六(甲氧基乙氧基乙氧基)三聚磷腈的合成与表征

以六氯三聚磷腈和甲氧基乙氧基乙醇为主要原料,合成了全取代的六(甲氧基乙氧基乙氧基)三聚磷腈,并用IR、31P NMR、1HNMR、13C NMR、FABMS等现代谱学技术对其结构进行了表征。经生物活性试验证明,此化合物对腐生线虫Panagrellus redivivus具有一定的毒杀活性。     

一种无计有机聚合物中间体——六(甲基丙烯酸羟乙酯)三聚膦腈的合成

六氯三聚膦腈;一种无计有机聚合物中间体——六(甲基丙烯酸羟乙酯)三聚膦腈的合成     

杂质对六氯环三聚磷腈热聚合的影响

利用红外光谱、磷核磁共振谱、广角X射线衍射、差示扫描量热、凝胶色谱等分析手段,研究了六氯环三聚磷腈(HCCP)在存放过程中产生的杂质,以及不同纯化方法对这些杂质的去除效果,探讨了这些杂质对HCCP单体真空热开环聚合反应的影响.HCCP在存放过程中接触空气中的水汽在环上氯基团处易被水解,产生Trimer-1、Gem-2、Dimmer-3等杂质,重结晶能去除Gem-2、Dimmer-3和少量的Trimer-1,升华能较好地去除Trimer-1.杂质Gem-2、Dimmer-3中的羟基引发聚二氯磷腈交联,生成不可溶的交联态聚二氯磷腈,而Trimer-1则会降低聚合速度,并在聚合物中引入磷氧基和亚胺基杂链,从而影响后续聚磷腈取代产物的性质,表现为聚合物中晶态发生变异,结晶度降低,玻璃化温度、晶态转化温度和熔融温度出现差别.用重结晶结合升华的方法对HCCP单体进行纯化后,应用FTIR或31P-NMR分析来验证纯化效果,以确保能控制聚合速度和时间,使聚合顺利进行.     

聚[(甲氧基乙氧基乙氧基)1.0(乙氧基吡咯烷酮)1.0]膦腈的合成及性能研究

用三氯化铝催化六氯三聚膦腈开环聚合制得线性聚二氯膦腈(PDCP), 通过PDCP磷原子上的亲核取代反应, 合成了新的水溶性高分子聚[(甲氧基乙氧基乙氧基)_1.0(乙氧基吡咯烷酮)_1.0]膦腈(P3), 用³¹P NMR, ¹H NMR, ¹³C NMR和IR对其结构进行了确证, 用DSC测定了其玻璃化转变温度T_g和熔融温度T_m, 用蒸汽压渗透法(VPO)测定了其数均分子量. 改进了聚二(乙氧基吡咯烷酮)膦腈(P2)的合成方法. 体外降解实验表明, P3具有和P2类似的pH响应性降解行为, 降解速率在pH=5.0时最快, 而在pH=7.4和8.0时较慢. P3在所测试的3个pH缓冲溶液中均比P2降解慢. 用³¹P NMR、薄层色谱(TLC)和滴定法对降解产物进行了检测, 初步推断了P3在不同pH介质中的水解机理, 其在pH=5.0的缓冲溶液中的降解, 除侧链断裂外, 聚膦腈的骨架也裂解; 而在pH=7.4和8.0时的降解仅为侧链的断裂. 用噻唑蓝(MTT)比色法进行的体外细胞毒性评价实验表明, P3及其在pH=5.0的缓冲溶液中降解49 d后的产物均对细胞表现出了很好的生物相容性, 而且其降解产物在浓度为800 μg/mL时还表现出一定的促进细胞增殖作用.     

