A 3-D open network constructed from metallamacrocycle chains with a simple ‘corner’ ligand of 2,4-diamino-6-methyl-1,3,5-triazine(dmt) via cross-linked hydrogen bonds

The title polymer Ag(I) complex was synthesized through the reaction of 2,4-diamino-6-methyl-1,3,5-triazine(dmt) and Ag₂SO₄. X-ray structure analysis shows that the crystal structure of title complex consists a infinite 1-D polymer chains with novel metallamacrocycles, which are cross-linked to each other by four types of hydrogen bonds, resulting in the formation of a new 3-D open network with large channels.     

Lead(II) and cadmium(II) compounds with 2,4-dichlorophenoxyacetic acid (2,4D) and 2-(2,4-dichlorophenoxy)-propionic acid (2,4DP): Synthesis and properties

The paper presents the conditions under which compounds of the commercial herbicides, 2,4-dichlorophenoxyacetic acid (2,4D; C₈H₆O₃Cl₂) and 2-(2,4-dichlorophenoxy)-propionic acid (2,4DP; C₉H₈O₃Cl₂), with lead(II) and cadmium(II) are formed and the results of the examination of their properties.On the basis of the elemental analysis and Pb and Cd determination, the following molecular formulae for the obtained compounds were proposed: Pb(C₈H₅O₃Cl₂)₂.H₂O, Cd(C₈H₅O₃Cl₂)₂.₂H₂O, Pb(C₉H₇O₃Cl₂)2·H₂O and Cd(C₉H₇O₃Cl₂)₂·H₂O. Water solubility of the synthesized complexes at room temperature was examined. X-ray powder analysis was carried out. The discussion of IR spectra and conductivity data is presented. Thermal decomposition of these compounds in air was studied by TG/MS methods.This revised version was published online in November 2005 with corrections to the Cover Date.     

Cocrystals of 6‐methyl‐2‐thiouracil: presence of the acceptor–donor–acceptor/donor–acceptor–donor synthon

The results of seven cocrystallization experiments of the antithyroid drug 6‐methyl‐2‐thiouracil (MTU), C₅H₆N₂OS, with 2,4‐diaminopyrimidine, 2,4,6‐triaminopyrimidine and 6‐amino‐3H‐isocytosine (viz. 2,6‐diamino‐3H‐pyrimidin‐4‐one) are reported. MTU features an ADA (A = acceptor and D = donor) hydrogen‐bonding site, while the three coformers show complementary DAD hydrogen‐bonding sites and therefore should be capable of forming an ADA/DAD N—H...O/N—H...N/N—H...S synthon with MTU. The experiments yielded one cocrystal and six cocrystal solvates, namely 6‐methyl‐2‐thiouracil–2,4‐diaminopyrimidine–1‐methylpyrrolidin‐2‐one (1/1/2), C₅H₆N₂OS·C₄H₆N₄·2C₅H₉NO, (I), 6‐methyl‐2‐thiouracil–2,4‐diaminopyrimidine (1/1), C₅H₆N₂OS·C₄H₆N₄, (II), 6‐methyl‐2‐thiouracil–2,4‐diaminopyrimidine–N,N‐dimethylacetamide (2/1/2), 2C₅H₆N₂OS·C₄H₆N₄·2C₄H₉NO, (III), 6‐methyl‐2‐thiouracil–2,4‐diaminopyrimidine–N,N‐dimethylformamide (2/1/2), C₅H₆N₂OS·0.5C₄H₆N₄·C₃H₇NO, (IV), 2,4,6‐triaminopyrimidinium 6‐methyl‐2‐thiouracilate–6‐methyl‐2‐thiouracil–N,N‐dimethylformamide (1/1/2), C₄H₈N₅⁺·C₅H₅N₂OS⁻·C₅H₆N₂OS·2C₃H₇NO, (V), 6‐methyl‐2‐thiouracil–6‐amino‐3H‐isocytosine–N,N‐dimethylformamide (1/1/1), C₅H₆N₂OS·C₄H₆N₄O·C₃H₇NO, (VI), and 6‐methyl‐2‐thiouracil–6‐amino‐3H‐isocytosine–dimethyl sulfoxide (1/1/1), C₅H₆N₂OS·C₄H₆N₄O·C₂H₆OS, (VII). Whereas in cocrystal (I) an R₂²(8) interaction similar to the Watson–Crick adenine/uracil base pair is formed and a two‐dimensional hydrogen‐bonding network is observed, the cocrystals (II)–(VII) contain the triply hydrogen‐bonded ADA/DAD N—H...O/N—H...N/N—H...S synthon and show a one‐dimensional hydrogen‐bonding network. Although 2,4‐diaminopyrimidine possesses only one DAD hydrogen‐bonding site, it is, due to orientational disorder, triply connected to two MTU molecules in (III) and (IV).     

