New domino‐reaction for the synthesis of N4‐(5‐aryl‐1,3‐oxathiol‐2‐yliden)‐2‐phenylquinazolin‐4‐amines and 4‐[4‐aryl‐5‐(2‐phenylquinazolin‐4‐yl)‐1,3‐thiazol‐2‐yl]morpholine

The model morpholine‐1‐carbothioic acid (2‐phenyl‐3H‐quinazolin‐4‐ylidene) amide (1) reacts with phenacyl bromides to afford N⁴‐(5‐aryl‐1,3‐oxathiol‐2‐yliden)‐2‐phenylquinazolin‐4‐amines (4) or N⁴‐(4,5‐diphenyl‐1,3‐oxathiol‐2‐yliden)‐2‐phenyl‐4‐aminoquinazoline ( 5 ) by a thermodynamically controlled reversible reaction favoring the enolate intermediate, while the 4‐[4‐aryl‐5‐(2‐phenylquinazolin‐4‐yl)‐1,3‐thiazol‐2‐yl]morpholine ( 8 ) was produced by a kinetically controlled reaction favoring the C‐anion intermediate. ¹H nmr, ¹³C nmr, ir, mass spectroscopy and x‐ray identified compounds ( 4 ), ( 5 ) and ( 8 ).     

Reaktionen von 1,1,3,3‐Tetrakis(dimethylamino)‐1 λ5, 3 λ5‐diphosphet mit 5‐Cyano‐1‐pentin und mit 2‐(Cyanmethyl)‐1‐methylpyrrol

Diphosphabenzenes. VII. Reactions of 1,1,3,3‐Tetrakis(dimethylamino)‐1 λ⁵, 3 λ⁵‐diphosphete with 5‐Cyano‐1‐pentine and 2‐(Cyanomethyl)‐1‐methylpyrrol 5‐Cyano‐1‐pentine reacts with the equimolar amount of the λ⁵‐diphosphete 1 to give the λ⁵‐diphosphinine (λ⁵‐diphosphabenzene) ( 3 ), while reaction with the double equimolar amount of 1 yields the λ⁵‐diphosphinine ( 4 ). The acyclic compount 6 is the main product of the reaction between 1 and 2‐(cyanomethyl)‐1‐methylpyrrol, 5 . Melting points of 4 · CH₃CN and 6 , and mass, nmr and ir spectra of 3 , 4 , and 6 are reported. The crystal structure of 4 · CH₃CN shows an open‐chain ylidic CPCP‐sequence, which is linked to a λ⁵‐diphosphinine via an ethylene bridge. The X‐ray structure analysis of 6 confirms the existence as an acyclic conjugated double ylid.     

Synthesis of some new 1‐acyl‐5‐aryl‐3‐(5‐methyl‐1‐p‐tolyl‐1H‐1,2,3‐triazol‐4‐yl)‐4,5‐dihydro‐1H‐pyrazole

Some new compounds (E)‐3‐aryl‐1‐(5‐methyl‐1‐p‐tolyl‐1H‐1,2,3‐triazol‐4‐yl)‐prop‐2‐en‐1‐ones 5a–e were prepared by 1‐(5‐methyl‐1‐p‐tolyl‐1H‐1,2,3‐triazol‐4‐yl)‐ethanone and various aromatic aldehydes. Then one pot reaction was happened by compounds 5a–e with hydrazine hydrate in acetic acid or propionic acid, respectively, to give the title compounds 1acyl‐5‐aryl‐3‐(5‐methyl‐1‐p‐tolyl‐1H‐1,2,3‐triazol‐4‐yl)‐4,5‐dihydro‐1H‐pyrazoles 6a–i . All structures were established by MS, IR, CHN, ¹H‐NMR and ¹³C‐NMR spectral data. J. Heterocyclic Chem., (2012).     

Eine cyclische Methylendiphosphinsäure: 1,3‐Dihydroxy‐1,3‐dioxo‐1,2,3,4‐tetrahydro‐1λ5,3λ5‐[1,3]diphosphinin

A Cyclic Methylenediphosphinic Acid: 1,3‐Dihydroxy‐1,3‐dioxo‐1,2,3,4‐tetrahydro‐1λ⁵,3λ⁵‐[1,3]diphosphinine Strong acids protonate 1,3‐bis(dimethylamino)‐1λ⁵,3λ⁵‐[1,3]diphosphinine ( 5 ) to give the corresponding cation. The protonation is followed by hydrolytic cleavage of the dimethylamino groups resulting in the formation of the cyclic methylenediphosphinic acid ( 6 ).     

