Derivatives of 1,1,2,2-tetraaminoethane: I. Condensation of 1,2-diacetoxy-1,2-bis(acylamino)ethanes with nitrogen-containing nucleophiles

Reaction of 1,2-diacetoxy-1,2-bis(acylamino)ethanes with acetamide and urethane gave rise to 1,2-bis(acetylamino)-1,2-bis(acylamino)ethanes and 1,2-bis(acylamino)-1,2-bis(ethoxycarbonylamino)ethanes respectively. Condensation products were isolated of reactions between 1,2-diacetoxy-1,2-bis-(acylamino)ethanes with acetonitrile, diaminofurazan, and 4-phenylfurazan-3-ylamine.     

Synthesis of unsymmetrical 1,2-bis(diorganochlorosilyl)ethanes

Unsymmetrical 1,2-bis(diorganylsilyl)ethanes were synthesized by two procedures. Hydrosilylation of chloro(vinyl)silanes were used to obtain compounds of the general formula ClMe₂SiCH₂CH₂SiRMeCl with different substituents (R = Et, Vin, Ph) on the silicon atom. Chlorodealkylation of 1,2-bis(trialkylsilyl)ethanes gave compounds of the general formula ClAlk₂SiCH₂CH₂SiAlk₂Cl (Alk = Me, Et, Pr). It is established that the latter reaction provides high yields only with Me-and Et-substituted compounds, whereas Pr-substituted products are formed in poor yields. The mechamism of this reaction based on quantum-chemical calculations is offered.     

The reaction of alkylpyrazine anions with some electrophiles. Synthesis of 1,2-bis(2-pyrazyl)ethanes

The reaction of alkylpyrazine anions with iodine, 1,2-dibromoethylene or oxygen gives 1,2-bis-(2-pyrazyl)ethanes.     

Reductive deoxygenation of ortho-hydroxyaromatic aldehydes to 1,2-bis(hydroxyaryl)ethanes: application to the synthesis of ethylene bridged calixarene-analogous metacyclophanes

A novel and convenient protocol for the synthesis of hexahydroxy[2.1.2.1.2.1]- and octahydroxy[2.1.2.1.2.1.2.1]metacyclophanes from 4-substituted phenol in four steps has been developed. The synthetic route involved the preparation of the key intermediate 1,2-bis(5-substituted-2-hydroxyphenyl)ethanes in good yields via (i) formylation of 4-substituted phenol, (ii) reductive deoxygenation of 5-substituted 2-hydroxy aromatic aldehydes with low-valent titanium reagent and (iii) catalytic hydrogenation. The metacyclophanes were prepared by base-catalyzed macrocyclization of the above intermediates with formaldehyde in refluxing xylene in high yields.     

Regiospecific synthesis of 3-substituted imidazo[1,2-a]pyridines,imidazo[1,2-a]pyrimidines,and imidazo[1,2-c]pyrimidine

3-Substituted imidazo[1,2-a]pyridines, imidazo[1,2-a]pyrimidines, and imidazo[1,2-c]pyrimidine were obtained regiospecifically in yields of 35-92% in one pot by reaction of 2-aminopyridines or 2-(or 4-)aminopyrimidines, respectively, with 1,2-bis(benzotriazolyl)-1,2-(dialkylamino)ethanes.     

反-1,2-双[2-(5-取代苯基恶唑基)]环丙烷的合成与光性能的研究

合成了8个反 -1,2-双[2-(5-取代苯基恶唑基)]环丙烷和2个1,2-双[2-取代苯基恶唑基)]乙烷,其中9个为新化合物.讨论了化合物的结构与其电子光谱及荧光量子产率间的关系.发现恶唑环与三元环间存在一定程度的共轭,并解释了上述化合物荧光量子产率较低的现象.     