Catalytic C-phenylation of methyl acrylate with tetraphenylantimony(v) halides and carboxylates

Catalytic C-phenylation of methyl acrylate to methyl cinnamate with the Ph₄SbX complexes (X = F, Cl, Br, OH, OAc, O₂CEt) in the presence of the palladium compounds PdCl₂, Pd(OAc)₂, Pd₂(dba)₃, Pd(Ph₃P)₂Cl₂, and Pd(dppf)Cl₂ (dba is dibenzylideneacetone and dppf is bis(diphenylphosphinoferrocene)) was studied in organic solvents (MeCN, THF, DMF, MeOH, and AcOH). The highest yield of methyl cinnamate (73% based on the starting organometallic compound) was obtained for the Ph₄SbCl—PdCl₂ (1 : 0.04) system in acetonitrile.     

Reaction of aromatic aldehydes with β-dicarbonyl compounds in a catalytic system: Piperidinium acetate-1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid

Condensation of aromatic (heteroaromatic) aldehydes with 1,3-dicarbonyl compounds under the 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF₄]) ionic liquid-piperidinium acetate catalytic system (0.2 equiv. of each component) in the absence of a solvent affords, depending on the structures of the reagents, 2-arylidene derivatives of methyl acetoacetate and acetylacetone, diethyl 2,4-bis(trifluoroacetyl)-3-phenylpentanedioate, or dimethyl 2-aryl-4-hydroxy-6-oxocyclohexane-1,3-dicarboxylates. The reactions of the resulting 2-arylidene derivatives with O-methylisourea in the [Bmim][BF₄] ionic liquid produced methyl 2-methoxy-4-methyl-6-aryldihydropyrimidine-5-carboxylates and 1-(2-methoxy-4-methyl-6-phenyldihydropyrimidin-5-yl)ethanone (mixtures of 3,6- and 1,6-dihydro isomers), which were transformed into the corresponding 3,4-dihydropyrimidin-2(1H)-one derivatives. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1199–1204, May, 2005.     

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 ).     

Synthesis of fluorinated 2,6-heptanediones and 2-oxa-6- azabicyclo[2.2.2]octanes from 1,4-dihydropyridines

Electrophilic fluorination of Hantzsch-type 1,4-dihydropyridines with Selectfluor^® led to the formation of new fluorinated 2,6-heptanediones - dialkyl 2,4-diacetyl-2,4-difluoro-3-phenylpentanedioates. Novel 2,6-heptanedione derivatives in reaction with hydrazine hydrate easily form 6-amino-4,7-difluoro-3-hydroxy-1,3-dimethyl-5-oxo-8-phenyl-2-oxa-6-azabicyclo[2.2.2]octanes instead of the corresponding diazepine derivatives. The obtained 2-оxa-6-azabicyclo[2,2,2]octanes are thermally stable at the temperatures below 50°С. At higher temperatures rearrangement of 2-oxa-6-azabicyclo[2,2,2]octanes offers new fluorine-containing pyrazolinone derivatives - alkyl esters of 2-fluoro-2-((4-fluoro-3-methyl-5-oxo-4,5-dihydro-1H-pyrazol-4-yl)(phenyl)methyl)-3-oxobutanoates.     

