Intramolecular hydrogen bond strength and pK(a) determination of N,N'-disubstituted imidazole-4,5-dicarboxamides

N,N'-Disubstituted imidazole-4,5-dicarboxamides (I45DCs) form an intramolecular hydrogen bond worth an estimated 14 +/- 1 kcal/mol, as measured with a model structure in DMSO-d6 at 3 mM, thereby predisposing the molecular conformation to a folded rather than extended form. The I45DCs also show evidence of aggregation in both CDCl3 (>1 mM) and DMSO-d6 (>10 mM) solutions. These compounds are uncharacteristically weak bases in comparison with imidazoles bearing similar electron-withdrawing groups.     

An improved method for the synthesis of dissymmetric N,N'-disubstituted imidazole-4,5-dicarboxamides

Symmetrically and dissymmetrically disubstituted imidazole-4,5-dicarboxamides (I45DCs) have diverse bioactivities and therefore represent useful small molecules for lead structure identification in drug discovery. For this reason, an improved synthesis was developed as a first step in the preparation of greater numbers of analogues. The method involves the transformation of imidazole-4,5-dicarboxylic acid into dissymmetrically disubstituted I45DCs in four steps and in a minimum yield of 51%. This reflects an overall reduction of one synthetic step and a greater than 30% improvement in yield over the known method.     

Synthesis of substituted bis(heteroaryl)maleimides

Substituted bis(fur-2-yl), bis(fur-3-yl) and bis(thien-2-yl) maleimides with potential antidiabetic properties are described. Their synthesis involves, as a key step, a Suzuki cross-coupling between various boron derivatives and the diiodomaleimides. Therefore, a wide range of substituted symmetric and non-symmetric maleimide derivatives can be prepared.     

Synthesis of N-phosphoryl amino acids using bis(9-fluorenylmethyl)phosphite

Bis(9-fluorenylmethyl)phosphite (BFMP) was found to be an effective reagent for the N-phosphorylation of various amino acid methyl esters. BFMP was prepared from N,N-diisopropyl phosphoramidous dichloride in a one-pot two-step reaction and was obtained as a crystalline solid. N-Phosphorylation of the methyl esters of seven representative amino acids with BFMP was high-yielding and generally resulted in crystalline products. Complete deprotection of both the 9-fluorenylmethylphosphosphate esters and the amino acid methyl esters was accomplished concomitantly with LiOH to give N-phosphoryl amino acids.     

Synthesis of novel imidazole-4,5-dicarboxylic acid derivatives

A convenient general method for the synthesis of unsymmetrical imidazole-4,5-dicarboxylic acid derivatives is described. The key intermediates are 5,10-dioxo-5H,10H-diimidazo[1,5-a:1′,5′-d[pyrazine-1,6-dicarboxylic acid, -1,6-dicarboxylic ester and -1,6-dicarboxamide.     

Synthesis and characterization of laterally substituted bis(alkoxybenzoyloxy)hydroquinones

A new series of laterally substituted bis(alkoxybenzoyloxy)hydroquinone compounds has been synthesized and their mesomorphic properties studied. A number of hydroquinone compounds were synthesized with terminal n -alkoxy chains ranging from n -butyloxy to n -decyloxy. Additionally, lateral substituents ranging from n -butyl to n -octyl were incorporated through esterification at the remaining unsubstituted phenolic oxygen atoms. By optimizing the combination of the end group and lateral moieties we were able to tailor the molecular structure to form different liquid crystalline phases.     

Synthesis and characterization of laterally substituted bis(alkoxybenzoyloxy)hydroquinones

A new series of laterally substituted bis(alkoxybenzoyloxy)hydroquinone compounds has been synthesized and their mesomorphic properties studied. A number of hydroquinone compounds were synthesized with terminal n-alkoxy chains ranging from n-butyloxy to n-decyloxy. Additionally, lateral substituents ranging from n-butyl to n-octyl were incorporated through esterification at the remaining unsubstituted phenolic oxygen atoms. By optimizing the combination of the end group and lateral moieties we were able to tailor the molecular structure to form different liquid crystalline phases.     

1,2-二氰基-4,5-双十四烷氧基苯合成方法的改进

由邻苯二酚经溴代反应制得 １,２二溴４,５苯二酚,再与无水碳酸钾和 １溴代十四 烷反应制得 １,２二溴４,５双十四烷氧 基苯,最后在 Ｄ Ｍ Ｆ－ Ｎａ Ｉ体系中与氰 化亚铜反 应制得 １,２二氰基４,５双十四烷氧基苯。新化合物结构经元素分析、 Ｉ Ｒ,１ Ｈ Ｎ Ｍ Ｒ 等证实。     

Synthesis of esters of bis(alkoxymethyl) phosphinic acids

Conclusions A method was developed for the production of esters of bis(alkoxymethyl)phosphonic acids, and some of these esters were synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 710–716, 1969.     