Steric structure of some 1,2-diaryl-substituted ethanes

Conclusions In the investigated 1,2-diaryl-substituted ethanes, the content of the trans and gauche conformers relative to the C-C bond is practically identical; the trans form shows some predominance. In these compounds, the aromatic rings are orientated in parallel and are turned by an average of 120±10 relative to the central C-C bond.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 95–100, January, 1987.The authors are grateful to A. Kh. Plyamovatii for submitting the MAP-3 program.     

Synthesis of 1-(2-ethyl-3-indolyl)-1-(3-pyridyl)ethylene and related ellipticine analogues

Indole, 2-methylindole, and 3-etliylindole have been condensed with acetyl- and propionylpyridine, respectively. When propionylpyridine was used as the reactant, the product always was a 1-(pyridyl)-1-indoly[propylene. Condensation of 2-substituted indoles with 3-acetylpyridine gave similar products, whereas a similar condensation with 4-acetylpyridine gave 1,2-bis(3-indolyl)-1-(4-pyridyl)ethanes (e.g. 7a ). Condensation of unsubstituted indole with 3-or 4-acetylpyridine respectively, gave 1,1-bis(3-indolyl)-1-(pyridyl)ethanes (e.g. 6c ).     

Internal rotation in 1,2-di-(p-XC6H4)ethanes (X=H, Br, NO2): infrared spectra and compensation effect

Infrared absorption spectra and internal rotation of 1,2-di-(p-XC(6)H(4))ethanes (X=H, Br, NO(2)) in crystalline phase, liquid and solutions at various temperatures have been investigated. Band fitting was applied to conformationally sensitive regions of the spectra, and assignment of the peaks to trans and gauche conformations was performed. Enthalpy and entropy differences of the conformers (deltaH(0) and deltaS(0)) were found to be solvent-dependent, and it is interpreted in terms of previously discovered compensation effect. The values deltaH(0) and deltaS(0) for 1,2-di-(p-NO(2)C(6)H(4))ethane obtained are unusually large.     

Synthesis and reactivity of 1,2-bis(chlorodimethylgermyl)carborane and 1,2-bis(bromodimethylstannyl)carborane

The 1,2-bis(chlorogermyl)- (1) and 1,2-bis(bromostannyl)carborane (2) have been prepared by the reaction of dilithio-o-carborane with Me(2)GeCl(2) and Me(2)SnBr(2), respectively. Compounds 1 and 2 are found to be good precursors for the synthesis of a variety of cyclization compounds. The Wurtz-type coupling reaction of 1 and 2 using sodium metal afforded the four-membered digerma compound 3 and five-membered tristanna compound 4, respectively. The salt elimination reactions of 1 and 2 using Li(2)N(t)Bu and Li(2)PC(6)H(5) afforded the cyclic products [structure: see text]. The 1,2-bis(dimethylgermyl)carborane 9 and 1,2-bis(dimethylstannyl)carborane 10 were prepared by the reaction of 1 and 2 with sodium cyanoborohydride. The reactions of 9 and 10 with Pd(PPh(3))(4) afforded the bis(germyl)palladium 12 and bis(stannyl)palladium 13 complexes, respectively.     

Synthetic, spectroscopic and structural studies of two novel phosphanyl(organyl)borane compounds

The titanium (II) complex, Cp₂Ti(HBcat)₂, catalyzes the hydroboration of diphenylvinylphosphine by catecholborane and pinacolborane to afford exclusive anti-Markovnikov phosphanyl(organyl)boranes cleanly, rapidly and in good yields. Spectroscopic and X-ray studies of the phosphanyl(organyl)borane products show no evidence of boron-phosphorus interaction, indicating that the compounds preclude formation of Lewis pairs.     