An efficient synthesis of 5‐aryl‐4,5‐dihydro‐3‐(5‐methyl‐1‐p‐tolyl‐1H‐1,2,3‐triazol‐4‐yl)‐1‐(4‐phenylthiazol‐2‐yl)pyrazoles

Some new target products 5‐aryl‐4,5‐dihydro‐3‐(5‐methyl‐1‐p‐tolyl‐1H‐1,2,3‐triazol‐4‐yl)‐1‐(4‐phenylthiazol‐2‐yl)pyrazoles 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h , 5i , 5j have been synthesized by reaction of 2‐bromo‐1‐phenylethanone and compounds 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h , 4i , 4j which were prepared from the combination of thiosemicarbazide and (E)‐3‐aryl‐1‐(5‐methyl‐1‐p‐tolyl‐1H‐1,2,3‐triazol‐4‐yl)‐prop‐2‐en‐1‐ones 3a , 3b , 3c , 3d , 3e , 3f , 3g , 3h , 3i , 3j . All the structures were established by MS, IR, CHN, and ¹H NMR spectra data. Synthesis of structure diversity is applied. J. Heterocyclic Chem., (2011).     

Synthesis of 3‐[5‐methyl‐1‐(4‐methylphenyl)‐1,2,3‐triazol‐4‐yl]‐6‐substituted‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazoles

Several 3‐[5‐methyl‐1‐(4‐methylphenyl)‐1,2,3‐triazol‐4‐yl]‐6‐substituted‐1,3,4‐triazolo[3,4‐b]‐1,3,4‐thiadiazoles have been synthesized and the structures of these compounds were established by elemental analysis, MS, IR and ¹H NMR spectral data.     

Octafluor‐1, 2‐dimethylencyclobutan,ein perfluorierter Dien‐Komplexligand — Carbonyl(η5‐cyclopentadienyl)(η4‐octafluor‐1, 2‐dimethylencyclobutan)mangan

Octafluoro‐1, 2‐dimethylenecyclobutane, a Perfluorinated Diene Ligand — Carbonyl(η⁵‐cyclopentadienyl)(η⁴‐octafluoro‐1, 2‐dimethylenecyclobutane)manganese The [2+2]‐cycloaddition product of tetrafluoroallene ( 1 ), octafluoro‐1, 2‐dimethylenecyclobutane ( 2 ) reacts with tricarbonyl(η⁵‐cyclopentadienyl)manganese ( 4 ) replacing two carbonyl ligands to give carbonyl(η⁵‐cyclopentadienyl)(η⁴‐octafluoro‐1, 2‐dimethylenecyclobutane)manganese ( 5 ). According to the IR spectrum of 5 , the ligand 2 is a strong π acceptor. Among the less volatile by‐products of the dimerizationof 1 , the hydrolysis product of its trimer could be structurally characterized by X‐ray diffraction as the spirocyclic compound decafluoro‐5‐methylene‐spiro[3.3]heptane‐2‐carboxylic acid ( 3 ). The structure of 5 was also determined by an X‐ray crystal structure determination.     

Synthesis of new substituted 5‐methyl‐3,5‐diphenylimidazolidine‐2,4‐diones from substituted 1‐(1‐cyanoethyl‐1‐phenyl)‐3‐phenylureas

