对二羟基二苯基硫醚的合成

本文研究了对二羟基二苯基硫醚的合成，通过比较选择不同的溶剂、反应温度、反应物的物质的量比及滴加时间，得出以苯酚和二氯化硫为反应物合成对二羟基二苯基硫醚在苯溶剂中，反应温度15℃，反应物的物质的量的比2．2：1，滴加时间1．5h为最佳反应条件，产率为74％。     

新型双四氮唑硫醚类化合物的合成与结构表征

异硫氰酸苯酯与叠氮化钠反应得到1-苯基-5-巯基-1,2,3,4-四氮唑,该化合物分别与1,2-二溴丙烷、1,3-二氯丙酮、1,4-二(溴甲基)苯和1,3-二(溴甲基)苯反应合成了相应的双四氮唑硫醚类化合物3 a~3d,其结构经元素分析、MS和1H NMR确认,并对其质谱裂解途径进行了探讨。     

Synthesis of high refractive index polyamides containing thioether unit

Two kinds of aromatic dibenzoyl chloride monomer containing thioether unit 4,4′-Bis(4-chloroformylphenylthio)benzophenone (BP-DC) and 4,4′-thiodibenzoyl chloride (T-DC) were synthesized with two steps, which was reacted with diamine monomer containing thioether and amide unit to prepare a new kind of polyamide containing high quantity thio-ether group. The intrinsic viscosity of the polyamides was 0.76–0.90 dl/g obtained with optimum synthesis conditions. The polymers were found to have good optical properties: the optical transmittance of the aromatic polyamide film at 450 nm is higher than 80%, meantime the high quantity thio-ether unit provided the polymer with a high refractive index ranging from 1.691 to 1.696 and low birefringence of 0.007–0.008. At the same time the polymers had excellent thermal performance with glass transition temperature (T_g) of 226 °C–278 °C, initial degradation temperature (T_d) of 427 °C–439 °C. They showed improved solubility in polar aprotic solvents.     

白藜芦醇类似物的合成研究

以对硝基甲苯、3,4-二甲氧基苯甲醛为起始原料,经过缩合、还原、重氮化、亲核取代反应和酰化反应,最终合成新的5种目标化合物。用元素分析、红外光谱1、HNMR1、3CNMR及多种二维核磁共振谱确定了目标化合物的结构。     

手性HMPA类似物的合成

以磷酰氯为原料通过与手性肿胺的亲核取代反应高产率地合成了手性ＨＭＰＡ类似物。     

Synthesis of copolybibenzoates with thioether and ether groups in the flexible spacers

Main‐chain copolybibenzoates with flexible spacers bearing thioether and ether groups were obtained by melt‐transesterification of diethyl 1,1′‐biphenyl‐4,4′‐dicarboxylate and β‐thioether glycols (thiodiethylene glycol or thiotriethylene glycol), using titanium (IV) isopropoxide as catalyst. A side‐reaction of etherification occurred simultaneously with the polycondensation reaction, resulting in the formation of comonomer units with the structure of the dimer of the glycol. This side‐reaction was confirmed by the preparation of model compounds. The most probable mechanism for this etherification reaction is the formation of an intermediate three‐membered cyclic sulfonium ion by neighbouring sulfur participation. The thermal and X‐ray characterization of the synthesised copolymers indicated that a smectic mesophase was rapidly obtained on cooling the copolymers derived from thiodiethylene glycol from the melt and this phase was transformed slowly into a more ordered structure. In contrast, copolymers derived from thiotriethylene glycol did not exhibit liquid‐crystalline phases and their crystallisation from the isotropic melt was very fast. It was found that the copolymerization increased the mesophase stability. Finally, the results obtained were compared with those of corresponding homopolybibenzoates with methylene or oxymethylene spacers. Copyright © 2005 Society of Chemical Industry     

水杨醛—5—烯去甲基斑蝥腙及其类似物的合成

8种水杨醛-5-烯去甲基斑蝥腙及其类似物由 N-氨基-5-烯去甲基斑蝥胺分别与水杨醛、肉桂醛、苯甲醛、邻硝基苯甲醛、N,N-二甲氮基苯甲醛、苯乙酮、2-(6-甲氧基)萘乙酮和乙酰乙酸乙酯在无水乙醇溶液中进行缩合反应而制得,这些缩合产物具有敏锐的熔点。元素分析和红外图谱确定了其结构,证明都是首次合成的新化合物。     

N-取代去甲基斑蝥酰亚胺及其类似物的合成

合成了 N-取代去甲基斑蝥酰亚胺、去甲基斑蝥素等23种化合物,对其结构做了元素分析、红外光谱鉴定     

Synthesis and metal coordination of thioether containing cyclo‐ and poly(organophosphazenes)

