一种合成聚酰胺,羟基聚酰胺和聚酯的新方法

本文研究了四氢噻唑-2-硫酮(TTT)双活泼酰胺与胺的N-酰基化反应,与醇的O-酰基化反应及与羟胺的选择性N-酰基化反应。以四氢噻唑-2-硫酮的双活泼酰胺作为双功能团单体,合成了一系列聚酰胺、羟基聚酰胺和聚酯化合物。对所合成化合物的结构用IR、NMR和元素分析方法进行了验证,测定了聚合物的比浓粘度。     

O,O-(2,2’联苯基)二硫代磷酸酯及四(O,O-二烷基二硫代磷酰基)对-苯醌的合成

作者为了获得O,O-(2,2′-联苯基)二硫代磷酸酯及具有醌基的二硫代磷酸酯供试验其杀虫、杀菌活性之用,合成了上述两类新化合物共十六个。今将合成反应,操作手续及有关这些化合物的数值简报如下。 应用五硫化二磷和羟基化合物按文献一般方法制得了O,O-(2,2′-联苯基)二硫代磷酸及其酯十一个。     

N,N-二(2-氯乙基)-磷酰基双硫脲的合成及除草活性研究

采用N,N-二(2-氯乙基)-磷酰基双异硫氰酸酯与不同的芳胺反应合成了7个N,N-二(2-氯乙基)-磷酰基双硫脲衍生物,它们的结构经1^H NMR、IR和元素分析证实。初步生测结果表明它们对单、双子叶植物根的生长具有较好的抑制活性。     

二元活性酯胺解法合成米格列奈及其区域选择性的探讨

通过(S)-2-苄基丁二酸二元活性酯中间体选择性胺解的方法得到米格列奈, 实验中发现三个活性酯胺解反应中具有不同程度的区域选择性, 其中对硝基苯酚和N-羟基琥珀酰亚胺(HOSu)活性酯选择性非常高(100∶0, 98.9∶1.1), 而N-羟基苯并三氮唑(HOBt)活性酯的选择性则只有73.6∶26.4. 采用模拟退火方法得到了三个活性酯分子的低能构象, 并采用Hartree-Fock方法在6-31G*基组水平上对其进行全几何优化, 通过对构象的分析对产生区域选择性的因素进行了初步探讨, 发现分子一端的酯基团与侧链的苄基芳环之间存在着π-π堆积作用, 并导致了低能构象中相关原子对两端羰基形成不同程度的屏蔽, 并由此产生了反应的区域选择性.     

α-氨基烃基膦酸及其衍生物的合成与反应

本文报导合成α-氨基烃基膦酸(1)及其衍生物的新方法与反应。(一)提出用苯甲酰胺(或丙烯酰胺)和醛、亚磷酸三苯酯反应,经水解合成(1);(二)在BF_3·Et_2O催化下用磷酰胺或代磷酰胺、醛和亚磷酸三苯酯或苯基亚磷酸二苯酯反应,生成α-磷胺酰氨基(或硫代磷酰胺基)取代苄膦酸二苯酯或次膦酸苯酯(2)。经选择性脱去氨基保护基生成α-氨基膦酸二苯酯溴代盐(3);(三)二苯氧基氯磷、醛和磷酰胺(或硫代磷酰胺)在 ZnCl_2等路易斯酸存在     

8-羟基喹啉丙烯酸活性酯的合成及其聚合物与蛋白质的偶联

<正> 近些年来,关于丙烯酸活性酯、活性酰胺的研究已有较多的报道。这些活性酯或活性酰胺大多是含有氮、氧等杂原子的杂环化合物。报道较多的是N-羟基丁二酰亚胺(NHS)、苯骈三氮唑等的衍生物,我们曾将NHS、苯骈三氮唑引至大孔水不溶性球状聚乙烯醇上,制备了亲水性的活性酯反应性载体。8-羟基喹啉的羟基旁边因有带孤对电     

