由丙酮还原偶联合成2,3—二甲基丁烯—2的研究

本文报道了利用ＭｃＭｕｒｒｙ反应，由丙酮还原偶联合成２，３—二甲基丁烯—２（ＤＭＢ—２）的实验结果。实验考察了镁粉还原四氯化钛的时间、丙酮与四氯化钛之比等因素对ＤＭＢ—２收率的影响。探讨了低价钛试剂活性物的价态与ＤＭＢ—２收率之间的关系。实验表明，大部分ＤＭＢ—２是在最初几分钟内生成的，每摩尔的低价钛试剂最多可转化９摩尔以上的丙酮。     

TRIPLET STATE OF METALLOPORPHYCENES: ZnPCl, PdPC2, PtPC2, and NiPC2

We report on a study of the photoexcited triplet state, at low temperatures in ordered liquid crystals, and at room temperatures in the liquid phase, of some new metalloporphycenes: normal zincporphycene, ZnPCl; Pd(II), and Ni(II) complexes of 2,7,12,17-tetra- n -propylporphycene, PdPC2, PtPC2, and NiPC2, respectively. The triplet state at low temperature is obtained by selective laser excitation and its magnetization response is detected by EPR in the 250 ns time scale. From triplet EPR line shapes and triplet spin polarization directions it is concluded that the zinc cation lies above the molecular plane and the palladium cation fits into the porphycene's cavity. Such a proposed structure implies a strong spin-orbit interaction in PdPC2, thus resulting in an out-of-plane active spin state (z-axis), whereas that in ZnPCl, having a smaller spin-orbit interaction, in-plane ( x,y -axes) are the active spin states. Laser photolysis of the metalloporphycenes gives rise to detectable triplets of ZnPCl, PdPC2 and PtPC2 with triplet lifetimes of 26, 5 and 0.2 µs, respectively. The sensitization experiment, using β-acetonaphthone as a sensitizer to produce the triplet, results in detectable transients of only ZnPCl and PdPC2 with much longer triplet lifetimes of 85 and 20 µs, respectively. The short triplet lifetime of PtPC2 (and probably that of NiPC2) do not allow for triplet detection with the present sensitizer. However, the latter two metalloporphycenes quench the triplet lifetime of β-acetonaphthone from 29 to 10µs.     

穴醚[2, 2, 2]和穴醚[2, 2]对镉离子萃取行为的研究

本文研究了穴醚[2,2,2]和穴醚[2,2]在硝基甲烷中对镉的萃取行为。探讨了溶剂、穴醚浓度,碱浓度,无机酸浓度,盐效应及共存离子对镉萃取的影响。实验结果表明,硝基甲烷ε=35.6,μ=3.4德拜宜作为穴醚的溶剂。当穴醚[2,2,2]——硝基甲烷的浓度为2×10~(-3)M,Me_4NOH浓度为4×10~(-2)M时对镉的萃取最为有利。无机酸的引入使穴醚质子化程度加大,盐效应对镉的萃取无明显影响。十八种共存离子对镉萃取无干扰,因而选择性高。实验结果为用穴醚[2,2,2]萃取镉提供了依据。     

NaCl、KCl、Na_2CO_3、K_2CO_3等电解质溶液对含水卵磷脂液晶结构影响的SAXS研究

关于电解质溶液对卵磷脂液晶结构的影响前人有过报导。例如Chapman和G. Shiply等在研究碱金属氯化物对卵磷脂液晶结构的影响时指出:随着Li~ 到Cs~ 离子半径增加,脂双层的厚度也发生相应变化。Plainer等也指出KCI,NaCl溶液使磷脂层厚度发生变化。关于磷脂蛋白复合膜与Na~ ,K~ 、Ca~(2 )离子的作用也有一些报导。本文报导用小角X射线散射(SAXS)方法研究几种电解质溶液对卵磷脂形成液晶结构的影响。     

温度对4-甲基丙烯酸2,2,6,6-四甲基哌啶醇酯与苯乙烯自由基共聚活性的影响

本文研究了4-甲基丙烯酸2,2,6,6-四甲基哌啶醇酯和苯乙烯在不同温度下的自由基共聚合反应。发现在石油醚、苯和二甲基甲酰胺等溶剂中,反应温度对共聚活性的影响不同。用NMR法测定了单体与溶剂的络合常数;计算了单体与溶剂相互作用的活化能和活化熵,依此对共聚活性与温度之间的关系进行了讨论。     