Synthesis and electrochemical characterization of complexes of 1,2-bis[2-(pyridylmethylideneamino)phenylthio]ethanes with transition metals (CoII, NiII, CuII)

Transition metal (Ni^II, Co^II, and Cu^II) complexes with 1,2-bis[2-(3-pyridylmethylideneamino)phenylthio]ethane (1) and 1,2-bis[2-(4-pyridylmethylideneamino)phenylthio]ethane (2) were synthesized for the first time by slow diffusion of solutions of compounds 1 or 2 in CH₂Cl₂ into solutions of MX₂ · nH₂O (M = Ni, Co, or Cu; X = Cl or NO₃; n = 2 or 6) in ethanol. The reactions with Co^II and Cu^II chlorides afford complexes of composition M(L)Cl₂ (L = 1 or 2). The reactions of compound 1 with Ni^II salts produce complexes with 1,2-bis(2-aminophenylthio)ethane. The molecular structure of dinitrato[1,2-bis(2-aminophenylthio)ethane]nickel(ii) was confirmed by X-ray diffraction. The ligands and the complexes were investigated by cyclic voltammetry and rotating disk electrode voltammetry. The initial reduction of the complexes proceeds at the metal atom. The oxidation of the chlorine-containing complexes proceeds at the coordinated chloride anion. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 350–355, February, 2008.     

Heteroatomic derivatives of aziridine. 14. Reactions of 1-(carbomethoxyethyl)-, 1-[1,2-bis(carbethoxy)ethyl]-, and 1-[1,2-bis(carbomethoxy)vinyl]aziridine with thiols, 1,2-ethanedithiol,and thiolcarboxylic acids

The reactions of 1-(carbomethoxyethyl)-, 1-[1,2-bis(carbethoxy)-ethyl]-, and 1-[1,2-bis(carbomethoxy)vinyl]aziridine with thiols and thiolcarboxylic acids produce the corresponding sulfides and esters of S-substituted N-(2-mercaptoethyl) amino acids. The reaction of 1-[1,2-bis(carbethoxy)ethyl]aziridine with 1,2-ethane-dithiol results in the formation of {1,8-bis[1,2-bis(carbethoxy)-ethyl]amino}-3,6-dithiaoctane. Cyclization of the latter by condensation with phthaloyl chloride gives 9,10-benzo-8,11-dioxo-1,4-dithia-7,12-bis[1,2-bis(carbethoxy)ethyl]-7,12-diazacyclotetradec-9-ene.For report 13 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1340–1342, October, 1984.     

Catalysis of Hydrosilylation. VIII. Addition of tri(chloro,methyl)silanes to vinyltri(chloro,methyl)silanes catalyzed by palladium phosphine complexes

Catalytic, synthetic, and analytical investigations of the hydrosilylation of vinyltri(chloro, methyl)silanes by tri(chloro, methyl)silanes in the presence of palladium phosphine complexes show the process to occur giving mostly 1,2-bis(silyl)ethanes (β-adducts) except in the case of all chloro substituents at both silicons of the substrates. The latter reaction was reported earlier [3] to give selectively 1,1-bis(trichlorosilyl)ethane (α-adduct). All results allow to propose a general scheme of the mechanism of catalysis of vinylsilane hydrosilylation by palladium phosphine complexes.     

Synthesis of 1,2-bis(methoxyamino)cycloalkanes from alicyclic 1,2-bis(hydroxyamines)

Derivatives of 1,4-dihydroxypiperazine-2,3-dione were obtained by reaction of cis-1,2-bis(hydroxyamino)cycloalkanes with diethyl oxalate. Their alkylation with CH₂N₂ or Mel afforded 1,4-dimethoxypiperazine-2,3-diones. Hydrolysis of the latter gave 1,2-bis(methoxyamino)cycloalkanes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 925–929, April, 1996.     

Vanadium catalyzed enantioselective oxidation of sulfides: easy transformation of bis(arylthio)alkanes into C2 symmetric chiral sulfoxides

A facile and selective method for the title transformation is described. The two-phase oxidation of bis-sulfides with hydrogen peroxide catalyzed by vanadium complex of chiral Schiff base leads to the corresponding chiral mono- and bis-sulfoxides. In the case of 1,2-bis(arylthio)ethanes the respective optically active bis-sulfoxides are formed in up to over 95% e.e.     

