9,9-二甲基-2-(N-联苯基)氨基芴的合成

以芴为原料,苄基三甲基三溴化铵为溴化试剂,室温下在甲醇和二氯甲烷中溴化得到2-溴芴,然后以四氢呋喃为溶剂,在叔丁醇钾作用下与碘甲烷反应合成9,9-二甲基-2-溴芴,最后与4-联苯胺通过Buchwald-Hartwig偶联反应合成目标化合物9,9-二甲基-2-(N-联苯基)氨基芴,总收率为56.0%～62.4%。通过1HNMR、13CNMR、MS、IR和元素分析确证了其结构。     

含有4,5-二氮芴-9-酮锌(Ⅱ)、钴(Ⅱ)化合物的合成和晶体结构

Two compound crystals of (Hdafo)₂[ZnCl₄]·2H₂O (1) and (Hdafo)₂[CoCl₄]·2H₂O (2) were obtained when we tried synthesizing the mixed ligand compounds of Zinc (Ⅱ) and Cobalt(Ⅱ) with 4,5-diazafluorene-9-one(dafo) and o-phthalic acid, respectively. Their structure was determined by single crystal X-ray diffraction. The crystals all belong to monoclinic system, C2/c space group with crystallographic data:(Hdafo)₂[ZnCl₄]·2H₂O, a=1.6768(5)nm, b=1.2052(3)nm, c=1.3888(4)nm, β=116.793(3), V=2.5053(12)nm³, Z=4, F(000)=1232, M_r=609.57, D_c=1.616g·cm^-3, μ(MoKα)=1.444mm^-1, R₁=0.0373, wR₂=0.0765; (Hdafo)₂[CoCl₄]·2H₂O, a=1.6787(4)nm, b=1.2078(3)nm, c=1.3911(4)nm, β=116.665(3)°, V=2.5204(11)nm³, Z=4, F(000)=1220, M_r=603.13, D_c=1.589g·cm^-3, μ(MoKα)=1.142mm^-1, R₁=0.0257, wR₂=0.0654. The constitutes of the two compounds were proved by elemental, IR Spectra and thermal analyses. CCDC: 1, 198516; 2, 198517.     

4,4’-二葡萄糖苷-2,2’-二苯酚基异丙烷的合成

糖番(Glycophane)[1-3]是由醛糖化合物和芳基化合物反应生成的大环分子,其合成设计思想是在醛糖衍生物的结构单元中插入具有亲脂性的芳基化合物,使合成的受体分子既具有天然环糊精的手性环境,亲脂性空腔和良好的水溶性,又有合成环番的π电子作用特性,因此它兼有环糊精和环番的性质.     

噻吩甲酰三氟丙酮和4，5-二氮芴-9-酮及4，5-二氮芴-9-酮连氮铕(Ⅲ)三元配合物的合成和表征

合成了Eu(TTA)₃L1(Ⅰ)和［Eu(TTA)₃］₂L2(Ⅱ)二种新的铕(Ⅲ)三元配合物(TTA=噻吩甲酰三氟丙酮一价阴离子、L1=4,5-二氮芴-9-酮、L2=4,5-二氮芴-9-酮连氮)。用元素分析、IR、UV和溶液荧光光谱对配合物进行了表征。探讨了溶剂对Eu(Ⅲ)三元配合物荧光光谱的影响，发现在CH₃CN中Eu(Ⅲ)三元配合物发光效果最好，而溶剂DMF会使配合物荧光减弱。     

3,3′-(1,1′-二苯基-4,4′-二基)-二丙烯酸的合成新方法

通过Heck反应,以4,4′-二碘联苯和丙烯酸为原料,壳聚糖负载钯为催化剂,合成了3,3′-(1,1′-二苯基-4,4′-二基)-二丙烯酸.考察了反应温度、时间、原料配比等因素对产率的影响.结果表明最佳反应条件为:反应温度为100℃,时间为20h,原料配比为1∶3.测试了壳聚糖负载钯催化剂的重复使用性能,并用IR、1 H NMR和MS对产物进行了表征.     

三(2,4-二溴苯基)磷酸酯的合成研究

Tris(2,4-dibromophenyl)phosphate(BPP) is an additive flame-retardant for plastic with the properties of low melt point,good compatibility and excellent thermal stability.Chloroform with high value of AN was selected as the solvent based on the solvent effect,the flame retardant tris(2,4-dibromophenyl)phosphate(BPP) was synthesized by POCl3 reacting with 2,4-dibromophenol(mol tatio was 1.0∶3.1) under reflux conditions,the yield was 96.4%.     