The reaction of substituted phenyl isocyanates with 2‐amino‐2‐phenylpropanenitrile and 2‐amino‐2‐(4‐nitrophenyl)propanenitrile has been used to prepare substituted 1‐(1‐cyanoethyl‐1‐phenyl)‐3‐phenylureas. In anhydrous phosphoric acid the first products to be formed from 1‐(1‐cyanoethyl‐1‐phenyl)‐3‐phenylureas are phosphates of 4‐methyl‐4‐phenyl‐2‐phenylimino‐5‐imino‐4,5‐dihydro‐1,3‐oxazoles, which on subsequent hydrolysis give the respective ureidocarboxylic acids. On prolongation of the reaction time, the phosphates of 4‐methyl‐4‐phenyl‐2‐phenylimino‐5‐imino‐4,5‐dihydro‐1,3‐oxazoles rearrange to give phosphates of 5‐methyl‐4‐imino‐3,5‐diphenylimidazolidin‐2‐ones, and these are subsequently hydrolysed to the respective substituted 5‐methyl‐3,5‐diphenylimidazolidin‐2,4‐diones. The ureidocarboxylic acids were also prepared by alkaline hydrolysis of 5‐methyl‐3,5‐diphenylimidazolidin‐2,4‐diones. The 5‐methyl‐3,5‐diphenylimidazolidin‐2,4‐diones and ureidocarboxylic acids were characterised by their ¹H and ¹³C NMR spectra. Structure of the 5‐methyl‐5‐(4‐nitrophenyl)‐3‐phenylimidazolidine‐2,4‐dione was verified by X‐ray diffraction. The alkaline hydrolysis of individual imidazolidine‐2,4‐diones was studies spectrophoto‐metrically in sodium hydroxide solutions at 25 °C. The rate‐limiting step of the base catalysed hydrolysis consists in decomposition of the tetrahedral intermediate. The reaction is faster if electron‐acceptor sub‐stituents are present in the 3‐phenyl group of imidazolidine‐2,4‐dione cycle. The pK_a values of individual 5‐methyl‐3,5‐diphenylimidazolidine‐2,4‐diones have been determined kinetically.     

Synthesis and antimicrobial activity of 2‐substituted‐2,3‐dihydro‐5‐propoxy‐1H‐1,3,2‐benzodiazaphosphole 2‐Oxides

Several 2‐alkylcarbamato/thiocarbamato/aryloxy/trichloromethyl‐2,3‐dihydro‐5‐propoxy‐1H‐1,3,2‐benzodiazaphosphole 2‐oxides ( 4 and 6 ) were synthesised by reacting 4‐propoxy‐o‐phenylenediamine ( 1 ) with various N‐dichlorophosphinyl carbamates ( 3 ), aryl phosphorodichloridates ( 5a‐f ) and trichloromethyl phosphonic dichloride ( 5g ) in the presence of triethylamine at 45‐65 °C. Their ir, ¹H, ¹³C, ³¹P nmr and mass spectral data are discussed. The compounds were screened for antifungal activity against Curvularia lunata and Aspergillus niger and for antibacterial activity against Bacillus subtilis and Escherichia coli. Most of these compounds exhibited moderate activity in the assays.     

Synthesis of 1‐substituted 5‐aryl‐3‐(3‐coumarinyl)‐2‐pyrazolines by the reaction of 3‐aryl‐1‐(3‐coumarinyl)propen‐1‐ones with hydrazines

1‐Acetyl‐ and 1‐propionyl‐2‐pyrazolines 11‐27 have been synthesized by the reaction of (3‐coumarinyl)chalcones 1‐10 with hydrazine in hot acetic acid or propionic acid. While 5‐aryl‐3‐(3‐coumarinyl)‐1‐phenyl‐2‐pyrazolines 28‐35 have been prepared by the reaction of (3‐coumarinyl)chalcones 1,3,5‐10 with phenylhydrazine in hot pyridine. Structures of all new compounds have been elucidated by microanalyses, ¹H and ¹³C nmr spectroscopies.     

Synthesis of 5‐(6‐Pyridazinone‐3‐yl)‐2‐Glycosylamino‐1,3,4‐Oxadiazoles

N‐Glycosyl‐2‐(1,4,5,6‐tetrahydropyridazin‐6‐one‐3‐carbonyl)‐hydrazinecarbothioamides 3a‐3g and N‐glycosyl‐2‐(1,6‐dihydropyridazin‐6‐one‐3‐carbonyl)‐hydrazinecarbothioamides 5a‐5g were prepared by the reaction of glycosyl isothiocyanates with the compounds 1,4,5,6‐tetrahydro‐3‐hydrozinecarbonyl‐6‐pyridazinone ( 1 ) and 1,6‐dihydro‐3‐hydrozinecarbonyl‐6‐pyridazinone ( 2 ). The terminal heterocyclic compounds 1,3,4‐oxadiazole derivatives were obtained from cyclization of compounds ( 3a‐3g ) and ( 5a‐5g ) by mercuric acetate. Their structures were confirmed by IR, ¹H NMR, MS and elemental analyses.     