Synergistic solvent extraction of lanthanides with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one and aliphatic amines: Influence of the ammonium salt ions

Summary The synergistic solvent extraction of Pr, Gd, and Yb with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one (HP) and tridodecylammonium (TDAHA), trioctylammonium (TOAHA), and dioctylammonium (DOAHA) salts (A ^–=Cl^–, NO ₃ ^– , and ClO ₄ ^– ) in C₆H₆ has been studied. The composition of the extracted species has been determined asAmH⁺[LnP ₄]^– (AmH⁺: ammonium salt cation). The values of the equilibrium constant have been calculated. The influence of the ammonium salt ions on the extraction process is discussed.

---

Synergetische Extraktion von Lanthaniden mit Mischungen aus 1-Phenyl-3-methyl-4-benzoyl-pyrazol-5-on und aliphatischen Aminen: Einfluß der Ammoniumsalzionen

Zusammenfassung Die synergetische Extraktion von Pr, Gd und Yb mit Mischungen aus 1-Phenyl-3-methyl-4-benzoyl-pyrazol-5-on (HP) und Tridodecylammonium-(TDAHA), Trioctylammonium-(TOAHA) und Dioctylammoniumsalzen (DOAHA) (A ^–=Cl^–, NO ₃ ^– und ClO ₄ ^– ) in C₆H₆ wurde untersucht. Die Zusammensetzung der Extraktionskomplexverbindungen wurde zuAmH⁺[LnP ₄]^– bestimmt; die Gleichgewichtskonstanten wurden berechnet. Der Einfluß der Ionen des Ammoniumsalzes auf die Extraktion wird diskutiert.

     

Preparation of linear α‐olefins to high‐molecular weight polyethylenes using cationic α‐diimine nickel(II) complexes containing chloro‐substituted ligands

A series of α‐diimine nickel(II) complexes containing chloro‐substituted ligands, [(Ar)N?C(C₁₀H₆)C?N(Ar)]NiBr₂ ( 4a , Ar = 2,3‐C₆H₃Cl₂; 4b , Ar = 2,4‐C₆H₃Cl₂; 4c , Ar = 2,5‐C₆H₃Cl₂; 4d , Ar = 2,6‐C₆H₃Cl₂; 4e , Ar = 2,4,6‐C₆H₂Cl₃) and [(Ar)N?C(C₁₀H₆)C?N(Ar)]₂NiBr₂ ( 5a , Ar = 2,3‐C₆H₃Cl₂; 5b , Ar = 2,4‐C₆H₃Cl₂; 5c , Ar = 2,5‐C₆H₃Cl₂), have been synthesized and investigated as precatalysts for ethylene polymerization. In the presence of modified methylaluminoxane (MMAO) as a cocatalyst, these complexes are highly effective catalysts for the oligomerization or polymerization of ethylene under mild conditions. The catalyst activity and the properties of the products were strongly affected by the aryl‐substituents of the ligands used. Depending on the catalyst structure, it is possible to obtain the products ranging from linear α‐olefins to high‐molecular weight polyethylenes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1964–1974, 2006     

Cocrystals of 2,6‐dichloroaniline and 2,6‐dichlorophenol plus three new pseudopolymorphs of their coformers

The structures of cocrystals of 2,6‐dichlorophenol with 2,4‐diamino‐6‐methyl‐1,3,5‐triazine, C₆H₄Cl₂O·C₄H₇N₅, (III), and 2,6‐dichloroaniline with 2,6‐diaminopyrimidin‐4(3H)‐one and N,N‐dimethylacetamide, C₆H₅Cl₂N·C₄H₆N₄O·C₄H₉NO, (V), plus three new pseudopolymorphs of their coformers, namely 2,4‐diamino‐6‐methyl‐1,3,5‐triazine–N,N‐dimethylacetamide (1/1), C₄H₇N₅·C₄H₉NO, (I), 2,4‐diamino‐6‐methyl‐1,3,5‐triazine–N‐methylpyrrolidin‐2‐one (1/1), C₄H₇N₅·C₅H₉NO, (II), and 6‐aminoisocytosine–N‐methylpyrrolidin‐2‐one (1/1), C₄H₆N₄O·C₅H₉NO, (IV), are reported. Both 2,6‐dichlorophenol and 2,6‐dichloroaniline are capable of forming definite synthon motifs, which usually lead to either two‐ or three‐dimensional crystal‐packing arrangements. Thus, the two isomorphous pseudopolymorphs of 2,4‐diamino‐6‐methyl‐1,3,5‐triazine, i.e. (I) and (II), form a three‐dimensional network, while the N‐methylpyrrolidin‐2‐one solvate of 6‐aminoisocytosine, i.e. (IV), displays two‐dimensional layers. On the basis of these results, attempts to cocrystallize 2,6‐dichlorophenol with 2,4‐diamino‐6‐methyl‐1,3,5‐triazine, (III), and 2,6‐dichloroaniline with 6‐aminoisocytosine, (V), yielded two‐dimensional networks, whereby in cocrystal (III) the overall structure is a consequence of the interaction between the two compounds. By comparison, cocrystal–solvate (V) is mainly built by 6‐aminoisocytosine forming layers, with 2,6‐dichloroaniline and the solvent molecules arranged between the layers.     