手性吡啶-2,6-双酰胺钴（Ⅲ）配合物的合成与光谱分析

合成了配体2,6-双{N-［（1′-甲基羟基-2′-苯基）乙基］氨基甲酰胺}吡啶及其钴（Ⅲ）配合物,利用核磁共振氢谱、核磁共振碳谱、红外光谱和元素分析对配体的结构进行确证,经表征配合物组成为{［Co（L-2H）］2O2}?2H2O。红外光谱分析表明,该配体为四齿配体,通过2个酰胺氮原子和2个羟基氧原子参与钴（Ⅲ）配位。运用圆二色谱对目标配体和配合物的光学活性进行分析,结果表明两者均为手性化合物。     

N-1，3，4-噁二唑基-N′-呋喃甲酰基硫脲的合成及杀菌活性研究

N-1;3;4-噁二唑基-N′-呋喃甲酰基硫脲的合成及杀菌活性研究;呋喃;噁二唑;酰基硫脲;合成;杀菌活性     

N,N′-双(2-羟基-4-甲氧基二苯酮)乙二亚胺合铜(Ⅱ)、镍(Ⅱ)、钴(Ⅱ)配合物的合成

固液合成;N;N′-双(2-羟基-4-甲氧基二苯酮)乙二亚胺合铜(Ⅱ)、镍(Ⅱ)、钴(Ⅱ)配合物的合成     

4-二甲胺苯酰甲酸乙酯的合成及反应副产物的分离鉴定

α-酮酸酯是重要的有机合成中间体。前文报道了以Grignard试剂与草酸二乙酯反应,合成一系列脂肪族α-酮酸酯的方法。为了进一步了解和掌握这一方法,我们研究了合成4-二甲胺基苯酰甲酸乙酯(1)的反应。1的收率随反应温度、溶剂及原料配比的不同而有显著差别。在本文报道的条件下,收率高达90％。此外,从反应混合物中还分得了2-羟基-2,2-双(对-二甲胺基苯基)乙酸乙酯(2),4,4’-双(二甲胺基)-二苯基乙二酮(3),2-羟基-1,2,2-三(对-二甲胺基苯基)乙酮(4)及4,4’-双(二甲胺基)联苯(5)等副产     

Synthesis of polyamides from active O,O′-diacyl derivatives of N-hydroxy compounds and diamines under mild conditions

Two new routes to polyamides were established, based on the polycondensation of two new typical active diesters: the active diester of N-hydroxy-5-norbornene-2,3-dicarboximide, such as N,N′-(terephthaloyldioxy)bis(5-norbornene-2,3-dicarboximide), and the active diester of 3-hydroxy-4-oxo-3,4-dihydro-1,2,3-benzotriazine, such as 3,3′-(isophthaloyldioxy)bis(4-oxo-3,4-dihydro-1,2,3-benzotriazine) with diamines. The polycondensation occurred at room temperature in solution without added catalyst. Dipolar aprotic solvents which included dimethyl sulfoxide and N-methyl-2-pyrrolidone were used as solvents for polymerization. Before polymer synthesis the aminolysis of two active monoesters was carried out as a model compound study.     

A NEW ACTIVE DIESTER FOR SELECTIVE POLYMERIZATION TO FORM FUNCTIONAL POLYAMIDES

A new synthetic route to polyamides and hydroxyl polyamides was established, based on the selecting (?)-acylation of three novel typical active diesters: the active diester of N-hydroxy- (?) 4-epoxy-5-cyclohexene-2, 3-dicarboximide( HOEC), such as N, N'-(temphthaloyldioxy) bis(1, 4- epoxy - 5 - cyclohexene- 2, 3 - dicarboximide.) ( PBOEC), N, N'- ( isophthaloyl - dioxy) bis (1,4-epoxy-5-cyclohexene-2, 3-dicarboximide)(IPBOEC) and N, N' -(adipoyldioxy) his (1,4-epoxy-5-cyclohexene-2, 3-dicarboximide) ( ADOEC)with aliphatic diamines and 1,3-diamino-2-hydroxypropane. The polycondensation occurs at room temperature in solution without added catalyst. Dipolar aprotic solvents which include dimethyl sulfoxide, N- methyl - 2- pyrrolidone and dimethylformamide were used as solvents for polymerization. The selective N-acylation of two active diesters was performed as a model reaction study.     

