The crystal structures of α, ω-diaminoalkanecadmium(II) tetracyanonickelate(II)-Aromatic molecule inclusion compounds. V. Toluidine clathrates of the hosts built of the diamines, 1,4-diaminobutane, 1.5-diaminonentane,and 1,8-diaminooctane

The crystal structures have been analyzed for the threeo-toluidine clathrates,catena-[catena--(1,4-diaminobutane)cadmium(II) tetra--cyanonickelate(II)]-o-toluidine(2/3),4-o,catena-[catena--(1,5-diaminopentane)cadmium(II) tetra--cyanonickelate(II)]-o-toluidine(3/4),5-o, andcatena-[catena--(1,8-diaminooctane)cadium(II) tetra--cyanonickelate(II)]-o-toluidine(1/1),8-o, for am-toluidine onecatena-[catena--(1,5-diaminopentane)cadmium(II) tetra--cyano-nickelate(II)]-m-toluidine(1/1),5-m, and for ap-toluidine onecatena-[catena--(1,8-diaminooctane)cadium(II) tetra--cyanonickelate(II)]-p-toluidine(1/1),8-p. 4-o crystallizes in the triclinic space groupP,a/Å = 9.806(3),b/Å = 14.388(3),c/Å = 7.725(2), /° = 89.71(2), /° = 89.96(2), /° = 98.12(2),V/ų = 1078.8(5),Z = 2, 3750 reflections,R = 0.056;5-o: tetragonalP4lmmm, (a = b)/Å = 7.485(7),c/Å = 10.06(3),V/ų = 563(2),Z = 1, 573 reflections,R = 0.19;8-o: monoclinicP2/m,a/Å = 11.513(4),b/Å = 7.626(1),c/Å = 7.101(1), /° = 109.63(3),V/ų = 587.2(2),Z = 1, 1682 reflections,R = 0.058;5-m: orthorhombicPbam,a/Å = 12.254(6),b/Å = 20.62(1),c/Å = 7.804(1),V/ų = 1972(1),Z = 4, 2240 reflections,R = 0.059; and8-p: triclinic,P,a/Å = 11.52(1),b/Å = 7.632(3),c/Å = 7.039(4), /° = 88.93(4), /° = 109.71(5), /° = 82.81(9),V/ų = 576.9(6),Z = 1, 2598 reflections,R = 0.042. Their structures are substantially similar to the already-known structure ofcatena-[catena--(1,6-diaminohexane)cadmium(II) tetra--cyanonickelate(II)]-o-toluidine(1/1): the guest toluidine molecules are accommodated in the cavities formed betweencatena-[cadmium(II) tetra--cyanonickelate(II)] layers bridged by the ambidentate ,-diaminoalkane ligands at the cadmium(II) atoms. The carbon chain length of the ,-diaminoalkane influences the number of cavities per formula unit and the deformation of the metal complex layers.     

A Study on the Reaction of 1-（3-Pyridyl）-2,2-di-substituted Ethylenes with 1-Benzyl-1,4-dihydronicotinamide

The reaction of a series of 1-（3-pyridyl）-2,2-di-substituted ethylenes with 1-benzyl-1,4-dihydronicotinamide （BNAH） in deaerated acetonitrile produces the corresponding 1-（3-pyridyl）-2,2-di-substituted ethanes in contrast to benzylidenemalononitrile （BM） which does not react with BNAH under the same conditions.     

Reactions of cyclic enehydrazino ketones with arylidenemalononitriles. Synthesis of 11-aryl-1-oxo-2,3,4,5,10b,11-hexahydro-1H-indolo[2,3-b]quinoline-10b-carbonitriles

A general and convenient method for the synthesis of 11-aryl-1-oxo-2,3,4,5,10b,11-hexahydro-1H-indolo[2,3-b]quinoline-10b-carbonitriles was elaborated. The method is based on the novel stereoselective rearrangement of fused N-arylamino-substituted 1,4-dihydropyridines. The structures of the synthesized compounds were studied using ¹H NMR spectroscopy and X-ray diffraction analysis.     

多氮杂大环配体La~(3+)、Gd~(+3)络合物的合成

在NaOH存在下，N，N′，N″，N-四乙酸-1，4，7，10-四氮杂环十二烷、N，N′，N″，N-四乙酸-1，4，8，11-四氮杂环十四烷、N，N′，N″，N-四甲磷酸-1，4，7，10-四氮杂环十二烷和N，N′，N″，N-四甲磷酸-1，4，8，11-四氮杂环十四烷分别与LaCl3·7H2O或GdCl3·6H2O通过大环配体络合物直接合成法，得到八个络合物，产率为46．7％～90．7％。     

A new and efficient method for conjugate addition of trialkylphosphites to 3-acylsubstituted coumarins

A new and efficient conjugate addition of trialkylphosphites to 3-ω-bromoacetylcoumarin 1 catalysed by p-toluenesulfonic acid (TsOH) has been studied. Under the same conditions, an enolphosphate gave the corresponding esters of 3-acetyl-4-phosphono-2-oxochromans in high yields. The use of TsOH in the reaction of 3-acetyl-, 3-benzoyl-, and 3-ethoxycarbonyl coumarins led mainly to 1,4-addition products—the corresponding 3-acyl-4-dialkylphosphono-2-oxochromans—in very good yields.     

