α-Ureidoalkylation of 1,3-bis(hydroxymethyl)-imidazolidin-2-one

The α-ureidoalkylation of imidazolidine-2,4-dione, urea, carboxylic acid amides, and sulfonamides has been studied using 1,3-bis(hydroxymethyl)-imidazolidin-2-one as ureidoalkylating agent. Methods have been developed for the synthesis of 1,3-bis(2,4-dioxoimidazolidin-1-ylmethyl)-, 1,3-bis(acetylaminomethyl)-, 1,3-bis(benzoylaminomethyl)-, 1,3-bis(phenylsulfonylaminomethyl)-, and 1,3-bis(p-toluenesulfonylaminomethyl)imidazolidin-2-ones. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1655–1659, November, 2007.     

Excess Enthalpies of Binary Mixtures of Propanediamine+Propanediol at 298.15 K

The molar excess enthalpies of 1,2- and 1,3-propanediamine+1,2- and 1,3-propanediol have been determined at 298.15 K by using a twin-microcalorimeter which requires each component liquid 1 to 1.5 cm³ for a series of runs over the whole range of mole fraction. All excess enthalpies are exothermic and large. An equilibrium constant K₁ expressed in terms of mole fractions and standard enthalpy of formation of 1:1 complex have been evaluated by ideal mixtures of momomeric molecules and their associated complexes. This revised version was published online in August 2006 with corrections to the Cover Date.     

1，3-二(三甲基硅基)-2-叔丁基锂与铁(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)、钛(Ⅳ)的反应及结构

1，3-二(三甲基硅基)-2-叔丁基锂与氯化镍或四氯化钛反应合成了内消旋的1，3-二(三甲基硅基)-2-叔丁基偶联化合物(1)；与氯化钴和氯化亚铁反应分别生成了二配位的1，3-二(三甲基硅基)-2-叔丁基钴和铁配合物(2，3)。用NMR,元素分析和X-射线衍射对其单晶的结构进行了分析，结果表明：化合物1属三斜晶系；化合物2和3均属单斜晶系，配合物2中心钴为六配位畸变的八面体构型。配合物3与2结构相类似。     

Coordination networks of 2,3-bis(4,5-dimethylthio-1,3-dithiole-2-ylidene)succinonitrile with silver salts: A study of network connectivity and topology as a function of counterion

Complexes of 2,3-bis(4,5-dimethylthio-1,3-dithiole-2-ylidene)succinonitrile (L) with AgX salts have been prepared and fully characterized by elemental analysis, IR and single-crystal X-ray analysis. The structural topology in the solid state is found to depend on the type of counterions. With AgNO₃, a 3D coordination network of composition [Ag₂(L)(NO₃)₂]_n (1) forms in which Ag(I) is six-coordinated, bonding to two sulfur atoms of ligand L, a neighboring ligand nitrogen atom and totally three oxygen atoms of bridging nitrate anions. Changing the counterion to triflate produces a 2D coordination network of composition [Ag₂(L)(CF₃SO₃)₂]_n (2) in which Ag(I) is five-coordinated and bonds to two sulfur atoms of ligand L and totally three oxygen atoms of bridging triflate anions. Obviously, in the latter case, the nitrile groups of L are non-coordinating.     

OLEFIN SYNTHESIS VIA THE LITHIUM DERIVATIVE OF THE N,N,N′,N′-TETRAMETHYLDIAMIDES OF ARYLMETHANEPHOSPHONIC ACIDS. 3 SYNTHESIS OF SOME β-DISUBSTITUTED STYRENES

Abstract

The reaction of Li-derivatives of N,N,N′,N′-tetramethyldiamides of arylmethanephosphonic acids (1-Li) with alkanones, cycloalkanones, alkylaryl-and diarylketones 2a-h is studied. It is found that in THF at-70°C adducts 3-Li and 4-Li are formed, the corresponding hydroxyl compounds 3 and 4 being isolated in 36–81% yields, while by elevated temperatures the reaction is completely shifted to the starting 1-Li and 2. By thermolysis of 3 and 4 in neutral medium olefins 5 and 6 are obtained even from readily enolysable ketones. The stereochemistry of the addition reaction with nonsymmetrical ketones as well as the influence of the substituents at the carbonyl groups on the conformation and adsorption properties of the adducts are discussed.     

