Synthesis, crystal structure and antibacterial activity of a group of mononuclear manganese(II) Schiff base complexes

Five mononuclear complexes of manganese(II) of a group of the general formula, [MnL(NCS)₂] where the Schiff base L = N,N′-bis[(pyridin-2-yl)ethylidene]ethane-1,2-diamine (L¹), (1); N,N′-bis[(pyridin-2-yl)benzylidene]ethane-1,2-diamine (L²), (2); N,N′-bis[(pyridin-2-yl)methylidene]propane-1,2-diamine (L³), (3); N,N′-bis[(pyridin-2-yl)ethylidene]propane-1,2-diamine (L⁴), (4) and N,N′-bis[(pyridin-2-yl)benzylidene]propane-1,2-diamine (L⁵), (5) have been prepared. The syntheses have been achieved by reacting manganese chloride with the corresponding tetradentate Schiff bases in presence of thiocyanate in the molar ratio of 1:1:2. The complexes have been characterized by IR spectroscopy, elemental analysis and other physicochemical studies, including crystal structure determination of 1, 2 and 4. Structural studies reveal that the complexes 1, 2 and 4 adopt highly distorted octahedral geometry. The antibacterial activity of all the complexes and their respective Schiff bases has been tested against Gram(+) and Gram(−) bacteria.     

Condensation of Propan-2-one with Formaldehyde and Propane-2-thiol

Three-component condensation of propan-2-one with formaldehyde and propane-2-thiol in the presence of sodium hydroxide afforded 3-{[(propan-2-yl)sulfanyl)]methyl}but-3-en-2-one or 4-[(propan-2-yl)sulfanyl]-3-{[(propan-2-yl)sulfanyl]methyl}butan-2-one, depending on the amount of the base. The formation of 4-[(propan-2-yl)sulfanyl]-3-{[(propan-2-yl)sulfanyl]methyl}butan-2-one from 4-[(propan-2-yl)sulfanyl]butan-2-one involved aldol condensation of the latter with formaldehyde and subsequent nucleophilic addition of propane-2-thiol to the C=C double bond of intermediate 3-{[(propan-2-yl)sulfanyl]methyl}but-3-en-2-one in the presence of sodium hydroxide.     

Cyclopropanation of 2-arylmethylidenemalononitriles,alkyl 3-aryl-2-cyanoprop-2-enoates,and N-substituted 3-aryl-2-cyanoprop-2-enamides with bromine-containing zinc enolates

Zinc enolates derived from 2,2-dibromoindan-1-one and 2,2-dibromo-1,2,3,4-tetrahydronaphthalen-1-one reacted with 2-arylmethylidenemalononitriles, alkyl 3-aryl-2-cyanoprop-2-enoates, and N-substituted 3-aryl-2-cyanoprop-2-enamides to give, respectively, 3-aryl-1′-oxo-1′,3′-dihydrospiro[cyclopropane-1,2′-indene]-2-2-dicarbonitriles, 3-aryl-1′-oxo-3′,4′-dihydro-1′H-spiro[cyclopropane-1,2′-naphthalene]-2,2-dicarbonitriles, alkyl 3-aryl-2-cyano-1′-oxo-1′,3′-dihydrospiro[cyclopropane-1,2′-indene]-2-carboxylates, alkyl 3-aryl-2-cyano-1′-oxo-3′,4′-dihydro-1′H-spiro[cyclopropane-1,2′-naphthalene]-2-carboxylates, and N-substituted 3-aryl-2-cyanol-1′-oxo-3′,4′-dihydro-1′H-spiro[cyclopropane-1,2′-naphthalene]-2-carboxamides as a single diastereoisomer. The stereoconfiguration of the products was determined by ¹H and ¹³C NMR spectroscopy.     

