3-[N-(4-甲基苯基)氨基羰基]-5-[4-(4-甲酸基苯甲氧基)苯亚甲基]-2,4-噻唑烷二酮的合成

以对甲苯胺和对甲基苯甲酸甲酯为起始原料,经NBS溴化、亲核取代、酸水解和Knoevenagel缩合等6步反应合成了抗细菌生物膜化合物—3-[N-(4-甲基苯基)氨基羰基]-5-[4-(4-甲酸基苯甲氧基)苯亚甲基]-2,4-噻唑烷二酮,总收率57.3％,其结构经1H NMR,ESI-MS和元素分析确证.     

Synthesis and characterization of poly[4-(4-hydroxyphenoxy) benzoic acid]

Poly[4-(4-hydroxyphenoxy) benzoic acid] was prepared by the bulk polycondensation of 4-(4-acetoxyphenoxy) benzoic acid. Polycondensation was conducted at 350°C for 3 h under a reduced pressure of 0.1 mmHg and gave a polymer with X?n of 255. The polymer was characterized by elemental analysis, IR spectroscopy, differential scanning calorimetry, and wide-angle X-ray measurement. The crystal/nematic and nematic/isotropic phase transition temperatures of polymer, which depend on the molecular weight, were observed at about 300°C and 410°C, respectively. The polymers with low molecular weights showed nematic textures above 300°C. This nematic/isotropic phase transition temperature is lower than that of poly (4-hydroxybenzoic acid). This thermal behavior of polymer comes from ether units, which increase the flexibility (the rotation or torsion of skeletal bonds) of the polymer chain. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of 3-phenyl-4[H]-4-[one]-benzopyran (isoflavone) derivatives as potential mesogens

With few mesogenic chromone derivatives in the literature the synthesis of 7-[4'-n-alkyloxybenzoyloxy) isoflavones was carried out. The resulting homologous series was characterized by elemental analysis and spectroscopic techniques. The first four members of the series only exhibit a nematic phase. In addition to the nematic phase, the smectic phase commences from the pentyloxy derivative. The decyloxy and higher derivatives only exhibit a smectic phase. The smectic phase observed in the present series is the smectic A type. Differential scanning calorimetry studies served the dual purpose of confirming the microscopic transition temperatures, as well as the calculation of the enthalpies of the various phase transitions.     

Synthesis and characterization of novel 4-benzyloxyphenyl 4-[4-(n-dodecyloxy)benzoyloxy]benzoate liquid crystal

Liquid crystal (LC) compound 4-Benzyloxyphenyl 4-[4-( n -dodecyloxy)benzoyloxy]benzoate (BDBB) was prepared and characterized. Inverse gas chromatography (IGC) was to be a beneficial analysis method for the research of thermodynamic characteristics of the new LC. Acetate and alcohol isomers were used to examine LC selectivity via the IGC technique at temperatures between 333.2 K and 483.2 K. The retention diagrams of n -heptane, n -octane, n -nonane, n -decane, undecane, dodecane, tridecane, n -butyl acetate, isobutyl acetate, ethyl acetate, n -propylbenzene, isopropylbenzene, ethylbenzene, chlorobenzene, and toluene on BDBB were plotted with temperatures of 483.2–493.2 K. Flory–Huggins interaction parameter and weight fraction activity coefficient at infinite dilution were researched for BDBB.     

Synthesis and Extraction Property of Novel Thiacalix[4]biscrown: Thiacalix[4]-1,3-2,4-aza-biscrown

The novel thiacalix[4]-1,3-2,4-aza-biscrown 3 in 1,3-alternate conformation, was facilely prepared by “1 + 2” cyclocondensation of p-tert-butylthiacalix[4]arene tetrahydrazide derivative 2 with o-phthalaldehyde in yield of 78%. The liquid–liquid extraction experiment showed that compound 3 was excellent receptor for zwitterionic α-amino acids and soft cations Ag⁺ and Hg²⁺. The extraction percentage of methionine was as high as 78%.     

Synthesis and characterization of 6-[4-(trans -4-pentylcyclohexyl)phenoxy]hexyl acrylate homopolymer and copolymers

The compound 6-[4-(trans -4-pentylcyclohexyl)phenoxy]hexyl acrylate (2) was prepared and homopolymerized. The block copolymer and copolymer of 2 with styrene were synthesized by photopolymerization and solution techniques, respectively. These polymers were characterized by IR and ¹H NMR spectra and size exclusion chromatography. Polarizing optical microscopy (POM) and X-ray diffraction (XRD) studies revealed that these polymers exhibited smectic A (SmA) phases. POM showed that the homopolymer showed a higher order SmA phase than did the block copolymer and copolymer. After magnetically forced alignment the samples exhibited similar optical texture but the domain size of the liquid crystalline phase increased. Differential scanning calorimetry, POM and XRD data suggest that the SmA domain size decreased in the order hompolymer > block copolymer > copolymer.     

