四溴代对苯二甲酸根桥联的双核钴（II）配合物的合成和表征

本文报道了四种新的双核钴（Ⅱ）配合物，即［Ｃｏ２（４Ｂｒ－ＴＰＨＡ）（Ｌ）４］（ＣｌＯ４）（４Ｂｋ－ＴＰＨＡ＝四溴代对苯二甲酸根阴离子，Ｌ＝１，１０－菲咯啉（ｐｈｅｎ）（１），５－硝基－１，１０－菲咯啉（ＮＯ２－ｐｈｅｎ）（２），２，２＇－联吡啶（ｂｐｙ）（３）和４，４＇－二甲基－２，２＇－联吡啶（Ｍｅ２ｂｐｙ）（４））的合成的表征，基于ＩＲ光谱、元素分析、电导测量等方法推定配合物具有四溴代对苯二     

(R)-1，1′-联萘手性单元通过溶胶凝胶法合成杂化硅干凝胶(英)

Precursor molecule (R)-6,6′-bis(triethoxysilylethen-2-yl)-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (R-2) was synthesized by Pd-catalyzed Heck reaction of (R)-6,6′-dibromo-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (R-1) intermediate with vinyltriethoxysilane. The hydrolysis and polycondensation of the precursor R-2 produced the corresponding xerogel. Both precursor and xerogel were analysed by NMR, FTIR, UV, CD spectra, fluorescent spectroscopy, polarimetry and elemental analysis. The precursor and xerogel can emit strong blue fluorescence and are expected to have a potential application in the separation of chiral molecules as fluorescent sensor. The precursor exhibits strong Cotton effect in its circular dichroism (CD) spectrum indicating a highly rigid structure.     

2,2'-二乙炔基-1,1'-联萘为模板构筑的新的环芳化合物的合成及其光学性质

基于2,2'-二取代的联萘衍生物在手性构型上高度稳定的特点,分别以光学活性的(R)-和(S)-2,2'-二乙炔基-1,1'-联萘为模板,设计了2个有趣的拓扑环芳分子四联萘笼状对映异构体(R,R,R,R)-2和(S,S,S,S)-2.其合成路线涉及保护基的控制导入、苯连接桥的链接、保护基的脱去以及偶合成环反应4个步骤.用MS,IR,UV-Vis,1HNMR,13CNMR和元素分析等技术对其进行了表征,并比较了其光学性质.研究结果表明,采用这种模板合成方法能够有效地获得具有单一手性的目标化合物.镜像特征的圆二色(CD)谱和比旋光度[α]D的测定结果清楚地反映了它们的对映异构关系.     

混合价四核锰配合物[Mn4O2(ClCH2COO)7(bipy)2]•H2O的合成、晶体结构及性质研究

在乙腈溶液中, 由混合价三核锰配合物[Mn₃O(ClCH₂COO)₆(py)₂]•(H₂O) (py为吡啶)与2,2′-联吡啶(bipy)反应合成了混合价(Mn₃^IIIMn^II)四核锰配合物[Mn₄O₂(ClCH₂COO)₇(bipy)₂]•H₂O. 采用元素分析、红外光谱、热分析和X射线单晶衍射法确定了其组成和结构. 标题化合物晶体属于三斜晶系, 空间群P-1, 晶胞参数: a＝0.89854(13) nm, b＝1.4027(2) nm, c＝1.9037(3) nm, α＝93.518(3)°, β＝96.736(3)°, γ＝94.875(3)°, V＝2.3680(6) nm³, Z＝2, D_c＝1.734 g/cm³, F(000)＝1238, GOF＝1.036, R₁＝0.0592, wR₂＝0.1162 [I＞2σ(I)]. 在标题化合物中, 配位结构单元中心为一蝶型[Mn₄(μ₃-O)₂]^7＋多核簇, 含有2个Mn₃(μ₃-O)单元, 具有近似C₂对称轴. 4个Mn离子均为六配位, 外围配体为7个氯乙酸根和2个2,2′-联吡啶, 处于变形的八面体环境. 变温磁化率研究表明标题化合物在整体上表现为反铁磁性耦合作用, 但在低温下的磁相互作用较为复杂.     