Synthesis and some heterocyclization reactions of new diethyl (1,1-difluoro-3,3-dicyano-2-trifluoromethylallyl)phosphonate and ethyl 3,3-dicyano-2-[(diethoxyphosphoryl)difluoromethyl]acrylate

A new CF₂X-analogue of 1,1-bis(trifluoromethyl)-2,2-dicyanoethylene (X = P(O)(OEt)₂), diethyl (1,1-difluoro-3,3-dicyano-2-trifluoromethylallyl)phosphonate, has been synthesized from diethoxyphosphoryl pentafluoroacetone 1. A similar phosphoryl analogue of ethyl 3,3-dicyano-2-trifluoromethylacrylate, ethyl 3,3-dicyano-2-[(diethoxyphosphoryl)difluoromethyl]acrylate, has been obtained from ethyl 3-(diethoxyphosphoryl)-3,3-difluoro-2-oxopropionate 2. By heterocyclization of these new ethylenes with 3-methyl-2-pyrazoline-5-ones, 3(5)-aminopyrazoles, dimedone, 2-aminopyridines, 1-aryl-3-methyl-5-aminopyrazoles, 1,3,3-trimethylisoquinolines, as well as by condensation with anilines and ketones, the difluoromethylphosphonate-substituted derivatives of 1,4-dihydropyrano[2,3-c]pyrazole, 4,5-dihydropyrazolo[1,5-a]pyrimidine, 5,6,7,8-tetrahydro-4H-chromene, 2H-pyrido[1,2-a]pyrimidine, 4,7-dihydro-1H-pyrazolo[3,4-b]pyridine, 1,4-dihydropyridine, 4,5,6,7-tetrahydro-1H-[1]pyrindine, 1,4,5,6,7,8-hexahydroquinoline, and 6,7-dihydro-2H-pyrido[2,1-a]isoquinoline have been obtained in one stage.     

Synthesis of methyl 4-aryl-4-oxo-2-[(4-sulfamoylphenyl)amino]but-2-enoates and their reaction with ninhydrin

The reaction of methyl 4-aryl-2,4-dioxobut-2-enoates with 4-aminobenzenesulfonamide in acetic acid–ethanol (1: 1) afforded methyl (2Z)-4-aryl-4-oxo-2-(4-sulfamoylanilino)but-2-enoates which reacted with ninhydrin in glacial acetic acid to give 3-aroyl-4-(4-sulfamoylanilino]-5H-spiro[furan-2,2′-indene]-1′,3′,5-triones.     

Synthesis of ansa-2,2′-bis[(4,7-dimethyl-inden-1-yl)methyl]-1,1′-binaphthyl and nsa-2,2′-bis[(4,5,6,7-tetrahydroinden1-yl)methyl]-1,1′-binaphthyltitanium and -zirconium dichlorides

2,2′-Bis[(4,7-dimethyl-inden-1-yl)methyl]-1,1′-binaphthyl and [2,2′-bis[(4,5,6,7-tetrahydroinden-1-yl)methyl]-1,1′-binaphthyl]titanium and -zirconium dichlorides have been synthesized from 2,2′-bis(bromomethyl)-1,1′-binaphthylene. 2,2′-Bis(bromomethyl)-1,1′-binaphthylene was alkylated with the lithium salt of 4,7-dimethylindene to yield 2,2′-bis[1-(4,7-dimethyl-indenylmethyl)]-1,1′-binaphthylene (S)-(−)-9. The lithium salt of 9 was metalated with either titanium trichloride followed by oxidation or zirconium tetrachloride to give titanocene dichloride (S)-(+)-10 and zirconocene dichloride 11. The known complexes ansa-[2,2′-bis[(1-indenyl)methyl]-1,1′-binaphthyl]titanium and -zirconium dichlorides were formed and hydrogenated to ansa-[2,2′-bis[(4,5,6,7-tetrahydroinden-1-yl)methyl]-1,1′-binaphthyl]titanium and -zirconium dichlorides 12 and 14 or to ansa-[2,2′-bis[(4,5,6,7-tetrahydroinden-1-yl)methyl]-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl]titanium dichloride 13 whose solid state structure was determined by X-ray crystallography. Complex 13 adopts a C₁-symmetrical conformation in the solid state, but is conformationally mobile in solution, exhibiting C₂-symmetry in its room temperature NMR spectra.     

Functional sulfur-containing compounds. 10. Alkylation of ch-acids with 2-[(organylthio)methyl]oxirans

In the reaction of 2-[(organylthio)methyl]oxirans (I) with malonic, acetoacetic and cyanoacetic esters mixtures of 4- and 5-[(organylthio)methyl]-3-(methoxy-carbonyl-, acetyl-, cyano-)-4, 5-dihydro-2(3H)-furanones (II)-(VII) are formed. The ratio of the isomers depends on the nature of the CH-acid. The reaction of 2-[(ethylthio)methyl]oxiran (Ia) with bis(butylsulfonyl)methane leads to a mixture of 3-(ethylthio)-1-[bis(butylsulfonyl)methyl]-propan-2-ol (XIa) and 3-(ethylthio)-2-[bis(butylsulfonyl)methyl]propan-1-ol (XIIa) in a 11 ratio. In the reaction of epoxides (I) with acetylacetone 4-[(organylthio)methyl]-2-methyl-2-acetonyl-1, 3-dioxolanes (XIII) are formed.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2829–2832, December, 1991.     

