1,3,5-三[(4’-乙炔基苯基)乙炔基]苯的合成

设计了多种合成路线制备芳香炔基树枝状化合物中间体1,3,5-三[(4’-乙炔基苯基)乙炔基]苯,通过一系列的合成路线和反应条件的对比,发现多官能团的端基炔化合物与芳基溴化合物之间发生多重Sonogashira反应时,常会生成不同取代程度的极性相似化合物,因而难以分离.采用多官能团的端基炔化合物与芳基碘化合物反应可以避免这种情况.最终确定以1,3,5-三溴苯和2-甲基-3-丁炔-2-醇为原料,制得中间产物1,3,5-三乙炔基苯;再以对碘苯胺和三甲基硅乙炔为原料,经重氮化化、卤代反应制得4-三甲基硅乙炔基碘苯;后者与1,3,5-三乙炔苯经Sonogashira反应、裂解去保护反应,制得化合物1,3,5-三[(4’-乙炔基苯基)乙炔基]苯.用1H NMR,13C NMR,元素分析等表征手段确认了中间体及最终产物的结构.     

带有不同端炔保护基团的新型苯乙炔树枝状化合物的合成

以1,3,5-三溴苯为原料,通过Sonogashira反应,设计并合成了两种带有不同端炔保护基团的1,3,5-取代的苯乙炔树枝状化合物:1,3,5-三[3-(3-甲基-3-羟基-1-丁炔基)-5-(三异丙基硅乙炔基)苯基乙炔基]苯(B1)和1,3,5-三[3-(三甲基硅乙炔基)-5-(三异丙基硅乙炔基)苯基乙炔基]苯(B2),并对合成路线的选择进行了比较和讨论.用1H NMR,13C NMR,质谱,元素分析等表征手段确认了中间体及最终产物的结构.这两种苯乙炔树枝状化合物各自带有两类不同的周边端炔保护基团,可根据其脱保护条件的不同引入不同的周边功能基团.     

1,3,5—三氨基—2,4,6—三硝基苯的合成新法

1,3,5-三氨基-2,4,6三硝基苯(TATB)是一种性能优良的耐热炸药,在深井爆破,航天技术等领域有着特殊的用途。目前多以1,3,5-三氯代苯为原料,经硝化、胺化反应生产。这一工艺路线存在原料难得,成本高,成品含氯化物影响使用等问题。Atkins等曾提出过     

1,3,5-苯三甲醛的合成与应用研究进展

介绍了1,3,5-苯三甲醛的合成与应用。在1,3,5-苯三甲醛的众多合成方法中,以氧化还原方法最常见,此外水解、聚合等方法各具优点,在满足高产率和绿色化学方面有了更多选择。1,3,5-苯三甲醛是一种具有广泛开发应用前景的化学合成中间体,以其为原料合成的大分子物质具有优异的化学、物理特性和生物活性,在催化、光电、抗病毒,以及分子吸附和药物包材等方面具有广泛的应用。     

两种立体构型的1,3,5,-三-α-萘基苯的合成

通过Adole反应和Grigard反应合成了相应的两种立体异构的1,3,5-三-α-萘基苯. 报道了它们的UV, IR, FD-MS和NMR . 论了两种异构体的^1H NMR 和^1^3C NMR的区别.     

新型阻燃剂1 ,3 ,5-三(5 ,5-二甲基-1 ,3-二氧杂己内磷酸酯基)苯的合成及表征

以1,3,5-三羟基苯、新戊二醇、三氯氧磷等为原料,采用简洁、高效的合成路线,通过两步反应合成了新型阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂己内磷酸酯基)苯.通过红外光谱、核磁共振氢谱、质谱、元素分析以及热失重分析等对产物结构和热性能进行了表征和研究.热失重分析表明:该阻燃剂起始分解温度为295.26℃ ,在295.26℃ ~343.38℃和350.40℃ ~578.04℃温区迅速炭化;当阻燃剂被加热到681.03℃时,炭残余量高达43.33 %.     

异黄酮类化合物的合成新方法

提出了一种新颖的合成异黄酮类化合物1, 2和3的方法. 以1,3-二甲氧基苯或1,3,5-三甲氧基苯为原料, 经Hoesch反应或Friedel-Crafts酰化反应、脱甲基反应、增碳关环一系列反应得到关键的甲氧基异黄酮化合物, 然后甲氧基异黄酮经过不同浓度氢溴酸的选择性水解反应制得含一个或多个羟基的异黄酮类化合物.     