一种新型的高聚物的光稳定剂——4-(水杨酸)2,2,6,6-四甲基哌啶醇酯的合成及其光稳定能力的评价

<正> 自1967年日本Sankyo公司发现2,2,6,6-四甲基哌啶化合物具有良好的光稳定能力以来,对该类化合物的研究与开发工作已取得很大的进展。不同结构的衍生物作为正式商品不断问世,同时作为添加剂已在许多大品种烯类聚合物制品中得到广泛的应用,然而它作为一种光稳定剂其稳定效能在某些方面仍不能令人满意,如对紫外辐射屏蔽作用,由于它在300—350 nm波长范围内只有较小的克分子吸收系数,因此是不够理想     

2-BENZAZEPINES III1, 2 IMPROVED SYNTHESIS OF 2, 3, 4, 5-TETRAHYDRO-2-BENZAZEPIN-1-ONE

3-Methylfuran is an important building block of terpenoid compounds¹⁾ and some of these compounds are biologically active, for example as a defence substance of animal.²⁾ Though many methods have been developed for the syntheses of 3-substituted furan derivatives,³⁾ most of them lack the generality as a synthetic method of (3-furanyl) methyl derivative. Tannis has recently reported the construction of 3-substituted furan derivative by using 3-(lithiomethyl) furan or 3-(chloromagnesium methyl) furan, and demonstrated the generality of his method.⁴⁾     

DIELECTRIC PROPERTIES OF 1, 2-POLYBUTADIENES

The dielectric permittivity and loss tangent of 1,2-polybutadienes with different chain structures were determined as a function of temperature from-180℃ to 100℃ at different frequencies, and the frequency and structure dependence of the dielectric propertie of 1,2-polybutadienes have been investigated. It is found that a maximum of the permittivity occurs in the glass-transition region. The width of the glasstransition peak increases with increasing frequency while its height has little change. With a rise in the content of 1,2-units, the permittivity decreases and the height of the glass-transition peak slightly grows. A maximum of the width of the glass-transition peak appears when the content of 1,2-units is about 45%. Both the permittivity and dielectric loss drop down as the growth of the content of syndiotactic 1,2-units.     

CRYSTAL STRUCTURE OF 2, 4-DITHIONE-3-AMINO-1, 3, 2-OX-AZAPHOSPHORINEBENZO-2-THIONO PYRIDINIUM

<正> The structure of title compound [C7H6N2OPS3]-·[HNC5H5]+ was determined by x-ray diffraction. It belongs to monoclinic system with space group P21/a, a = 16.745(2), b= 8.563(2), c=21. 050(5)(?), β=93.32(1)°, V= 3013. 6(?)3, Z = 8, Mr = 341. 4, F (000) = 1536, Dc=1. 504 g. cm-3,μ= 53. 0 cm-1. The crystal is composed of discrete cations C5H5NH+ and anions CrH6N2OPS3-. There are two pairs of the cations and the anions in each asymmetric unit. The stability of the anion is increased by the formation of (d-p)π bonding involving the 3d orbital of the P atom and the lone electron pairs of the S atoms.     

CRYSTAL AND MOLECULAR STRUCTURE OF SUEFATOAQUO-2, 3-DIMETHYL-2, 3-BUTYLDIAMINEPLATINUM

[PtDMBA(SO4)H2O]H2O crystals belong to the orthorhombic system,a=11.073(3),b=9.672(2),c=21.156(7)A,space group C2cb,z=8.The diffraction data (Moka) were collected with Nicolet R3 four-circle di-ffractometer.The structure was determined by heavy atom method and refined by the least square program,R=0.0716.In the systematic study of anticancer action of a series of platinum compounds,our Coordination Chemistry Research Institute has synthesized PtDMBASO4 2H2O(where DMBA=2,3-dimethyl-2,3-butyldiamino) and found it has antitumor activity against L-1210 in mice.In order to study the relationship between the structure and the anticancer effects of the platinum compounds,the crystal structure of the compound has been determined.     

A FACILE SYNTHESIS OF 2-AND 2,4-UNSATURATED AMIDES

A convenient method for preparing unsaturated amides via telluro-nium salts employing solid potassium carbonate as a base with high stereo-selectivity in excellent yields has been developed.     