Mercury(II) iodide coordination polymers generated from polyimine ligands

A series of new HgI₂ organic polymeric complexes, [Hg₂(L1)I₄]_n (1), [Hg(L2)I₂]_n (2), [Hg(L3)I₂]_n (3), [Hg₂(L4)I₄]_n (4), [Hg(L5)I₂]_n (5), [Hg(L6)I₃](HL6) (6) {L1 = 1,4-bis(2-pyridyl)-2,3-diaza-1,3-butadiene, L2 = 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene, L3 = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, L4 = 2,5-bis(2-pyridyl)-3,4-diaza-2,4-hexadiene, L5 = 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene and L6 = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene} was prepared from reactions of mercury(II) iodide with six organic nitrogen donor-based ligands under thermal gradient conditions using the branched tube method. All these compounds were structurally characterized by single-crystal X-ray diffraction. The HgI₂ coordination polymers obtained with the ligands L2, L3 and L5 show one-dimensional zig-zag motifs and in these compounds the HgI₂ units are connected to each other by the ligands L2, L3 and L5 through the pyridyl nitrogen atoms. The L1 and L4 ligands in the compounds 1 and 4 act as both a chelating and bridging group. In the compound 6 the ligand L6 acts as a monodentate ligand, resulting form a discrete compound. The thermal stabilities of compounds 1–6 were studied by thermal gravimetric (TG) and differential thermal analyses (DTA).     

希土高氯酸盐与N,N''—二(2—吡啶亚甲基)—1,2—乙二胺配合物的合成及性质研究

自六十年代以来,希土离子与芳香胺及其衍生物的配合物研究受到人们的普遍重视。     

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.     

New poly(amide-imide)s syntheses. VIII. Preparation and properties of poly (amide-imide)s derived from 2,3-bis(4-aminophenoxy)naphthalene,trimellitic anhydride,and various aromatic diamines

The new polymer-forming diimide-diacid, 2,3-bis(4-trimellitimidophenoxy) naphthalene (I), was readily obtained by the condensation reaction of 2,3-bis (4-aminophenoxy) naphthalene with trimellitic anhydride. A series of novel aromatic poly (amide-imide)s were prepared by the direct polycondensation of diimide-diacid I with various aromatic diamines using triphenyl phosphite in N-methyl-2-pyrrolidone (NMP)/pyridine solution containing dissolved calcium chloride. The resultant polymers have inherent viscosities in the range of 0.65–1.02 dL/g at 30°C in N, N-dimethylacetamide. These polymers were readily soluble in various organic solvents and could be cast into transparent, tough, and flexible films. Their casting films showed tensile strength at break up to 86 MPa, elongation to break of 5–9%, and initial moduli up to 2.35 GPa. The wide-angle X-ray diffraction revealed that those polymers containing p-phenylene or p-oxyphenylene group are partially crystalline, and the other polymers are evidenced as amorphous patterns. These polymers show a glass transition in the range of 213–290°C in their differential scanning calorimetry (DSC) traces. The thermal stability of the polymers was evaluated by thermogravimetry analysis, which showed the 10% weight-loss temperatures in the range of 508–565°C in nitrogen and 480–529°C in air atmosphere. © 1994 John Wiley & Sons, Inc.     

Structure of 1,3-Bis-(3-benzoxazolonyl)-2-hydroxypropane

We have studied the ¹H NMR spectrum of the synthesized 1,3-bis(3-benzoxazolonyl)-2-hydroxypropane. The nature of the splitting of the signals in the spectrum and computer modeling indicate that free rotation is possible about all non-ring bonds in the compounds.     

Excess enthalpies of binary mixtures of some propylamines + some propanols at 298.15 K

The molar excess enthalpies of 1,2- and 1,3-propanediamine + 1- or 2-propanol and 1,2- and 1,3-propanediol + 1- or 2-propaneamine have been determined at 298.15 K using a twin-microcalorimeter for a series of runs over the whole range of mole fractions. All excess enthalpies were large exothermic, in particular, the systems of amines + propanediols were more than −5 kJ mol⁻¹ at the minimum. Primary or secondary alcohols and amines showed systematically different enthalpic behaviors. Equilibrium constant K1 expressed in terms of mole fractions and standard enthalpy of the formation of a 1:1 complex have been evaluated by ideal mixtures of momomeric molecules and their associated complexes.     

N,N'-二-[5-甲氧基-3-溴-2(5H)-4-呋喃酮基]-1,2-乙二胺的合成及其晶体结构(英文)

通过串联迈克尔加成-消除反应合成了N,N'-二-[5-甲氧基-3-溴-2(5H)-4-呋喃酮基]-1,2-乙二胺,利用IR、UV、1H NMR、13C NMR、MS、元素分析和X射线单晶衍射对其进行表征.X射线单晶衍射结果表明:标题化合物包含两个平面的呋喃酮环和两个手性中心,并通过N(1)-H(1A)…O(1)分子间氢键和Br(1)…O(2)近距离作用形成超分子结构.     

Photochromic dihetarylethenes. 10. Photochromic 1,2-bis[2-(benzothiazol-2-yl)-3-thienyl]- and 1,2-bis[2-(benzothiazol-2-yl)benzothiophen-3-yl]ethenes

Dithienylethenes containing the thiophene rings with benzothiazolyl substituents in position 2 were synthesized. 1,2-Bis[2-(benzothiazol-2-yl)benzothiophen-3-yl]hexafluorocyclopentene and 1,2-bis[2,5-di(benzothiazol-2-yl)-3-thienyl]hexafluorocyclopentene possess photochromic properties. The open forms of 1,2-bis(2-benzothiazolylhetaryl)ethenes fluoresce, but introduction of the benzothiazole rings into dihetarylethenes significantly lowers the fatigue resistance of photochromes and favors thermal reversibility.     