An Expeditious Synthesis of Methyl Jasmonate

We present an efficient three‐step, two‐pot synthesis of methyl jasmonate (trans‐ 1 ) based on Diels–Alder cycloaddition of cyclopent‐2‐enone ( 2 ) and chloroprene (= 2‐chlorobuta‐1,3‐diene; 3d ) in either CHCl₃ or CH₂Cl₂, catalyzed by SnCl₄ (0.2 mol‐equiv.) at 20° (75% yield). Subsequent ozonolysis of a cis/trans 55 : 45 mixture of the cycloadduct 4d in either CH₂Cl₂ or AcOEt at ? 78°, followed by addition of Me₂S and MeOH in the presence of NaHCO₃, afforded, in 64% yield, a cis/trans 40 : 60 mixture of the known aldehyde 5c . The latter was reacted at ? 50° under salt‐free conditions with the propyl Wittig reactant to furnish 1 as a cis/trans 20 : 80 mixture ((E/Z) 3 : 97). Alternatively, a cis/trans 7 : 93 mixture ((E/Z) 4 : 96) was obtained in 88% yield from epimerized 5c (AcOH, H₂O, 40°; 99%) under usual Wittig conditions at ? 20°.     

The hydrogen‐bonded complex bis(tert‐butylammonium) 2,6‐dichlorophenolate 2,4‐dichlorophenol–2,4‐dichlorophenolate tetrahydrofuran disolvate containing a chiral R53(10) hydrogen‐bonded ring as a supramolecular synthon

A fixed hydrogen‐bonding motif with a high probability of occurring when appropriate functional groups are involved is described as a `supramolecular hydrogen‐bonding synthon'. The identification of these synthons may enable the prediction of accurate crystal structures. The rare chiral hydrogen‐bonding motif R₅³(10) was observed previously in a cocrystal of 2,4,6‐trichlorophenol, 2,4‐dichlorophenol and dicyclohexylamine. In the title solvated salt, 2C₄H₁₂N⁺·C₆H₃Cl₂O⁻·(C₆H₃Cl₂O⁻·C₆H₄Cl₂O)·2C₄H₈O, five components, namely two tert‐butylammonium cations, one 2,4‐dichlorophenol molecule, one 2,4‐dichlorophenolate anion and one 2,6‐dichlorophenolate anion, are bound by N—H…O and O—H…O hydrogen bonds to form a hydrogen‐bonded ring, with the graph‐set motif R₅³(10), which is further associated with two pendant tetrahydrofuran molecules by N—H…O hydrogen bonds. The hydrogen‐bonded ring has internal symmetry, with a twofold axis running through the centre of the 2,6‐dichlorophenolate anion, and is isostructural with a previous and related structure formed from 2,4‐dichlorophenol, dicyclohexylamine and 2,4,6‐trichlorophenol. In the title crystal, helical columns are built by the alignment and twisting of the chiral hydrogen‐bonded rings, along and across the c axis, and successive pairs of rings are associated with each other through C—H…π interactions. Neighbouring helical columns are inversely related and, therefore, no chirality is sustained, in contrast to the previous case.     