二水合二氯化-氯四水二(2,2''-联吡啶-N,N''-二氧化物)合钕(Ⅲ)的合成、表征与结构

在无水乙醇中合成出2,2′-联吡啶-N,N′-二氧化物与氯化钕形成的配合物单晶Nd(bipyO₂)₂Cl₃·6H₂O.通过元素分析、红外光谱、差热、热重分析等对该晶体进行了组成及性质鉴定.X射线结构分析表明、该配合物晶体属单斜晶系,空间群为C_2/C.晶胞参数a=17.456Å,b=7.491Å,c=21.078Å,α=γ=90°,β=100.66°,V=2708.9ų.Nd³⁺离子与两个bipyO₂,四个H₂O分子和一个Cl^-离子形成配位数为九的配阳离子,其中Nd-O(bipyO₂)平均键长为2.511A,Nd-O(H₂O)平均键长为2.500Å,Nd-Cl键长为2.899Å。     

二水合二氯化—氯四水二(2,2''''—联吡啶—N,N''''—二氧化物)合钕(Ⅲ)的合成、表征与结构

在无水乙醇中合成出2,2′-联吡啶-N,N′-二氧化物与氯化钕形成的配合物单晶Nd(bipyO_2)_2Cl_3·6H_2O.通过元素分析、红外光谱、差热、热重分析等对该晶体进行了组成及性质鉴定.X射线结构分析表明、该配合物晶体属单斜晶系,空间群为C_(2/C).晶胞参数a=17.456A,b=7.491A,c=21.078A,α=γ=90°,β=100.66°,V=2708.9A~3.Nd~(3+)离子与两个bipyO_2,四个H_2O分子和一个Cl~-离子形成配位数为九的配阳离子,其中Nd-O(bipyO_2)平均键长为2.511A,Nd-O(H_2O)平均键长为2.500A,Nd-Cl键长为2.899A。     

用苯乙烯和4-(甲基丙烯酸)2,2,6,6-四甲基哌啶醇酯共聚物共混改性聚丙烯纤维的研究

用苯乙烯和4-(甲基丙烯酸)-2,2,6,6-四甲基哌啶醇酯共聚物与聚丙烯共混,进行纺丝,得到了一种洁白的消光纤维,纺丝温度显著降低,纤维的抗大气老化性能好,并可用偶氮型分散染料染色,改进了聚丙烯纤维的一些缺点。     

4-丙烯酸-2,2,6,6-四甲基哌啶醇酯自由基共聚合的研究(Ⅰ)

本文从单体浓度、共聚单体配比、引发体系、温度等条件对带有易生成稳定自由基的4-甲基丙烯酸-2,2,6,6-四甲基哌啶醇酯与苯乙烯的自由基共聚合行为进行了探讨。发现在一般情况下符合自由基聚合规律。在不长的时间内可得到高产率(80％以上),较高分子量(～10~4)的白色粉末状共聚物。哌啶环上的亚胺基未表现出明显的阻聚作用。另外,用IR、NMR、VPO、元素分析等方法对共聚物的结构与性能进行了表征。此共聚物在多种普通有机溶剂中可溶,热稳定性能良好,毒性试验证明基本无毒。     

CHLOROSULFONATION OF N-PHENYLMORPHOLINE,BENZOTHIAZOLE, 2-METHYL BENZOTHIAZOLE AND TRIPHENYLOXAZOLE

Abstract

N-Phenylmorpholine (1) reacted with chlorosulfonic acid to give the p-sulfonyl chloride (2), which was characterized as the sulfonamides (3–5). Benzothiazole (6) was converted into the sulfonyl chloride (7) by sequential treatment with hot chlorosulfonic acid and thionyl chloride. Reaction of (7) with amines afforded the derivatives (8–10); NMR spectral analysis of the dimethylamide (8) indicated that it was a mixture of the 4- and 7-isomers. Chlorosulfonation of 2-methylbenzothiazole (11) was achieved by heating with chlorosulfonic acid with or without thionyl chloride. The chloride (12) was converted into amides (13–19). Study of the NMR spectra indicated that mixtures of the 5- and 6-isomers were formed. 2,4,5-Triphenyloxazole (20) reacted with chlorosulfonic acid to give either the mono-(21), bis (23) or bis-tris sulfonylchlorides (23, 34); these were converted into 14 sulfonamides. 2-(p-Nitrophenyl)-4,5-diphenyloxazole (41) reacted with hot chlorosulfonic acid to give the bis-sulfonyl chloride (42), characterized as the dimethylsulfonamide (43). Attempts to form the pure monosulfonyl chloride and to mono nitrate 2,4,5-triphenyloxazole (20) were unsuccessful.     