Synthesis of polyamide containing optically active thymine derivative as a grafted pendant

A new route to polyamides containing optically active thymine groups as pendants has been established. The method is based on the grafting of (–) and (±)-2-(thymin-1-yl)propionic acid [(–) and (±) TPA] onto a polyamide containing hydroxyl groups. The hydroxy polyamide was prepared by selective N-acylation of an active diester of N-hydroxy-5-norborene-2,3-dicarboxamide (HONB), N,N'-(isophthaloyl-dioxy)-bis(5-norbornene-2,3-dicarboximide) (IPBONB), with 1,3-diamino-2-hydroxypropane (AHP). Model compounds (?) and (±)-(1,3-dibenzoylamino-2-propyl)2-(thymin-1-yl)propionate[(?) and (±) (BAPTP)] were prepared by direct, low-temperature esterification before synthesizing the polymer.     

固定化酶新载体-N′-ε-甲基丙烯酰胺基己酸酯的研究

合成了一种新的反应性聚合物聚N-ε-甲基丙烯酰胺基己酰氧-5-降冰片烯-2,3-双甲酰亚胺[P(MACONB)],其相应的新单体N-ε-甲基丙烯酰胺基己酰氧-5-降冰片烯-2,3-双甲酰亚胺(MACONB),是由N-ε-甲基丙烯酰胺基己酸(MACOH)与N-羟基-5-降冰片烯-2,3-双甲酰亚胺(HONB)在环己基羰二亚胺存在下经偶联成酯反应而得。反应性聚合物P(MACONB)是一个较好的固定化胰蛋白酶的载体,它极易与胰蛋白酶在温和反应条件下进行胺解反应,形成一个具有较高酶活力的固定化胰蛋白酶。     

Studies of some new bioactive acrylic esters

Four typical bioactive esters of acrylic monomers, N-p-acryloxybenzoyloxysuccinimides, 3-ac-ryloxy-4-oxo-3,4-dihydro-1,2,3-benzotriazines, N-acryloxy-5-norbornene-2,3-dicarboximides, and I-p-acryloxybenzoyloxybenzotriazoles, were Synthesized and polymerized as reactive polymers. Twelve new monomers were prepared by coupling acrylic acid, methacrylic acid, p-acryloxybenzoic acid, or p-methacryloxybenzoic acid with four N-hydroxy compounds such as N-hydroxysuccinimide (HOSu), 3-hydroxy-4-oxo-3,4-dihydro-1,2,3-benzotriazine (HOObt), N-hydroxy-5-norbornene-2,3-dicarboximide (HONB), and I -hydroxybenzotriazole (HOBT) in the presence of dicyclohexylcarbodimide. All monomers polymerized readily in solution with azobisisobutyronitrile (AIBN) as free radical initiator. The resulting reactive polymers with reactive ? OSu, ? OObt, ? ONB, or ? OBT group on the side chain are equally reactive toward n-butylamine at room temperature in the formation of corresponding polyacrylamides. Reactive polymers were used to immobilizetrypsin. It has been found that poly(N-p-methacryloxybenzoyloxy-5-norbornene-2,3-dicarboximide)-trypsin matrix had high activity around three times that of the poly(N-methacryloxy-5-norbornene-dicarboximide)-trypsin matrix. It is proposed that this activity may be due to the presence of a long spacer arm with a hydrophobic and rigid benzene ring between the ligand and matrix. The reactive poly(N-p-methacryloxybenzoyloxysuccinimide-p-methacryloxybenzoic acid) copolymer was used to immobilize the serum protein. This immobilized protein was a hopeful bioactive solid immunoadsorbent.     