Synthesis and Crystal Structure of [1‐(η5‐9‐Fluorenyl)‐2‐(η5‐1‐indenyl)ethane]hafnium Dimethyl

The synthesis and characterization of the unsymmetric hafnium dialkyl [1‐(η⁵‐9‐fluorenyl)‐2‐(η⁵‐1‐indenyl)ethane]HfCl₂ ( 2 ) and corresponding dimethyl complex [1‐(η⁵‐9‐fluorenyl)‐2‐(η⁵‐1‐indenyl)ethane]Hf(CH₃)₂ ( 3 ) is described. The dialkyl hafnocene ( 3 ) crystallizes in monoclinic space group P2₁/c (No. 14) with a = 9.458(8), b = 8.541(8), c = 23.733(11) Å, β = 93.16(5) deg., V = 1914(3) ų, Z = 4. Further on, complex 3 was activated with methylaluminiumoxane (MAO) and utilized as a catalyst in ethene polymerization.     

立体选择性合成2-(a-噻吩甲酰基)-3-取代苯基-4-乙氧羰基-5-甲基-反式-2,3-二氢呋喃

溴化(a-噻吩甲酰基)甲基三苯鉮1与3-取代苯甲叉基-2,4-戊二酮 2以碳酸钾为碱,在苯中55℃条件下反应,可以较好的收率、高立体选择性地生成反-2-(a-噻吩甲酰基)-3-取代苯基-4-乙氧羰基-5-甲基-2,3-二氢呋喃3。产物结构均经波谱予以确定。本文还提出了生成产物的可能机理。     

Synthesis and Heterocyclization of 1‐Aryl‐2‐methyl‐4‐oxo‐1,4,5,6‐tetrahydropyridine‐3‐carboxylates

A series of novel isoxazole, dihydropyrazolone, and tetrahydropyridine derivatives were synthesized by the reaction of corresponding ethyl 1‐substituted aryl‐2‐methyl‐4‐oxo‐1,4,5,6‐tetrahydropyridine‐3‐carboxylates with different hydrazines and hydroxylamine. Reaction of tetrahydropyridone with N ,N‐dimethylformamide dimethyl acetal provided 1‐(5‐chloro‐2‐methylphenyl)‐2‐[2‐(dimethylamino)ethenyl]‐4‐oxo‐1,4,5,6‐tetrahydropyridine‐3‐carboxylate, which was cyclized into a bicyclic compound on treatment with ammonium acetate. The structures of all synthesized compounds were confirmed by IR, ¹H NMR, and ¹³C NMR spectroscopy data. The structure of 5‐(5‐chloro‐2‐methylphenyl)‐4‐methyl‐2‐phenyl‐2,5,6,7‐tetrahydro‐3H‐pyrazolo[4,3‐c]pyridin‐3‐one was unambiguously assigned by means of X‐ray analysis data.     

Synthesis and characterization of new α,β‐unsaturated γ‐lactones: Alkyl 3‐acetyl‐4‐hydroxy‐2‐methyl‐5‐oxo‐2,5‐dihydrofuran‐2‐ylcarbamates

A convenient procedure for the preparation of carbamate derivatives of 5‐oxo‐2,5‐dihydrofuran ( 3 ) was described. The method is based on the Michael type addition of three alkyl carbamates ( 2 ) with 4‐acetyl‐5‐methyl‐2,3‐dihydro‐2,3‐furandione ( 1 ). According to ¹H nmr spectra of compounds show tautomeric forms ( 3,4,5 ) in CDC1₃. In the solid state the synthesized compounds are enol forms ( 3 ). The products were characterized with molecular spectroscopic methods.     

Synthesis of N‐(Substituted aryl/cyclohexyl)‐N'‐[5‐bromo‐5‐nitro‐2‐oxido‐1,3,2‐dioxaphosphorinane‐2‐yl]ureas

N‐(Substituted aryl/cyclohexyl)‐N'‐[5‐bromo‐5‐nitro‐2‐oxido‐1,3,2‐dioxaphosphorinane‐2‐yl]ureas RR'P(O)NHC(O)NHR' (5) were synthesized by the reactions of 2‐bromo‐2‐nitro‐1,3‐propanediol (4) with chlorides of aryl/cyclohexyl carbamidophosphoric acids (3) in the presence of triethylamine at room temperature. Their ir, ¹H, ¹³C and ³¹P nmr spectral data are discussed.     

