SYNTHESIS OF CHIRAL CONJUGATED POLYBINAPHTHYLS BY SONOGASHIRA REACTION

Chiral polymers P-1 and P-2 were synthesized by the polymerization of （R）-3,3＇-diiodo-2,2＇-bisbutoxy-1,1＇- binaphthyl （M- 1 ） with 2,5-di（4-ethynylphenyl）- 1,3,4-oxadiazole （M-3） and （R）-3,3＇-diethylnyl-2,2＇-bisbutoxy- 1,1 ＇-binaphthyl （M-2） with 1,2-di（4-bromophenyl）acetylene （M-4） under Sonogashira reaction, respectively. Both monomers and polymers were analyzed by NMR, MS, FT-IR, UV-Vis spectroscopy, DSC-TGA, fluorescence spectroscopy, GPC and CD spectroscopy. CD spectra of P-1 and P-2 are similar due to the same chiral center units and main chain structure. The long wavelengths CD effect of P-1 and P-2 can be regarded as the more extended conjugated structure and a highly rigid backbone in the polymer chain. Polymers have strong blue fluorescence due to the efficient energy migration from the extended n-electronic structure of the polymers to the chiral binaphthyl core and are expected to provide understanding of the relationship between molecular structure and fluorescent property of the chiral polymers.     

SYNTHESIS OF POLYBINAPHTHYLS INCORPORATING CHIRAL (R)-1,1′-BI-2,2′-NAPHTHOL ENTITIES WITHp-DIVINYLBENZENE BY Pd-CATALYZED HECK REACTION

Polymer (Ⅰ) and polymer (Ⅱ) were obtained by the polymerization of (R)-6,6′-dibromo-2,2′-binaphtho-20-crown-6(M-1) and (R)-6,6′-dibromo-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (M-2) with p-divinylbenzene under Pdcatalyzed Heck reaction. The UV, fluorescence and CD spectra of polymer (Ⅰ) and (Ⅱ) are similar due to the same linkers present in their polymer chain. Polymers (Ⅰ) and (Ⅱ) can emit strong blue fluorescence and are expected to have potential applications in polarized blue-light emitting sensors. The chiral conjugated polymers (Ⅰ) and (Ⅱ) exhibit a strong Cotton effect in their circular dichroism (CD) spectra, indicating a high rigidity of polymer backbone.     

SYNTHESIS OF POLYBINAPHTHYLS INCORPORATING CHIRAL(R)-1,1''''-BI-2,2''''-NAPHTHOL ENTITIES WITH p-DIVINYLBENZENE BY Pd-CATALYZED HECK REACTION

INTRODUCTION(R) or (S) 2,2'-binaphthnol (BINOL) have often been used as the starting materials for obtaining chiral binaphthylcompounds. The 2,2'-hydroxyl groups of BINOL can be easily converted into other functional groups and the3,3'-and 6,6'-positions of naphthyl skeletal structure of BINOL can be selectively functionalized, leading to avariety of binaphthyl derivatives which can exhibit remarkably stable chiral configuration as well as high chiralinduction in many asymmetric proc…     

POLYBINAPHTHYLS INCORPORATING (R)-2,2’-BINAPHTHO-20-CROWN-6 AND NAPHTHYL MOITIES

Chiral polymer was synthesized by the polymerization of （R）-6,6＇-bistributylstannyl-2,2＇-binaphtho-20-crown-6 （M-1） with 1,4-dibromo-2,3-bisbutoxy-naphthyl （M-2） by Pd（PPhs）4 catalyzed Stille coupling reaction. Both monomer and polymer were analyzed by NMR, MS, FT-IR, UV, polarimetry, DSC-TGA, CD, fluorescent spectroscopy and GPC. The major difference between monomer and polymer is that a long wavelength Cotton Effect was observed for the polymer due to its more extended conjugation in the repeating unit and a highly rigid backbone in the polymer chain. Polymer has strong blue fluorescence due to the efficient energy migration from the extended n-electronic structure of the repeating unit of the polymer to the chiral binaphthyl core and is expected to have potential application in the materials of fluorescent sensors and chiral chromatographic packing for resolution ofracemic amino acid.     

Polybinaphthyls of （R）—3,3‘—Diiodo—2,2’—binaphtho—20—crown—6 with p—Divinylbenzene via Heck Cross—coupling Reaction

The present paper deals with the polybinaphthyls of (R）-3,3‘-Diiodo-2,2‘-binaphtho-20-crown-6 with p-divinylbenzedne under Heck-coupling reaction condition.Both the monomers and the polymer were analyzed by NMR,FTIR,UV,CD,fluorescent spectroscopy,polarimetry,GPC and elemental analysis.The polymer can emit a strong blue fluorescence and is expected to have the potential application in the polarized bluelight emitting sensors.The chiral conjugated polymer exhibits a strong Cotton effect in its Circular Dichroism (CD-) spectrum,indicating the high rigidity of the polymer backbone.     