A novel class of Cd(II), Hg(II) turn-on and Cu(II), Zn(II) turn-off Schiff base fluorescent probes

N,N'-((5,5'-(quinoxaline-2,3-diyl)bis(1H-pyrrole-5,2-diyl))bis(methanylylidene))bis(4-methoxyaniline) 4 and N,N'-((5,5'-(quinoxaline-2,3-diyl)-bis(1H-pyrrole-5,2-diyl))bis(methanylylidene))dianiline 5 have been prepared and structurally characterized. The X-ray crystal structures of compounds 4 and 4a have been determined. These compounds displayed good sensitivity toward transition metal ions with Cd(II), Zn(II) turn-on and Cu(II), Hg(II) turn-off in fluorescence. It is an elegant example of on/off behavior like a lamp. When Cd(II) or Zn(II) is added into compounds 4 or 5, the lamp will switch on, and then when Cu(II) or Hg(II) is added into the mixture, the lamp will switch off. The binding properties of 4 and 5 for cations were examined by fluorescence spectroscopy. The fluorescence data and crystal structure indicate that a 1:1 stoichiometry complex is formed between compound 4 (or 5) and metal ions, and the binding affinity is very high. The recognition mechanism between compound 4 (or 5) and metal ion was discussed based on the their chemical constructions and the CHEF/CHEQ effect when they interacted with each other.     

OPTICALLY ACTIVE AND FLAME-RETARDANT POLY(AMIDE-IMIDE)S BASED ON PHOSPHINE OXIDE MOIETY AND N,N′-(PYROMELLITOYL)BIS-L-AMINO ACID IN THE MAIN CHAIN:SYNTHESIS AND CHARACTERIZATION

<正>Six new optically active and flame-retardant poly(amide-imide)s PAIs 5a-5f containing phosphine oxide moiety as a flame-retardant unit in the main chain were synthesized from direct polycondensation reaction of six chiral N,N′-(pyromellitoyl)-bis-L-amino acid 3a-3f with bis(3-aminophenyl)phenyl phosphine oxide 4 in a medium consisting of N-methyl-2-pyrrolidone(NMP),triphenyl phosphite(TPP),calcium chloride(CaCl_2) and pyridine.The polymerization reactions produced a series of optically active poly(amide-imide)s with good yield and good inherent viscosity of 0.34-0.70 dLg~(-1).The resulted polymers were fully characterized by means of FTIR and ~1H-NMR spectroscopy,gel permeation chromatography(GPC),elemental analyses,inherent viscosity and solubility tests.Thermal properties and flame-retardant behavior of the PAIs 5a-5f were investigated using thermal gravimetric analysis(TGA and DTG) and limiting oxygen index(LOI).Data obtained by thermal analysis(TGA and DTG) revealed that these polymers showed good thermal stability.Furthermore,high char yield in TGA and good LOI values indicated that the resulting polymers were capable of exhibiting good flame retardant properties.N,N′-(pyromellitoyl)-bis-L-amino acids 3a-3f were prepared in quantitative yields by the condensation reaction of pyromellitic dianhydride(1,2,4,5-benzenetetracarboxylicacid-1,2,4,5-dianhydride) 1 with L-alanine 2a,L-valine 2b,L-leucine 2c,L-isoleucine 2d,L-phenyl alanine 2e and L-2-aminobutyric acid 2f in acetic acid solution.     