Pd2(dba)3/BINAP催化合成[4,4′-(4,4′-二苯亚胺基)二苯甲酰胺基]二苯醚

在三乙胺催化下,4-溴苯甲酰氯与4,4′-二氨基二苯醚反应制得[4,4 ′-(4,4′-二溴)-二苯甲酰胺基]二苯醚(1);1与苯胺在Pd2 (dba) 3/BINAP催化下合成了新化合物——[4,4′-(4,4′-二苯亚胺基)二苯甲酰胺基]二苯醚,其结构经1 H NMR和FT-IR表征.     

4,5-二氮芴-9-酮Cu(Ⅱ),Zn(Ⅱ)配合物的合成、晶体结构、热分析及理论计算

合成了4,5-二氮芴-9-酮(dafo)的Cu(Ⅱ), Zn(Ⅱ)配合物[Cu(dafo)₂(H₂O)₂] (NO₃)₂和[Zn(dafo)₂ (H₂O)₂] (NO₃)₂,通过单晶X射线衍射法确定了它们的结构.晶体结构分析表明,配合物分子中Cu(Ⅱ), Zn(Ⅱ)分别和来自两配体的四个氮原子及两个水分子中的氧原子配位,处于六配位的配位环境中,两配体基本处于同一平面,两水分子垂直于两配体所在平面,Cu(Ⅱ)处于畸变八面体中心,Zn(Ⅱ) 处于正常八面体中心,对两种配合物进行了元素分析、红外和热分析表征,在实验的基础上,采用Gaussian-98w中的DFT-B3LYP/LANL2DZ对两种配合物进行了全几何优化以及后续计算.     

B-[9,9-双(4-甲基苯基)-9H-芴-2-基]硼酸的合成工艺优化

以2-溴-9-芴酮为原料,经亲核加成、取代、氧化还原、氧化反应合成B-[9,9-双(4-甲基苯基)-9H-芴-2-基]硼酸,其结构经¹H NMR确证。采用响应面法重点对氧化还原步骤进行优化。确定较优合成条件为：反应时间5.4 h,催化剂用量为0.4 eq.,反应温度为108 ℃,目标产物收率92.15%,相对误差0.54%。      

4,5-二氮芴-9-酮Cu(II),Zn(II)配合物的合成、晶体结构、热分析及理论计算

合成了 4,5 二氮芴 9 酮 (dafo)的Cu(II) ,Zn(II)配合物 [Cu(dafo) 2 (H2 O) 2 ] (NO3 ) 2 和 [Zn(dafo) 2 (H2 O) 2 ] (NO3 ) 2 ,通过单晶X射线衍射法确定了它们的结构 .晶体结构分析表明 ,配合物分子中Cu(II) ,Zn(II)分别和来自两配体的四个氮原子及两个水分子中的氧原子配位 ,处于六配位的配位环境中 ,两配体基本处于同一平面 ,两水分子垂直于两配体所在平面 ,Cu(II)处于畸变八面体中心 ,Zn(II)处于正常八面体中心 ,对两种配合物进行了元素分析、红外和热分析表征 ,在实验的基础上 ,采用Gaussian 98w中的DFT B3LYP/LANL2DZ对两种配合物进行了全几何优化以及后续计算     

Synthesis of 1,7-Bis(4-hydroxyphenyl)-3-hydroxy-1,3-heptadien-5-one

l,7-Bis(4-hydroxyphenyl)-3-hydroxy-1,3-heptadien-5-oneIIwagfirstlyisolatedfromtheseedsofAIPiniablepharocalyxK.Schum.(Zingiberaceae)asanoveldiarylheptanoid.Meanwhile,l,7-his(4-hydroxyphenyl)-3-hydroxy-l,3,6-heptatTien-5-one2,aknowndiarylheptanoid,wasisolatedaswell.Therecentpublication'reportedthatIstronglyinhibitedtheaggregationofplateletinducedbycollagen,arachidonicacidandadenosinediphosphate.AdditionalresearchZprovedthat2couldactasaninhibitoroftheHIV-1integrase.Byourfindings,thesynthesi…     

2,2-Bis(3-allyl-4-hydroxyphenyl)hexafluoropropane and fluorosiloxane as coating materials for nerve agent sensors

A simpler technique for the synthesis of 2,2-bis(4-allyoxyphenyl)hexafluoropropane has been achieved from 4,4′-(hexafluoroisopropylidene)diphenol for obtaining 2,2-bis(3-allyl-4-hydroxyphenyl)hexafluoropropane. This monomer and its corresponding hybrid organic/inorganic siloxane polymer are successfully used as a coating material for the detection of toxic chemical warfare agents.     