The Synthesis of Bis（carboxyalkylmethyl） Diselenides by Selenium Transfer Reaction of Aryl Selenoamides

Aryl selenoamides react smoothly with a-haloacetic acid in various alcohol to givecorresponding bis(carboxyalkylmethyl) diselenides in good yields.     

联萘衍生物的磺化反应研究

研究了1-和2-苯基萘, 1, 1'-和2, 2'-联萘, 2, 2-二羟基-, 2, 2'-二甲氧基和-2, 2'-甲基磺酰氧基-1, 1'-联萘等七种萘衍生物和三氧化硫的磺化反应。1-苯基萘和1, 1'-联萘的磺化先发生在4位上, 第二取代位置为6和7位。2-苯基萘和2, 2'-联萘均首先得到8位磺酸取代物, 进一步磺化得到8, 4'-和8, 8'-二磺酸取代物。2, 2'-二甲氧基-1, 1'-联萘以13:87的比例得到3位和6位磺酸取代物。2, 2'-二甲磺酰氧基-1, 1'-联萘以58:42的比例得到5位和6位磺酸取代物。2, 2'-二羟基-1, 1'-联萘的等摩尔磺化得到比例为35:65的5位和6位磺酸取代物, 和大于6摩尔的SO~3反应则以62:38的比例得到5位和6位磺酸取代物。     

A,C-Bridged Calix[6]arene： Relationship between the Length of Bridge and Conformation

Three new A,C-diamide bridged p-tert-butylcalix[6]arenes were synthesized from p-tert-butylcalix[6]arenes by bridging ClCH2CONH(CH2)nNHCOCH2Cl(n=3,4,6) in acetonitrile using K2CO3 as a base in 17%-25% yields.It was found that the bridged calix[6]arenes with shorter bridges (n=2,3,4 in N′,N′-bischloroacetodiamines) adopt cone conformation, but the last one (n=6) adopts alternate conformation, i.e., accompanying the lengthening of bridge, the conformation of A,C-bridged calix[6]arenes changes from cone to alternate.     

Baylis-Hillman Reactions of Sulfonyl Aldimines or Aryl Aldehydes with 3-Methylpenta-3,4-dien-2-one or 3-Benzylpenta-3,4-dien-2-one

The attempted Baylis-Hillman reactions of sulfonyl aldimines or aryl aldehydes with 3-methylpenta-3,4-dien-2-one or 3-benzylpenta-3,4-dien-2-one gave the corresponding Baylis-Hillman adducts in moderate yields in DMSO under the catalysis of DBU or PMe3, respectively. Moderate diastereoselectivities were observed in the reaction of 3-benzylpenta-3,4-dien-2-one with N-arylmethylidene-1-naphthalenesulfonamides catalyzed by chiral catalyst cinchona alkaloid derivative TQO {4-（3-ethyl-4-oxa-1-azatricyclo[4.4.0.0^3,8]dec-5-yl）quinolin-6-ol}.     

A High－efficiency Preparation, Properties and Structure of （R, S ）－and （ S, S）－Pyrrolidine－2－carboxylic Acid 3,5－Dioxa－4－boracvclo.hepta [ 2,1－α; 3,4－α′] dinaphthalen－4－yl Esters

A highly-efficient preparative procedure for ( R, S )- and ( S, S)-pyrroHdine-2-carboxyHc acid 3,5-dioxa-4-boracyclohepta[2, 1-α ; 3,4-α′] dlnaphthalen-4-yl esters [ namely ( R, S )-BNBAP and (S, S )-BNBAP] is described and the crystal structure of (R, S )-BNBAP was obtained. The data indicate that ( R, S )-BNBAP is a spirocyclic inner borate salt with almost normal te-trahedral configuration. This structural form may be the basic reason for their high chemical, optical and thermodynamic sta-bility.     

CO2监测分析仪在监测过程中对桥室温度的恒温控制

CO2监测分析仪在监测过程中,CO2监测值的精度是由CO2监测分析仪的桥室参比温度是否恒定而决定的.老式监测分析仪桥室温度是采用断续的双位恒温调节,其温度调节误差大,一般只能在±1℃左右,所以CO2监测值的精度低.采用微机交流调压的CO2监测分析仪桥室恒温调节,其温度调节器采用PID调节,使桥室温度误差可控制在±0.2℃,提高了CO2监测值的监测精度.