7‐Iodo‐8‐aza‐7‐deaza‐2′‐deoxy­adenosine and 7‐bromo‐8‐aza‐7‐deaza‐2′‐deoxyadenosine

The isomorphous structures of the title molecules, 4‐amino‐1‐(2‐deoxy‐β‐d ‐erythro‐pento­furan­osyl)‐3‐iodo‐1H‐pyrazolo‐[3,4‐d]pyrimidine, (I), C₁₀H₁₂IN₅O₃, and 4‐amino‐3‐bromo‐1‐(2‐deoxy‐β‐d ‐erythro‐pento­furan­osyl)‐1H‐pyrazolo[3,4‐d]­pyrimidine, (II), C₁₀H₁₂BrN₅O₃, have been determined. The sugar puckering of both compounds is C1′‐endo (^1′E). The N‐­glycosidic bond torsion angle χ¹ is in the high‐anti range [?73.2 (4)° for (I) and ?74.1 (4)° for (II)] and the crystal structure is stabilized by hydrogen bonds.     

Synthesis,properties and X‐ray structure of 5‐azido‐2‐methoxy‐1,3‐xylyl‐18‐crown‐5

5‐Azido‐2‐methoxy‐1,3‐xylyl‐18‐crown‐5 has been prepared by reacting p‐toluenesulfonyl azide with the carbanion generated from the reaction of 5‐bromo‐2‐methoxy‐1,3‐xylyl‐18‐crown‐5 with n‐butyl lithium. The asymmetric N₃ stretch of this product has been observed as a single band at 2110 cm^?1 in dichloromethane solution. Addition of solid NaSCN, KSCN and CsSCN shifts this band to 2115, 2113 and 2112 cm^?1, respectively. Computational studies of this azide at the B3LYP‐6‐31G* level in the presence and absence of Na⁺ predicted these bands to be at 2173 cm^?1 and 2184 cm^?1. For the salt‐containing solutions, additional bands were observed at 2066 cm^?1, 2056 cm^?1 and 2055 cm^?1, respectively, which are in the range expected for CN stretches. The X‐ray structure of this azide has been determined. The terminal and internal N? N bond lengths were found to be 1.127(2) and 1.245(2) Δ, respectively, which is the usual pattern for aromatic azides. The crown ether is looped over the face of the aromatic ring resulting in an angle of 38.94° between the plane defined by the aromatic ring and that defined by the five ring oxygen atoms. In addition, the CH₃ group is rotated out of the plane of the phenyl ring with C1‐C18‐O181‐C182 and C17‐C18‐O181‐C182 dihedral angles of 93.81(14)° and ‐90.54(14)°, respectively.     

Palladium(II)‐Komplexe des 1,1,3,3,5,5‐Hexakis(dimethylamino)‐λ5‐[1,3,5]triphosphinins

Palladium(II) Complexes of 1,1,3,3,5,5‐Hexakis(dimethylamino)‐λ⁵‐[1,3,5]triphosphinine 1,1,3,3,5,5‐Hexakis(dimethylamino)‐1λ⁵‐3λ⁵‐5λ⁵‐[1,3,5]triphosphinine ( 5 ) reacts with (benzonitrile)₂PdCl₂ to give the chelate complex dichloro(dodeca‐N‐methyl‐1λ⁵,3λ⁵,5λ⁵‐1,3,5‐triphosphinine‐1,1,3,3,5,5‐hexaamin‐C²,C⁴)palladium ( 6 ). In a pyridine‐d₅ solution of 6 the complex dichloro(dodeca‐N‐methyl‐1λ⁵,3λ⁵,5λ⁵‐1,3,5‐triphosphinine‐1,1,3,3,5,5‐hexaamin‐C²)((²H₅)pyridine‐N)palladium ( 7 ) is formed. The solute 7 could not be isolated as a solid, because elimination of the solvent regenerates 6 quantitatively. Properties, nmr and ir spectra of 6 and 7 are reported. 6 is characterized by the results of an X‐ray structural analysis.     

4‐Aminopyridinium 2‐(anthracen‐9‐yl)‐3‐oxo‐3H‐inden‐1‐olate monohydrate

The title compound, 2C₅H₇N₂⁺·2C₂₃H₁₃O₂⁻·H₂O, formed as a by‐product in the attempted synthesis of a nonlinear optical candidate molecule, contains two independent 4‐aminopyridinium cations and 2‐(anthracen‐9‐yl)‐3‐oxo‐3H‐inden‐1‐olate anions with one solvent water molecule. This is the first reported structure containing these anions. The two anions are not planar, having different interplanar angles between the anthracenyl and inden‐1‐olate moieties of 59.07 (5) and 83.92 (5)°. The crystal packing, which involves strong classical hydrogen bonds and one C—H...π interaction, appears to account for both the nonplanarity and this difference.