STUDIES ON 1,2,3-DIAZAPHOSPHOLE Ⅳ REACTION OF 1,2,3-DIAZAPHOSPHOLE WITH ALCOHOLS

Rapid addition of alcohols to 1,2,3-diazaphosphole 1 easily gave tricoordinatedphosphorus compounds,which were sulfurized to tetracoordinated phosphorus compounds.When ethylene glycol and aminoethanol were used separately to react with 1,the tricoordinatedphosphorus compounds which formed,rearranged to pentacoordinated phosphorus compoundsand the substituents at N_2 affected the rearrangement significantly.     

NiO-SiO2，NiO-Al2O3和NiO-Al2O3-SiO2催化剂上顺酐选择加氢性能的比较

以正硅酸乙酯和硝酸铝分别为硅源和铝源，硝酸镍为活性组分前驱物，采用溶胶-凝胶法制备了NiO-SiO2，NiO-Al2O3和NiO-Al2O3-SiO2催化剂。顺酐液相选择加氢活性和选择性评价结果表明：顺酐在三种催化剂上转化率都在99%以上，而产物的选择性有较大的差别，其中NiO-SiO2催化剂上γ-丁内酯的选择性达80.1%，NiO-Al2O3催化剂上丁二酸酐选择性达99%以上，NiOAl2O3SiO2催化剂上两种产物都有。XRD，TPR等体相结构和表面结构的表征说明，三种催化剂的相组成、NiO的分散性及与载体的相互作用存在明显差别，这些差别可能是造成不同选择加氢性能的原因。     

STRUCTURE AND PROPERTIES OF N,N-DI-n-BUTYLDITHIOCARBAMATO-1, 2-DICYANOETHENE-1, 2-DITHIOLATO-GOLD(III)

Abstract

The crystal and molecular structure and some spectral data of the compound N,N-di-n-butyldithiocarbamato-1, 2-dicyanoethene-1, 2-dithiolato-gold(III), AuS₂CN(C₄H₉)₂S₂C₂(CN)₂, are reported. The crystal structure has been determined from a three-dimensional single-crystal X-ray diffraction study. The orthorombic cell, space group Pbca, with a=14.066(3), b=28.980(2) and c=9.192(2) Å, contains eight formula units. Intensity data were collected on an automatic diffractometer. The structural parameters were refined by full-matrix least-squares methods to a conventional R-factor of 0.047 for 1587 independent non-zero reflections. The structure determination proved the compound to be a mixed dithiocarbamato-dithiolato complex, Au(dtc)(mnt), (dtc=N,N-di-n-butyl-dithiocarbamate, mnt=maleonitriledithiolate ≡ 1, 2-dicyanoethene-1, 2-dithiolate), as expected from spectral data. The gold atom is in approximately square-planar coordination, however, deviations from mm2 (C_2#) symmetry are considerable. Au-S bond distances in the dtc-moiety (2.329(5) Å and 2.324(5) Å) are significantly longer than those in the mnt-moiety (2.303(5) Å and 2.284(5) Å). The molecules are packed pairwise around inversion centres with relatively short intermolecular S-S distances.     

助剂对CH4,CO2和O2制合成气反应催化剂性能的影响

考察了NiCaO-Al2O3催化剂中添加碱金属、碱土金属、稀土金属氧化物、CuO助剂及CaO含量对催化剂性能的影响。结果表明,10Ni-2K-2Cu15CaO-Al2O3催化剂对CH4、CO2和O2制合成气反应具有较高的催化活性、选择性和较好的抗积炭性能。通过TPR、CO-TPD、XPS和XRD对催化剂进行表征,发现K2O、CuO和CaO的添加削弱了活性组分Ni与载体Al2O3间的相互作用,增加Ni的电子密度,加速了CO与H2的脱附,从而抑制了CH4深度裂解积炭和CO歧化积炭。此外,这些助剂的添加也提高了Ni的分散度,增强了催化剂的抗积炭能力。