矩形多环芳烃的合成

本文用3,4-二苯基-2,5-二(3,5-二溴苯基)环戊二烯酮(4a)与二苯乙炔(5a)通过Diels-Alder环加成反应得到1,2,4,5-四苯基-3,6-二(3,5-二溴苯基)苯(6a)。化合物6a通过经典的Suzuki偶联反应得到1,2,4,5-四苯基-3,6-二(3,5-二(4-十二烷基噻吩))苯基苯(8a),再利用Fe Cl3作为氧化剂发生Scholl氧化脱氢关环反应,得到目标化合物1a。采用类似合成方法,得到目标化合物1b。化合物的结构均通过1H NMR和MALDI-TOF MS表征,并对其光谱特征、热性能及电学性能进行了初步研究。     

两种新型咔唑衍生物的合成及其光电性能

以咔唑、三苯基氯硅烷及2-溴芴为原料,经甲基化、硼酸化、Ullmann偶联、Suzuki偶联等反应合成了两种新型咔唑衍生物--3,6-二(9,9-二甲基-9H-2-芴基)-9-苯基-9H-咔唑(1a)和3,6-二[(4-三苯硅基)苯基]-9-苯基-9H-咔唑(1b),其结构经1H NMR和元素分析表征.用UV-Vis,荧光光谱和循环伏安曲线研究了1a和1b的光电性能.     

3-(2-苯并呋喃酰基)薁-1-羧酸甲酯的有效合成

以苯基三甲铵三溴盐(PTAB)为溴化试剂, 对3-乙酰基薁-1-羧酸甲酯进行了溴代反应研究, 将其单溴代产物与水杨醛在温和反应条件下进行缩合, 以极优的收率高选择性得到3-(2-苯并[b]呋喃酰基)薁-1-羧酸甲酯类衍生物, 其结构经¹H NMR, IR及元素分析等得以证实.     

新型含嘧啶环的六芳基取代苯的合成

以1-十二烯为起始原料,通过Sonogashira反应、Suzuki偶联反应等制得未见文献报道的2,2’-二(十二烷基嘧啶)乙炔(5);5与四芳基环戊二烯酮经Diels-Alder环加成反应合成了新型含嘧啶环的六芳基取代苯,总收率7.7%,其结构经1H NMR和13C NMR表征。     

新型联苯基三苯胺聚合物的合成与性能研究

以4,4'-二溴联苯和苯胺为原料,经钯催化氨基化反应制得N,N'-二苯基联苯胺(1);以1为单体,分别与对二溴苯(2a),4,4'-二溴二苯砜(2b)和4,4'-二溴二苯甲酮(2c)通过钯催化的C-N交叉偶联反应,合成了3个新型的联苯基三苯胺聚合物:联苯基三苯胺苯(3a,收率88%),联苯基三苯胺砜(3b,收率94%)和联苯基三苯胺酮(3c,收率91%),其结构经1H NMR,IR和XRD表征。采用UV-Vis,TG,DSC,荧光光谱和循环伏安法对3a~3c的性能进行了研究。结果表明:3a~3c失重5%的温度分别为479℃,482℃和355℃;玻璃化转变温度分别为199℃,248℃和215℃;λmax分别位于354 nm,359 nm和385 nm;λem分别为489 nm,472 nm和518 nm;EHOMO值分别为-3.96 eV,-3.89 eV,-3.94 eV;ELUMO值分别为-1.16 eV,-1.17 eV和-1.39 eV。     

