1－硫脲乙基－2－芳基－2－咪唑啉化合物的合成

１－硫脲乙基－２－芳基－２－咪唑啉化合物的合成刘运廷，章荣玲（山东工业大学数理系济南，２５００１４）关键词咪唑啉，硫脲基，芳基，合成咪唑啉衍生物由于具有缓蚀、杀菌、抗癌等活性而迅速发展￣［１，５］。作者曾研究过各种咪唑啉衍生物的合成￣［６］，系采用通...     

[2+2]型Schiff碱大环化合物及其配合物的合成

利用Mn2 ,Ba2 作为模板离子,合成了一类新型的Schiff碱型大环化合物,Mn2 用于L1和L2的合成,并在洗涤时自动解络,L3和L4的合成以Ba2 为模板.L3和L4的Ba2 配合物经与Na2SO水溶液反应解络,得到自由配体L3和L4.上述大环配体和各种配合物均经元素分析,IR,1H NMR,MS等证实了它们的结构和组成.     

三(2-甲基-2-苯基丙基)锡芳氧乙酸酯的合成

三（２－甲基－２－苯基丙基）锡芳氧乙酸酯的合成刘宝殿,宁志刚,朱东升,包明（东北师范大学化学系,长春,１３００２４）关键词三（２－甲基－２－苯基丙基）锡芳氧乙酸酯,三（２－甲基－２－苯基丙基）氢氧化锡,芳氧乙酸,杀螨活性１９６６年Ｒｅｉｃｈｌｅ［１］...     

噁唑、苯并噁唑及1,3,4-噁二唑硫醚的合成及抗肿瘤活性研究

设计并以噁唑、苯并噁唑及1,3,4-噁二唑硫醇与卤代烃反应合成了14个硫醚类杂环化合物, 其中13个化合物未见文献报道. 目标化合物的结构均通过¹H NMR谱、MS和元素分析进行了表征. 采用MTT [3-(4,5-dimethylthiagol-2-yl)- 2,5-diphenyltetrogolium bromide]法对14个目标化合物进行了体外抗肿瘤活性测定, 结果表明: 在10^－5 mol/L 浓度下, 10个化合物对肿瘤细胞具有抑制活性.     

Thermal synthesis of the CeO2-PrO2-La2O3 pigments

The synthesis of new compounds based on CeO₂-PrO₂-La₂O₃, which can be used as pigments for colouring of ceramic glazes, is investigated in our laboratory. The optimum conditions for the syntheses of these compounds have been estimated. The first information about the temperature region of the formation of the pigments investigated is provided by thermal analysis. The synthesis of these compounds is followed by thermal analysis using STA 449/C Jupiter (Netzsch, Germany). This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis of 2-Ferrocenyl-2-(Dialkyl Hydroxymethyl)D-1,3-Dithianes

The reactions of lithiated 2-ferrocenyl-1,3-dithiane with alkyl carbonyl compounds are studied. Fifteen of title compounds which are new ferrocene derivatives were synthesized and structurally characterized by elemental analysis, IR and 1H NMR spectra. The 1H NMR spectra of the dithiane compounds are briefly discussed.     

Synthesis of 3-substituted-2-benzothiazolinone, 2-benzoxazolinone and benzothiazoline-2-thione

The reaction of 2-benzothiazolinone, 2-benzoxazolinone or benzothiazoline-2-thione under basic conditions with various electrophiles afforded the titled compounds 1-13, 29-31 and 40-48. The 3-(substituted-aminomethyl)-2-benzothiazolinone and related compounds 14-25 were prepared by the reaction of 3-(hydroxymethyl)-2-benzothiazolinone or the appropriate 2-benzothiazolinone and formaldehyde with the appropriate amine or substituted aniline. The reaction of 9, 13 or 25 with methyl iodide afforded the quaternary ammonium iodides 26-28. The reaction of the appropriate potassium salts of various phenol with 3-(chloromethyl)-2-benzothiazolinone afforded the 3-(substituted-phenoxymethyl)-2-benzothiazolinone and related compounds 32-39. The ethyl or isopropylxanthates 49-54 were synthesized by the reaction of 3-(chloromethyl)-2-benzo-thiazolinone and appropriate compounds with potassium ethyl or isopropyl xanthate. The reaction of 3-(chloromethyl)-2-benzothiazolinone with sodium sulfide afforded the sulfide 55.     

