2,5-Bis(vinyloxyalkylamino)-1,4-benzoquinones

Russian Journal of Organic Chemistry -     

Synthesis and Crystal Structure of 1,4-Bis(2-hydroxymethylphenyl)-1,4-dioxabutane

1 INTRODUCTION Macrocyclic ligands and their metal complexes have received much attention due to their applications in ion transport, ion separation and as models in biomimic researches[1~7]. The synthetic methods of macrocyclic ligands and their metal complexes are mainly divided into three kinds[8]. The first one is synthesizing free ligand, then forming the metal complexes; the second is template synthesis; and the third is synthesizing the end-off or side-off precursor ligand, then c…     

Synthesis of benzoates of 1,4-bis(2,5-dimethyl-4-hydroxypiperidino)-2-butene and 1,4-bis-(2,5-dimethyl-4-hydroxypiperidino)-2-butyne

1,4-Bis(2,5-dimethyl-4-hydroxypiperidino)-2-butene and 1,4-bis(2,5-dimethyl-4-hydroxypiperidino)-2-butyne (II and III) were obtained by the action of 1,4-dibromo-2-butene and 1,4-dibromo-2-butyne on the form of 2,5-dimethyl-4-piperidol (I). The benzoates (IV and V) were obtained by acylation of II and III with benzoyl chloride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 352–353, March, 1971.     

Synthesis of 1,4-Bis(Chloromethyl)-2-Methoxy-5-Phenoxy Benzene

Much attention has been paid to Poly(p-Phenylene Vinylene) (PPV) because they are associated with good electro-optical characterization, especially electro-luminescence which first discovered by Burroughes in 1990^[1]. 1,4-bis(chloromethyl) benzene is an important tool to synthesize PPV by dehydrochlorination. So the chloromethylation of substituted benzene becomes active. We once synthesized a series of dialkoxyl bischloromethyl benzene^[2]. Unfortunately, short chain alkoxyl-substituted PPV has poor solubility, which limits its utility. There are little reports on aryloxy PPV up to now, while aryloxy-substituted PPV may has good mechanical properties.     

Metal-mediated carbonyl-1,3-butadien-2-ylation by 1,4-bis(methanesulfonyl)-2-butyne or 1,4-dibromo-2-butyne in aqueous media: asymmetric synthesis of 3-substituted 3-hydroxy-beta-lactams

Metal-mediated 1,3-butadien-2-ylation reactions between 1,4-dibromo-2-butyne or 1,4-bis(methanesulfonyl)-2-butyne and optically pure azetidine-2,3-diones were investigated in aqueous media, offering a convenient asymmetric entry to the potentially bioactive 3-substituted 3-hydroxy-beta-lactam moiety. The diastereoselectivity of the addition reaction was controlled by the bulky chiral auxiliary at C4. However, while the regioselectivity of the process was full, the chemical yield of the addition was a function of the nature of both the metal reagent and the system solvent as well. In addition, 2-azetidinone-tethered 1,3-butadienes can easily be transformed into other functionalities via Diels-Alder reaction.     

Mercuric ion-catalyzed hydration of derivatives of 1,4-dichloro-2-butyne. Hydration of 1-aryloxy-4-arylthio-2-butynes, 1,4-bis(arylthio)-2-butynes,and 1,4-bis(arylsulfonyl)-1-butynes

The mercuric ion-catalyzed hydration of 1,4-bis(arylthio)-2-butynes and 1-aryloxy-4-arylthio-2-butynes was studied. The 1,4-bis(arylsulfonyl)-2-butynes afforded 1,4-bis(arylsulfonyl)-2-butanones (7). The 1,4-bis(arylthio)-2-butynes afforded a variety of products in acetic acid among which were: 1,4-bis(arylthiomethyl)vinyl acetate ( 18 ); 1,4-bis(arylthio)-2-butanone ( 15 ); 1-(arylthio)-3-buten-2-one ( 16 ); and 1-(arylthio)-4-acetoxy-2-butanone ( 17 ). Ketone 15 eliminates arylthiol in an acidic medium yielding 16 which undergoes Michael addition of solvent to give 17. Treatment of 7 with base in the presence of a nucleophile (ArSH) analogously leads to elimination of arylsulfinic acid, followed by Michael addition of arylthiol. Hydration of 5 in methanol cleanly gave 1-(arylthio)-4-methoxy-2-butanones ( 19 ). In contrast, 1-aryloxy-4-arylthio-24)utynes afforded chromenes ( 8 ) by intramolecular cyclization. No thiochromenes were formed in any of the examples investigated.     

Procedure for the Rapid Synthesis of the Monomer 1,4-Bis(chloromethyl)-2-(2-ethylhexyloxy)-5-methoxybenzene

The alkylation of 4-methoxyphenol with 2-ethylhexyl bromide was accelerated by using potassium tert-butoxide in dimethylformamide. Subsequent chloromethylation occurred quickly using acetic acid as a cosolvent to give the poly[(2-(2-ethylhexyloxy)-5-methoxy-p-phenylene)vinylene] (MEH-PPV) monomer in 61% overall yield on a 2-mol scale.     

Synthesis of silylallene glycosides and diene diglycosides by C-glycosidation of D-glucal with 1,4-bis(trimethylsilyl)-2-butyne

[reaction: see text] Silylmethylallenyl glycosides, symmetrical and unsymmetrical diene glycosides, were synthesized by C-glycosidation with 1,4-bis(trimethylsilyl)-2-butyne in good yield. The nature of the product is controlled by the choice of Lewis acid, BF(3).OEt(2), or SnCl(4). The efficient construction of unsymmetrical diene glycosides was achieved in one pot on the basis of the order of addition of sugar starting materials.     

1,4-双氯甲基-2-甲氧基-5-壬氧基苯的均聚和共聚

以对甲氧基苯酚和溴壬烷为原料,经过醚化和双氯甲基化反应得到１,４－双（氯甲基）－２－甲氧基－５－壬氧基苯（ＢＣＭＮＯＮＯＢ）,ＢＣＭＭＯＮＯＢ在强碱作用下通过脱氯化氢得到可溶性的聚（２－甲氧基－５－壬氧基）对苯乙炔（ＰＭＯＮＯＰＶ）;首次采用脱氯化氢消除反应实现了ＢＣＭＭＯＮＯＢ与１,４－双（氯甲基）－２,５－二甲基（ＢＣＭＤＭＢ）共聚。讨论了两种单体结构和縻尔比率及溶剂因素对聚合反应和共聚物溶解