1/2,5-二取代吲唑-3-甲酰胺衍生物的合成及其抗肿瘤活性

以吲唑-3-羧酸为原料,依次经溴代和酯化反应制得中间体5-溴吲唑-3-羧酸甲酯(2);2经N-烷基化并原位水解生成1/2-取代-5-溴吲唑-3-羧酸(3);3与吡啶酮甲胺类化合物经缩合反应制得酰胺(4);4与芳基频哪醇硼酸酯发生Suzuki偶联反应合成了14个新型二取代吲唑-3-甲酰吡啶酮甲胺衍生物(5a~5n),收率26%~32%,其结构经~1H NMR,~(13)C NMR和HR-MS(ESI-TOF)表征。通过NOE差谱确证了取代基在吲唑氮原子上的取代位置。采用MTT法研究了5a~5n对人B淋巴瘤细胞(Ramos)、人黑色素瘤细胞(CHL-1,WM-266-4)和乳腺癌细胞(BT-474)的体外抗肿瘤活性。结果表明:5a,5b,5m对Ramos细胞、5a,5b,5l对WM-266-4细胞、5a,5b,5d,5e,5h,5j,5m,5n对CHL-1细胞和5a,5b,5d,5h,5m对BT-474细胞具有较好的抑制活性(IC5010.0μmol.L-1)。     

新型扶手型分子石墨烯的合成

3,4-二苯基-2,5-二(3,5-二溴苯基)环戊二烯酮与二苯乙炔经Diels-Alder环加成反应制得1,2,4,5-四苯基-3,6-二(3,5-二溴苯基)苯(6);6经Suzuki偶联反应制得1,2,4,5-四苯基-3,6-二[3,5-二(4-十二烷基苯基)]苯基苯(8);8经路易斯酸催化的Scholl氧化脱氢关环反应合成了一个新的扶手型分子石墨烯,其结构经1H NMR,13C NMR和MALDI-TOF-MS表征。     

新型六[间-(β-噻吩基)苯基]苯衍生物的合成

3,3’-二溴二苯乙炔与β-噻吩频哪醇硼酸酯发生Suzuki偶联反应制得3,3’-二(2,5-二十二烷基-3-噻吩)二苯乙炔(7);Co2(CO)8催化7自身环三聚合成了新型六[间-(β-噻吩基)苯基]苯衍生物——六{3-[2’,5’-二(十二烷基)-3-噻吩]苯基}苯,产率86%,其结构经1H NMR和MS表征。     

新型维甲酸类化合物的合成及生物活性研究

以苯甲醚为起始原料,经Friedel-Crafts反应、溴化和亲核取代转化为硼酸中间体2.以羟基丙酮12为起始原料,经过Wittig反应、溴化、Arbuzov反应、Horner-Wadsworth-Emmons(HWE)反应后得到共轭烯烃溴代物3;化合物2分别与化合物3、4-溴-2-氟苯甲酸甲酯(4)和6-溴烟酸甲酯(5)经Suzuki偶联反应和水解反应,得到三个未见报道的维甲酸类似物1a~1c.同时,以溴苯为起始原料经Friedel-Crafts反应、硝化反应、三氟甲基化反应、硝基还原和亲核取代合成了含有三氟甲基的维甲酸类似物1d.化合物1a~1d的结构经过1H NMR,13C NMR,IR及HRMS的表征,并对四个化合物进行了HL-60细胞株分化活性能力的测试.结果表明化合物1a~1d都具有潜在的药物活性,其中含氟维甲酸类似物1b和1d拥有较商品化药物全反式维甲酸(ATRA)更低的IC50值.     

新型亲脂性菲啰啉衍生物的合成及其自组装性能

以1,10-菲啰啉为起始原料,经溴代、氧化、Suzuki偶联等反应合成了新型亲脂性菲啰啉衍生物——3,8-二(4-联苯基)-5,6-二(十二烷氧基)-1,10-菲啰啉(1),总收率11.24%,其结构经1H NMR,13C NMR和MALDITOF-MS表征。自组装性能研究结果表明,1的自组装体呈规整的微米球状结构。     

ω-Hydroxy and ω-Amino-carboxylic Acid Derivatives for the Preparation of Ester and Amide Crown Ethers

An oxymercuration reaction between methyl acrylate and the monobenzyl ethers (3) of mono-, di-, and triethylene glycol, followed by reduction with sodium borohydride, gives the expected polyether esters (4). These are converted by standard procedures into various derivatives of the ω-hydroxy and ω-amino acids (1) and (2) respectively.     