主链含酞和芴结构的无定形聚芳醚酮的合成

通过共聚改性在酚酞聚芳醚酮(PEK-C)的主链上引入含芴侧基,制备了一系列主链含酞和芴结构的线性高分子量无定形聚芳醚酮无规共聚物.通过傅里叶红外光谱(FTIR)、核磁共振谱(1H,13C NMR)等手段确定了共聚物结构.凝胶渗透色谱(GPC)数据表明,共聚物的Mn>6.0×104,Mw>1.0×105,PDI(Mw/Mn)范围在1.6~1.7之间.X射线衍射(XRD)数据表明共聚物系无定形结构,差示扫描量热法(DSC)和热重分析(TGA)测试表明聚合物具有良好的耐热性;初始热分解温度高于467℃;700℃时残炭率大于58.9%;共聚物呈现单一的玻璃化转变温度(Tg>243℃).当酚酞与双酚芴摩尔比在3∶7~5∶5范围时,共聚物的弹性模量和断裂伸长率显著提高,可分别达到3.1 GPa和58%,是酚酞聚芳醚酮的1.4倍和8.3倍.这类含酞和芴侧基的无定形聚芳醚酮保持了在氯仿、二氯甲烷、四氢呋喃(THF)和甲基吡咯烷酮(NMP)等极性非质子溶剂中良好的溶解性能,并显著提高了聚合物的力学性能和热性能.     

Syntheses and properties of aromatic polyamides and polyimides derived from 9,9-bis[4-(p-aminophenoxy)phenyl]fluorene

9,9-Bis[4-(p-aminophenoxy)phenyl]fluorene ( II ) was used as a monomer with various aromatic dicarboxylic acids and tetracarboxylic dianhydrides to synthesize polyamides and polyimides, respectively. The diamine II was derived by a nucleophilic substitution of 9,9-bis(4-hydroxyphenyl)fluorene with p-chloronitrobenzene in the presence of K₂CO₃ and then hydro-reduced. Polyamides IV _a-g having inherent viscosities of 0.73–1.39 dL/g were prepared by the direct polycondensation of the diamine II with various aromatic diacids using triphenyl phosphite and pyridine as condensing agents. All the aromatic polyamides were amorphous and readily soluble in various polar solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, and N-methyl-2-pyrrolidone. Transparent and flexible films of these polymers could be cast from the DMAc solutions. These aromatic polyamides had glass transition temperatures in the range of 283–309°C and 10% weight loss occurred up to 460°C. The polyimides were synthesized from diamine II and various aromatic dianhydrides via the two-stage procedure that included ring-opening poly-addition in DMAc to give poly(amic acid)s, followed by thermal or chemical conversion to polyimides. The poly(amic acid)s had inherent viscosities of 0.62–1.78 dL/g, depending on the dianhydrides. Most of the aromatic polyimides obtained by chemical cyclization were found to be soluble in NMP. These polyimides showed almost no weight loss up to 500°C in air or nitrogen atmosphere. © 1993 John Wiley & Sons, Inc.     

9, 9-二(3-氨基-4-羟基苯基)呫吨的合成

以醋酸酐为溶剂, 将9, 9-二(4-羟基苯基)呫吨与浓硝酸在15 ℃左右发生硝化反应1.5 h, 形成中间体-9, 9-二(3-硝基-4-羟基苯基)呫吨, 产率为88.5%;继而以Pd/C 为催化剂, 80%的水合肼为还原剂, 在乙醇和1, 4-二氧六环混合溶剂中, 于70 ℃将中间体进行还原反应10 h, 得到目标产物9, 9-二(3-氨基-4-羟基苯基)呫吨, 产率为90.8%, 两步反应总收率为80.4%。 中间体与目标化合物经NMR、FTIR和元素分析等确定了它们的结构。     

Synthesis of 2,5 -Bis(4-methyl-2-thienyl)thiophene and 2,5-Bis(4-methyl-2-thienyl)pyrrole

Syntheses of 2,5-bis(4-methyl-2-thienyl)thiophene 3 and 2,5-bis(4-methyl-2-thienyl)pyrrole 4 are described. The key step involves Stetter reaction between 4-methyl-2-thiophenecarboxaldehyde and divinyl sulfone. Cyclizaton of the resulting 1,4-bis-(4-methyl-2-thienyl)-1,4-butanedione 2 with Lawesson's reagent gives 2,5-bis(4-methyl-2-thienyl)thiophene 3, whereas condensation with ammonium acetate provides the 2,5-bis(4-methyl-2-thienyl)pyrrole 4.     