三异丙苯氧化法制备间苯三酚

以1,3,5-三异丙基苯(TIP)为原料,经初级氧化、二次氧化及酸分解合成了间苯三酚(1)。各步反应的较适宜条件为:初级氧化:TIP340g,氧气压力3.0MPa,于95℃反应28h～38h,4种三羟基氧化物的总收率为60%;二次氧化:以H2SO4/H2O2为氧化剂,甲苯为溶剂,于60℃反应2h,1,3,5-三[(2-羟过氧基)-2-甲基]乙基苯(THPO)的收率为77%;酸分解:以杂多酸为催化剂,丙酮为溶剂,于60℃反应2h,1收率85%(纯度99%)。     

1,3,5-均苯三羧酸根金属-有机多重框架结构配合物

综述了近年来1,3,5-均苯三羧酸(H3BTC)与金属配位形成金属配合物的研究进展。对1,3,5-均苯三羧酸根(BTC)作为桥基时的配位特点及其桥联多核配合物的合成方法和结构特点进行了简要介绍,并对今后BTC类超分子网络配合物应用与结构研究的发展方向进行了展望。     

铜催化腙酰卤与端炔的串联反应制备1,3,5-三取代吡唑衍生物

末端炔烃在亚铜盐的催化条件下,能够与取代芳基腙酰卤通过亲核取代及加成环化的串联反应生成1,3,5-三取代吡唑衍生物.该方法采用易合成的芳基腙酰卤和末端炔烃作为起始原料,在45℃的加热条件下,以绿色溶剂乙腈和水作为反应介质,高产率、区域专一性地生成1,3,5-三取代吡唑产物.而且该反应不受含活泼氢(羟基、羧基等)取代基的影响,通过该方法制备了17种包含不同类型取代基的吡唑衍生物,可作为1,3,5-三取代吡唑类化合物的通用合成法.     

The preparation of 3,5-disubstituted tetrahydro-4H-1,3,5-oxadiazine-4-thiones,tetrahydro-4H-1,3,5-thiadiazin-4-ones,and tetrahydro-4H-1,3,5-thiadiazine-4-thiones

The reaction of 1,3-disubstituted thioureas with formaldehyde under acidic conditions with removal of water yielded 3,5-disubstituted tetrahydro-4H-1,3,5-oxadiazine-4-thiones. When hydrogen sulfide was bubbled through the reaction mixture, the corresponding tetrahydro-4H-1,3,5-thiadiazine-4-thiones were formed. Similarly, starting from 1,3-disubstituted ureas, a number of tetrahydro-4H-1,3,5-thiadiazine-4-ones were prepared. The latter compounds were also oxidized to the corresponding sulfoxides and sulfones.     

New functionalized amino derivatives of 2-hydroxyphenyl-1,3,5-triazines

4-(2-Hydroxyphenyl)-1,3,5-triazin-2-ylcyanamides reacted with sodium azide to give N-(tetrazol-5-yl)-1,3,5-triazin-2-amines, and their reaction with allyl bromide afforded allyl(1,3,5-triazin-2-yl)cyanamides. Acetylation of 4-(2-hydroxyphenyl)-1,3,5-triazin-2-amines involved only the amino group with formation of diacetylamino derivatives, whereas the phenolic hydroxy group remained intact. The reaction of triazinamines with 2,5-dimethoxytetrahydrofuran in the presence of P₂O₅ gave pyrrolyl-substituted triazines.     

An efficient and facile one-pot synthesis of structurally unique 2,4,6-tris(arylchalcogeno)-1,3,5-triazine and 1,3,5-tris(arylchalcogeno)-2,4,6-trimethylbenzene

An efficient one-pot synthesis of a novel class of 2,4,6-tris(arylchalcogeno)-1,3,5-triazine (sulfur, selenium and tellurium) and 1,3,5-tris(arylchalcogeno)-2,4,6-trimethylbenzene (sulfur and selenium)-containing ligands has been developed based on the reaction of 2,4,6-trichloro-1,3,5-triazine and 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene with the corresponding arylchalcogenide anions generated in aqueous tetrahydrofuran.     

Synthesis of 1,3-dialkylpyrazolo [1,5-a]-1,3,5-triazine-2,4-diones isomers of 1,3-dialkylxanthines

The synthesis of a new series of alkylxanthine analogs containing a bridgehead nitrogen atom is reported. 1,3-Dialkylpyrazolo[1,5-a]-1,3,5-triazine-2,4-diones, were prepared by the treatment of 3-methylpyrazolo[1,5-a]-1,3,5-triazine-2,4-dione (3) with the corresponding alkyl iodide. Similarly, the reaction of 3-methyl-7-phenylpyrazolo[1,5-a]-1,3,5-dialkyl-7-phenylpyrazolo[1,5-a]-1,3,5-triazine-2,4-diones. The starting materials, 3 and 17 , were prepared via the reaction of an appropriate 3-aminopyrazole with ethoxycarbonyl isothiocyanate. Several 8-bromo derivatives were prepared by direct bromination of the 1,3-dialkylpyrazolo[1,5-a]-1,3,5-triazine-2,4-diones.     

A new advanced method for heterogeneous catalysed dechlorination of 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzenes in hydrocarbon solvent

A new advanced method for dechlorination of 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzenes in organic solvent catalysed by palladium on carbon support and solid hydrazine hydrochloride yields benzene in short reaction times. The catalyst system can be efficiently reused for several cycles. Ultrasound radiation of the heterogeneous catalyst reaction increases remarkably the rate of dechlorination.     

