(4-苯硫基-苯基)二苯基硫鎓六氟磷酸盐的合成研究

以P₂O₅为脱水剂,甲烷磺酸为溶剂,二苯亚砜与二苯硫醚反应制备了(4-苯硫基-苯基)二苯基硫六氟磷酸盐.对产物进行了元素分析、紫外光谱、红外光谱、气-质联用和核磁共振的结构确证.该硫盐对环氧树脂具有良好的固化性能.     

二苯基碘鎓盐引发乙烯基醚热聚合研究

合成了一种液态聚氨酯乙烯基醚预聚物 (PUE)并对其进行了表征 .研究发现二苯基碘六氟磷酸盐(PI810 )能够引发PUE和三缩乙二醇二乙烯基醚 (DVE 3)进行阳离子热聚合 ,热聚合温度远低于PI810的纯态热分解温度 ,且聚合转化率较高 .热聚合的机理初步认为是电子转移机理 .研究了乙烯基醚化合物、环氧树脂、二苯基碘六氟磷酸盐混合体系的热聚合 .     

香豆素类Schiff碱的合成

以乙酸和哌啶为催化剂,在正丁醇中通过4-(N,N-二乙氨基)水杨醛与硝基乙酸乙酯的缩合反应合成了3-硝基-7-(N,N-二乙基)香豆素(2);2经SnCl2/HCl还原制得3-氨基-7-(N,N-二乙基)香豆素(3);3与芳香醛反应合成了六个新的香豆素类Schiff碱,其结构经UV,1H NMR和MS表征.     

固相研磨合成4,4′-联吡啶季铵盐

采用室温固相研磨的方法,4,4′-联吡啶与连有阻塞基的乙氧乙醇磺酸酯(或苄溴)反应,得到单取代的4,4′-联吡啶六氟磷酸盐(2),2再与α,α′-二(溴甲基)-2,2′-联吡啶反应,得到哑铃型化合物——2,2′-联吡啶桥连的双-4,4′-联吡啶六氟磷酸盐(3),收率约90%。2和3的结构经1HNMR,13CNMR和MS表征。     

(S)-5,5'-二氨基-2,2'-双二苯基膦基-1,1'-联萘的绿色合成

以2,2'-双二苯基磷基-1,1'-联萘[(S)-1]为原料,与H2O2经氧化反应制得(S)-2,2'-双二苯基磷氧基-1,1'-联萘[(S)-2];(S)-2经酸性树脂催化硝化制得(S)-5,5'-二硝基-2,2'-双二苯基磷氧基-1,1'-联萘[(S)-3)];(S)-3经Pd/C催化硝基氢化还原制得(S)-5,5'-二氨基-2,2'-双二苯基磷氧基-1,1'-联萘[(S)-4];(S)-4经HSi Cl3/PPh3还原制得(S)-5,5'-二氨基-2,2'-双二苯基膦基-1,1'-联萘,总产率65.6%,其结构经1H NMR,31P NMR和IR确证。     

O-(1-芳硫基-3-铵基)异丙基-O-2-(N3-替加氟)乙基硫代磷酯的合成及其抗癌活性

六乙基亚磷酰三胺与羟乙基替加氟、1-芳硫基甘油及硫一锅反应得到环甘油硫代磷脂替加氟缀合物(2),三乙胺对2进行亲核开环合成了O-(1-芳硫基-3-铵基)异丙基-O-2-(N3-替加氟)乙基硫代磷酯(3)。2和3的结构经1HNMR,31PNMR和元素分析表征。生物活性测试结果表明,3对膀胱癌细胞PGA1有一定的抑制作用。     

固相研磨合成4,4''''-联吡啶季铵盐

采用室温固相研磨的方法,4,4'-联吡啶与连有阻塞基的乙氧乙醇磺酸酯(或苄溴)反应,得到单取代的4,4'-联吡啶六氟磷酸盐(2),2再与α,α'-二(溴甲基)-2,2'-联吡啶反应,得到哑铃型化合物--2,2'-联吡啶桥连的双-4,4'-联吡啶六氟磷酸盐(3),收率约90%.2和3的结构经1H NMR, 13C NMR和MS表征.     

基于四苯乙烯的四齿唑盐:合成和对离子的选择性识别（英文）

合成和表征了两种新型的基于四苯基乙烯的四齿唑盐:1,1,2,2-四[(2'-(N-甲基咪唑-1-基)乙氧基苯基)]乙烯六氟磷酸盐(1)和1,1,2,2-四[(2'-(N-吡啶甲基苯并咪唑-1-基)乙氧基苯基)]乙烯六氟磷酸盐(2)通过荧光光谱, UV/vis光谱, HRMS,1H NMR和红外光谱研究了1对阴离子和2对阳离子的识别性能.结果表明:通过荧光方法, 1能够将H 2P O4-与其他阴离子区分开, 2能够将Ag+与其他阳离子区分开.     

(3-叠氮基-2, 2-二硝基)丙基取代硝胺的合成

本文报道了由(2, 2-二硝基-3-羟基)丙基取代硝胺经相应三氟甲基磺酸酯合成(3-叠氮基-2, 2-二硝基)丙基取代硝胺的合成方法。     

O-(1,3-二芳硒基)异丙基-O-2-(N3-替加氟)乙基硫代磷酯的合成及其抗癌活性

六乙基亚磷酰三胺依次与羟乙基替加氟、1-芳硒基甘油及硫反应,得到环甘油硫代磷脂替加氟缀合物(2a～2e);通过苯硒化钾对2进行亲核开环,得到O-(1,3-二芳硒基)异丙基-O-2-(N-替加氟)乙基硫代磷酯(3a～3e),其结构经1H NMR,31P NMR,MS及元素分析确证.3对膀胱癌细胞PGA1有一定的抑制作用.     

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%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

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.     

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.