Synthesis of optically active copoly(vinylamine–vinylalcohol) containing a pair of adeninyl and thyminyl pendant groups

Preparation of novel model polymers of polynucleotides with copoly(vinylamine–vinylalcohol) [P(Vam–Val)] backbone and a pair of adeninyl and thyminyl pendant groups is described. At first, direct, low temperature esterification was used to attach (?) and (±)-2-(thymin-1-yl)propionic acid [(?)TPA and (±)TPA], to the N–Cbz protected hydroxy polymer P(Vamz–Val) which was prepared by selective N-protection of N-benzyloxycarbonyloxy-5-norbornene-2,3-dicarboximide (CbzONB) with P(Vam–Val), at the hydroxy group via an ester bond. Two novel precursors P(Vamz–Ve(?)T) and P(Vamz–Ve(±)T) were obtained. Then the Cbz protecting group of P(Vamz–Ve(?)T) and P(Vamz–Ve(±)T) were removed by hydrobromic acid to give the hydrobromide salt of P(Vam–Ve(?)T) and P(Vam–Ve(±)T), respectively. Finally, the attachment of (±)-2-(adenine-9-yl)propionic acid [(±)APA] to linear P(Vam–Ve(?)T) and P(Vam–Ve(±)T) by selective N-acylation with N-hydroxy-5-norbornene-2,3-dicarboximide (HONB). This procedure gave the corresponding P(Vam–Val) having a pair of adeninyl and thyminyl pendant groups, such as P(Va(±)Ad–Ve(?)T) and P(Va(±)Ad–Ve(±)T). In contrast to the corresponding polymer models, the related segment model compounds were also prepared from threo-2-amino-4-pentanol without N-blocking-deblocking operations. The segment model compounds including four stereoisomers of highly optical purities, were separated and purified by reverse phase HPLC technique.     

Kinetics of the crosslinking reaction of a bisnadimide model compound in thermal and microwave cure processes

The kinetic studies of the crosslinking reaction of a nadic end-capped imide model compound, N,N′-(oxydi-3,4′-phenylene) bis(5-norbornene-2,3-dicarboximide), a bisnadimide, in thermal and microwave processes were investigated. The conversion of the endo isomer to exo isomer proceeds at a much lower temperature than the crosslinking reaction. The crosslinking reaction was monitored by the combined decrease in the infrared absorptions of the endo and exo isomers at 840 and 780 cm⁻¹, respectively. The decrease in the concentration of starting materials follows first-order kinetics in the thermal and microwave processes. At the same temperatures (230 or 280°C), the crosslinking reaction proceeds at about 10 times faster in the microwave process than in the thermal process. Solid-state ¹³C-NMR showed no significant loss in C=C double bond resonance in the cured products by comparison with the starting material. This study provides direct evidence that the microwave process may be an efficient method to cure nadic end-capped polyimides. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2653–2665, 1998     

RAPID SYNTHESIS OF NOVEL OPTICALLY ACTIVE POLY(AMIDE-IMIDE)S DERIVED FROM N,N''''-(PYROMELLITOYL)-BIS-L-ALANINE DIACID CHLORIDE AND HYDANTOIN DERIVATIVES UNDER MICROWAVE IRRADIATION

Eight novel poly(amide-imide)s were synthesized under microwave irradiation by using a domestic microwaveoven from the polycondensation reactions of N.N'-(pyromellitoyl)-bis-L-alanine diacid chloride(1)with eight differentderivatives of hydantoin compounds(2a-h)in the presence of a small amount of a polar organic medium such as o-cresol.The polycondensation proceeded rapidly,compared with the conventional solution polycondensation and was completedwithin 8-10 min,producing a series of new poly(amide-imide)s(3a-h)with inherent viscosities about 0.35-0.68 dL/g inhigh yields.The obtained PAIs(3a-h)were fully characterized by means of FT-IR spectroscopy,elemental analyses,inherentviscosity(ηinh),solubility and specific rotation measurements.All of the resulting polymers show optical rotation and areoptically active.Thermal properties of the poly(amide-imide)s were investigated by using thermal gravimetric analysis(TGA).