新颖的大环冠醚基对碘苯胺包合物：设计合成、晶体结构及介电性质

合成了新颖的有机-无机杂化超分子化合物,[(4-IA-NH3).(18-crown-6)]2.(Cu2Cl6)(1),4-IA-NH3=对碘苯胺离子,18-crown-6=18-冠-6。并通过红外光谱、粉末衍射、热重分析和单晶结构分析对化合物进行了充分表征。在转子定子型的超分子化合物1中,[(4-IA-NH3).(18-crown-6)]-超分子阳离子和(Cu2Cl6)2-阴离子交错堆积形成包合物结构。变温介电常数测量表明,在130~450 K范围内没有相变引起的介电异样。大环醚的热无序运动及由此引起的氢键偶极瞬间变化使得化合物在低频500 Hz和高温350 K以上具有较高的介电常数并伴随高的介电损耗。     

Anderson-B-型多金属氧酸盐[Co(2,2''-bipy)3]H-[Al(OH)6(Mo6O18)]·5H2O的合成及晶体结构

以AlCl3·6H2O、Na2MoO4·2H2O、CoCl2·6H2O和2,2'-联吡啶为主要原料合成了Anderson-B-型多金属氧酸盐[Co(2,2'-bipy)3]H[Al(OH)6(Mo6O18)]·5H2O,进行了红外光谱、紫外光谱、差热分析和单晶结构测定.晶体学测定结果表明,化合物属于三斜晶系,Pi空间群,晶胞参数:a=1.216 0(2),b=1.221 5(2),c=1.780 0(4)nm,α=86.83(3)°,β=88.76(3)°,γ=89.82(3)°,V=2.639 4(9)nm3,Z=2,R1=0.079 4,wR2=0.176 6.化合物结构分析表明,在晶体学上,标题化合物分子是由1个[Co(2,2'-bipy)3]2+配阳离子,1个H+离子,2个1/2[Al(OH)6(Mo6O18)]3-多阴离子和5个结晶水分子组成.多阴离子[Al(OH)6(Mo6-O18)]3-借助水分子和金属配离子通过超分子作用形成二维网状结构,网状结构之间又借助超分子作用形成三维无限伸展结构.差热分析表明,标题化合物的失重过程分为2步,多阴离子骨架破坏温度为547.5℃.     

Anderson-B-型多金属氧酸盐[Co(2,2-′bipy)_3]H-[Al(OH)_6(Mo_6O_(18))]·5H_2O的合成及晶体结构

以A lC l3.6H2O、Na2MoO4.2H2O、CoC l2.6H2O和2,2′-联吡啶为主要原料合成了Anderson-B-型多金属氧酸盐[Co(2,2-′b ipy)3]H[A l(OH)6(Mo6O18)].5H2O,进行了红外光谱、紫外光谱、差热分析和单晶结构测定。晶体学测定结果表明,化合物属于三斜晶系,Pī空间群,晶胞参数:a=1.216 0(2),b=1.221 5(2),c=1.780 0(4)nm,α=86.83(3)°,β=88.76(3)°,γ=89.82(3)°,V=2.639 4(9)nm3,Z=2,R1=0.079 4,wR2=0.176 6。化合物结构分析表明,在晶体学上,标题化合物分子是由1个[Co(2,2-′b ipy)3]2 配阳离子,1个H 离子,2个1/2[A l(OH)6(Mo6O18)]3-多阴离子和5个结晶水分子组成。多阴离子[A l(OH)6(Mo6-O18)]3-借助水分子和金属配离子通过超分子作用形成二维网状结构,网状结构之间又借助超分子作用形成三维无限伸展结构。差热分析表明,标题化合物的失重过程分为2步,多阴离子骨架破坏温度为547.5℃。     

三维超分子化合物[Mn(phen)3 ]2(H3O)O40 ]·2H2 O的水热合成与结构表征

利用水热合成方法制备了Keggin结构多金属氧酸盐[Mn(phen)3]2(H3O)·2H2O,用元素分析、红外光谱、热分析和X射线单晶衍射测试技术对其结构进行了表征. 结果表明,该化合物属于单斜晶系,C2/c空间群,a=2.728 5(3) nm,b=2.506 0(3) nm,c=1.633 6(18) nm,β=104.911(2)°,V=10.79 4(2) nm3,Z=4,R1=0.078 4,wR2=0.199 9. 化合物分子结构单元由1个Keggin结构多金属氧酸盐阴离子5-,2个配位阳离子[Mn(phen)3]2+,1个质子和2个结晶水分子构成. 化合物分子之间通过π-π堆积作用形成了三维超分子结构.     