Preparation and characterization of nano-Co-[4-chlorophenyl-salicylaldimine-methyl pyranopyrazole]Cl2 as a new Schiff base complex and catalyst for the solvent-free synthesis of 1-amidoalkyl-2-naphthols

By the reaction of 4-chlorobenzaldehyde with ethyl acetoacetate, malononitrile, and hydrazine hydrate, 6-amino-4-(4-chlorophenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile was prepared and then reacted with salicylaldehyde and CoCl₂·6H₂O to produce nano-Co-[4-cholorophenyl-salicylaldimine-methylpyranopyrazole]Cl₂ (nano-[Co-4CSMP]Cl₂). The prepared nano-Schiff base complex was reported for the first time and fully characterized by Fourier transform-infrared spectroscopy, thermal gravimetric analysis, differential thermal gravimetric analysis, scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, and Brunner–Emmett–Teller analyses and applied as an efficient catalyst for the synthesis of some 1-amidoalkyl-2-naphthol derivatives.     

Chemistry of Spontaneous Alkylation of Methimazole with 1,2-Dichloroethane

Spontaneous S-alkylation of methimazole (1) with 1,2-dichloroethane (DCE) into 1,2-bis[(1-methyl-1H-imidazole-2-yl)thio]ethane (2), that we have described recently, opened the question about its formation pathway(s). Results of the synthetic, NMR spectroscopic, crystallographic and computational studies suggest that, under given conditions, 2 is obtained by direct attack of 1 on the chloroethyl derivative 2-[(chloroethyl)thio]-1-methyl-1H-imidazole (3), rather than through the isolated stable thiiranium ion isomer, i.e., 7-methyl-2H, 3H, 7H-imidazo[2,1-b]thiazol-4-ium chloride (4a, orthorhombic, space group Pnma), or in analogy with similar reactions, through postulated, but unproven intermediate thiiranium ion 5. Furthermore, in the reaction with 1, 4a prefers isomerization to the N-chloroethyl derivative, 1-chloroethyl-2,3-dihydro-3-methyl-1H-imidazole-2-thione (7), rather than alkylation to 2, while 7 further reacts with 1 to form 3-methyl-1-[(1-methyl-imidazole-2-yl)thioethyl]-1H-imidazole-2-thione (8, monoclinic, space group P 2₁/c). Additionally, during the isomerization of 3, the postulated intermediate thiiranium ion 5 was not detected by chromatographic and spectroscopic methods, nor by trapping with AgBF₄. However, trapping resulted in the formation of the silver complex of compound 3, i.e., bis-{2-[(chloroethyl)thio]-1-methyl-1H-imidazole}-silver(I)tetrafluoroborate (6_, monoclinic, space group P 2₁/c), which cyclized upon heating at 80 °C to 7-methyl-2H, 3H, 7H-imidazo[2,1-b]thiazol-4-ium tetrafluoroborate (4b, monoclinic, space group P 2₁/c). Finally, we observed thermal isomerization of both 2 and 2,3-dihydro-3-methyl-1-[(1-methyl-1H-imidazole-2-yl)thioethyl]-1H-imidazole-2-thione (8), into 1,2-bis(2,3-dihydro-3-methyl-1H-imidazole-2-thione-1-yl)ethane (9), which confirmed their structures.     

Low‐dimensional coordination polymeric structures in alkali metal complex salts of the herbicide (2,4‐dichlorophenoxy)acetic acid (2,4‐D)