2,6-二[4-′(N,N-二苯基氨基)芪]苯并[1-2,4-5]二噁唑的合成与发光特性

通过对二苯氨基苯甲醛与2,6-二(4-氯甲基苯基)苯并[1-2,4-5]二唑之间的Wittig-Horner反应,设计并合成了一个2,6-二[4-′(N,N-二苯基氨基)芪]苯并[1-2,4-5]二唑新化合物,目的在于均二苯乙烯分子中同时引入空穴传输和电子传输结构单元,可望提高均二苯乙烯型发光材料的发光强度和光量子效率.采用UV-VisI、R1、HNMR和元素分析等分析方法对合成产物结构进行了确认,并考察了溶剂对其光致发光特性的影响.所合成化合物的相关分析数据表明:1)其分子中的两个均二苯乙烯基均为反式“芪”结构特征;2)随溶剂极性增高,其UV-Vis光谱和荧光光谱的λmax红移;3)可用作蓝色发光材料.     

Di[tris(trimethysilyl)methyl]-zinc and -cadmium

Tris(trimethylsilyl)methyllithium reacts with the anhydrous halides MC1₂ (M = Zn or Cd) to give the compounds [(Me₃Si)₃C]₂M, which show high thermal and chemical stability. They decompose only above 300°C, with formation of (Me₃Si)₃CH, and are not attacked by water in refluxing THF. The zinc compound can be steam-distilled without decomposition, and does not react with boiling concentrated hydrochloric acid or with bromine in carbon tetrachloride.     

Synthesis and conformational analysis of 1-[2,4-dideoxy-4-C-hydroxymethyl-alpha-l-lyxopyranosyl]thymine

Previously different types of nucleosides with a six-membered carbohydrate moiety have been evaluated for their potential antiviral and antibiotic properties and as building blocks in nucleic acid synthesis. However, a pyranose nucleoside with a 1,4-substitution pattern like 1-[2,4-dideoxy-4-C-hydroxymethyl-alpha-l-lyxopyranosyl]thymine (4) has not been studied yet. Modeling suggested that this nucleoside would show the (4)C(1) conformation in contrast to anhydrohexitol nucleosides (1) whose most stable conformation is (1)C(4). The key to the synthesis of 4 involves the stereoselective introduction of the hydroxymethyl group onto the C-4 carbon of the pyranose sugar. Attempts to achieve this via hydroboration/oxidation of a C-4'-exocyclic vinylic intermediate selectively yielded the undesired alpha-directed hydroxymethyl group. Therefore, we envisaged another approach in which the C-4 substituent was introduced upon treatment of 2,3-O-isopropylidene-1-O-methyl-4-O-phenoxythiocarbonyl-alpha-l-lyxopyranose with beta-tributylstannyl styrene. This allowed stereoselective beta-directed introduction of a 2-phenylethenyl group at C-4, which was converted via oxidation/reduction (OsO(4), NaIO(4)/NaBH(4)) into the desired 4-hydroxymethyl group (20). The resulting 1-O-methyl-2,3,6-tri-O-acetyl-protected sugar was coupled with silylated thymine, using SnCl(2) as Lewis acid (22). After suitable protection, Barton deoxygenation of the 2'-hydroxyl function of the obtained ribo-nucleoside yielded the desired 2'-deoxynucleoside 4, indeed showing the expected equatorial orientation of the thymine ring ((4)C(1)).     

硫杂杯-1,3-2,4-氮杂双冠醚的合成与氨基酸配合性能

对叔丁基硫杂杯四酰肼衍生物(2)与邻苯二甲醛发生分子内1+2缩合反应, 合成了首例1,3-交替构象的硫杂杯-1,3-2,4-氮杂双冠醚(3), 产率为65%. 其结构经元素分析、质谱、核磁共振谱等表征证实. 用UV-Vis光谱法和1H NMR谱研究了化合物3与系列α-氨基酸的识别配合性能, 并计算出其配合常数. 结果表明, 主体分子3对所测试的α-氨基酸有较好的配合作用, 主客体分子形成1∶1的配合物.     