The synthesis of 2-(2-furyl) 1,3-dicarbonyl compounds

2-furyl derivatives are easily synthesised by intermolecular condensation of 2,5-dihydro-2,5-dimethoxy furan (DHDMF) with active methylene compounds by a simple and cheap procedure. The reaction applies only to 1,3-dicarbonyl compounds and a general mechanism is proposed.     

N-(S)-(1'-氯甲基-2'-烷基)-2-乙基-2-(4S-烷基-4,5-二氢恶唑)丁酰胺的合成

由L-氨基酸不对称合成了4种新型手性化合物(6a，6b，7a，7b)，其结构经IR，^1HNMR，^1^3C NMR及MS等证实。     

2-芳氧甲基苯并咪唑类化合物的合成

以HCl为催化剂,合成了12种2-芳氧甲基苯并咪唑类化合物,其中6种尚未见文献报道。它们的结构经1H NMR,IR和元素分析确证。     

Theoretical studies on four-membered ring compounds with NF2, ONO2, N3, and NO2 groups

Density functional theory (DFT) method has been employed to study the geometric and electronic structures of a series of four-membered ring compounds at the B3LYP/6-311G** and the B3P86/6-311G** levels. In the isodesmic reactions designed for the computation of heats of formation (HOFs), 3,3-dimethyl-oxetane, azetidine, and cyclobutane were chosen as reference compounds. The HOFs for N(3) substituted derivations are larger than those of oxetane compounds with --ONO2 and/or --NF2 substituent groups. The HOFs for oxetane with --ONO2 and/or --NF2 substituent groups are negative, while the HOFs for N3 substituted derivations are positive. For azetidine compounds, the substituent groups within the azetidine ring affect the HOFs, which increase as the difluoroamino group being replaced by the nitro group. The magnitudes of intramolecular group interactions were predicted through the disproportionation energies. The strain energy (SE) for the title compounds has been calculated using homodesmotic reactions. For azetidine compounds, the NF2 group connecting N atom in the ring decrease the SE of title compounds. Thermal stability were evaluated via bond dissociation energies (BDE) at the UB3LYP/6-311G** level. For the oxetane compounds, the O--NO2 bond is easier to break than that of the ring C--C bond. For the azetidine and cyclobutane compounds, the homolyses of C--NX2 and/or N--NX2 (X = O, F) bonds are primary step for bond dissociation. Detonation properties of the title compounds were evaluated by using the Kamlet-Jacobs equation based on the calculated densities and HOFs. It is found that 1,1-dinitro-3,3-bis(difluoroamino)-cyclobutane, with predicted density of ca. 1.9 g/cm(3), detonation velocity (D) over 9 km/s, and detonation pressure (P) of 41 GPa that are lager than those of TNAZ, is expected to be a novel candidate of high energy density materials (HEDMs). The detonation data of nitro-BDFAA and TNCB are also close to the requirements for HEDMs.     

Crystal and molecular structure of cyclic sulfoxides: 2-cyano-2-ethoxycarbonyl-3,6-dihydro-4,5-dimethyl-2H-thiapyran 1-oxide and 2-phenyl-2-methoxycarbonyl-3,6-dihydro-2H-thiapyran 1-oxide

Crystal and molecular structures of the title compounds 1b and 1c have been determined by the X-ray method. Crystals of 1b are monoclinic, space group P2₁/c, and crystals of 1c are orthorhombic, space group P2₁2₁2₁. The sulfinyl oxygen atom and the alkoxycarbonyl group in both compounds are trans oriented, and the six-membered rings adopt a sofa conformation. The differences between conformation, bond lengths, and angles in the compounds investigated are discussed. © John Wiley & Sons, Inc.     

Effect of pH on inhibition and enhancement of luminol-H2O2-Co2+ chemiluminescence by phenolic compounds and amino acids

The effect of pH on inhibition and enhancement of luminol-H2O2-Co2+ chemiluminescence (CL) by 18 phenolic compounds and 20 amino acids was studied. It was found that most of the tested compounds showed an inhibiting effect at lower pH and an enhancing effect at higher pH. At a midrange pH, for some phenolic compounds with two ortho-position -OH, both an inhibiting and an enhancing peak were simultaneously observed. UV-visible spectra of the tested phenolic compounds at different pH values were studied. The mechanism for CL inhibition and enhancement was proposed. It is likely that the competition of the -OH or the -NH2 group and other reducing groups in the molecules with luminol for O2*- led to the CL inhibition. A reaction of -COO(-) and quinone or ketone formed by phenolic compounds at higher pH via deprotonation with O2*- also resulted in the CL enhancement.     

