New 3,6-dihalogencarbazole-containing monomers and polymers

Summary The synthesis of six novel electrono-donor monomers containing 3,6-dihalogencarbazole [N-(2-hydroxyethyl)-3, 6-dichlorocarbazolyl methacrylate, N-(2-hydroxyethyl)-3, 6-dichlorocarbazolyl acrylate, N-(2-hydroxyethyl)-3, 6-dibromocarbazolyl methacrylate, N-(2-hydroxyethyl)-3, 6-dibromocarbazolyl acrylate, N-(2-hydroxyethyl)-3, 6-diiodocarbazolyl methacrylate and N-(2-hydroxyethyl)-3,6-diiodocarbazolyl acrylate], of the corresponding polymers and of the monomeric models is described. The ionization potentials values of the monomeric models were determined.     

Base induced [1,2]- and [3,2]-rearrangements of N-(2-Thenyl)-N-benzyldimethylammonium ion

The title compound 4 underwent Sommelet and Stevens rearrangements induced by a number of bases. Ionization of the thenyl methylene group of 4 to the corresponding ylid 10 was the prevalent process, yielding subsequently N-[2-(2′-thienyl)-2-phenethyl]dimethylamine 12 and N-[α-(o-tolyl)-2-thenyl]-dimethylamine 13 . The strong trend of the 2-thenyl ylids to produce large relative amounts of the Sommelet amine was confirmed. Minor products are N-[2-(2′-thienyl)-1-phenethyl]dimethylamine 15 and N-[α-phenyl-2-(3-methylthienyl)]dimethylamine 16 derived from the benzyl ylid 11 .     

水溶性萘酰亚胺氢离子荧光分子探针的合成及性能

4 溴 1,8 萘酐与羟乙氧基乙胺反应合成了中间体N 羟乙氧基乙基 4 溴 1,8 萘酰亚胺。用该中间体分别与哌嗪、甲基哌嗪和羟乙基哌嗪反应 ,合成了 4 哌嗪基、4 (甲基哌嗪 )基和 4 (羟乙基哌嗪 )基 1,8 萘酰亚胺衍生物 (NP - 1、NP - 2和NP - 3)。这 3种化合物具有较好的水溶性 ,其水溶液的荧光强度随溶液由碱性到酸性变化 ,荧光强度增加在 5 0倍以上。NP - 1、NP - 2和NP - 3的pK′a值分别为 8 5、7 6和 6 7。     

Long chain carboxylic acids containing ether linkage: IV. The antibacterial activities of 0-(2-alkylaminoethyl)-3-oxypropionic and N-(2-alkyloxyethyl)-3-aminopropionic acids

The carboxylic amphoteric surfactants containing ether and substituted amine groups such as 0-(2-alkylaminoethyl)-3-oxypropionic-and N-(2-alkyloxyethyl)-3-aminopropionic acids were synthesized, and their antibacterial activities in terms of growth inhibition ofStaphylococcus aureus andEscherichia coli were examined. The structural effect, such as bonding position of ether and amino groups, and the chain length effect between undecyloxy-, dodecyloxy- and tridecyloxy radicals were examined, but no definite correlation between positional isomers and chain length and antibacterial activities was observed. Furthermore, to study the effect of the increase of the number of ether or amino groups on the antibacterial activities, N-(2-(2-dodecyloxyethyl)-aminoethyl)-3-aminopropionic acid and N-(2-(2-dodecyloxyethyl)oxyethyl)-3-aminopropionic acid were synthesized. Their antibacterial activities were almost as effective as the corresponding amino or ether acids. Moreover aqueous solution of these substituted propionic acids showed better surface activities at pH 4.0, 7.0 and 10.0.     

