Solid state reaction of aromatic ketones with heteroaromatics

The solid state reactions of p-nitroacetophenone,acetyl-ferrocene with indole were catalyzed by anhydrous zinc chloride or aluminum chloride,and gave exclusively the 1:2 condensation products.The solid state condensation of aromatic ketones with l-phenyl-3-methyl-5-pyrazolone was also investigated,and the 1:1 and 2:1 condensation products were obtained.The structures of eleven new products were determined by IR,MS,1H NMR and elemental analysis.     

Solid State Photochemistry of Nitrobenzaldehydes

The photochemical reaction of nilrobenzaldehyde with indole and antipyrine was investigated in solid state.The structures of the new products were identified by means of IR,MS,'H NMR and elemental analysis,and the crystal structure of audition product 2c was determined by X-ray diffraction analysis.The mechanism of this reaction was also proposed.     

Synthesis and photoreaction of polymethylenediamine bis(4-methyl-7-coumarinyl)oxyacetic amides

A series of polymethylenediamine bis(4-methyl-7-coumarinyl)oxyacetic amides have been synthesized and their intramolecular photochemical cyclodimerizations have been investigated It was found that only syn-HT configuration products were obtained when these bisamides were directly irradiated in dimethyl sulfoxide solution and the yields of the products decreased with the intrease of the chain length.The structures of long chain amides and their intramolecular photoryrlizatum products were determined by IR,MS,1H NMR and elemental analysis.     

Methylation of 5-Amino-3-methylthio-1H-pyrazole Derivatives and Two Related Crystal Structures

5-Amino-3-methylthio-1H-pyrazoles are very important building blocks from which a wide variety of pyrazole derivatives can be prepared. When substituted 5-amino-3-methylthio-1H-pyrazole was treated with CH3I, the methylation occurres at endocyclic two nitrogens at the same time. The ratio of isomers in products was depended upon the nature of 4-position substituent in the pyrazole ring. The products were characterized by X-ray diffraction analysis, and the ratios of isomer were explained by means of the results of ab inito calculation.     

A New Solution—phase Parallel Synthesis of 2—Alkyamino—3—aryl—5—phenylmethylene—3,5—dihydro—4H—imidazol—4—ones

Thirteen new 2-alkylaminoimidazolones(4) wre rapidly synthesized by a new solution-phase parallel synthetic method,which includes aza-Wittig reaction of iminophosphorane(1) with aromatic isocyanate to give carbodi-imide(2) and subsequent reaction of 2 with various aliphatic primary amine in a parallel fashion.The products were confirmed by ^1H NMR,MS,IR and X-ray crystallographic analysis.The unusual selectivity of the cyclization was probably due to the deometry of the guanidine intermediate.     

Stereocontrol of the Schiff Base of Substituted Benzaldehyde to Staudinger Cycloaddition Reaction

Syntheses of 4 novel chiral azetidin-2-one derivatives,which were characterized by ^1H NMR,IR,specific rotation and elemental analysis,through Staudinger cycloaddition reaction of Schiff base of benzaldehyde with chlorine substitution at different position in benzene ring,were described.For the first time,this type of 3S,4R configuration azetidin-2-one monocrystals with many chiral centers [(3S,4R)-3-hydroxy-N-[(S)-(1-phenyl)ethyl]-4-(2‘‘-chlorophenyl)-azetidin-2-one monocrystal]were obtained,the structures of which were determined by X-ray diffraction analysis.The effects of Schiff base of benzaldehyde with chlorine substitution at different position in benzene ring on stereoselectivity of Staudinger cycloaddition reaction products were discussed and the results are showed as below:2-chlorophenyl Schiff base favored to yield 3S,4R configuration product,but 4-chlorophenyl Schiff base favored to yield 3R,4S configuration product.The reaction orientation of 2,4-dichlorophenyl Schiff base was determined by corporate effect of 2- and 4-chlorine,and that of the 4-chlorine was more obvious.In contrast to 4-chlorophenyl,although the main product was 3R,4S configuration,3-chlorophenyl owned lower selectivity.     

Synthesis of Thiourea Derivatives on Soluble Polymeric Support

A modified poly(ethylene glycol) (PEG) has been developed as the soluble polymeric supports for liquid phase synthesis of novel thiourea derivatives.In each step of the sequence,the PEG-bound products were precipitated in cold Et2O and the unreacted materials and by-products were removed by simple filtration.The progress of reaction,purity of the isolation and the structure of the PEG-bound products were easily monitored by TLC,IR and ^1H NMR spectra.Representative thiourea derivatives were obtained in moderate yields with excellent purity from this modified PEG-bound product by the cleavage with 50% TFA/H2O.     