TRANSITION METAL COMPLEXES OF 1,2-BIS(PHENYLSULFINYL) METHANE AND 1,2-BIS(PHENYLSULFINYL) ETHANE

Abstract

Complexes of the meso and racemic forms of the disulfoxides 1,2-bis(phenylsulfinyl) methane and 1,2-bis (phenylsulfinyl) ethane have been synthesized and characterized. Bond type and ligand field parameters have been determined from infrared and visible-uv diffuse reflectance spectroscopy. There were essentially no observed differences in the properties of complexes of the meso and racemic forms of the ligands.     

A new route to achiral and chiral 1,2-bis(phosphino)ethanes, 1-arsino-2-phosphinoethanes, and 1,3-bis(phosphino)propanes and the molecular structure and catalytic activity of some rhodium(I) complexes derived thereof

A series of unsymmetrical 1,2-bis(phosphino)ethanes R(2)PCH(2)CH(2)PR'(2) and 1-arsino-2-phosphinoethanes R(2)AsCH(2)CH(2)PR'(2) mainly with bulky substituents R and R' were prepared from the cyclic sulfate by stepwise cleavage of the carbon-oxygen bonds by LiPR(2) and LiPR'(2) or LiAsR(2) and LiPR'(2), respectively. Analogously, racemic mixtures of R(2)PCH(2)CH(Me)PPh(2)(R =iPr, Cy ) as well as the enantiomers (R)-, (R)- and (R)-tBu(2)PCH(2)CH(Me)PPh(2)(R)- were obtained from the corresponding unsymmetrical cyclic sulfates and (S)-. On a similar route, the racemates of the 1,3-bis(phosphino)propanes R(2)PCH(2)CH(2)CH(Me)PPh(2)(R =iPr, tBu ), optically pure (R)- and (S,S)-iPr(2)PCH(Me)CH(2)CH(Me)PPh(2)(S,S)- were prepared. The reaction of [[RhCl([small eta](4)-C(8)H(12))](2)] with chelating ligands L-L, where L-L is R(2)PCH(2)P(men)(2)(R =iPr, Ph; men =(1S,2R,5S)-menthyl), Cy(2)AsCH(2)P(men)(2), or (R)-, (R)-, (R)-, (R)- and (S,S)-, in the presence of AgPF(6), gave the complexes [Rh(eta(4)-C(8)H(12))(L-L)]PF(6) which were used as pre-catalysts in the hydrogenation of the methyl ester of alpha-acetamidocinnamic acid (ACM). Depending on L-L, the solvent, the temperature and the pressure of H(2), optical yields of up to 69% ee were achieved. For two of the rhodium complexes, and, the molecular structures were determined by X-ray crystallography.     

Directed and undirected asymmetric dihydroxylation reactions: application in the synthesis of a C-linked analogue of allolactose

The complex OsO4.(S,S)-1,2-diphenyl-N,N'-bis(2,4,6-trimethylbenzyl)ethane-1,2-diamine is an effective reagent for the desymmetrisation of meso-1,2-bis(3,6-dihydro-2H-pyran-2-yl)ethanes by asymmetric dihydroxylation; this process, whose sense of diastereoselectivity depends on substitution and stereochemistry, has been exploited in the synthesis of a C-linked analogue of allolactose.     

Synthesis of thiazoles and thiadiazoles from 1,2-bis(diazoacetyl)ethane

The reaction of 1,2-bis (diazoacetyl) ethane (diazan) with phenyl isothiocyanate and urea leads to the formation of 1,4-diketo-1,4-bis(5-phenylamino-1,2,3-thiadiazolyl)-butane and 1,2-bis(2-amino-1,3-thiazolyl)ethane, respectively. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 209–211, February, 1980.