Synthesis and characterization of soluble polyamides based on 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and 2,2-bis[4-(4-aminophenoxy)phenyl]propane and diacid chlorides

Aromatic soluble polyamides and copolyamides having hexafluoroisopropylidene and isopropylidene moieties in the molecular structure of polymer chain were prepared by reacting the aromatic diacid chlorides and fluorine or nonfluorine containing aromatic diamines using low-temperature polycondensation process. Polymers were produced with high yield and moderate to high inherent viscosity. All polyimides and copolyamides showed thermal stability above 440°C and glass transition temperature above 200°C. Some of the polyamides were cast into transparent bulk films which were further characterized by mechanical, x-ray, and water absorption analysis. Fluoro polyamides showed superior structural properties as compared to nonfluoro polyamides. © 1996 John Wiley & Sons, Inc.     

(Z,Е)-1[1-(2,4-二氧吡咯烷-3-亚基)乙基]-4-烃基氨基脲类衍生物的合成与除草活性

以取代胺为原料合成6种N4-取代氨基脲,然后与5种3-(1-羟基亚乙基)-吡咯烷-2,4二酮类化合物反应合成了22种新型缩氨基脲类衍生物,即(Z,Е)-1[1-(2,4二氧吡咯烷-3-亚基)乙基]-4-烃基氨基脲,其结构经1H NMR,MS,IR和元素分析确证.初步生物活性测定表明,这类化合物对油菜根和稗草茎的生长具有抑制作用.     

Synthesis of (Z)-4-hydroxytamoxifen and (Z)-2-[4-[1-(p-hydroxyphenyl)-2-phenyl]-1butenyl]phenoxyacetic acid

The synthesis of (Z)-4-hydroxytamoxifen and (Z)-2-[4-[1-(p-hydroxyphenyl)-2-phenyl]-1-butenyl]phenoxyacetic acid was accomplished using a McMurry reaction as the key step. The perfluorotolyl derivatives of the McMurry products enabled the separation of the minor undesirable geometrical isomer. The methodology proceeds without E,Z isomerization, employs a very mild final debenzylation step compatible with a large array of functional groups, and can be applied to the generation of a variety of 4-hydroxytamoxifen analogues.     

Synthesis and characterization of new polyamides derived from 1,6-bis[4-(4-aminophenoxy)phenyl]diamantane

A series of new polyamides 3 were synthesized by direct polycondensation of the 1,6-bis[4-(4-aminophenoxy)phenyl]diamantane (1) with various dicarboxylic acids. The polyamides had inherent viscosities of 0.45–1.90 dL/g and number-average molecular weights (M_n) of 24,000–110,000. Dynamic mechanical analysis (DMA) reveals that polymers 3 have two relaxations on the temperature scale between −100 and 400°C. Their α relaxations occurred at high temperatures, ranging from 338 to 389°C. Moreover, these polymers remained quite stable at high temperatures and maintained good mechanical properties (G′ = ca. 10⁸ Pa) up to temperatures close to the main transition markedly exceeding 350°C. Due to the bulky diamantane elements and the flexible ether segments, the polymers 3 were amorphous and soluble in a number of organic solvents such as pyridine, N-methyl-2-pyrrolidone (NMP), and N,N-dimethylacetamide (DMAc). The polyamides 3 have tensile strengths of 56.7–90.2 MPa, elongation to breakage values of 7.5–27.7%, and initial moduli of 1.8–2.1 GPa. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2185–2192, 1998     

5-[{4-[2-(5,6,7,8-四氢-5,5,8,8-四甲基)萘氧-2-基]乙氧基}苄基]-2,4-噻唑烷二酮的合成

以2,5-二甲基-2,5-己二醇为原料,经氯化、傅一克反应、烷化、Knoevenagel缩合、还原反应制得5-【{4-[2-(5,6,7,8-四氢-5,5,8,8-四甲基)萘氧-2-基]乙氧基}苄基】-2,4．噻唑烷二酮,其结构经元素分析,IR和1H NMR证实。总收率6．3％。     

Synthesis of 4-[3-(1H)-indolyl]-2-[N-guanidinomethyl]thiazole dihydrochloride

The title compound 3b was synthesized in three steps from acetaminothioacetamide ( 4b ) in 15% overall yield. This represents the first synthesis of a 2-guanidinomethylthiazole, which is a homolog of an important pharmacophore, 2-guanidinothiazole.     

N-[4-(三氟甲氧基)苯基]氨基甲酸苯酯的合成

以三氟甲氧基苯为起始原料,经硝化、加氢还原和酰化反应合成了N-[4-(三氟甲氧基)苯基]氨基甲酸苯酯,总收率84.6%,纯度98.9%,其结构经¹H NMR和MS（ESI）确证。