聚[2-(2-氯乙氧基)乙氧基)_x(三氟乙氧基)_(2-x)]磷腈合成和气体分离性能研究

六氯环三聚磷腈经二次重结晶一次减压升华纯化后,通过真空热开环聚合和亲核取代反应,用不同摩尔比的2-(2-氯乙氧基)乙醇钠和三氟乙醇纳(1∶3;1∶5;1∶6.5)作为亲核取代试剂混取代聚二氯磷腈,再经多次非溶剂沉淀纯化得到目标聚合物聚[(2-(2-氯乙氧基)乙氧基)x(三氟乙氧基)2-x]磷腈.利用31P-NMR监测,以确保得到纯化的聚合物.采用1H-NMR、FT-IR、GPC、DSC、XRD等测试手段对所得到的聚合物进行了结构表征和性能测试,并利用自制的压力法透气性能测定仪测定了这些聚合物的气体渗透系数.结果表明,三氟乙氧基和2-(2-氯乙氧基)乙氧基两种基团已接枝在聚磷腈侧链上,分别得到x值为0.19,0.18和0.08的3种聚[(2-(2-氯乙氧基)乙氧基)x(三氟乙氧基)2-x]磷腈,其玻璃化温度分别为-6.37℃,-12.85℃和-25.68℃,重均分子量为5.4×105,6.8×105和1.5×105,在同样的反应条件下,三氟乙氧基较2-(2-氯乙氧基)乙氧基有更强的竞争取代率.这种混取代聚磷腈较单一取代基的聚三氟乙氧基磷腈结晶度小,在本实验中两种取代基比例适中的聚[(2-(2-氯乙氧基)乙氧基)0.18(三氟乙氧基)1.82]磷腈的结晶度降至10.1%,这种聚合物显示出较高的气体渗透系数,CO2和He的气体渗透系数达到88.9和60.6 barrer,CO2/CH4和He/CH4的选择系数达到24.1和16.4,在天然气行业显露出良好的应用潜力.此外这类聚合物表现出特殊的H2/N2选择性,选择系数在0.2左右,N2的渗透系数为8.5 barrer,因而在合成氨行业显示出特殊的应用潜力.     

含咔唑生色团的三聚磷腈分子玻璃的合成

含咔唑生色团的三聚磷腈分子玻璃的合成;三聚磷腈;后重氮偶合;咔唑;光折变分子玻璃     

2,2,4,4—四对羟甲基酚氧基—6,6—二苯基三聚磷腈的合成

通过Friedel－Crafts反应，将本基引入到六氯环三磷腈上，然后由亲核取代反应和氢化还原反应，合成了2，2，4，4-四对羟甲基酚氧基-6，6-二苯基三聚磷腈，探索了各步的合成、分离方法，并对化合物的结构进行了表征．     

新型环磷腈类化合物的合成

六氯环三磷腈(1)分别与间苯二胺(2)和二苯氨基脲(3)经亲核取代反应合成了两个新型的环磷腈类化合物——六间苯二胺环三磷腈(4)和六二苯氨基脲环三磷腈(5),其结构经1H NMR,31P NMR和IR表征。合成4的最佳反应条件为:1 7.2 mmol,n(2)∶n(1)=6.17,于70℃反应12 h,产率72.68%。合成5的最佳反应条件为:1 2.8 mmol,n(3)∶n(1)=6.10,于70℃反应12 h,产率46.57%。     

正交法研究六氯环三磷腈的合成

利用正交法研究了六氯环三磷腈的合成反应;针对较典型的四个因素,分别取四水平L16(45)正交表进行正交试验,确定了合成目标产物的主要影响因素和优化反应条件.结果表明,先将2/3的固体五氯化磷与2%无水氯化锌和30%吡啶(以五氯化磷物质的量计)混合,再缓慢滴加入剩余的五氯化磷氯苯溶液,最高产率可达84%以上;方差分析结果...     

Fluoroscence Phenomena—New Properties of Hexakis （4—Aminophenoxy）Cyclotriphosphazene

Investigations of the absorption and fluorescence spectra of hexakis(4-aminophenoxy)-cyclotriphosphazene at room temperature in three solvents of different polarity (N,N-dimethyl-formamide,tetrahydrofuran and toluene)have been conducted.And fluorescence lifetimes of these three solutions were also measured. Major reasons of such spectral behavior are discussed.     