The Li, Rb and Cs complexes with the herbicide (2,4‐dichlorophenoxy)acetic acid (2,4‐D), namely poly[[aqua[μ₃‐(2,4‐dichlorophenoxy)acetato‐κ³O¹:O¹:O^1′]lithium(I)] dihydrate], {[Li(C₈H₅Cl₂O₃)(H₂O)]·2H₂O}_n, (I), poly[μ‐aqua‐bis[μ₃‐(2,4‐dichlorophenoxy)acetato‐κ⁴O¹:O^1′:O^1′,Cl²]dirubidium(I)], [Rb₂(C₈H₅Cl₂O₃)₂(H₂O)]_n, (II), and poly[μ‐aqua‐bis[μ₃‐(2,4‐dichlorophenoxy)acetato‐κ⁵O¹:O^1′:O^1′,O²,Cl²]dicaesium(I)], [Cs₂(C₈H₅Cl₂O₃)₂(H₂O)]_n, (III), respectively, have been determined and their two‐dimensional polymeric structures are described. In (I), the slightly distorted tetrahedral LiO₄ coordination involves three carboxylate O‐atom donors, of which two are bridging, and a monodentate aqua ligand, together with two water molecules of solvation. Conjoined six‐membered ring systems generate a one‐dimensional coordination polymeric chain which extends along b and interspecies water O—H...O hydrogen‐bonding interactions give the overall two‐dimensional layers which lie parallel to (001). In hemihydrate complex (II), the irregular octahedral RbO₅Cl coordination about Rb⁺ comprises a single bridging water molecule which lies on a twofold rotation axis, a bidentate O_carboxy,Cl‐chelate interaction and three bridging carboxylate O‐atom bonding interactions from the 2,4‐D ligand. A two‐dimensional coordination polymeric layer structure lying parallel to (100) is formed through a number of conjoined cyclic bridges, including a centrosymmetric four‐membered Rb₂O₂ ring system with an Rb...Rb separation of 4.3312 (5) Å. The coordinated water molecule forms intralayer aqua–carboxylate O—H...O hydrogen bonds. Complex (III) comprises two crystallographically independent (Z′ = 2) irregular CsO₆Cl coordination centres, each comprising two O‐atom donors (carboxylate and phenoxy) and a ring‐substituted Cl‐atom donor from the 2,4‐D ligand species in a tridentate chelate mode, two O‐atom donors from bridging carboxylate groups and one from a bridging water molecule. However, the two 2,4‐D ligands are conformationally very dissimilar, with one phenoxyacetate side chain being synclinal and the other being antiperiplanar. The minimum Cs...Cs separation is 4.4463 (5) Å. Structure extension gives coordination polymeric layers which lie parallel to (001) and are stabilized by intralayer water–carboxylate O—H...O hydrogen bonds.     

Reactions of Aromatic S‐ and O‐Enynes with Two Methyl Substituents on the Olefinic Unit Assisted by a Ruthenium Complex: Tandem Cyclization and Product Selectivity

Ruthenium‐assisted cyclizations of two enynes, HC≡CCH(OH)(C₆H₄)X? CH₂CH?CMe₂ (X=S ( 1a ), O ( 1b )), each of which contains two terminal methyl substituents on the olefinic parts, are explored. The reaction of 1a in CH₂Cl₂ gives the vinylidene complex 2a from the first cyclization and two side products, 3a and the carbene complex 4a with a benzothiophene ligand. The same reaction in the presence of HBF₄ affords 4a exclusively. Air oxidation of 4a in the presence of Et₃N readily gives an aldehyde product. In MeOH, tandem cyclizations of 1a generate a mixture of the benzothiochromene compound 10a and the carbene complex 7a also with a benzothiochromene ligand. First, cyclization of 1b likewise proceeds in CH₂Cl₂ to give 2b . Tandem cyclization of 1b in MeOH yields comparable products 10b and 7b with benzochromene moieties, yet with no other side product. The reaction of [Ru]Cl with HC≡CCH(OH)(C₆H₄)S? CH₂CH?CH₂ ( 1c ), which contains no methyl substituent in the olefinic part, in MeOH gives the carbene complex 15c with an unsubstituted thiochromene by means of a C? S bond formation. Structures of 3a and 15c are confirmed by X‐ray diffraction analysis. The presence of methyl groups of enynes 1a and 1b promotes sequential cyclization reactions that involve C? C bond formation through carbocationic species.     