Novel Reaction of Some Azoles with Dimethyl Sulfoxid

The compounds 4a～4j were prepared by 3a～3j which were prepared from 1a～1j through 2a～2j. The compounds 6a～6j were prepared by the reaction of the products of 4a～4j with dimethyl sulfoxid via Dimroth rearrangement.[1] The compounds ethyl 5-arylamino-1H-1,2,3-triazol-4-carbonates (5a～5d) and ethyl 2-methylthiamethylene-5-arylamino-2H-1,2,3-triazol-4-carbonates (6a～6j) are established by MS, IR, elemental analysis and 1H NMR spectral data. The route of syntheses is shown in Scheme 1.     

Solid state reactions of nitrogenous heterocyclic compounds(Ⅰ)——Solid state reactions of 3-methyl-l-phenyl-5-pyrazolone with carbonyl compounds

The solid state reaction of 3-methyl-1-phenyl-5-pyrazolone (MPP) with aromatic aldehydes and ke-tones benzil derivatives and imides,and the solid state Michael addition reaction of MPP with 4-arylidene-3-methyl-1-phenyl-5-pyrnzolone 2 were investigated.Some new solid state reactions between the reactants were found,from which a series of new compounds were obtained The structures of the products were identified by IR,1H NMR,MS,elemental analyses and also by X-ray crystal analysis,and the reaction mechanism of MPP with aromatic aldehydes and ketones was proposed     

Synthesis of Some Novel Phenyl Substituted Oxothiazolidin- 1’’,3’’,4’’-thiadiazolo-[3’,4’-b]thiazoline of 3β-Substituted Cholestane

Three title compounds 4a—4c have been synthesized by the cyclodehydration of 1’-benzylidine-4’-(3β-substituted-5α-cholestane-6-yl)thiosemicarbazones 2a—2c with thioglycolic acid followed by the treatment with cold conc. H2SO4 in dioxane. The compounds 2a—2c were prepared by condensation of 3β-substituted-5α-cholestan- 6-one-thiosemicarbazones 1a—1c with benzaldehyde. These thiosemicarbazones 1a—1c were obtained by the reaction of corresponding 3β-substituted-5α-cholestan-6-ones with thiosemicarbazide in the presence of few drops of conc. HCl in methanol. The structures of the products have been established on the basis of their elemental, analytical and spectral data.     

Radiolysis of liquid propylene: Ion-molecule condensation

Radiolysis of propylene gives mainly hydrogen, and dimeric, trimeric, and other low molecular weight polymeric hydrocarbons.

Detailed analysis of the dimer shows the products to be, in order of concentration, 4-methyl-1-pentene, 1,5-hexadiene, 1-hexene, 2-methylpentane, 2,3-dimethylbutane, 4-methyl-2-pentene, 2-methyl-1-pentene, 2-hexene, and n-hexane.

The relative product concentrations, and the isotope species distribution in the products obtained from radiolysis of a 50:50 mixture of propylene and propylene-d₆, demonstrate that the alkanes, the diene, and much of the olefinic products are formed by combinations of n-propyl, isopropyl, and allyl radicals.

Isotopic species distributions in 4-methyl-1-pentene, 1-hexene, and 2-hexene demonstrate that appreciable fractions of each of these products are formed by a direct condensation of two propylene molecules with intramolecular hydrogen rearrangement. The previously postulated direct dimerization is thus verified, and the idea of its being an ion-molecule condensation receives further support.     

O-乙酰基-吡喃木糖热解反应机理的理论研究

为了从微观上理解半纤维素热解过程及其主要产物的形成演变机理,采用密度泛函理论方法B3LYP/6-31G++(d,p),对O-乙酰基-吡喃木糖的热解反应机理进行了量子化学理论研究。在热解过程中,O-乙酰基-吡喃木糖中的O-乙酰基首先脱出,形成乙酸和中间体IM₁,该步反应能垒为269.4 kJ/mol。IM₁进一步发生开环反应形成IM₂,开环反应能垒较低,为181.8 kJ/mol。对中间体IM₂设计了四种可能的热解反应途径,对各种反应的反应物、产物、中间体和过渡态的结构进行了能量梯度全优化,计算了各热解反应途径的热力学和动力学参数。计算结果表明,反应路径(4)和反应路径(2)是O-乙酰基-吡喃木糖热解的主要反应通道,乙酸、乙醛、乙醇醛、丙酮、CO、CO₂、CH₄等小分子产物是热解的主要产物。这与相关实验结果分析是一致的。     

