Synthesis and structural investigations of N(1-methyl-2-carbomethoxyindolyl-3-sulfonyl)-N′-hetarylureas

We have carried out synthetic and physicochemical investigations of N-(1-methyl-2-carbomethoxyindolyl-3-sulfonyl)-N-hetarylureas which are a new generation of potential herbicides and plant growth regulators.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 359–368, March, 1994.     

Synthesis of 2-(3-hydroxy-2-methyl-1-alkenyl)-1-pyrrolines and 2-(3-hydroxybutyl)-1-pyrroline using α-lithiated 2-methyl-1-pyrroline

Condensation of 2-methyl-1-pyrroline with chloroacetone or 3-chloro-2-butanone using LDA in THF afforded novel 2-(3-hydroxy-2-methyl-1-alkenyl)-1-pyrrolines via a peculiar reaction mechanism instead of the anticipated 2-(3-oxobutyl)-1-pyrrolines. The intermediacy of 2-(2,3-epoxy-2-methylalkyl)-1-pyrrolines in the latter transformation was demonstrated by immediate reductive epoxide ring opening utilizing lithium aluminium hydride in diethyl ether. Furthermore, 2-(3-oxobutyl)-1-pyrroline was prepared via an alternative approach through alkylation of 2-methyl-1-pyrroline with 3-chloro-2-(methoxymethyloxy)-1-propene using LDA in THF, followed by acid hydrolysis. Reduction of 2-(3-oxobutyl)-1-pyrroline by sodium borohydride in methanol afforded the corresponding 2-(3-hydroxybutyl)-1-pyrroline in good yield.     

Synthesis of 1-alkoxy-3-methyl-1-triazene 2-oxides and 3, 3´-methylene-bis(1-alkoxy-3-methyl-1-triazene 2-oxides)

Russian Chemical Bulletin - A method for the synthesis of 1-alkoxy-3-methyl-1-triazene 2-oxides and their salts with alkali metals was developed. 3,...     

Synthesis and steric structure of 3,4-dimethyl-2-(3-methyl-1-phenylbuta-1,2-dienyl)-5-phenyl-1,3,2λ<Superscript>5</Superscript>-oxazaphospholane 2-oxide

Allenic 1,3,2-oxazaphospholanes on the basis of d-pseudoephedrine were synthesized. The steric structure of 3,4-dimethyl-2-(3-methyl-1-phenylbuta-1,2-dienyl)-5-phenyl-1,3,2λ⁵-oxazaphospholane 2-oxide was determined by X-ray diffraction.     

Unusual crystal and molecular structure of palladium iminoquinonoid complex Pd2Cl2(PPh3)2L (L = N,N′-di(4-methyl-4-trichloromethylcyclohexa-2,5-dien-1-ylidene)hydrazine)

The structure of the first iminoquinonoid complex Pd₂Cl₂(PPh₃)₂L·0.4(Me₂CO), where L = N,N′-di(4-methyl-4-trichloromethylcyclohexa-2,5-dien-1-ylidene)hydrazine, was established by X-ray crystallography. The centrosymmetric and non-centrosymmetric molecules of meso-form (RS) and the molecule of optically active (SS) threo-form were found to be simultaneously present (cocrystallize) in the crystal. The molecule in the crystal has a general formula [Pd(meso-L)]₂[Pd(threo-L)].     

Preparation and Structure of (E)-1-(3′-Hydroxy-2-Furanyl)-3-(3″-Hydroxy-4″-Methoxyphenyl)-2-Propen-1-One

Abstract

A facile procedure is presented for the synthesis of (E)-1-(3′-hydroxy-2′-furanyl)-3-(3″-hydroxy-4″-methoxyphenyl)-2- propen-1-one (6). Galactosylisomaltol (1) was condensed with isovanillin (2) under strong alkaline conditions at 25 [ddot]C to form (E)-1-(3′-O-β-D-galactopyranosyloxy-2′-furanyl)-3-(3″- hydroxy-4″-methoxyphenyl)-2-propen-1-one (4). (E)-1-(3′-hydroxy-2′-furanyl)-3-(3″-hydroxy-4″-methoxyphenyl)-2-propen-1-one (6) was obtained by acid hydrolysis of 4 in a 53.9% yield. This hetero-cyclic 2-propen-1-one was characterized on the basis of spectral data (IR and ¹H NMR), physicochemical properties, and conversion to a mono-O-acetyl derivative.     

