and vapour pressure osmometry. Under the similar reaction conditions, the condensation of meso-phenyl-substituted tripyrrane derivative afforded an unprecedented tetrapyrrolic macrocycle fused with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone unit at their α-pyrrolic positions. The X-ray crystallographic analysis of the macrocycle revealed a twisted core structure, and nonaromatic nature was elucidated.     

Novel polyviologens: Photochromic redox polymers with film-forming properties

Several novel polyamides containing the N,N′-dialkyl-4,4′-dipyridinium (“viologen”) system were made by interfacial condensation of N,N′-bis(aminoalkyl)-4,4,-dipyridinium salts with di-, tri-, or tetrafunctional acid chlorides. These materials are useful redox polymers which turn deeply colored when reduced chemically or electrically, or when exposed to light.     

Syntheses and polymerizations of some vinyl monomers containing nitro- or fluorophthalimides

4-Nitro-N-vinylphthalimide ( 4 ) was synthesized by two different procedures. Compound 4 was not polymerizable or copolymerizable by AIBN. Poly(N-vinylphthalimide) ( 17 ) was prepared and partially nitrated at 10–25°C. N,N′-(1,2-Ethanediyl)bis(4-nitrophthalimide) ( 15 ) and N,N′-(1,3-propanediyl)bis(4-nitrophthalimide) ( 16 ) were prepared by the condensation of the corresponding diamine with phthalic anhydride followed by nitration of the condensation products. 4-Nitrophthalic anhydride was prepared by the hydrolysis of 15 . Four styrene-substituted phthalimide monomers were synthesized. These include N-(4-vinylphenyl)phthalimide ( 25a ), N-(4-vinylphenyl)-3-fluorophthalimide ( 25b ), N-(4-vinylphenyl)-3-nitrophthalimide ( 25c ), and N-(4-vinylphenyl)-4-nitrophthalimide ( 25d ). Monomers 25a and 25b were polymerized by freeradical initiator (AIBN), whereas monomers 25c and 25d were not polymerizable or copolymerizable by AIBN due to a strong inhibitive effect exerted by the nitrophthalimide group. Monomers 25c and 25d were cationically polymerized (BF₃·OEt₂). Monomer 25b and styrene were copolymerized and their reactivity ratios were r₁ = 1.7 and r₂ = 0.55, respectively. The prepared polymers are useful as backbone polymers for grafting living anionic polymers.     

Use of the mannich reaction in the synthesis of bispidine

A three-step synthesis of bispidine ( 1 ) is described. Mannich condensation of N-benzyl-4-piperidone, formaldehyde, and benzylamine afforded N,N′-dibenzylbispidinone ( 5 ), which was reduced under modified Wolff-Kishner conditions to yield N,N′ -dibenzylbispidine ( 6 ). Catalytic debenzylation of this compound gave 1 .     

Synthesis of substituted dihydroisocarbostyrils from 5-hydroxyamides obtained from dilithio-N-substituted o-toluamides

δ-Hydroxyamides, prepared by condensation of ketones or aldehydes at the 2-methyl group of Nsubstituted o-toluamides by means of n-butyllithium, were cyclodehydrated with sulfuric acid to form 2,3-disubstituted and 2,3,3-trisubstituted 3,4-dihydroisocarbostyriIs. Also, δ-hydroxyamides obtained from condensation of ketones at the 2-benzyl group of N-methyl-o-benzylbenzamide, were cyclodehydrated to give 2,3,3,4-tetrasubstituted 3,4-dihydroisocarbo-styrils. All of the products appeared to be new. This new method, which involves an unusual acid catalyzed cyclodehydration, is convenient and apparently quite general.     

La(O-i-Pr)3 CATALYZED THREE-COMPONENT CONDENSATION REACTION: A CONVENIENT SYNTHESIS OF N,N-DIALKYL-α-CYANOAMINES

ABSTRACT

In the presence of 10 mol% of La(O-i-Pr)₃, a three-component condensation reaction of aldehyde, secondary amine and trimethylsilylcyanide proceeded smoothly to afford N,N-dialkyl-α-cyanoamine in good yield.     

REACTIVITE DES N 1-TOSYLAMIDRAZONES VIS-À-VIS DU TRICHLORURE DE THIOPHOSPHORYLE ET DU DISULFURE DE CARBONE: OBTENTION DES TRIAZAPHOSPHOLINES ET DES TRIAZOLETHIONES

The condensation of N ¹ -tosylamidrazones with thiophosphorus trichloride and carbone disulfide forms a new synthetic method for access to new phosphorus or sulfur heterocycles such as triazaphospholines and triazolethiones.     

β-Dicéto énamines hétérocycliques: 2. (Pyridyl-4)-2 indanediones-1,3 C-et N-substituées

The authors have studies the regulation of the position of substitution in 2-(4-pyridy)-1-,3-indandiones and the precise methods for introducing functionalised substitutents on teh dihydropyridine nitrogen. These N-substituted compounds can also be synthetised by (a) condensation of momo- or polymethlated pyridines on dialkyl and monoalkyl phthalates and (b) by the oxidative condensation of Nalkylpyridinium btomides on 1,3-indandione. The negative solvatochromy observed in the electronic spectra of the N-substituted 2-(1,4-dihydrp-4-pyridylidèene)-1,3-indandiones leads us to propose a betaïne structure for these compounds.