Reactions of 6-Amino-5-Cyano-3-Methyl-1,4-Diphenyl-1H 4H-Pyrano[2,3-C]Pyrazole and its Methanimidate

Reaction of 6-amino-5-cyano-3-methyl-1,4-diphenyl- 1H,4H-pyrano[2,3-c]pyrazole 1 with triethyl orthoformate in acetic anhydride gave its methanimidate 2, which reacts with primary aliphatic and aromatic amines to give 4,6-dihydro-3-methyl-1,4-diphenyl-6- (alkyl)pyrazolo[4′,3′:5,6]pyrano[2,3-d]pyrimidine-5(lH)- imine 3 and the starting compound 1 , respectively. Treatment of 1 with o-aminophenol gave 5-(2-benzoxalyl)- 1,4-dihydro-3-methyl-1,4-diphenylpyrano[2,3-c]pyrazol- 6-amine 9.     

Steric effects on forming different by-products in the formylation reaction of 2,4-dialkylphenol (dialkyl = t-Bu/t-Bu, t-Bu/Me and Me/Me) proved by their structural and spectral characterizations

In the formylation reaction of 2,4-dialkylphenol (2,4-di-tert-butylphenol, 2-tert-butyl-4-methylphenol and 2,4-dimethylphenol) in the presence of hexamethylenetetramine, steric effects of alkyl groups play important roles in forming different types of by-products, namely 2,4-di-tert-butyl-6-[(6,8-di-tert-butyl-2H-1,3-benzoxazin-3(4H)-yl)methyl]phenol (1), 2-tert-butyl-4-methyl-6-[(6-tert-butyl-8-methyl-2H-1,3-benzoxazin-3(4H)-yl)methyl]phenol (2) and tris(2-hydroxy-3,5-dimethylbenzyl)amine hydrochlorate (3). These three compounds are fully characterized and single-crystal structures of 1 and 3 are further elucidated.     

Electroreduction of Polychlorobenzenes Using Either Lead or Copper Electrodes

Polychlorobenzenes can be reduced electrolytically to dichlorobenzenes by using either lead or copper as the electrodes in a MeOH/THF solution. Among the resultants of dichlorobenzenes, 1,4‐dichlorobenzene is a major product that might be due to a low enthalpy of formation. A chlorine atom situated at the ortho position of another chlorine atom in the benzene ring is removed prior to others. However, the sequence of reactivities of the polychlorobenzenes for electroreducing by lead electrodes in this study is as follows: 1,2,3,4‐C₆H₂Cl₄ > 1,3,5‐C₆H₃Cl₃ > C₆HCl₅ ～ 1,2,4,5‐C₆H₂Cl₄ > 1,2,3,5‐C₆H₂Cl₄ ～ 1,2,3‐C₆H₃Cl₃ > 1,2,4‐C₆H₃Cl₃ >C₆Cl₆.     

A Tail Does Not Always Make a Difference: Assembly of cds Nets from Co(NCS)2 and 1,4-bis(n-Alkyloxy)-2,5-bis(3,2′:6′,3″-terpyridin-4′-yl)benzene Ligands

The consistent assembly of a (6⁵.8) cds net is observed in reactions of cobalt(II) thiocyanate with 1,4-bis(n-alkyloxy)-2,5-bis(3,2′:6′,3″-terpyridin-4′-yl)benzene ligands in which the n-alkyloxy substituents are n-propyl (ligand 3), n-butyl (4), n-pentyl (5), n-hexyl (6), n-heptyl (7), and n-octyl (8). Crystals were grown by layering a methanol solution of Co(NCS)₂ over a 1,2-dichlorobenzene solution of each ligand. The choice of crystallization solvents is critical in directing the assembly of the cds net. Single-crystal structures of [Co(NCS)₂(3)]_n^.3.5nC₆H₄Cl₂, [Co(NCS)₂(4)]_n^.5.5nC₆H₄Cl₂, [Co(NCS)₂(5)]_n^.4nC₆H₄Cl₂, [Co(NCS)₂(6)]_n^.3.8nC₆H₄Cl₂, [Co(NCS)₂(7)]_n^.3.1nC₆H₄Cl₂, and [Co(NCS)₂(8)]_n^.1.6nC₆H₄Cl₂^.2nMeOH (C₆H₄Cl₂ = 1,2-dichlorobenzene) are presented and compared. The n-alkyloxy chains exhibit close to extended conformations and are accommodated in cavities in the lattice without perturbation of the coordination framework.