New poly(amide-imide) syntheses. XII. Preparation and properties of poly(amide-imide)s based on the diimide-diacid condensed from 9,9-bis[4-(4-aminophenoxy)phenyl] fluorene and trimellitic anhydride

A dicarboxylic acid ( I ) was prepared from the condensation of 9,9-bis[4-(4-aminophenoxy) phenyl] fluorene and trimellitic anhydride. A new family of poly(amide-imide)s having inherent viscosities of 0.75-1.04 dL/g was prepared by the triphenyl phosphite activated polycondensation from the diimide-diacid I with various aromatic diamines in a medium consisting of N-methyl-2-pyrrolidone (NMP), pyridine, and calcium chloride. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 262–325°C and the 10% weight loss temperatures were above 525°C in air. © 1994 John Wiley & Sons, Inc.     

9,9-二(4-羟基苯基)呫吨、1,4-二(4-氟苯甲酰基)苯和双酚A三元共聚物聚醚醚酮酮的合成与表征

通过亲核取代反应,将9,9-二(4-羟基苯基)呫吨(BHPX)、1,4-二(4-氟苯甲酰基)苯和双酚A(BPA)进行三元共缩聚反应,合成了几种主链含二甲基甲烷和呫吨结构的聚醚醚酮酮无规共聚物(PEEKK-X/PEEKK-A),并以FTIR、DSC、TG、WAXD等对其结构和性能进行了表征.结果表明,共聚物的玻璃化转变温度(Tg)为185～218℃,均为无定形结构,其数均分子量为39500～41600,多分散性指数为1.94～2.05.在氮气、空气气氛中,在430℃之前不分解,5%的热失重温度(Td5)分别为490～511℃、480～505℃,在氮气中700℃时的残炭率均在40%以上;在常温下易溶于非质子极性溶剂(如NMP和DMAc)以及极性较弱的溶剂(如THF和CHCl3)中.共聚物均可通过溶液浇铸成膜,所得到的薄膜韧性好,透明且耐折,其拉伸强度为58～75MPa,杨氏膜量为1.95～2.70GPa,断裂伸长率为8%～13%.当双酚单体BHPX和BPA摩尔比为60/40～50/50时,所得到的PEEKK-X/PEEKK-A共聚物更有潜在的应用前景.     

Photocrosslinkable polymers based on 4-[5-(4-hydroxyphenyl)-3-oxopenta-1,4-dienyl]phenyl-2-methacrylate: photocrosslinking studies and reactivity ratios with vinylcyclohexane

1,5-Bis(4-hydroxyphenyl)penta-1,4,dien-3-one (HPD) was synthesized using p-hydroxybenzaldehyde and acetone in the presence of hydrogen chloride gas. Acrylated derivative of HPD 4-[5-(4-hydroxyphenyl)-3-oxopenta-1,4-dienyl]phenyl-2-methacrylate (HPPMA) was synthesized by reacting HPD and methacryloyl chloride in the presence of triethylamine at 0-5 °C. Homo- and co-polymer (with vinylcyclohexane (VC)) of HPPMA was carried out in methyl ethyl ketone using benzoyl peroxide (BPO) under nitrogen atmosphere at 70 ± 1 °C. All the monomer and polymers were characterized by IR and NMR techniques. Monomer reactivity ratios were calculated using Fineman-Ross (FR), Kelen-Tudos (KT) and extended Kelen-Tudos (ex-KT) methods. Photocrosslinking nature of the polymer samples were carried out in solution phase using tetrahydrofuran (THF) solvent under high frequency UV light. Rate of photocrosslinking of the polymer samples were measured for poly(HPPMA) and for poly(VC-co-HPPMA). Thermal stability of the polymer samples was recorded using thermogravimetric analysis (TGA) method. Molecular weights (M_w and M_n) of the polymer samples were determined using gel permeation chromatographic (GPC) technique.     

四(对羟基苯基)钴卟啉的合成新方法

本研究用丙酸和DMF混合液作为溶剂,采用溶剂热合成的方法这一新型的合成方法,由吡咯,对羟基苯甲醛,以及CoCl2.6H2O直接合成四羟基苯基钴卟啉配合物。探讨了诸因素对反应的影响,找出最佳的反应过程以及最适宜的反应条件:在140℃时,吡咯,对羟基苯甲醛,金属盐CoCl2.6H2O,丙酸,DMF的摩尔比为4∶4∶1∶134∶86时得最高产率,达到43.2%,这相比于传统方法的10%～30%有了一定的提高。