化学生物组合法合成米格列醇及其表征

以葡萄糖和乙醇胺为原料,催化加氢生成N-羟乙基葡糖胺,葡萄糖转化率为89%。氧化葡萄糖酸杆菌Gouv2007的静息细胞在通气下氧化N-羟乙基葡糖胺脱氢生成米格列醇的前体物质6-脱氧-6-羟乙基氨基-α-L-呋喃山梨糖,再催化加氢生成米格列醇,对从N-羟乙基葡糖胺生成米格列醇的底物转化率为77.3%。采用熔程测定、红外光谱分析、质谱分析对N-羟乙基葡糖胺和米格列醇进行了表征,结果表明:所合成的产物分别被鉴定为N-羟乙基葡糖胺和米格列醇。     

抗高血压药缬沙坦的新合成方法

以2N-三苯甲基-5-(4'-溴甲基联每2-基)四氮唑为原料,与L-缬氨酸甲酯盐酸盐反应制得N-[[2'-(2N-三苯甲基-四氮唑-5-基)-(1,1'-二苯基)-4-基]-甲基]-L-缬氨酸甲酯,然后经过脱三苯甲基保护、酰化、水解得到标题化合物,总收率49.8%.     

N- Vs. C- Tricyanovinylation of Ring-Substituted Dimethylanilines. The Spectral Properties of the Products.

Methods for changing the selectivity in the N- vs. C- tricyanovinylation are discussed. In acetonitrile, 2,3-, 2,4-, 3,4- and 3, 5-dimethylanilines are N-tricyanovinylated, 2,6-dimethyl- and 2, 6-diethylanilines are p-tricyanovinylated, and 2,5-dimethyl- and 2-ethylaniline give mixtures of N- and p-tricyanovinyl derivatives. The UV, IR, NMR and mass spectra of the products are discussed in relation to the position of the tricyanovinyl group and to electronic and steric effects.     

新型双酰胺衍生物的合成及抗癌活性

以取代苯甲酸为起始原料,设计合成了10个含苯并噻唑基双酰胺类化合物,其结构经1HNMR、13CNMR、IR及元素分析确证。采用MTT法进行化合物抑制PC3、BGC-823癌细胞体外活性测试,结果表明,所合成的化合物具有不同程度地抑制癌细胞活性,其中化合物N-[2-(6-甲基苯并噻唑-2-氨基甲酰基)-4-甲基苯基]-4-氯苯甲酰胺(Ⅳa)和N-[2-(4-甲基苯并噻唑-2-氨基甲酰基)-4-甲基苯基]-2-甲基苯甲酰胺(Ⅳe)在10μmol/L浓度下对PC3的抑制率为70.8%和68.4%,N-[2-(苯并噻唑-2-氨基甲酰基)-4-甲基苯基]-2-甲基苯甲酰胺(Ⅳd)在10μmol/L浓度下对BGC-823的抑制率为65.9%。     

旋光性N-(2,6-二甲苯基)-N-酰基丙氨酸甲酯类化合物的合成及生物活性研究

以α-氯丙酸、甲醇、2,6-二甲基苯胺为起始原料,合成了N-(2,6-二甲苯基)丙氨酸甲酯。以S(-)-α-甲基苄胺为化学拆分剂,利用非对映异构体在不同溶剂中溶解度的差异,分离得到了R(+)、S(-)-N-(2,6-二甲苯基)-丙氨酸的两个旋光异构体和反-R(+)、反-S(-)、顺-R(+)和顺-S(-)-二氯菊酸的4个旋光异构体。两个N-(2,6-二甲苯基)-丙氨酸旋光异构体与甲醇反应得到两种N-(2,6-二甲苯基)丙氨酸甲酯的旋光异构体。最后N-(2,6-二甲苯基)-丙氨酸甲酯的旋光异构体与二氯菊酰氯的7个异构体进行反应,合成了19个N-(2,6-二甲苯基)-N-酰基丙氨酸甲酯类化合物,其中18个具有旋光性。这些化合物的结构经GC-MS、FTIR测定后确认。对19个标题化合物进行了杀菌、杀虫生物活性实验,结果表明,部分化合物显示出较高的杀虫、杀菌活性。     