Several small molecule cyclotriphosphazenes and high polymeric poly(organophosphazenes) with methylthio groups (CH₃SR) have been synthesized: [NP(OCH₂CH₂SCH₃)₂]_n (n = 3, 1; n = 15,000, 5); [NP(OCH₂CH₂CH₂CH₂SCH₃)₂]_n (n = 3, 2; n = 15,000, 6); [NP(OCH₂CH₂CH(SCH₃)CH₂CH₂CH₃)₂]_n (n = 3, 3; n = 15,000, 7); and [NP(OCH₂C₆H₄SCH₃)₂]_n (n = 3, 4; n = 15,000, 8). Both series of compounds possess multiple thioether coordination sites for potential binding to metals. The methylthioethoxide substituent readily oxidizes to the sulfoxide derivatives in the presence of peroxides. All the phosphazenes were characterized by ¹H‐, ¹³C‐, and ³¹P‐NMR spectroscopy and elemental analysis, and the small molecule cyclotriphosphazenes were examined by mass spectrometry. Gel permeation chromatography (GPC) and differential scanning calorimetry (DSC) were also employed to characterize the polymers. Metal complexation and extraction capabilities of both the small molecule and polymeric systems are described. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 650–661, 2000     

Synthesis and properties of novel organosoluble copoly(arylene ether nitriles) containing thioether moiety

In this work, a series of novel organosoluble copoly(arylene ether nitriles) containing thioether moiety (PENS) were synthesized via nucleophilic aromatic substitution polymerization of 2,6-dichlorobenzonitrile with bisphenol A and sodium sulfide nonahydrate, using N-Methyl-2-Pyrrolidone as solvent in the presence of anhydrous potassium carbonate. The chemical structures of PENS were characterized by FTIR and ¹H NMR. The derived copolymers showed high glass transition temperatures in the range of 167–178 °C and excellent thermal stability with the 5% weight loss temperatures ranging from 465 °C to 503 °C. Meanwhile, all of the PENS were amorphous and can be readily cast into transparent films with a tensile strength exceeding 77 MPa and a breaking elongation over 4.8%.In addition, the dielectric constant of all the PENS copolymers showed weak frequency dependence, the dielectric loss showed slight decrease with increasing frequency over the range of 100 Hz to 200 kHz. Therefore, this kind of organosoluble copoly(arylene ether nitriles) containing thioether moiety could be a good candidate as matrix resins for high-performance polymeric materials.     

An unusual epimerization of a thioether

Reaction of 6-exo-methylthio-2-exo-phenylbicyclo[2.2.1]heptan-2-endo-ol with sodium azide and acid afforded the corresponding 2-exo-azide. This azide was reduced and acetylated to give a crystalline derivative whose structure was unequivocally established by X-ray crystallographic analysis. Surprisingly, the isomeric 6-endo-methylthio-2-exo-phenylbicyclo[2.2.1]heptan-2-endo-ol on reaction with sodium azide and acid yielded the same azide as the 6-exo-methylthio analogue. Evidence for the mechanism of thioisomerization is presented.     

新型芳腙基噻唑衍生物的合成及抗菌活性研究

以取代苯甲醛与氨基硫脲为原料合成了11种芳基噻唑衍生物,经IR、1HNMR、MS及元素分析确定了化合物的结构,并分别测试了这些化合物对8种革兰氏阳性、阴性菌和3种真菌的抑菌活性。     

Functional polyamides. 3. Synthesis and chelating properties of a new poly(amide thioether)

Polymerization of β,β′-(ethylenedithio)dipropionitrile

1 IUPAC name: 4,7-dithiadecane dinitrile.

with formaldehyde in the presence of sulfuric acid was carried out in order to permit the synthesis of polymides containing thioether groups. The obtained poly(amide thioether)s were characterized; they coordinate mercury (II) with a high degree of selectivity.     

Synthesis and antitumor activity of 1-β-D-arabinofuranosylcytosine conjugates of optical isomers of ether and thioether lipids

Four 1-β-D-arabinofuranosylcytosine conjugates (ara-C) (1a, b and 2a, b) ofsn−1 andsn−3 isomers of 1-O-octadecyl-2-O-palmitoylglycerol and its 1-S-alkyl analogue have been synthesized, and their antitumor activity against L1210 lymphoid leukemia in mice were compared with those of the previous conjugates (3a, b) of racemates in order to determine the significance of chirality of the glycerol moieties for activity. Administration (i.p.) of a single dose (300 mg/kg) of conjugates ofsn−1 (1a),sn−3 (2a) andrac (3a) isomers of the ether lipid increased lifespan of i.p. implanted L1210 lymphoid leukemic DBA/2J mice by 169, 175 and 236%, respectively. Thesn−1 (1b),sn−3 (2b), andrac (3b) isomers of the thioether lipid with a single dose of 300 mg/kg produced an increase in lifespan values of 238, 263 and 250%, respectively. The results indicate that chirality of the glycerol moieties appears not to be critical for the activity, and racemates 3a and 3b are promising prodrugs of ara-C for further clinical investigations. This material was presented in part at the 81 st Annual Meeting of the American Association for Cancer Research in Washington, D.C., May, 1990 (Abstract No. 2493).     