New heterometallic copper zinc alkoxides: synthesis, structure properties and pyrolysis to Cu/ZnO composites

The copper compound [(THF)KCu(O^tBu)₃]_∞ 1 was obtained by interaction of a 1:1 mixture of ZnCl₂/CuCl₂ with KO^tBu. Bi- and trifunctional aminoalcohols were used to synthesize the intramolecularly donor stabilized Cu(II) alkoxides Cu(OCH(R)CH₂NMe₂)₂ (3: R=Me, 4: =CH₂NMe₂) where 4 was structurally characterized. Lewis acid–base adduct formation with (Me₃Si)₃CZnCl gave the heterodinuclear compounds (Me₃Si)₃CZnCl · Cu(OCH(R)CH₂NMe₂)₂ (5: R=Me, 6: R=CH₂NMe₂), which were characterized by X-ray single-crystal structure analysis. The two metal centers Cu and Zn of 5 and 6 are bridged by two oxygen atoms to form a Cu–O–Zn core. Pyrolysis of compounds 5 and 6 in dry argon or a H₂/N₂ mixture at atmospheric pressure forms metallic copper and zinc oxide, whereas pyrolysis under O₂/Ar forms additionally oxidized copper species. Elemental analysis of the pyrolysis products showed carbon and nitrogen contamination. Scanning electron microscopy and energy dispersive X-ray analysis were performed to get information on the morphology and the chemical composition of the pyrolysis products.     

Unexpected sulfonylamino migration in the reactions of carbazole derivatives with fluoroalkanesulfonyl azides

The reactions of fluoroalkanesulfonyl azides 1 with carbazole derivatives have been studied in detail. At room temperature 1 reacted with 1,2,3,4-tetrahydrocarbazole 2 readily to afford ring-contraction spiroindole derivatives 3 together with an unexpected 4a-fluoroalkanesulfonylamino-1,2,3,4-tetra-hydrocarbazoles 4. However, in the case of 9-methyl-1,2,3,4-tetrahydrocarbazole 5, unexpected sulfonylamino migration occurred and a similar product 9-methyl-1-fluoroalkanesulfonylamino-2,3,4,9-tetrahydro-1H-carbazoles 6 were obtained as major products in moderate yields. These new products were fully characterized by spectral methods and single X-ray diffraction analyses. Possible mechanisms for these reactions were proposed.     

锅炉腐蚀产物的穆斯堡尔谱研究

本文测定了高、中压锅炉腐蚀产物的穆斯堡尔谱^[1,2]并鉴定其相组成。(一)实验部分1.中压锅炉腐蚀产物锈样A、B、C取自广州发电厂2^#锅炉水冷壁管内壁,管内压力40kg/cm²,温度250℃。锈样D、E分别取自过热器管(425℃)和省煤器管(150℃)内壁.2.高压锅炉腐蚀产物锈样F、G、H取自广东韶关发电厂3^#锅炉的水冷壁管内壁,管内压力110kg/cm²,温度320℃。     

Chemical Evolution of LiCoO2 and NaHSO4·H2O Mixtures with Different Mixing Ratios During Roasting Process

Mixtures of NaHSO₄·H₂O and LiCoO₂ extracted from spent lithium-ion batteries were prepared with molar ratios of 1:1, 1:2 and 1:3. The chemical evolution of the LiCoO₂ and NaHSO₄·H₂O mixtures during the roasting process was investigated by means of thermogravimetric analysis and differential scanning calorimetry (TG-DSC), X-ray diffraction(XRD), scanning electron microscopy(SEM), and X-ray photoelectron spectroscopy (XPS). The results show that the chemical reactions in the LiCoO₂ and NaHSO₄·H₂O mixtures proceed during the roasting process. The Li element in the product of the roasting process is in the form of LiNa(SO₄). With the increase of the proportion of NaHSO₄·H₂O in the mixtures, the Co element evolves as follows: LiCoO₂→Co₃O₄→ Na₆Co(SO₄)₄→Na₂Co(SO₄)₂. The roasting products exhibit dense structures and irregular shapes, and the bonding energy of Co increases.     