Allgemeiner Zugang zu Polyaminen mit Ethan-1,2-diamin-Einheiten: Synthese von nicht natürlich vorkommenden homologen und isomeren N1,4-Di(4-cumaroyl)sperminen

█tl="American"█The synthesis of the three N,N′-di(4-coumaroyl)tetramines, i.e., of (E,E)-N-{3-[(2-aminoethyl)amino]propyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(ethane-1,2-diyl)bis[prop-2-enamide] ( 1a ), (E,E)-N-{4-[(2-aminoethyl)amino]butyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(ethane-1,2-diyl)bis[prop-2-enamide] ( 1b ), and (E,E)-N-{6-[(2-aminoethyl)amino]hexyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(ethane-1,2-diyl)bis[prop-2-enamide] ( 1c ), is described. It proceeds through stepwise construction of the symmetric polyamine backbone including protection and deprotection steps of the amino functions. Their behavior on TLC in comparison with that of 1,4-di(4-coumaroyl)spermine (=(E,E)-N-{4-[(3-aminopropyl)amino]butyl}-3,3′-bis(4-hydroxyphenyl)-N,N′-(propane-1,3-diyl)bis[prop-2-enamide]; 2 ) is discussed.     

Synthesis of 1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide

The reaction of methyl 2-bromo-6-(trifluoromethyl)-3-pyridinecarboxylate ( 1 ) with methanesulfonamide gave methyl 2-[(methylsulfonyl)amino]-6-(trifluoromethyl)-3-pyridine-carboxylate ( 2 ). Alkylation of compound 2 with methyl iodide followed by cyclization of the resulting methyl 2-[methyl(methylsulfonyl)amino]-6-(trifluoromethyl)-3-pyridinecarboxylate ( 3 ) yielded 1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide ( 4 ). The reaction of compound 4 with α,2,4-trichlorotoluene, methyl bromopropionate, methyl iodide, 3-trifluoromethylphenyl isocyanate, phenyl isocyanate and 2,4-dichloro-5-(2-propynyloxy)phenyl isothiocyanate gave, respectively, 4-[(2,4-dichlorophenyl)methoxy]-1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazine 2,2-dioxide ( 5 ), methyl 2-[[1-methyl-2,2-dioxido-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4-yl]oxy]propanoate ( 6 ), 1,3,3-trimethyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide ( 7 ), 4-hydroxy-1-methyl-7-(trifluoromethyl)-N-[3-(trifluoromethyl)phenyl]-1H-pyrido[2,3-c][1,2]thiazine-3-carboxamide 2,2-dioxide ( 8 ), 4-hydroxy-1-methyl-7-(trifluoromethyl)-N-phenyl-1H-pyrido[2,3-c][1,2]thiazine-3-carboxamide 2,2-dioxide ( 9 ) and N-[2,4-dichloro-5-(2-propynyloxy)phenyl]-4-hydroxy-1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2] thiazine-3-carboxamide 2,2-dioxide ( 10 ).     

Cyclization tendencies in the free radical polymerization of allyl acrylate derivatives: A computational study

In this study density functional theory (DFT) has been used to model the elementary steps and rationalize the free radical polymerization kinetics in allyl methacrylate (AMA), allyl 2‐cyanoacrylate (ACA) and methyl α‐[(allyloxy)methyl]acrylate. The models used in this study have revealed the fact that while methyl α‐[(allyloxy)methyl]acrylate, cyclopolymerizes via 5‐membered rings, AMA and ACA do not. The cyclization tendency of methyl α‐[(allyloxy)methyl]acrylate is attributed to the similar hybridization (sp³) of C3 and C5 favoring a quasi cyclic structure for the reactive rotamer. On the other hand, the presence of the cyano (CN) group in ACA facilitates the initiation step as compared to AMA. The chain transfer reaction does not seem to play a major role in the monomers of interest. This study highlights the usage of quantum chemistry in determining the cyclization tendencies of allyl acrylate derivatives in their free radical polymerization reactions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of 6-(arylthio)- and 6-[(arylmethyl)thio] -1,2,4,5-tetrazin-3-amines and n-phenyl- and n-(phenylmethyl)-1,2,4,5-tetrazine-3,6-diamines as potential antimalarial agents