Covalent binding of amino,carboxy, and nitro-substituted aminopropyltriethoxysilanes to oxidized silicon surfaces and their interaction with octadecanamine and octadecanoic acid studied by X-ray photoelectron spectroscopy and ellipsometry

Three silanized silicon substrates were prepared by treating cleaned oxidized silicon wafers with N-(3-triethoxysilylpropyl)octadecanamide (1), 9-[N-(triethoxysilylpropyl)amino]-9-oxononanoic acid methyl ester (2), and N-(3-triethoxysilylpropyl)-12-nitrododecanamide (4). The carbomethoxyl of 2 immobilized on silicon was hydrolysed to yield the corresponding ω-carboxylic surface (3) and the nitro group of the surface 4 reduced to afford the ω-amino surface (5). All five silanized surfaces were treated with octadecanoic acid and octadecanamine used as models for acidic and basic polymeric adhesives and the interactions were followed by ellipsometry and X-ray photoelectron spectroscopy. While the surfaces 1 and 2 reacted only by physisorption, the carboxylic surface 3 and the amino surface 5 showed a strong reaction with octadecanamine and octadecanoic acid, respectively. The nitro surface 4 exhibited a strong interaction with both probes, but by different pathways.     

EGF受体配基N2S2-Quinazoline的合成

以6-硝基喹唑啉酮为原料,经过氯化亚砜氯化,间碘苯胺连接,氯化亚锡还原,制得6-氨基-4-[(3-碘苯基)氨基]-喹唑啉,再与氯乙酰氯反应,二硫二氮缩合连接,最后与醋酸汞硫化氢反应脱巯基保护基得到标记前体N-[[4-(3-碘苯基)氨基]-喹唑啉-6-基]-2-[N-(2-巯基乙基)-N-[[N-(2-巯基乙基)氨基]甲酰甲基]]乙酰胺,主要产物得到核磁和质谱表征,总收率2.5%。     

Long chain carboxylic acids containing ether linkage: V. N-methyl substituted glycine-type amphoterics containing alkoxy radical

The substituted glycine-type amphoteric surfactants containing long chain alkoxy and methylated amino groups, such as N-(2-alkoxyethyl)methylaminoacetic acids and (N-[2-alkoxyethyl]-N-[carboxymethyl] dimethylammonium) chlorides, or N-(N-[2-alkoxyethyl]-2-aminoethyl) aminoacetic acids were synthesized, and their growth inhibitory activities against g positive, g negative bacilli, and some fungi were studied. The effect of substitution of methyl groups upon the amino group of the long chain alkoxyaminoacetic acids on their antimicrobial activities was examined, and the increasing effect, due to methyl substitution, was confirmed. The introduction of an aminoethyl radical between the alkoxyethyl and amino radicals of the substituted glycines also increased their antimicrobial activities. Dimethylsubstituted betain-type amphoterics showed less antimicrobial activities than the corresponding glycinetype amphoterics. Moreover, aqueous solution of these substituted glycine-type amphoteric compounds showed better surface activities at pH 4.0, 10.0 than at neutral pH.     

氟噻草胺的合成

改进了除草剂氟噻草胺的合成方法。以肼基二硫代甲酸甲酯、三氟乙酸为原料合成2-甲砜基-5-三氟甲基-1,3,4-噻二唑(4),反应收率81.5%;以对氟硝基苯、丙酮经过催化加氢、酰化、醇解合成N-(4-氟苯基)-N-异丙基-2-羟甲基乙酰胺(8)。化合物(4)与(8)反应合成氟噻草胺,得率94.2%。改进后的工艺反应条件温和,三废少,产品纯度和收率高。     

N-Alkylation During the Removal of a Carbamate-Type Protecting Group

Acidolysis of 2-(p-biphenylyl)isopropyl N-(5-nitro-2-pyridyloxy)carbamate (IV) resulted in loss of carbon dioxide and formation of N-2-(p-biphenylyl)isopropyl-O-(5-nitro-2-pyridyl) hydroxylamine (V). The mechanism of this unusual reaction is discussed.     