四甲基萘并二呋喃的合成和DNA嵌入性能及其结构的分子模拟研究

将2,7-二羰烷氧基萘(2)在三氯氧磷中环化成73%不对称及27%对称的四甲基萘并二呋喃(4和5).在盐酸作用下2环化成3,随后在乙酰乙酸乙酯/二氯甲烷中及三溴化硼作用下生成区域选择性环化产物(5).采用荧光强度测定法发现4对小牛胸腺DNA有嵌入作用。分子模拟方法指出4与5在DNA嵌入性能上的差别主要是由它们分子平面性不同所致。     

硼化合物的研究Ⅹ。B10H102-、B10H122-及B3H8-双二茂铁季铵盐及环状二茂铁季铵盐的合成

众所周知,二茂铁类和硼氢类化合物都具有特殊的化学结构,并且有可能作为高能材料得到应用。作者通过B₁₀H₁₀^2-、B₁₂H₁₂^2-及B₃H₈^-与(N,N-二甲基胺甲基)二茂铁和1,1'-双(N,N-二甲基胺甲基)二茂铁卤化铵反应,曾合成了一系列新的化合物并研究了它们的反应性能和晶体结构^[1-4]。     

类Mannich反应合成2,5-二苯基-3,3-二取代-2,3-二氢-1,4,2-氧氮磷杂环戊烯-2-氧化物

本文报道了以苯甲酰胺,醛(或酮)苯基二氯化膦为原料进行的Mannich反应,其产物经部分水解合成了α-(N-苯甲酰氨基)二取代甲基苯基膦酸(Ⅰ),此化合物脱水关环得2,5-二苯基-3,3-二取代-2,3-二氢-1,4,2-氧氮磷杂环戊烯-2-氧化物(Ⅱ).经¹HNMR及元素分析证明了Ⅰ和Ⅱ的结构,并对反应机理进行了探讨。     

γ-radiolysis and pulse radiolysis of aqueous 4-chloroanisole

Using pulse radiolysis and steady state γ-radiolysis in combination with product analysis by HPLC the radiolytic degradation mechanism of 4-chloroanisole (4-ClAn) has been elucidated. Pulse radiolysis experiments show that OH radicals react in neutral aqueous N₂O saturated solutions with 4-ClAn by addition to all aromatic ring positions to yield hydroxycyclohexadienyl radicals (OH-adducts), k(OH + 4-ClAn) = 6.5 × 10⁹dm³mol⁻¹s⁻¹. Those OH-adducts formed on ipso positions of the molecule subsequently undergo HCl or CH₃OH elimination forming methoxyphenoxyl- and chlorophenoxyl radicals. Their yield corresponds to 20% of the OH-radicals, whereby the distribution is roughly 3:1 in favor of the methoxyphenoxyl radicals, which reflects the stronger ortho-, para-directing activity of the methoxy group. The OH-adducts decay second order, 2k = 1 × 10⁹dm³mol⁻¹s⁻¹. The presence of oxygen leads to its addition on the hydroxycyclohexadienyl radicals, k(OH-adduct + O₂) = 3.2 × 10⁸dm³mol⁻¹s⁻¹. In airfree solution the reaction of H-atom with the substrate, k(H + 4-ClAn) = 1.2 × 10⁹dm³mol⁻¹s⁻¹, results in H-adducts which decay in bimolecular reactions, 2k = 8.2 × 10⁸dm³mol⁻¹s⁻¹. The rate constant for the reaction of the solvated electrons has been determined to k(e_aq⁻ + 4-ClAn) = 2 × 10⁹dm³mol⁻¹s⁻¹. The absorption spectra of H- and OH-adducts were measured in the range of 280–450 nm. The products analysed by HPLC after γ-radiolysis in dependence of dose (100–600 Gy) are given for N₂O-, air-, oxygen- and argon saturated neutral aqueous solutions. In conditions favoring the OH radical oxidation 4-chlorophenol, 4-methoxyphenol, 5-chloro-2-methoxyphenol and 2-chloro-5-methoxyphenol were determined as final products. In the presence of Ar, where about equal amounts of OH and e_aq⁻ are present, additionally anisole could be detected. Under both reaction conditions the amount of identified products is about 20% of decomposed 4-ClAn. The reaction of e_aq⁻ leads to reductive dechlorination which corresponds quantitatively to the degradation of the substrate. In the presence of air or solutions saturated with pure oxygen predominantly hydroquinone, 4-chlorophenol and muconic acids are formed and the material balance is 50%. The efficient dechlorination (60% of the decomposed 4-ClAn) as well as ring fragmentation products as intermediates en route to complete mineralization in oxygenated solution indicate that high energy radiation is a promising method for degradation of halogenated aromatic compounds in water. Variation of dose rates from 79 Gy min⁻¹ to 266 Gy min⁻¹ did not show any influence on the product distribution.