Alkylation of tetrahydro-1,2,4,5-tetrazine-3,6-dithione with iodomethane and 1,2-dichloro-4-(chloromethyl)benzene, respectively (Scheme 1, 4 ) followed by oxidation afforded 3,6-bis(methylthio)- and 3,6-bis[[(3,4-dichlorophenyl)methyl]thio]-1,2,4,5-tetrazines ( 6, 15 ). The reaction of 15 with amines provided the 6-[(arylmethyl)thio]-1,2,4,5-tetrazin-3-amines ( 16) while sequential displacement of both methylthio groups in 6 afforded the tetrazine-diamines 8 and 10 . Hydrolysis of N,N-dimethyl-6-(methylthio)-1,2,4,5-tetrazin-3-amine ( 11 ) with potassium hydroxide afforded the tetrazin-3-ol ( 12 ) which was chlorinated and then treated with 4-chlorobenzenethiol to provide 13 . The target 6-substituted-1,2,4,5-tetrazin-3-amines displayed negligible antimalarial activity.     

Synthesis of new functionally substituted hetarylcarbamates from methyl {4-[(2<Emphasis Type="Italic">E</Emphasis>)-3-(4-methoxyphenyl)-prop-2-enoyl]phenyl}carbamate

Three-component condensation of methyl {4-[(2E)-3-(4-methoxyphenyl)prop-2-enoyl]phenyl}- carbamate with ninhydrin and L-proline in methanol–water (10: 1) afforded methyl {4-[1,3-dioxo-1′- (4-methoxyphenyl)-1,1′,2′,3,5′,6′,7′,7a′-octahydrospiro[indene-2,3′-pyrrolizin]-2′-ylcarbonyl]phenyl}carbamate. Heating of methyl {4-[(2E)-3-(4-methoxyphenyl)prop-2-enoyl]phenyl}carbamate with isatin and benzylamine in methanol gave methyl {4-[4′-(4-methoxyphenyl)-2-oxo-5′-phenyl-1,2-dihydrospiro[indole-3,2′-pyrrolidin]-3′-ylcarbonyl]phenyl}carbamate. The condensation of methyl {4-[(2E)-3-(4-methoxyphenyl)prop-2- enoyl]phenyl}carbamate with sarcosine and 11H-indeno[1,2-b]quinoxalin-11-one generated in situ from ninhydrin and o-phenylenediamine in boiling ethanol led to the formation of methyl {4-[4′-(4-methoxyphenyl)-1′-methyl-11,11a-dihydro-5aH-spiro[benzo[b]phenazine-6,2′-pyrrolidin]-3′-ylcarbonyl]phenyl}carbamate.     

Synthetic studies directed toward the pseurotins. Part II. Synthesis of related highly functionalized furan-3(2H)-ones

The synthesis of 2,2-bis(hydroxymethyl)-4-methyl-5-phenylfuran-3(2H)-one ( 9 ), 5-[(1S,2S,Z)-1,2-(ethylidenedioxy)hex-3-enyl]-2,2-bis(hydroxymethyl)-4-methylfuran-3(2H)-one ( 24 ), and 5-[(1S,2S,Z)-1,2-(ethylidenedioxy)hex-3-enyl]-2-(hydroxymethyl)-4-methylfuran-3(2H)-one ( 28 ), which represent more advanced, suitably functionalized intermediates for the synthesis of pseurotin A ( 1 ), a secondary metabolite of Pseudeurotium ovalis STOLK , is described.     

Synthesis of new dendrimers—trimesic acid derivatives

The efficient synthesis of new dendrimeric polyesters up to generation 3 that consist of 1,3,5-benzenetricarboxylic acid building blocks with potential applications in drug delivery is described. The dendrimers possess hydroxy or allyl functional groups on the surface and were prepared through a divergent approach using readily available 2-(hydroxymethyl)-2-ethylpropan-1,3-diol and 1,3,5-benzenetrimethanol as central cores, with 3,5-bis[(allyloxy)methyl]benzoic acid being an essential unit of the dendrimer. The latter compound was synthesized, in high yield, from 1,3,5-benzenetricarboxylic acid, applying selective hydrolysis of the corresponding triester as the key step.     