Structure of Products of Reaction between Benzoylacetylene and 1,5-Diphenyldithiobiuret

Reaction of benzoylacetylene with 1,5-diphenyldithiobiuret in glacial AcOH in the presence of equimolar amounts of HClO₄ leads exclusively to 2-benzoylmethyl-4,6-di(phenylimino)-1,3,5-dithiazinium perchlorate. In MeOH, benzene, and MeCN medium, the reaction proceeds nonselectively and a mixture is formed that includes 2-benzoylmethyl-4,6-di(phenylimino)-1,3,5-dithiazine, 2-benzoylmethyl-4-benzoylvinylthio-3-phenyl-6-phenylimino-1,3,5-thiadiazine, 2-benzoylmethyl-4,6-di-(thiocarbonyl)-1,3-diphenyl-1,3,5-triazine, and N-benzoylvinyl-N'-phenylthiourea.     

A simple and efficient synthesis of 1,3,5-tris[2-(3,5-diethynylphenyl)ethynyl]benzene from 1,3,5-triethynylbenzene

A concise and convenient three-step process is reported for preparation of 1,3,5-tris[2-(3,5-diethynylphenyl)ethynyl]benzene from 1,3,5-triethynylbenzene and 2-hydroxypropyl group-protected peripheral monomers via a Sonogashira coupling?Cdeprotection reaction sequence. This approach had several advantages, for example high yields, short reaction time, and simple separation procedure. In the key step a modified Sonogashira reaction was developed, under which conditions the coupling of 1,3,5-triethynylbenzene and substituted iodobenzenes proceeded rapidly, giving the desired products in good to excellent yields.     

Preparation, properties, and reactions of metal-containing heterocycles: Part CVI. Three-dimensional water-soluble platinacyclophanes

Trifunctional primary phosphines of the type 1,3,5-[PH₂(CH₂)_n]₃C₆H₃ (3b–d) were obtained via an Arbusov reaction between the 1,3,5-tris(bromoalkyl)benzenes 1b–d and P(OEt)₃ followed by a reaction of the trisphosphonates 1,3,5-[(EtO)₂P(O)(CH₂)_n]₃C₆H₃ (2b–d) with LiAlH₄. A straightforward conversion of these sensitive key phosphines 3b–d to the corresponding water-soluble ligands 1,3,5-tris[bis(hydroxymethyl)phosphinylalkyl]benzenes 4b–d and 1,3,5-tris[bis(2′-diethylphosphonatoethyl)phophinylalkyl]benzenes 5b–d was achieved by formylation with formaldehyde and hydrophosphonation with diethyl vinylphosphonate, respectively. A five component self-assembly consisting of three equivalents of the platinum(II) complex Cl₂Pt(NCPh)₂ and two equivalents of the ligands 5b–d under high dilution conditions resulted in the formation of the nanoscaled, water-soluble triplatinacyclophanes 6b–d in high yields. However, comparable reactions with the ligands 4b–d led only to polymeric materials, which are insoluble in all organic solvents and water. The structures of the metallacyclophanes 6b–d were elucidated by ³¹P{¹H}-, ¹³C{¹H}-, and ¹⁹⁵Pt{¹H}-NMR spectroscopic investigations.     

Reaction of Ethoxymethylenemalonate with Cyanothioacetamide in the Presence of Triethylamine: Formation of 1,5-Diamino-2,4-dicyano-5-thioxopenta-1,3-diene-1-thiolate and Unexpected Aminomethylation Result

The reaction of cyanothioacetamide with ethoxymethylenemalonate and triethylamine in ethanol upon heating is non-selective and leads to the formation of a mixture of triethylammonium 1,5-diamino-2,4-dicyano-5-thioxopenta-1,3-diene-1-thiolate and triethylammonium 6-oxo-3-cyano-5-ethoxycarbonyl-1H-pyridin-2-thiolate with a predominance of the latter. When treating with primary amines and 37% formalin in boiling aqueous alcohol, the reaction product gives only 4-(1,3,5-thiadiazinan-2-ylidene)-2-(3,4-dihydro-2H-1,3,5-thiadiazin-6-yl)pent-2-enedinitrile instead of the expected pyrido[2,1-b][1,3,5]thiadiazine derivatives. Triethylammonium 6-oxo-3-cyano-5-ethoxycarbonyl-1H-pyridin-2-thiolate does not react under these conditions.     

Reactions of 1,3,5-triazinylnitroformaldoxime 4.* synthesis of (5-R-1,2,4-oxadiazol-3-yl)-1,3,5-triazines

Heating 4-R-methoxy-1,3,5-triazin-2-ylnitroformaldoximes with nitriles leads not to the formation of 1,2,4-oxadiazoles but rather to dimerization of the intermediate 1,3,5-triazinylnitrile oxides to give furoxanes. The reaction of 4-R-6-methoxy-1,3,5-triazin-2-ylnitroformaldoximes with ammonia and amines gives 1,3,5-triazinylamidoximes, which upon acylation and subsequent intramolecular cyclization yield (5-R-1,2,4-oxadiazol-3-yl)-1,3,5-triazines.