1-(2-Quinoxalyl)-, 1-[3,5-Di(trifluoromethyl)phenyl]-, 1-(2-Carboxyphenyl)-, and 1-Ethoxycarbonyl-4-oxo-4,5,6,7-tetrahydroindazoles

The corresponding 1-(2-quinoxalyl)-, 1-[3,5-di(trifluoromethyl)phenyl]-, and 1-ethoxycarbonyl-3-methyl-4-oxo-4,5,6,7-tetrahydroindazoles have been obtained from reactions of 2-acetyl-1,3-cyclohexanedione, its 5,5-dimethyl and 5-(2-furyl) derivatives, with 2-hydrazinoquinoxaline, 3,5-di(trifluoromethyl)phenylhydrazine, and ethoxycarbonylhydrazine. On interaction with ethoxycarbonylhydrazine the intermediate 2-[1-(-ethoxycarbonyl)hydrazino]ethylidene-1,3-cyclohexanediones were also isolated. From the potassium salt of 2-formyldimedone and 2-carboxyphenylhydrazine hydrochloride, 2-(2-carboxyphenyl)hydrazinomethylene-5,5-dimethyl-1,3-cyclohexanedione was obtained, the cyclization of which in ethanol in the presence of HCl led to 1-(2-carboxyphenyl)- and 1-(2-ethoxycarbonylphenyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole.     

One-Pot Synthesis and Methylation of 3-[2-(1H-Benzimidazol-2-yl-Sulfanyl)-Acetyl]-Chromen-2-Ones

Abstract

3-(2-Bromoacetyl)coumarins (I), when treated with 2-mercatobenzimidazole (II) in acetone containing K₂CO₃ (mild base) and tetrabutylammonium bromide (TBAB) as a phase transfer catalyst, at room temperature yielded the title compound 3-[2-(1H-benzimidazole-2-yl-sufanyl)-acetyl]-chromen-2-one (III) in a one-pot synthesis. Alternatively, III could also be prepared by treating dithiocarbonic acid O-ethyl ester, S-[2-oxo-2-(2-oxo-2H-chromen3-yl)-ethyl] ester (V), with o-phenylenediamine (VI). The methylation of the title compound III was performed with dimethyl sulfate (DMS), in acetonitrile containing TBAB and K₂CO₃ at room temperature, resulting in 3-[2-(N-methyl-benzimidazol-2-yl-sulfanyl)]-acetyl-chromen-2-ones (VII). Alternatively, methylation of III could also be performed with DMS in acetonitrile containing K₂CO₃ as base and clay as surface catalyst. All the compounds were synthesized in good yields and their structures were confirmed by spectral and analytical data.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: ¹H NMR of IIIB, VB and VIIB]     

1-[2-(N,N-二甲氨)乙基]-5-巯基-1H-四氮唑的制备与表征

头孢菌素类药物是抗生素发展最为迅速的品种之一.在头孢菌素母体(7-ACA)的C3位修饰含氮化合物是开发长高效型头孢菌素的主要方向,1-[2-(N,N-二甲氨)乙基]-5-巯基-1H-四氮唑是制备新一代口服长效型药物头孢替安脂C3位的化学修饰物[1].     

5-氟尿嘧啶-聚[N-(2-羟乙基)-L-谷酰胺]的合成及缓释性能研究

以聚谷氨酸苄酯为原料,用乙醇胺进行胺解得水溶性的可生物降解的聚[N-(2-羟乙基)-L-谷酰胺];用光气/甲苯液活化5-氟尿嘧啶,将其以共价键形式键合在高分子上,得5-氟尿嘧啶的高分子前药。用IR、UV、1HNMR及DSC对其结构进行表征,用紫外光谱测定其药物含量,载药高分子的接药率约为38.4%,高分子前药在pH=7.2的磷酸盐介质中42天内的药物累积释放量为57.53%。实验结果表明,5-氟尿嘧啶以共价键的形式键合在聚[N-(2-羟乙基)-L-谷酰胺]之上,在体外有明显的缓释效果。     