Reaction of Potassium 1,1,3,3-Tetracyano-2-(2,2-dimethylpropanoyl)propenide with 2-Sulfanylethanol

The reaction of potassium 2-(2,2-dimethylpropanoyl)-1,1,3,3-tetracyanopropenide with an equimolar amount of 2-sulfanylethanol afforded 2-{5-amino-2-(tert-butyl)-4-cyano-2-[(2-hydroxyethyl)sulfanyl]- 2,3-dihydrofuran-3-ylidene}propanedinitrile, whereas 4-amino-1-(tert-butyl)-1,6-bis[(2-hydroxyethyl)- sulfanyl]-3-imino-1,3-dihydrofuro[3,4-c]pyridine-7-carbonitrile was obtained in the reaction with excess 2-sulfanylethanol.     

2-Nitroguanidine derivatives: XI. Reactions of <Emphasis Type="Italic">N</Emphasis>′-nitrohydrazinecarboximidamide and 2-methylidene-<Emphasis Type="Italic">N</Emphasis>′-nitrohydrazinecarboximidamide with glyoxal

The reaction of glyoxal with N′-nitrohydrazinecarboximidamide (1-amino-2-nitroguanidine) in the presence of sodium hydroxide at a molar ratio of 1 : 1 : 1 gave N′-nitro-2-(2-oxoethylidene)hydrazinecarboximidamide as a mixture of syn and anti isomers, whereas at a reactant ratio of 1:2:2 N′-nitro-2-[(5-nitroamino-2H-1,2,4-triazol-3-yl)methyl]hydrazinecarboximidamide and 3-nitroamino-4,5-dihydro-1,2,4-triazin-5-ol were formed. N′-Nitro-2-(2-oxoethylidene)hydrazinecarboximidamide reacted with N′-nitrohydrazinecarboximidamide in boiling ethanol to give N′-nitro-2-[(5-nitroamino-2H-1,2,4-triazol-3-yl)methyl]hydrazinecarboximidamide, while in glacial acetic acid 2,2′-(ethane-1,2-diylidene)bis(N′-nitrohydrazinecarboximidamide) was obtained. The latter was also formed in the reaction of glyoxal with N′-nitrohydrazinecarboximidamide in acetic acid at room temperature. The reaction of 2-methylidene-N′-nitrohydrazinecarboximidamide with glyoxal led to the formation of 3-nitroimino-2,3,4-5-tetrahydro-1,2,4-triazine-5-carbaldehyde or 1-(methylideneamino)-2-(nitroimino)imidazolidine-4,5-diol, depending on the conditions.     

Recyclization of Pyrrolediones with Arylaminoindenones. Synthesis of Indeno[1,2-<Emphasis Type="Italic">b</Emphasis>]pyridines

Dimethyl 1-aryl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2,3-dicarboxylates reacted with 3-arylamino-1H-inden-1-ones to give the corresponding methyl 1-aryl-3-[2-(arylamino)-2-oxoacetyl]-2,5-dioxo-2,5-dihydro-1H-indeno[1,2-b]pyridine-4-carboxylates.     

Cyclization of dialkylpropyn‐1‐yl(allyl)(3‐isopropenylpropyn‐2‐yl)ammonium bromides and water‐base cleavage of 2,2‐dialkyl‐5‐methyl‐2,6,7,7a‐tetrahydro‐1h‐isoindolium and 2,2‐dialkyl‐5‐methylisoindolinium bromides

Dialkylpropyn‐1‐yl(or allyl)(3‐isopropenylpropyn‐2‐yl)ammonium bromides under base‐catalyzed condition instantly undergo intramolecular cyclization. The cyclization of dialkylpropyn‐1‐yl(3‐isopropenylpropyn‐2‐yl)ammonium bromides leads to the formation of 2,2‐dialkyl‐5‐methylisoindolinium salts. In case of allyl analogs, instead of the expected 2,2‐dialkyl‐6‐methyl‐3a,4‐dihydroisoindolinium salts their isomeric forms ‐ 2,2‐dialkyl‐5‐methyl‐2,6,7,7a‐tetrahydro‐1H‐isoindolium bromides are obtained. In alkaline medium they are transform into the dihydroisoindolinium salts, the cleavage of which in two directions ‐ 1,2 and 1,6 leads to the mixture of isomeric dialkyl‐1,4‐dimethyl‐ and 2,4‐dimethylbenzyl‐amines. Study of the behavior of 2,2‐dialkyl‐5‐methylisoindolinium salts under conditions of water‐base cleavage showed, that only spiro[5‐methylisoindolyn]morpholinium bromide undergoes 1,2‐elimination, forming 5‐methylisoindoline 2‐vinyl ethyl ester.     