Facile Synthesis of Tris(alkoxydimethylsilyl)methane Derivatives via Alcoholysis Under Open-Flask and Mild Conditions

The reactions between a variety of functionalized alcohols and tris(dimethylsilyl)methane, (HMe₂Si)₃CH, are described. Alcohols such as ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, triethylene glycol monomethyl ether, 2-chloroethanol, 1-octanol, benzyl alcohol, glycidol, and allyl alcohol were converted in the presence of Karstedt's catalyst into the corresponding tris(alkoxydimethylsilyl)methanes, (ROMe₂Si)₃CH, in a convenient one-pot operation under aerobic conditions. The appearance of the products coincides with the generation of colloidal Pt(0) species. Moreover, poly(4-chloromethyl)styrene containing tris(dimethylsilyl)methyl groups reacts with benzyl alcohol or 2-chloroethanol in the presence of Karstedt's catalyst to give new macromolecules bearing tris(alkoxydimethylsilyl)methyl groups. The reaction rate is greatly influenced by the concentration of catalyst.     

Novel approach to the synthesis of 3-acyl substituted indolizines. The synthesis of 3-(indolizinyl-2)alanine and 4-(indolizinyl-3) homoalanine derivatives

A novel approach to the synthesis of 3-acylindolizines and the transformations of some acids into tryptophane analogues are described. Reaction of ethyl 2-pyridinylacetate and methyl 2-quinolinylacetate with N-trifluoroacetyl-5-bromo-4-oxonorvaline methylester led to N-trifluoroacetyl-3-(1-ethoxycarbonylindolizinyl-2) alanine methyl ester and N-trifluoroacetyl-3-(3-methoxycarbonylpyrrolo [1,2-a]quinolinyl-2) alanine methyl ester, respectively. Treatment of ethyl 2-pyridinylacetate and 2-pyridinylacetonitrile, first with N,N-dimethylformamide dimethyl acetal (DMFDMA), followed by reaction with phenacyl bromide, gave the corresponding 3-benzoylindolizines, while the reaction of ethyl 2-pyridinylacetate and 2-pyridinylacetonitrile with DMFDMA, followed by treatment with (S)-N-trifluoroacetyl-5-bromo-4-oxonorvaline methyl ester, gave the corresponding N-trifluoroacetyl-4-oxo-4-(indolizinyl-3)homoalanine methyl esters.     

Methyl (<Emphasis Type="Italic">Z</Emphasis>)-3-bromo-3-(4-methylbenzenesulfonyl)prop-2-enoate: Synthesis and reactions with dimethyl malonate and methyl acetoacetate

Bromination–dehydrobromination of methyl (E)-3-(4-methylbenzenesulfonyl)prop-2-enoate gave methyl (Z)-3-bromo-3-(4-methylbenzenesulfonyl)prop-2-enoate whose structure was determined by X-ray analysis. Methyl (Z)-3-bromo-3-(4-methylbenzenesulfonyl)prop-2-enoate behaved as a synthetic equivalent of methyl 3-(4-methylbenzenesulfonyl)prop-2-ynoate in reactions with dimethyl malonate and methyl acetoacetate, which afforded the corresponding Michael adducts, trimethyl 3-(4-methylbenzenesulfonyl)prop-1-ene-1,1,2-tricarboxylate and dimethyl (Z)-2-acetyl-3-(4-methylbenzenesulfonyl)but-2-enedioate, respectively, via nucleophilic attack on the β-position with respect to the sulfonyl group.     

Silica Gel Catalyzed Conversion of Dimethyl 2-(5-Bromo-2-hydroxyphenyl)-3-(triphenylphosphoranylidene)butanedioate to Methyl 6-Bromo-2-oxo-2H-chromene-4-carboxylate in Solvent-Free Conditions

Protonation of the highly reactive 1:1 intermediates, produced in the reaction between triphenylphosphine and dimethyl acetylenedicarboxylate, by 4-bromophenol leads to vinyltriphenylphosphonium salt, which undergoes aromatic electrophilic substitution reaction with conjugate base to produce dimethyl 2-(5-bromo-2-hydroxyphenyl)-3-(triphenylphosphoranylidene)butanedioate. Silica gel was found to catalyze conversion of dimethyl 2-(5-bromo-2-hydroxyphenyl)-3-(triphenylphosphoranylidene)butanedioate to methyl 6-bromo-2-oxo-2H-chromene-4-carboxylate in solvent-free conditions at 80°C in fairly high yield.     