2个新颖的(3,4,6)和(3,6)连接的多核金属有机骨架化合物的合成、结构与性质

在水热和溶剂热条件下合成了2个新颖的金属有机骨架化合物{[Cu_3(BCPBA)_2(bpmp)(H_2O)]·2DMF}n(1)和{Zn3(BCPBA)_2(bip)(H_2O)_2}n(2)[H3BCPBA=3,5-双(4-羧基-苯氧基)苯甲酸;bpmp=1,4-二(吡啶-4-亚甲基)哌嗪;bip=1,3-二(咪唑基)丙烷].通过单晶及粉末X射线衍射、红外光谱、元素分析和热重分析对这2个化合物进行了表征.结果表明,化合物1属于单斜晶系,C2/m空间群,是由羧酸连接3个二级结构单元[Cu_2(CO_2)4]形成的具有自穿插结构的三维骨架结构,其骨架拓扑符号为(4·8~2)(8~6)(4~2·6~8·8~3·9·10);化合物2属于三斜晶系,P1空间群,其骨架是由1个新颖的二级结构单元组成的拓扑结构为(4~2·6)_2(4~4·6~2·8~8·10)的三维超分子网络.     

13X分子筛负载Fe催化剂上1,4-二氧六环在空气中完全氧化(英文)

采用浸渍法制备了不同Fe含量的13X分子筛负载的Fe催化剂(Fe/X13),运用N_2吸附-脱附法测得其BET比表面积和BJH孔径分布,采用X射线衍射、扫描电镜、程序升温还原和NH_3程序升温脱附法表征了该催化剂的织构性质.在固定床流动反应器中,以空气为氧化剂、在100-400℃范围内考察了Fe/X13催化剂上1,4-二氧六环的完全氧化反应性能,研究了反应温度、金属担载量和气体空速(GHSV)等条件对催化氧化降解二氧六环反应性能的影响,并在400℃测定了该催化剂反应50h的稳定性,结果表明,6 wt%Fe/13X催化剂表现出最高的催化性能,在400℃,GHSV=24000 h~(-1)的条件下,二氧六环转化率为97%,生成CO和CO_2的选择性达95%,降解产物还包括少量的乙醛、乙二醇-甲酸酯、乙二醇二甲酸、1,4-二氧六环-2醇、1,4-二氧六环-2酮及2-甲氧基1,3二氧戊环.基于这些经色谱-质谱联用仪检测出的产物,提出了可能的1,4-二氧六环降解机理。     

胶液法制备高顺式端羟基聚丁二烯液体橡胶

以工业顺丁胶原液为起始原料,先经氧化裂解反应制得醛基封端的聚丁二烯液体橡胶,再经还原反应制得了端羟基聚丁二烯液体橡胶.结果表明,反应过程中顺丁胶的微观结构未发生异构化,所得的端羟基聚丁二烯液体橡胶的顺式含量高(cis-1,495%);分子量通过控制氧化裂解反应物与丁二烯结构单元的化学计量比,在2200~7000间可调(~1H-NMR法);分子量分布指数维持在1.5~2.1范围;官能度(fn)在2.0左右.与阴离子聚合型丁羟胶和自由基聚合型丁羟胶相比,氧化裂解法制备的丁羟胶微观结构更规整,顺式含量更高,能够保持极低的玻璃化转变温度.此外,以工业顺丁胶原液为原料,既省去了顺丁块胶生产的水析凝聚、干燥压块等过程,又免去了胶块剪切破碎、溶胀溶解等过程,大幅度减少了能量消耗,且反应条件温和、可控、高效、经济,具有良好的工业化前景.     

Facile Synthesis of Naphtho[2,3‐d]thiazoles,Naphtho[2,3‐e][1,3,4]thiadiazines and Bis(naphtho[2,3‐d]thiazolyl)copper(II) Derivatives from Heteroylthiosemicarbazides

A one step synthesis protocol for the conversion of heteroylthiosemicarbazides and 2,3‐dichloro‐1,4‐naphthoquinone to naphtho[2,3‐d]thiazoles, naphtho[2,3‐e][1,3,4]thiadiazines as well as bis(naphtho[2,3‐d]thiazolyl)copper(II) derivatives is described. The products were conclusively confirmed by single crystal X‐ray analyses. A mechanism for the formation of the products is presented.     

Ring-opening polymerization of 1,4-oxathian-2-one and its copolymerization with δ-valerolactone

Monomer 1,4-oxathian-2-one ( OX ) was synthesized by a one pot two-step method, and it was oxidized to the sulfone ester monomer, 1,4-oxathian-2-one-4,4-dioxide ( OX-SO ₂ ). Three organic catalysts, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and diphenyl phosphate (DPP) were screened for the ring-opening polymerization (ROP) of OX in dichloromethane at 30°C. It was found that OX has a high polymerizability, the TBD-catalyzed ROP is very fast but with serious side reactions, the DBU-catalyzed ROP is moderately controlled, and the DPP-catalyzed ROP is well controlled until the polymerization reach equilibrium. Bulk ROP of OX-SO ₂ was achieved with stannous octoate ((Sn[Oct]₂) at 130°C. Poly(OX) is a semicrystalline polyester (T_m = 40-60°C, T_g = −39.6°C), while Poly(OX-SO ₂ ) is a highly crystalline polyester(T_g = 55°C, T_m = 211°C with decomposition). Kinetics experiments of OX and δ-valerolactone (VL) revealed that VL polymerized faster than OX with DPP as the catalyst. Thermodynamic parameters of the ROP of OX and VL under identical conditions were measured; the ROP of OX is thermodynamically more favorable than that of VL. A series of random copolymers of OX and VL was prepared using TBD as the catalyst and confirmed that the in-chain heteroatom greatly affected the crystallization of the copolymers.