Three-component reaction of methyl 2,4-dioxo-4-phenylbutanoate and methyl 2,4-dioxopentanoate with aromatic aldehydes and propane-1,2-diamine and chemical properties of the products

The reactions of methyl 2,4-dioxo-4-phenylbutanoate and methyl 2,4-dioxopentanoate with a mixture of an aromatic aldehyde and propane-1,2-diamine, depending on the initial reactant ratio, gave 4-acyl-1-(2-aminopropyl)-5-aryl-3-hydroxy-2,5-dihydro-1H-pyrrol-2-ones and 1,1′-(propane-1,2-diyl)bis(4-acetyl-3-hydroxy-5-phenyl-2,5-dihydro-1H-pyrrol-2-one). Reactions of substituted 1-(2-aminopropyl)-2,5-dihydro-1H-pyrrol-2-ones with aromatic amines and hydrazines were studied, and the structure of one of the products, 5-(2-aminopropyl)-3,4-diphenylpyrrolo[3,4-c]pyrazol-6-one, was proved by X-ray analysis.     

Reaction of azulene with 1,2-bis[4-(dimethylamino)phenyl]-1,2-ethanediol in a mixed solvent of methanol and acetonitrile in the presence of hydrochloric acid: a facile one-pot synthesis and properties of new triarylethylenes possessing an azulen-1-yl group

Reaction of azulene (1) with 1,2-bis[4-(dimethylamino)phenyl]-1,2-ethanediol (2) in a mixed solvent of methanol and acetonitrile in the presence of 36% hydrochloric acid at 60 °C for 3 h gives 2-(azulen-1-yl)-1,1-bis[4-(dimethylamino)phenyl]ethylene (3) (8% yield), 1-(azulen-1-yl)-(E)-1,2-bis[4-(dimethylamino)phenyl]ethylene (4) (28% yield), and 1,3-bis{2,2-bis[4-(dimethylamino)phenyl]ethenyl}azulene (5) (9% yield). Besides the above products, this reaction affords 1,1-di(azulen-1-yl)-2,2-bis[4-(dimethylamino)phenyl]ethane (6) (15% yield), a meso form (1R,2S)-1,2-di(azulen-1-yl)-1,2-bis[4-(dimethylamino)phenyl]ethane (7) (6% yield), and the two enantiomeric forms (1R,2R)- and (1S,2S)-1,2-di(azulen-1-yl)-1,2-bis[4-(dimethylamino)phenyl]ethanes (8) (6% yield). Furthermore, addition reaction of 3 with 1 under the same reaction conditions as the above provides 6, in 46% yield, which upon oxidation with DDQ (=2,3-dichloro-5,6-dicyano-1,4-benzoquinone) in dichloromethane at 25 °C for 24 h yields 1,1-di(azulen-1-yl)-2,2-bis[4-(dimethylamino)phenyl]ethylene (9) in 48% yield. Interestingly, reaction of 1,1-bis[4-(dimethylamino)phenyl]-2-(3-guaiazulenyl)ethylene (11) with 1 in a mixed solvent of methanol and acetonitrile in the presence of 36% hydrochloric acid at 60 °C for 3 h gives guaiazulene (10) and 3, owing to the replacement of a guaiazulen-3-yl group by an azulen-1-yl group, in 91 and 46% yields together with 5 (19% yield) and 6 (13% yield). Similarly, reactions of 2-(3-guaiazulenyl)-1,1-bis(4-methoxyphenyl)ethylene (12) and 1,1-bis{4-[2-(dimethylamino)ethoxy]phenyl}-2-(3-guaiazulenyl)ethylene (13) with 1 under the same reaction conditions as the above provide 10, 2-(azulen-1-yl)-1,1-bis(4-methoxyphenyl)ethylene (16), and 1,3-bis[2,2-bis(4-methoxyphenyl)ethenyl]azulene (17) (93, 34, and 19% yields) from 12 and 10 and 2-(azulen-1-yl)-1,1-bis{4-[2-(dimethylamino)ethoxy]phenyl}ethylene (18) (97 and 58% yields) from 13.