Synthesis and structure of N,N′-bis(dihexylphosphorylmethyl)-1,4-diaminobutane

Russian Journal of General Chemistry - N,N′-Bis(dihexylphosphorylmethyl)-1,4-diaminobutane has been obtained via the Kabachnik–Fields reaction. Crystal structure of its salt with nitric...     

Synthesis and Structure of 5,5-Disubstituted N-[4-Methyl-3-phenylfuran-2(5H)-ylidene]-N′-phenylthioureas

Russian Journal of Organic Chemistry - The reaction of 5,5-disubstituted 4-methyl-3-phenyl-2,5-dihydrofuran-2-imines with phenyl isothiocyanate afforded...     

Synthesis and characterization of mononuclear and dinuclear zinc-arylazoimidazole complexes. single-crystal x-ray structure of [Zn(HaaiEt)4](ClO4)2 and [Zn(HaaiMe) (μ-1,1-N3)(N3)]2 [HaaiEt = 1-ethyl-2-(phenylazo)imidazole; HaaiMe = 1-methyl-2-(phenylazo)imidazole]

Zn(ClO₄)₂·6H₂O reacts with 1-alkyl-2-(arylazo)imidazoles [RaaiR′, where R?=?H (a), Me (b); R′?=?Me (1), Et (2)] affording orange–yellow [Zn(RaaiR′)₄](ClO₄)₂ (3,4) complexes. When excess sodium azide is added to the reaction, orange–red, dimeric azido-complexes of the type [Zn(RaaiR′)(N₃)(μ-1,1-N₃)]₂ (5,6) are obtained. Both types of complex were characterized. Structures were confirmed by single-crystal X-ray diffraction studies of [Zn(HaaiEt)₄](ClO₄)₂ (3b) and [Zn(HaaiMe)(N₃)(μ-1,1-N₃)]₂ (5a).     

Synthesis and molecular and crystal structure of 3-(1-amino-2,2,2-trifluoroethylidene)-2-imino-1,1,4,5,6,7-hexafluoroindan and its N-methyl and N,N′-dimethyl derivatives

3-(1-Amino-2,2,2-trifluoroethylidene)-2-imino-1,1,4,5,6,7-hexafluoroindan (2) and its N-methyl and N,N′-dimethyl derivatives were synthesized by the reaction of perforo-1-ethylideneindan with ammonia and methylamine or by methylation of compound 2 with dimethylsulfate. Single crystals were grown and the molecular and crystal structure of the emaninoimine products was investigated. The density functional theory (DFT) quantum chemical calculations were performed to determine possible tautomeric equilibrium of the emaninoimine products.     

Oxidative reactions of azines. 2.* Synthesis and molecular structure of 3,4-dihydroxy-1-methyl-2-oxo-4-(γ-pyridyl)piperidine

The oxidative ketodihydroxylation of a 1,2,3,6-tetrahydropyridine is reported. Using PMR and x-ray structured analysis, the product was shown to be 3,4-dihydroxy-1-methyl-2-oxo-4-(-pyridyl)piperidine.For communications 1, see [1].Russian University of National Friendship, Moscow 117198. L. Ya. Karpov Physicochemical Science Research Institute, Moscow 103603. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1372–1375, October, 1996. Original article submitted June 20, 1996.     

Synthesis and some transformations of trans-1-methyl-2-[β-(2′-thienyl)vinylene]-1H-benzimidazole

The condensation of 1,2-dimethylbenzimidazole with thiophene-2-aldehyde in the presence of fused zinc chloride results in 1-methyl-2-[β-(2-thienyl)vinylene]-1H-benzimidazole. Its electrophilic substitution reactions (nitration, bromination, sulfonation, formylation, acylation) were studied. All the reactions occur in the 5-position of the thiophene ring. Only in the case of bromination in dichloroethane 5′,5(6)-dibromo-derivative was obtained. Data of the quantum-chemical calculations of the total positive charge on the carbon atoms of the protonated molecules of thienylbenzimidazoles including the vinylene group and without it are reported.     