1,1′-联萘-2,2′-二胺的合成及在不对称合成中的应用

综述了 1,1′ 联萘 2 ,2′ 二胺 (联萘胺 )化合物的制备 ,讨论了它们作为手性辅助基或配体在烯烃、酮、亚胺的不对称氢化及在烯烃的不对称环丙烷化、醛的烷基化反应、醛的不对称烯丙基化反应、不对称烯丙位取代反应和不对称Diels Alder反应等反应中的应用 .     

Catalytic Preparation of Optically Active 1,1′—Binaphthalene—2,2′—Diol by Chiral Benzoimidazole—Cu（Ⅱ）Complex

Inthepastseveraldecades ,muchattentionhasbeenpaidtoopticallyactive ,C2 asymmetric1,1′ bi naphthalene 2 ,2′ diolanditsderivativesbecauseoftheirapplicationininducingchiralityinasymmetricsynthesis[1,2 ] .Enantiomericallypure1,1′ binaphtha lene 2 ,2′ diolhasbeen preparedbymanymethodsrangingfromtheclassicalresolutionviacrystalliza tionofthediastereoisomericsalts[3] toasymmetricox idativecoupling[4～ 6 ] .However ,theuseofexpensivechiralreagentsandthetediousnessoftheprocessessetalimitontheuseof…     

NMR方法表征联萘衍生物 I2,2′-二(对氨苯氧基)-1,1′-联萘

用１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ和二维核磁共振技术研究了２，２′－二（对氨苯氧基）－１，１′－联萘的结构，并通过１Ｈ－１Ｈ质子同核相关及１３Ｃ－１Ｈ异核相关谱提供的信息确定了其１Ｈ谱和１３Ｃ谱中各谱峰的归属，为聚合物的表征提供了依据。     

用硅胶担载三氯化铁催化氧化偶联2-萘酚制备(±)2,2′-二羟基-1,1′-联萘

2,2′-二羟基 - 1 ,1′-联萘 ,由于存在受阻 C- C键轴 ,可通过拆分获得对映体纯手性双膦配体BINAP的前体 [1] ,或经不对称氧化转化成催化剂前体 [2 ] ,或用作手性试剂 ,近年来备受人们的重视 .其常用制备方法多以 Fe3 、 Mn3 及 Cu2 氧化 2 -萘酚 .尤以 Fe3 [3～ 5] 为氧化剂制备 (± ) 2 ,2′-二羟基 -1 ,1′-联萘最为经济 .传统上以甲醇 /水 ( 1 /1 ,体积比 )为介质 ,用 Fe Cl3 氧化 2 -萘酚制 (± ) 2 ,2′-二羟基 - 1 ,1′-联萘 ,产率不太高 [5] .近年来 ,Toda等 [5]利用固态反应及超声波制备此化合物 ,收率明显提高 ,但…     

SYNTHESIS OF NEW AROMATIC POLY（AMIDE IMIDE）S FROM UNSYMMETRICAL EXTENDED DIAMINE CONTAINING A PHTHALAZINONE MOIETY

The direct polymerization of an unsymmetrical kink non-coplanar heterocyclic diamine (1) with various aromatic bis(trimellitimide)s (2a-e) using triphenyl phosphite and pyridine as condensing agents could generate a series of new aromatic poly(amide imide)s (3a-e) containing the kink non-coplanar phthalazinone heterocyclic units in the polymer main chains with inherent viscosities of 0.58-0.66 dL/g. The polymers are readily soluble in a variety of solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidinone, pyridine and m-cresol and can be cast to form flexible and tough films. The glass transition temperatures of polymers (T8) are in the range of 301-327℃, and the temperatures for 5% weight loss in nitrogen are in the range of 498-521℃.     

含多个(R)-1,1''''-联萘手性高分子合成与结构表征

单体（R）．3，3＇-二碘-2，2＇-二正丁氧基-1，1＇-联萘（（R）-M-1），（R）-6，6＇-二溴-2，2＇-二正丁氧基-1，1’-联萘（（R）-M-2）分别与1，4-二乙烯基-2，3-二丁氧基萘（M-3），在钯催化下，通过Heck交叉耦合反应合成手性高分子P-1与P-2．单体和高分子进行了^1H—NMR、^13C-NMR、FT-IR、旋光度、GPC、UV、热分析、荧光光谱和CD等测试分析．高分子侧链上引入丁氧基后使得手性高分子溶解性增强并具有良好的成膜性，手性高分子P-1和P-2都能发射较强的蓝绿色荧光，荧光量子效率分别为0．42和0．48．     

含多个(R)-1,1′-联萘手性高分子合成与结构表征

单体(R)-3,3′-二碘-2,2′-二正丁氧基-1,1′-联萘((R)-M-1),(R)-6,6′-二溴-2,2′-二正丁氧基-1,1′-联萘((R)-M-2)分别与1,4-二乙烯基-2,3-二丁氧基萘(M-3),在钯催化下,通过Heck交叉耦合反应合成手性高分子P-1与P-2.单体和高分子进行了1H-NMR1、3C-NMR、FT-IR、旋光度、GPC、UV、热分析、荧光光谱和CD等测试分析.高分子侧链上引入丁氧基后使得手性高分子溶解性增强并具有良好的成膜性,手性高分子P-1和P-2都能发射较强的蓝绿色荧光,荧光量子效率分别为0.42和0.48.     