Conformation analysis of aspartame-based sweeteners by NMR spectroscopy, molecular dynamics simulations, and X-ray diffraction studies

We report here the synthesis and the conformation analysis by 1H NMR spectroscopy and computer simulations of six potent sweet molecules, N-[3-(3-hydroxy-4-methoxyphenyl)-3-methylbutyl]-alpha-L-aspartyl-S-tert-butyl-L-cysteine 1-methylester (1; 70 000 times more potent than sucrose), N-[3-(3-hydroxy-4-methoxyphenyl)-3-methylbutyl]-alpha-L-aspartyl-beta-cyclohexyl-L-alanine 1-methylester (2; 50 000 times more potent than sucrose), N-[3-(3-hydroxy-4-methoxyphenyl)-3-methylbutyl]-alpha-L-aspartyl-4-cyan-L-phenylalanine 1-methylester (3; 2 000 times more potent than sucrose), N-[3,3-dimethylbutyl]-alpha-L-aspartyl-(1R,2S,4S)-1-methyl-2-hydroxy-4-phenylhexylamide (4; 5500 times more potent than sucrose), N-[3-(3-hydroxy-4-methoxyphenyl)propyl]-alpha-L-aspartyl-(1R,2S,4S)-1-methyl-2-hydroxy-4-phenylhexylamide (5; 15 000 times more potent than sucrose), and N-[3-(3-hydroxy-4-methoxyphenyl)-3-methylbutyl]-alpha-L-aspartyl-(1R,2S,4S)-1-methyl-2-hydroxy-4-phenylhexylamide (6; 15 000 times more potent than sucrose). The "L-shaped" structure, which we believe to be responsible for sweet taste, is accessible to all six molecules in solution. This structure is characterized by a zwitterionic ring formed by the AH- and B-containing moieties located along the +y axis and by the hydrophobic group X pointing into the +x axis. Extended conformations with the AH- and B-containing moieties along the +y axis and the hydrophobic group X pointing into the -y axis were observed for all six sweeteners. For compound 5, the crystal-state conformation was also determined by an X-ray diffraction study. The result indicates that compound 5 adopts an L-shaped structure even in the crystalline state. The extraordinary potency of the N-arylalkylated or N-alkylated compounds 1-6, as compared with that of the unsubstituted aspartame-based sweet taste ligands, can be explained by the effect of a second hydrophobic binding domain in addition to interactions arising from the L-shaped structure. In our examination of the unexplored D zone of the Tinti-Nofre model, we discovered a sweet-potency-enhancing effect of arylalkyl substitution on dipeptide ligands, which reveals the importance of hydrophobic (aromatic)-hydrophobic (aromatic) interactions in maintaining high potency.     

Syntheses of 2-(N-2-hydroxyalkyl-N,N-dimethylammonio)ethyl hydrogen phosphates and their physicochemical and antimicrobial properties

A series of new phosphate type of amphoterics having a 2-hydroxyalkyl group as a hydrocarbon chain, 2-(N-2-hydroxyalkyl-N,N-dimethylammonio)ethyl hydrogen phosphates (alkyl[R]:dodecyl, tetradecyl, hexadecyl), was synthesized and their physicochemical properties—isoelectric point, critical micelle concentration (CMCs), occupied area/molecule at interface and the change of free energy of micellization—and antimicrobial properties were investigated in comparison with those of sodium 2-(N-alkyl-N-methylamino)ethyl hydrogen phosphates. It was found that the CMCs and the occupied areas were observed to decrease due to a phosphobetaine moiety and a 2-hydroxyethyl group. Solution properties of the binary system of SDS/2-(N-2-hydroxytetradecyl-N,N-dimethylammonio)ethyl hydrogen phosphate in aqueous solutions were studied in terms of surface tension and pH value. On the other hand, it was observed that the Minimum inhibitory concentration (MICs) of 2-(N-2-hydroxyhexadecyl-N,N-dimethylammonio)ethyl hydrogen phosphate against fungi were smaller than those of chlorhexidine digluconate.     