N-[1-(取代苯基)乙基]-2-羟基苯甲酰肼的合成、表征及抑菌活性

依据邻羟基二苯醚及芳香肼类化合物的抗菌特性, 以邻羟苯基为分子核心, 酰肼键为桥基, 设计合成了7种未见报道的N-(取代苯基)乙基-2-羟基苯甲酰肼类化合物. 以水杨酸甲酯为原料, 经肼解反应后与取代苯乙酮缩合, 再与硼氢化钠反应制得目标化合物, 化合物结构经IR, ¹H NMR和元素分析等证实. 抗菌活性测试结果表明, 该类化合物对不同菌株的抑菌活性具有明显的选择性和特异性. 当质量浓度为1×10^-4 g/mL时, 化合物3b和3e对大肠杆菌和白色念珠菌的抑菌率高达100%, 有极强的抑菌活性; 所有化合物对金黄色葡萄球菌的抑菌率均大于70%, 有一定的抑菌活性. 构效关系分析结果表明, 苯基中引入Cl或Br等卤原子能显著增强化合物的抑菌活性, 而引入-NO₂及-CH₃基团则会降低其抑菌活性.     

(Z)-1-[2-(二苯基碘化锡基)乙烯基]-1-环己醇的合成、晶体结构和性质

报道了标题化合物的合成、晶体结构及性质。该晶体属于单斜晶系，空间群为P2~1，晶胞参数a=0.9255(3)nm，b=1.0504(3)nm，c=1.0217(3)nm，β=100.99(2)°，V=0.9750nm^3，Z=2，D~c=1.790g/cm^3，R=0.025，晶体结构由直接法解出。标题化合物分子中的锡原子被配体的三个碳、一个碘和一个氧原子配位；配位原子是畸变的三角双锥构型；标题化合物具有与卤素发生取代反应而不发生加成反应的性质。     

Synthesis of 1-(2-Ethoxyethyl)-4-hydroxy-4-[2-(1-hydroxycyclohexyl)ethynyl]piperidine and Heterocyclization under the Conditions of Hydration

The reaction of 1-(2-ethoxyethyl)piperidin-4-one with ethynylcyclohexanol led to the synthesis of a glycol, the hydration of which gave a mixture of spirocyclic compounds with a carbonyl group at various positions in the furan ring. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1649–1652, November, 2005.     

Preparation and Characterization of Hexakis[2-methoxy-4-(2,3-dimethylphenylimino)phenylato]cyclotriphosphazene

Hexakis[2-methoxy-4-(2,3-dimethylphenylimino)phenylato]cyclotriphosphazene was prepared by the reaction of hexakis[2-methoxy-4-formylphenoxy]cyclotriphosphazene and 3,4-dimethylaniline. The structure of new cyclotriphosphazene derivative was determined by elemental analysis, IR, ¹H NMR, ¹³C NMR spectra, thermal analysis, and X-ray diffraction.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Synthesis and Crystal Structure of 1-（4-Fluorophenyl）-2-hexylthiobenzo[4,5]-furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5（1H）-one

The crystal structure of the title compound 1-(4-fluorophenyl) -2-hexylthio-benzo [4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5(1H) -one(C23H21FN4O2S,Mr = 436.5) has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic,space group P21/n with a = 13.9854(3) ,b = 17.2678(4) ,c = 18.1828(5) ,β = 99.364(2) °,V = 4332.58(18) 3,Z = 4,Dc = 1.338,F(000) =1824,μ = 0.185 mm-1,MoKa radiation(λ = 0.71073) ,R = 0.0538 and wR = 0.1162 for 4728 observed reflections with I > 2σ(I) . X-ray diffraction analysis reveals the fused rings of benzo[4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a] pyrimidin-5(1H) -one system are nearly coplanar. The crystal packing is mainly stabilized by weak intermolecular C-H···O hydrogen bond and π-π interactions.