Synthesis and biological evaluation of nonylprodigiosin and macrocyclic prodigiosin analogues

Nonylprodigiosin (4) and various of its analogues have been prepared by Suzuki cross-coupling reactions of a well accessible pyrrolyl triflate with (hetero)aryl boronic acid derivatives bearing alkenyl side chains. The resulting alkenes or dienes were subjected to metathesis dimerization or ring-closing metathesis (RCM) reactions, respectively, by using a ruthenium indenylidene complex as the catalyst. The biological activity of the products thus obtained was tested in two different assays monitoring i) the proliferation of murine spleen cells induced by lipopolysaccharides (LPS) and concanavalin A (Con A), and ii) the vacuolar acidification of baby hamster kidney (BHK) cells. Compounds 4 and 21 suppressed Con A-induced T-cell proliferation much more potently than LPS-induced B-cell proliferation. Furthermore, compounds 4 and 26 markedly inhibited vacuolar acidification, although other compounds exhibited no or only marginal effects. Thus, the immunosuppressive activity of prodigiosins toward T-cell proliferation seems to be mediated through cellular targets distinct from vacuolar acidification, and the prodigiosin analogues might be powerful tools to dissect these biological responses. The X-ray crystal structure of the macrocyclic product 25 has been determined, showing that the replacement of one pyrrole ring of the parent compound 4 by a phenyl group does not alter the overall electronic features of the remaining heterocyclic ring system of these alkaloids.     

含氮姜黄素类似物的合成及其酪氨酸酶抑制效应

通过芳香醛与4-乙酰基吡啶在酸碱条件下催化缩合,合成了4个单羰基姜黄素类似物A1～A4,并研究了其对酪氨酸酶的抑制活性。结果表明,3-(4-羟基-3,5-二甲氧基苯基)-1-(4-吡啶基)-2-烯-1-酮对酪氨酸酶具有强抑制活性,半数抑制浓度（IC50）为45.1μmol/L,是姜黄素（IC50= 97.1μmol/L）的抑制活性的2.2倍。抑制动力学研究表明,3-(4-羟基-3,5-二甲氧基苯基)-1-(4-吡啶基)-2-烯-1-酮对酪氨酸酶的抑制作用类型属于竞争性抑制。     

Synthesis and biological investigation of novel tricyclic benzodiazepinedione-based RGD analogues

Integrins, a widely expressed family of heterodimeric cell surface adhesion proteins, are expressed in a variety of cell types. They play a decisive role in cell-cell adhesion or cell to extracellular matrix adhesion events. Antagonists of alpha(v)beta(3) or alpha(IIb)beta(3) integrin may have a potential use in suppression of pathological processes. We present the synthesis of novel tricyclic benzodiazepinedione-based RGD analogues, which were subsequently tested in a solid-phase receptor assay in order to investigate their binding affinities towards alpha(v)beta(3) and alpha(IIb)beta(3) integrin.     

Synthesis of a thioether modified hyperbranched polyglycerol and its template effect on fabrication of CdS and CdSe nanoparticles

A thioether‐containing hyperbranched polyglycerol (PG) was synthesized by a simple and effective two‐step reaction; first a part of the hydroxyls of PG was transformed to carbamates by the reaction with the highly reactive 2‐chloroethyl isocyanate, and then the chlorine group was S‐alkylated with HS(CH₂)_nOH (n = 2, 6, 11). The resulting PGs with various molecular weights were successfully used as template for synthesis of nanoscale cadmium chalcogenide quantum dots (QDs). It was found that the size of these QDs was dependent on the polymer template. Moreover, after solvent evaporation, the polymer was assembled into large cluster, and a variety of morphologies were formed by the cluster inside the QDs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3679–3684, 2006     

Stereospecific synthesis of antitumor active thioether PAF analogs

A novel stereospecific synthesis of antitumor active thioether analogs of platelet-activating factor (PAF) is reported. The synthesis is based upon: i) the use ofD-serine to provide the chiral center for the construction of the optically active phospholipid molecule; ii) development of thesn-1-thioalkyl function via thioacetate displacement of methanesulfonate-activated primary hydroxyl group followed by alkylation of thesn-1-thiolate function; and iii) introduction of the phosphocholine moiety through the 2-chloro-2-oxo-1,3,2-dioxaphospholane/trimethylamine sequence. The entire scheme relies on the use of a single protecting group. The synthetic thioether phospholipid 1-S-hexadecyl-2-N-acetamidodeoxy-sn-glycero-3-phosphocholine has been shown to be a potent antitumor active phospholipid, exhibiting tumor cytotoxicity against a lymphoblastoid lymphoma (Li-A) cell line and a malignant histiocytic (DHL-4) cell line of human origin at the same level of potency as ET-18-OMe and 1-O-octadecyl-2-N-acetamidodeoxy-sn-glycero-3-phosphocholine. The synthetic method described has a great deal of flexibility, providing a convenient general route to a wide range of thioether PAF analogs. Based on a paper presented at the Third International Conference on Platelet-Activating Factor and Structurally Related Alkyl Ether Lipids, Tokyo, Japan, May 1989.