h-线敏感光致产碱剂PNCDP的合成与表征

设计并合成了一种对高压汞灯发射光谱中的h-线(405 nm)敏感的新型光致产碱剂(PBG)——N-{[(5-哌啶-2-硝基苄基)氧]-羰基}-2,6-二甲基哌啶(PNCDP).通过红外(IR)、核磁(NMR)以及元素分析对PNCDP的结构进行了表征.紫外-可见光谱(UV-Vis)测试结果表明,与传统的i-线(365 nm)敏感PBG——N-{[(4,5-二甲氧基-2-硝基苄基)氧]-羰基}-2,6-二甲基哌啶(DNCDP)相比,PNCDP的最大紫外吸收波长为395.5 nm,较DNCDP红移了52.5 nm.初步光刻实验表明,PNCDP对h-线具有较好的敏感度.     

内和外N-烷基酰亚胺的杀虫增效活性研究

利用硅胶柱层析方法 ,提纯增效剂 A1得到内 ( endo) N- ( 2 -乙基 )己基 - 1 -异丙基 - 4-甲基二环 [2 ,2 ,2 ]- 5-辛烯 - 2 ,3-二甲酰亚胺 ( 1 )。由 α-松油烯合成外 ( exo) α-松油烯 -马来酸酐加成物 ,再与 2 -乙基己胺反应合成外 ( exo) N- ( 2 -乙基 )己基 - 1 -异丙基 -4-甲基二环 [2 ,2 ,2 ]- 5-辛烯 - 2 ,3-二甲酰亚胺 ( 2 )。利用元素分析、IR和 1H NMR对 1和 2的结构进行鉴定。杀虫增效活性试验证明 :内型结构 ( endo) 1的增效活性强于外型结构 ( exo) 2。     

Synthesis,Structural Characterization,Spectroscopic Properties,and Theoretical Investigations of Aminoacridine Derivatives

Synthesis of four N-(heterocyclic)-9-aminoacridine derivatives was investigated. The synthesized compounds, N-thiazolyl-9-aminoacridine (AC1), N-(1,3,4-thiadiazolyl)-9-aminoacridine (AC2), N-(5-methyl-1,3,4-thiadiazolyl)-9-aminoacridine (AC3), and N-(5-phenyl-1,3,4-thiadiazolyl)-9-aminoacridine (AC4) were characterized by FT-IR, ¹H NMR, mass-spectral, and elemental analysis. Amine-imine tautomerism was suggested by density functional theory (DFT) calculations. The optimized structures were obtained using B3LYP/6–311++G(d,p) level of theory. The UV–Vis absorption spectra were measured in various organic solvents. The synthesized compounds AC1–AC4 exhibit absorption spectra characteristic of typical donor–acceptor compounds. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) analysis have been used to explain the internal charge transfer (ICT) phenomena within the molecules. Also, simulated UV spectra were calculated using TD-DFT (B3LYP/6–311++G(d,p) and the results were compared with the experimental values.     

Dreikomponentenreaktionen. XIV. 2-Imidazoline und 1,2,4-Triazole durch Ringschlußreaktionen von N-(2-Chlor-alkyl)imidchloriden mit Hydrazin und Hydrazonen

Three Component Reactions. XIV. 2-Imidazolines and 1,2,4-Triazoles by Ring Closure Reactions of N-(2-Chloro-alkyl)imidchlorides with Hydrazine and Hydrazones N-(2-Chloro-alkyl)benzimidchlorides ( 1a and 1b ) give with hydrazine in dependence on the reaction medium 1,1′-bis(2-imidazolines) ( 4 ), 1-benzamido-2-imidazolines ( 5 ) or 1,2,4-triazoles ( 6 and 7 ) and also N-(2-chloro-alkyl)benzamides ( 8 ). From imidchlorides ( 1a–c ) and hydrazones Schiff bases ( 10 ) of 1-amino-2-imidazolines are obtained. They are not cleavable into free 1-amino-2-imidazolines.