Crystal structure and properties of (Z)-N′-((E)-2-(hydroxyimino)-1-phenylethylidene) isonicotinohydrazide

Compound I contains in its molecule pyridyl, monoxime and hydrazone functions. A non-merohedral twin crystal of the compound with two reciprocal lattices differently oriented and giving rise to double diffraction spot sets with the 0.5:0.5 ratio of the twin components was studied. The hydrazone and oxime units are approximately planar. The dihedral angles between this plane and the planes of the pyridine and phenyl rings are 30.79(19)° and 18.43(13)°, respectively. Both the oxime and hydrazone units in I have an E configuration. The molecules of I are linked via C-H⋯O and O-H⋯N hydrogen bonds forming a 3D framework. The compound was also characterized by IR, ¹H NMR and elemental analyses.     

Synthesis and Antimicrobial Studies of Organophosphates Derived From 2-(2″-Hydroxynaphthyl)Benzoxazole

Abstract

A series of biologically active phenoxy derivatives of 2-substituted benzoxazole organophosphates have been synthesized by the reaction of O-(naphthyl benzoxazolyl-2-) phosphorodichloridate/phosphorodichloridothioate with phenol/4-chlorophenol/4-nitroph- enol in 1:1 and 1:2 molar ratios. These compounds have been characterized on the basis of elemental analysis, IR, ¹H NMR, ³¹P NMR, and mass spectral studies. The antibacterial activity of these 2-substituted benzoxazole phenoxy derivatives has been evaluated against pathogenic bacteria Staphylococcus aureus (+ve) and Escherichia coli (?ve). The antifungal activity of these 2-substituted benzoxazole phenoxy derivatives has been evaluated against pathogenic fungi Aspergillus niger and Fusarium oxysporium. All compounds were found to have significant antibacterial and antifungal activity.     

Synthesis and molecular structure of [1, 3-(Me3Si)2C5H3]2Lu(μ-Cl)2

Cp^* ₂Lu(-Cl)₂ (1) was isolated following the reaction of Cp^*Na (Cp^* = 1, 3-(Me₃Si)₂C₅H₃) with LuCl₃ in THF and subsequent treatment with toluene at 80°C. An X-ray structural investigation of1 was performed (MoK radiation, 2933 reflections,R = 0.020). The crystals are triclinic,a = 10.744(3) Å,b=11.821(2) Å, c=12.966(3) Å, a=71.54(1)°, =85.32(2)°, =74.83(1)°,Z = 2, space groupP-1. Two Lu atoms withdistorted tetrahedral coordination are linked by two chloride bridges with a mean Lu-Cl distance equal to 2.62 Å.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 568–570, March, 1993.     

Synthesis and Crystal Structure of 7α-[(R)-1-Hydroxyl-1-methyl-3-(thien-2-yl)-propyl]-6,14-endoethanotetrahydrothebaine

The crystal structure of 7α-[(R)-1-hydroxyl-1-methyl-3-(thien-2-yl)propyl]-6,14-endoethanotetrahydro thebaine (C29H37NO4S, Mr = 495.66) has been determined by single-crystal X-ray diffraction analysis. The crystal belongs orthorhombic, space group P212121 with a = 10.063(4), b = 12.571(5), c = 19.626(8) (A), V = 2482.9(17) (A)3, Z = 4, Dc = 1.326 g/cm3,μ = 0.167 mm-1, F(000) = 1064, the final R = 0.0537 and wR = 0.0888. The C(7) substituent is 1-hydroxyl-1-methyl-3-(thienyl-2-)propyl group adopting R-configuration. The N-methyl group is located at the equatorial position as expected. The crystal structure shows the presence of intra-molecular hydrogen bonds,O(1)-H(1 )…O(2).