新颖的大环冠醚基对碘苯胺包合物:设计合成、晶体结构及介电性质

合成了新颖的有机-无机杂化超分子化合物, [(4-IA-NH₃)·(18-crown-6)]₂·(Cu₂Cl₆) (1), 4-IA-NH₃=对碘苯胺离子, 18-crown-6=18-冠-6。并通过红外光谱、粉末衍射、热重分析和单晶结构分析对化合物进行了充分表征。在转子定子型的超分子化合物1中, [(4-IA-NH₃)·(18-crown-6)] -超分子阳离子和(Cu₂Cl₆)^2-阴离子交错堆积形成包合物结构。变温介电常数测量表明, 在130~450 K范围内没有相变引起的介电异样。大环醚的热无序运动及由此引起的氢键偶极瞬间变化使得化合物在低频500 Hz和高温350 K以上具有较高的介电常数并伴随高的介电损耗。     

铬酸根作为抗衡离子的钕18-冠-6配合物的合成与晶体结构

Nd2O3,Cr O3,18-冠-6在稀HCl,稀HBr,蒸馏水3种不同条件下混合反应,分别合成得到了3个不同的新型配合物[Nd(H_2O)9](18-crown-6)3(Cr O3Cl)3·0.5H_2O(1),[Nd(H_2O)9](18-crown-6)3(Cr O3Br)3·0.5H_2O(2),[Nd(18-crown-6)(Cr_2O_7)(H_2O)]2(Cr_2O_7)·H_2O(3)。单晶结构分析表明配合物1和2属于异质同晶,结晶于R-3空间群,而配合物3结晶于P-1空间群。配合物1和2中Nd3+与9个配位水形成单核[Nd(H_2O)9]3+阳离子,该阳离子通过氢键作用被3个对称性相关的18-冠-6分子包裹起来,形成一个具有三次轴对称性的{[Nd(H_2O)9](18-crown-6)3}3+超分子笼。配合物3中Nd3+也是九配位的,它被1个18-冠-6分子的6个氧原子所螯合,并进一步与2个(Cr_2O_7)2-阴离子中的2个O原子和1个水分子配位,相邻的Nd3+通过桥联的(Cr_2O_7)2-阴离子的配位作用形成一维链状结构。     

基于大环醚和三价卤化铋阴离子的超分子杂化化合物：合成、结构及性质

基于大环自组装和多卤阴离子合成了有机-无机杂化超分子化合物,[（1,4-PMNH₃）·（18-crown-6）]·[（H₃O）·（18-crown-6）]₂·[（H₂O）·（18-crown-6）]·（18-crown-6）·（Bi₂Cl₉）（1）。化合物属正交晶系,Pca2₁空间群,a=2.4830（3）nm,b=1.1618（3）nm,c=3.3161（2）nm,V=9.566（2）nm³。并通过其红外光谱、粉末衍射、热重分析和单晶结构分析对化合物进行了充分表征。在转子定子型的超分子化合物1中,大环超分子阳离子和（Bi₂Cl₉）^3-阴离子交错堆积形成包合物结构。并在室温下对其固体荧光性质进行测试表征。通过DSC对其热稳定性进行了详细分析。     

两种钴离子支撑钼磷多金属氧酸盐的水热合成及晶体结构

利用水热技术合成了2个新型钴支撑的磷钼多金属氧酸盐超分子化合物:(C2N2H10)5[(P4Mo6O25(OH)6)2Co](1)和(Co(H2O)6)2(C5NH6)6[(P4Mo6O25(OH)6)2Co]·10H2O(2).并通过元素分析、红外光谱、热重分析和X射线单晶衍射对2个化合物进行了表征.结果表明:化合物1属于三斜晶系,P-1空间群;晶胞参数a=1.179 9(2)nm,b=1.337 7(2)nm,c=1.479 7(3)nm,α=73.435(2)°,β=74.383(2)°,γ=66.499(2)°,V=2.020 5(6)nm3,F(000)=1 327,Z=1;化合物2属于属于三斜晶系,P-1空间群;晶胞参数a=1.220 68(11)nm,b=1.381 08(13)nm,c=1.687 18(15)nm,α=92.275(1)°,β=104.774(1)°,γ=114.475(1)°,V=2.468 8(4)nm3,F(000)=1 649,Z=1.     

一种镍取代型有机-无机杂化三维超分子多酸:合成、结构与表征（英文）

在水热条件下,成功合成了一例新的过渡金属镍修饰的有机-无机杂化型三维超分子多酸化合物[Ni(en)2(H2O)2][Ni(en)3]2[Ni(en)2(H2O)]2[Ni4(α-PW9O34)2(H2O)2]·14H2O(1)(en=乙二胺),并通过元素分析、红外光谱、热分析和X射线单晶及粉末衍射对化合物进行了表征和研究.从超分子化学的角度来看,化合物1中的夹心型簇阴离子之间通过广泛的氢键作用,进而形成三维超分子网络结构.     

Na2[(VO)12O6B18O39(OH)3]·(11H3O)·4H2O的水热合成和晶体结构

以V2O5, Na2B4O7·0H2O, NaH2PO4·2H2O, 乙二胺和H2O为原料, 按物质的量比0.5∶1∶1∶2.24∶111在180 ℃条件下晶化, 得到棕色晶体Na2[(VO)12O6B18O39(OH)3]·(11H3O)*4H2O. 单晶结构分析结果表明该化合物属单斜晶系, P21/n空间群, 晶胞参数 a=1.389 70(8) nm, b=1.661 59(9) nm, c=1.427 48(8) nm, β=95.691 0(10)°. Z=4, R=0.054 9. 该化合物的结构主要由阴离子簇[(VO)12O6B18O39(OH)3]13-构成. 该阴离子簇由B18O39(OH)3十八元环夹在两个以共边方式交替相连形成的V6O15簇中间, 通过共用氧原子形成三明治式结构新颖的硼-钒-氧阴离子簇, 结构中Na+以离子键方式将阴离子簇相互连接, 形成二维层状结构. 层与层之间通过分子间氢键相互作用. 价态计算结果表明, 结构中n(VⅣ)∶n(VⅤ)=5∶1.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.