POLYBINAPHTHYLS INCORPORATING (R)-2,2''''-BINAPHTHO-20-CROWN-6 AND NAPHTHYL MOITIES

Chiral polymer was synthesized by the polymerization of (R)-6,6'-bistributylstannyl-2,2'-binaphtho-20-crown-6 (M-1) with 1,4-dibromo-2,3-bisbutoxy-naphthyl (M-2) by Pd(PPh3)4 catalyzed Stille coupling reaction. Both monomer and polymer were analyzed by NMR, MS, FT-IR, UV, polarimetry, DSC-TGA, CD, fluorescent spectroscopy and GPC. The major difference between monomer and polymer is that a long wavelength Cotton Effect was observed for the polymer due to its more extended conjugation in the repeating unit and a highly rigid backbone in the polymer chain. Polymer has strong blue fluorescence due to the efficient energy migration from the extended n-electronic structure of the repeating unit of the polymer to the chiral binaphthyl core and is expected to have potential application in the materials of fluorescent sensors and chiral chromatographic packing for resolution of racemic amino acid.     

Polybinaphthyls of (R)-3,3′-Diiodo-2,2′-binaphtho-20-crown-6 with p-Divinylbenzene via Heck Cross-coupling Reaction

IntroductionFunctional polymers bearing chiral moietiesand the extended conjugatedπ system have attract-ed considerable attention during the pastdecade[1,2 ] .The enantiodifferation properties ofsuch macromolecules give rise to multiple applica-tions in the fields of asymmetric catalysis,chiralsensors,polarized light emission and nonlinear op-tical materials[3 ,4] .Especially the incorporation ofoptically active binaphthyls in the main chain ofconjugated polymers can lead to an efficient ands…     

POLYBINAPHTHYLS INCORPORATING (R)-20,''-BINAPHTHO-20-CROWN-6AND NAPHTHYL MOITIES

Chiral polymer was synthesized by the polymerization of (R)-6,6'-bistributylstannyl-2,2'-binaphtho-20-crown-6(M-1) with 1,4-dibromo-2,3-bisbutoxy-naphthyl (M-2) by Pd(PPh3)4 catalyzed Stille coupling reaction. Both monomer and polymer were analyzed by NMR, MS, FT-IR, UV, polarimetry, DSC-TGA, CD, fluorescent spectroscopy and GPC. The major difference between monomer and polymer is that a long wavelength Cotton Effect was observed for the polymer due to its more extended conjugation in the repeating unit and a highly rigid backbone in the polymer chain. Polymer has strong blue fluorescence due to the efficient energy migration from the extended π-electronic structure of the repeating unit of the polymer to the chiral binaphthyl core and is expected to have potential application in the materials of fluorescent sensors and chiral chromatographic packing for resolution ofracemic amino acid.     

以苯甘氨酸基为侧链的光学活性甲基丙烯酰胺聚合物的合成及手性识别能力

合成了N-[(R)-α-叔丁氧基羰基苄基]甲基丙烯酰胺((R)-BCBMAM),通过自由基聚合法获得相应的光学活性聚合物(P(R-BCBMAM)),并以三氟乙酸为水解催化剂除去叔丁基而得到(P(R-CBMAM)).用1H-NMR,IR,CD和GPC对聚合物进行了结构表征,发现聚合溶剂和聚合物分子量对所得聚合物P(R-BCBMAM)的光学活性没有明显影响,P(R-BCBMAM)水解后光学活性有较大的改变.与单体相比,聚合物的比旋光度有较大的区别,且在对应于其侧基的紫外吸收处呈现明显不同于单体的Cotton效应,说明聚合物的主链可能形成了一定的二级结构.以P(R-BCBMAM)和P(R-CBMAM)制备的2种涂敷型高效液相色谱用手性固定相,对部分对映体具有一定的手性拆分能力.利用1H-NMR技术研究了上述2种聚合物与1,1'-联-2-萘酚(BINOL)的相互作用,它们对BINOL都具有良好的手性识别能力.     

（2R,3S）—2甲基—3—羟基戊酸甲酯的手性合成

１引言烟草甲ＬａｊｓｔｏｄｅｒｍａｓｅｒｒｉｃｏｒｎｅＦａｂｒ。ｉｎｓ是一种主要危害烟草、香烟、干燥植物以及谷物、面粉的农业害虫。这种害虫在我国主要分布在淮河以南地区以及世界各地的温暖地带［‘］。（２,３Ｓ）－２一甲基一３一羟基成酸甲酯是我们设计的合成烟草甲性信息素的一个重要中间体。我们以丙快醇为基本原料合成了该化合物。丙炔醇参照文献ｌ’］方法制得２一戊炔一ｌ一醇２,催化还原条件下,炔键可被部分加氢得到（Ｑ－２一戊烯一卜醇３。在四异丙氧基钛、Ｄ－（）一酒石酸＄［Ｊ４Ａ分于筛催化条件下,顺式烯丙醇…