F2Al(mu-eta2:eta2-O2)AlF2: an unusual, stable aluminum peroxo compound

The oxidation processes in the industrial production of aluminum from cryolite melts are not fully understood. Oxidation of AlOF2- leads initially to AlOF2 radicals. The structure of the AlOF2 dimer and several oxidized and reduced forms of this compound are investigated by theoretical methods and compared to analogous boron and gallium compounds. The thermodynamic stability of these compounds is investigated. It is shown that the dimeric compound of AlOF2 contains a symmetric peroxo bridge and is unexpectedly stable toward decomposition.     

M2(hpp)4Cl2 and M2(hpp)4, where M = Mo and W: preparations, structure and bonding, and comparisons with C2, C2H2, and C2Cl2 and the hypothetical molecules M2(hpp)4(H)2

The reaction between M(2)Cl(2)(NMe(2))(4), where M = Mo or W, and Hhpp (8 equiv) in a solid-state melt reaction at 150 degrees C yields the compounds M(2)(hpp)(4)Cl(2) 1a (M = Mo) and 1b (M = W), respectively, by the elimination of HNMe(2) [hpp is the anion derived from deprotonation of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine, Hhpp]. Purification of 1a and 1b is achieved by sublimation of the excess Hhpp and subsequent recrystallization from either CH(2)Cl(2) or CHCl(3) (or CDCl(3)). By single-crystal X-ray crystallography, the structures of 1a and 1b are shown to contain a central paddlewheel-like M(2)(hpp)(4) core with Mo-Mo = 2.1708(8) A (from CH(2)Cl(2)), 2.1574(5) A (from CDCl(3)), W-W = 2.2328(2) A (from CDCl(3)), and M-N = 2.09(1) (av) A. The Cl ligands are axially ligated (linear Cl-M-M-Cl) with abnormally long M-Cl bond distances that, in turn, depend on the presence or absence of hydrogen bonding to chloroform. The quadruply bonded compounds M(2)(hpp)(4), 2a (M = Mo), and 2b (M = W), can be prepared from the reactions between 1,2-M(2)R(2)(NMe(2))(4) compounds, where R = (i)()Bu or p-tolyl, and Hhpp (4 equiv) in benzene by ligand replacement and reductive elimination. The compounds 2a and 2b are readily oxidized, and in chloroform they react to form 1a and 1b, respectively. The electronic structure and bonding in the compounds 1a, 1b, 2a, and 2b have been investigated using gradient corrected density functional theory employing Gaussian 98. The bonding in the M-M quadruply bonded compounds, 2a and 2b, reveals M-M delta(2) HOMOs and extensive mixing of M-M pi and nitrogen ligand lone-pair orbitals in a manner qualitatively similar to that of the M(2)(formamidinates)(4). The calculations indicate that in the chloride compounds, 1a and 1b, the HOMO is strongly M-Cl sigma antibonding and weakly M-M sigma bonding in character. Formally there is a M-M triple bond of configuration pi(4)sigma(2), and the LUMO is the M-M delta orbital. An interesting mixing of M-M and M-Cl pi interactions occurs, and an enlightening analogy emerges between these d(4)-d(4) and d(3)-d(3) dinuclear compounds and the bonding in C(2), C(2)H(2), and C(2)Cl(2), which is interrogated herein by simple theoretical calculations together with the potential bonding in axially ligated compounds where strongly covalent M-X bonds are present. The latter were represented by the model compounds M(2)(hpp)(4)(H)(2). On the basis of calculations, we estimate the reactions M(2)(hpp)(4) + X(2) to give M(2)(hpp)(4)X(2) to be enthalpically favorable for X = Cl but not for X = H. These results are discussed in terms of the recent work of Cotton and Murillo and our attempts to prepare parallel-linked oligomers of the type [[bridge]-[M(2)]-](n)().     

Iridium complex-catalyzed highly enantio- and diastereoselective [2+2+2] cycloaddition for the synthesis of axially chiral teraryl compounds

An asymmetric [2+2+2] cycloaddition of an alpha,omega-diyne, possessing ortho-substituted aryl groups on its terminus, and a monoalkyne with oxygen functionalities gave various axially chiral teraryl compounds. The coupling proceeded with extremely high enantio- (>99.5% ee) and diastereoselectivities (dl/meso = >95/5) when catalyzed by an iridium-chiral phosphine complex. As the products were readily transformed into diol compounds by deprotection without racemization, the present procedure provides access to a new chiral pool of diol compounds with C2 symmetry.     