Effect of methyl substituents on the NMR spectra of aromatic protons of some nitrobenzene derivatives

Proton NMR spectra were recorded and analysed for 1-bromo-4-nitrobenzene, 2-bromo-5-nitroluene, 3-bromo-6-nitrotoluene and 2-bromo-5-nitro-p-xylene, as well as for the corresponding compounds having p-CH₃C₆H₄S in place of Br. Chemical shifts and coupling constants generally agree with expected values; however, a deshielding effect of the methyl group on aromatic protons was observed in one case.     

Biocatalytic reduction system for the production of chiral methyl (R)/(S)-4-bromo-3-hydroxybutyrate

An effective method for producing methyl 4-bromo-3-hydroxybutyrate enantiomers was developed using an engineered protein. Escherichia coli transformant cells containing a mutant β-keto ester reductase (KER-L54Q) from Penicillium citrinum and a cofactor-regeneration enzyme such as glucose dehydrogenase (GDH) or Leifsonia sp. alcohol dehydrogenase (LSADH) were used to produce methyl (S)-4-bromo-3-hydroxybutyrate from methyl 4-bromo-3-oxobutyrate. On the other hand, the production of methyl (R)-4-bromo-3-hydroxybutyrate was achieved by asymmetric reduction of methyl 4-bromo-3-oxobutyrate with a mutant phenylacetaldehyde reductase (PAR-HAR1) from Rhodococcus sp. ST-10.     

Vibrational analysis of mononitro substituted benzamides, benzaldehydes and toluenes. Part II. Transferability of valence force constants

A zero-order normal coordinate analysis of both the in-plane and out-of-plane vibrations was made for p-, m- and o-methylbenzaldehydes; 3,5-dichloro-p-anisamide; 3,5-dibromo-p-anisamide; 4-chloro-3-nitrotoluene; 2-bromo-4-nitrotoluene and 2-bromo-5-nitrotoluene by transferring the force constants obtained before hand. The observed and calculated frequencies agreed reasonably well demonstrating the transferability of the force field. On the basis of calculated potential energy distributions and eigen vectors, several assignments suggested by earlier workers have been revised.     

Photochemical coupling of 5-bromo-1,3-dimethyluracil and its 6-alkyl derivatives to 3-methylindole and N alpha-acetyl-L-tryptophan methyl ester

Photochemical reactions between 5-bromo-1,3-dimethyluracils and 3-substituted indoles in acetone solution were studied. Irradiation (lambda greater than 290 nm) of 5-bromo-1,3-dimethyluracil (1) and N alpha-acetyl-L-tryptophan methyl ester (2) yields, in addition to 5-(2-indolyl)uracil (3), a new photoadduct 5-(7-indolyl)uracil (4). 5-Bromo-1,3-dimethyluracils with 6-alkyl substituents irradiated in the presence of 2 give the 5-(2-indolyl)uracil-type photoadducts exclusively.     

Polyesters based on bromine-containing bis(p-methoxycarbonylphenoxymethyl)-methylphosphine oxide

A phosphorus- and bromine-containing bifunctional monomer has been prepared from bis(chloromethyl)methylphosphine oxide and the sodium salt of methyl 3-bromo-4-hydroxybenzoate. From this monomer, bis(2-bromo-4-methoxycarbonylphenoxymethyl)methylphosphine oxide and glycols, polyesters have been obtained by transesterification in the melt. Similarly, using dimethyl terephthalate and ethylene glycol, copolymers containing different amounts of Br and P have been prepared. They are actually polyethyleneterephthalates containing different amounts of phosphorus and bromine. The critical oxygen index is used in the evaluation of the resistance of copolyesters to combustion. It is shown that the P- and Br-containing copolyesters possess a significantly higher resistance to combustion than similar P- and P- and Cl-containing polymers with the same P content.