Synthesis and molecular structure of [Re2(μ:η-C24H18N4)(CO)6] containing the rtct-tetrakis(2-pyridyl)cyclobutandiyl ligand, derived from the reaction of [Re2(CO)8(MeCN)2] and 1,2-bis(2-pyridyl)ethene

The reaction of the labile compound [Re₂(CO)₈(CH₃CN)₂] with trans-1,2-bis(2-pyridyl)ethene (C₁₂H₁₀N₂) at room temperature in tetrahydrofuran affords the compounds [Re₂(μ:η³-C₁₂H₁₀N₂)(CO)₈] (1) and the oxidative addition product [Re₂(μ-H)(μ:η³-C₁₂H₉N₂)(CO)₇] (2). When the reaction is carried out at temperatures of refluxing tetrahydrofuran, besides compounds 1 and 2, the oxidative addition product [Re₂(μ-H)(μ:η⁴-C₁₂H₉N₂)(CO)₆] (3), the insertion product [Re₂(μ:η⁴-C₁₂H₁₀N₂)(CO)₈] (4) and [Re₂(μ:η⁶-C₂₄H₁₈N₄)(CO)₆] (5) are obtained. Compound 5 contains the organic ligand rtct-tetrakis(2-pyridyl)cyclobutandiyl which is derived from a [2 + 2] cycloaddition of 1,2-bis(2-pyridyl)ethene mediated by its coordination to the bimetallic framework. The molecular structures of 1, 2, 4 and 5 were confirmed by X-ray crystallographic studies.     

2-[2-(2,3-Dihydrobenzimidazolylidene)]- and 2-[2-(2,3-Dihydropyrido[2,3-d]imidazolylidene)]-5,5-dimethyl-1,3-cyclohexanediones

The reaction of 2-aminocarbonyl-5,5-dimethyl-1,3-cyclohexanedione with 2,3-diaminopyridine, 1,2-phenylenediamine (and its 4-methyl, 4-nitro, 4-carboxy, and 4-benzoyl derivatives), and 3,3-diaminobenzidine gave the corresponding 2-[2-(2,3-dihydrobenzimidazolylidene)]- and 2-[2-(2,3-dihydropyrido[2,3-d]imidazolylidene)]-5,5-dimethyl-1,3-cyclohexanediones. Their structure was confirmed by ¹H NMR spectroscopic data and X-ray analysis.     

Synthesis of aliphatic 1,2-bishydroxylamines from 1,3- dihydroxyimidazolidines.

Reduction of l-hydroxy-3-imidazoline-3-oxides with NaBH₄ gives 1,3-dihydroxyimidazolidines. The latter on subsequent treatment with NH₂OH · HCl in EtOH or in hydrochloric acid afford 1,2-bishydroxylamines. An X-ray study of 1,2-bishydroxylaminocycloalkanes has shown them to becis-configurated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 896–901, May, 1993.     

Copolymerization of ethylene/carbon monoxide by a cationic hydridoaquopalladium complex

The cationic hydridoaquopalladium (II) complex, trans-[(PCy₃)₂Pd(H)(H₂O)]⁺BF^?₄, is an excellent catalyst for the ethylene/carbon monoxide alternating copolymerization in the presence of a bidentate phosphorus ligand and p-toluenesulphonic acid. © 1995 John Wiley & Sons, Inc.     

Reactions of 1,3-bis(ω-bromoalkyl)-6-methyluracils with 2-(dialkylamino)ethylphosphonates and 2-(dialkylamino)ethyl phosphates

1,3-Bis(4-bromobutyl)-6-methyluracil reacts with diethyl 2-(dimethylamino)ethylphosphonate to form a bisquaternary ammonium salt, whereas the reaction of 1,3-bis-(6-bromohexyl)-6-methyluracil with diethyl 2-(diethylamino)ethyl phosphate gives 1,3-bis-[(6-diethoxyphosphoryloxy)hexyl]-6-methyluracil and 1,1,4,4-tetraethylpiperazinium dibromide. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1130–1132, June, 2000.     

REACTION OF HINDERD α,β - UNSATURATED KETONES WITH 2,4-BIS(4-METHOXYPHENYL)-1,3,2,4- DITHIADIPHOSPHETANE-2,4-DISULFIDE

Abstract

Six new hindered α,β-unsaturated ketones (22c-h) were prepared. Though the reaction of α,β-unsaturated ketones (22a,b) with 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphet-ane-2,4-disultide (23) in refluxing benzene gave the corresponding 2-arylidene-1-thiotetral-one dimers (26a,b) and 3H-1,2-thiaphospholene-2-sulfides (28a,b), the reaction of hindered α,β-unsaturated ketones (22d-h) with 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphet-ane-2,4-disultide (23) in retluxing benzene gave only identified 3H-1,2-thiaphospholene-2-sulfides (28c-g).