Synthesis and application of mono-2A-azido-2A-deoxyperphenylcarbamoylated beta-cyclodextrin and mono-2A-azido-2A-deoxyperacetylated beta-cyclodextrin as chiral stationary phases for high-performance liquid chromatography

Two novel chiral stationary phases (CSPs) were prepared based upon the regioselective immobilizations of beta-cyclodextrin (beta-CD) at its C2 position to the silica support. The mono-2A-azido-2A-deoxyperphenylcarbamoylated beta-cyclodextrin and mono-2A-azido-2A-deoxyperacetylated beta-cyclodextrin were synthesized by selective tosylation and azidolysis followed by perfunctionalisation. The derivatised cyclodextrins were then immobilized onto the aminised silica gel via the Staudinger reaction to provide new chiral stationary phases. Their application to high-performance liquid chromatography (HPLC) enantioseparation of racemic compounds was demonstrated using beta-adrenergic blockers, flavonone compounds, benzodiazepinones, antihistamines and weakly protolytic compounds, of which good separations were achieved for some racemic compounds, for instance, bendroflumethiazide (Rs 6.26), oxazepam (Rs 5.99), temazepam (Rs 2.85) and althiazide (Rs 1.13) when compared with the corresponding CSPs where the beta-CD molecule was regioselectively immobilized at the C6 position. The enantiodiscriminatory properties of these CSPs were found to be affected by the orientation of the CD cavity under reversed-phase conditions, and also by the derivitising groups of the CD. The HPLC results inferred that the mono-6A-azido-6A-deoxyperphenylcarbamoylated CD CSP (CD bonded at C6 position to silica) exhibited slightly better chiral recognition ability than mono-2A-azido-2A-deoxyperphenylcarbamoylated CD CSP under the normal-phase and reversed-phase modes on the separation of 31 different racemic compounds and drugs. On the contrary, higher chiral recognition abilities were observed on the mono-2(A)-azido-2A-deoxyperacetylated CD CSP compared to mono-6A-azido-6A-deoxyperacetylated CD CSP.     

FUNCTIONAL POLYMERS 65. SYNTHESIS AND BRIEF CHARACTERIZATION OF SURFACE ACTIVE 2(2-HYDROXYPHENYL)2H-BENZO-TRIAZOLE ULTRAVIOLET STABILIZERS

A number of 2(2-hydroxyphenyl)2H-benzotriazoles substituted in the 5-position with reactive hydroxyl and carboxyl groups have been synthesized. They include compounds with a tert butyl substitution in the 3-position or without substitution. The latter compounds were subjected to a reaction with N-hydroxy-methyl-(meth)acrylamide to form acrylic polymerizable 3(meth)acrylamidomethyl-2(2-hydroxyphenyl)2H-benzotriaz-oles. Hydroxyl reactive compounds were allowed to react with long chain acids, compounds with carboxyl groups with long chain hydrocarbon, fluorocarbon or silicon oligomer alcohols. The polymerizable 2(2-hydroxyphenyl)2H-benzotriazoles were then copolymerized with methyl methacrylate. Films made from such polymers showed by contact angle measurements, substantial migration of the fluorocarbon or silicon component to the surface of the film.     

Infrared spectra of Li2SeO4.H2O,Li2SO4.H2O and Li2(S,Se)O4.H2O

On of the hydrogen bonds formed by water molecules in lithium selenate monohydrate is evidently stronger than in the corresponding sulfate, whereas the other one is weaker. The temperature dependence of the stretching and bending modes of water is similar in both compounds, their frequencies decreasing on lowering the temperature. The study of mixed sulfate—selenate compounds made it possible to clearly show that the effective symmetry of the tetrahedral ions is higher than their local crystallographic one.     

Syntheses and Olfactory Characters of Some Endo-α-Substituted-Bicyclo[2. 2. 2]-Octenyl (or Octanyl) Methanols

Sixteen title compounds were synthesized, twelve of which are new ones. Their structures were determined by 1H NMR, IR and MS, the refractive indices or melting points were measured. Odors of all the title compounds were evaluated and the structure-odor relationship was briefly discussed.