相转移催化法合成双3－苯丙烯酰基取代硫脲及双3－苯丙烯酰基取代胺衍生物

以3－苯丙烯酸为原料，经酰氯化，得到3－苯丙烯酰氯，在PEG－400为催化剂 的固液相转移催化条件下与硫氰酸铵及二胺类反应，一锅法制得双3－苯丙烯酰基 取代硫脲化合物。3－苯丙烯酰氯在PEG－600为催化剂的液液相转移催化条件下和 二胺类反应得到双－苯丙烯酰基取代胺化合物。反应条件温和、产率高。化合物经 元素分析、IR及^1H NMR证实。初步的生理活性研究表明，部分化合物具有良好的 抗炎活性。     

Synthesis,crystal structure and magnetic property of bis(tetra-n-butylammonium) bis(4,5-dicyanobenzene-1,2-dithiolato) oxovanadium complex

The bis(dithiolene) oxovanadium complex, namely (n-Bu₄N)₂[(dcbdt)₂VO] (dcbdt = 4,5-dicyanobenzene-1,2-dithiolato), was unprecedentedly obtained from the reaction of Na₂dcbdt and vanadium trichloride. An X-ray structure analysis indicated that [(dcbdt)₂VO] moieties are surrounded by n-Bu₄N cations and there was no direct interaction among these moieties. Although there was no direct interaction among them, several S⋯H, C⋯H and N⋯H van der Waals contacts between n-Bu₄N cations and [(dcbdt)₂VO] moieties were observed. The ESR and SQUID measurement showed that the vanadium atom is in the state of V(IV) (S = 1/2) and these magnetic moments interact with each other very weakly antiferromagnetically (θ = -0.371 K).     

Synthesis of bis(aryloxymethyl)phosphonic acids and their esters

Conclusions Synthetic methods were developed and bis(aryloxymethyl)phosphonic acids and their esters were synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 951–953, April, 1969.     

Synthesis of a symmetric cylindrical bis(crown ether) host and its complexation with paraquat

The first cylindrical host for paraquat derivatives was prepared and characterized by X-ray analysis. Its complex with paraquat has 1:2 stoichiometry. The complexation is statistical and strong as shown by proton NMR characterization, electrospray mass spectrometry, and X-ray analysis.     

Synthesis of substituted bis(3,3-dialkyl-3,4-dihydro-1-isoquinolyl)methanes

Symmetrical and non-symmetrical substituted bis(3,4-dihydro-1-isoquinolyl)methanes were synthesized by fusion of substituted 1-methylthio-3,4-dihydroisoquinolines with 1-methyl-3,4-dihydroisoquinolines and by the Ritter reaction of 1,1-dialkyl-2-arylethanols with 1-cyanomethylidene-1,2,3,4-tetrahydroisoquinoline or malononitrile.     

Synthesis of 4(5)-hydroxymethylimidazoles by hydroxymethylation and decarboxylation of imidazole-4(5)-carboxylic acids

4(5)-Hydroxymethylimidazoles were prepared by hydroxymethylation and decarboxylation of imidazole-4(5)-carboxylic acid esters. The reaction was simply carried out with aqueous formaldehyde solution in the presence of base.     

Synthesis of bis(sigma-aryl)dirhodium(III) caprolactamates by oxidative arylation with arylboronic acids

Recently discovered stable bis(sigma-phenyl)dirhodium(III) caprolactamate and its substituted derivatives are conveniently prepared in high yields from dirhodium(II) caprolactamate and commercially available arylboronic acids in a copper-catalyzed process.     

Synthesis of β-(4,5-dihalofuryl)acrylic and -propiolic acids

Reaction of 4,5-dihalofurfurals with acetaldehyde and with carbethoxybromomethylenephosphorane gave, respectively, 4,5-dihalofurylacroleins and -(4,5-dihalo-2-furyl)--bromoacrylic acid esters. The latter were converted to 4,5-dihalo-2-furylpropiolic acids by the action of alkali.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 315–317, March, 1978.     

Synthesis and characterization of uranium (IV) complexes with various amino acids

Complexes of uranium in its IV oxidation state, using cysteine, glycine, serine and aspartic acid as ligands, have been synthesized. Semi-microanalysis of the complexes indicate 1:1 metal to ligand ratio for all the synthesized complexes. Infrared spectra of solid complexes have been employed to establish the groups, coordinated to the metal ion. Effective magnetic moment of the complexes were also estimated.