1,4—双（氯甲基）—2—甲氧基—5—壬氧基苯的均聚和共聚研究

以１，４－双（氯甲基）－２，５一二甲基苯（ＢＣＭＤＭＢ）和１，４－双氯甲基－２－甲氧基－５－壬氧基苯（ＢＣＭＭＯＮＯＢ）为单体，采用脱氯化氢法，合成了聚（２，５－二甲基）对亚苯基亚乙烯（ＰＤＭＰＶ）和聚（２－甲氧基－５－壬氧基）对亚苯基亚乙烯（ＰＭＯＮＯＰＶ）；并对ＢＣＭＤＭＢ和ＢＣＭＭＯＮＯＢ的共聚进行了研究。结果表明，适宜的反应条件为：碱与单体的摩尔比为２０∶１，在室温下聚合时间为３０ｈ，碱的ｐＨ＝１４时产率最高。用ＩＲ、１Ｈ－ＮＭＲ、ＵＶ—Ｖｉｓ对聚合物进行了表征。     

2—溴代对苯二甲酸根桥联双核钴（Ⅱ）配合笺的合成,磁性及抗癌活性

合成了三种以２－溴代对苯二甲酸为桥联配体的新型双核钴（Ⅱ）的配合物，即［Ｃｏ２（ＢＴＰ）（ｐｈｅｎ）４］（ＣｌＯ４）２．Ｈ２Ｏ（配合物１）、［Ｃｏ２（ＢＴＰ）（Ｎｐｈｅｎ）４］（ＣｌＯ４）２．２Ｈ２Ｏ（配合物２）和［Ｃｏ２（ＢＴＰ）（Ｂｐｙ）４］ＣｌＯ４）２，２ＨＯ（配合物３）（ＢＴＰ＝２－溴代对苯二甲酸根，ｐｈｅｎ＝１，１０－菲罗啉，Ｎｐｈｅｎ＝５－硝基－１，１０－菲罗啉，Ｂｐｙ－２，２＇联吡啶     

具有不同类型桥基的双核Cu（Ⅱ）—Schiff碱配合物的合成 …

合成了３个分别以Ｃ２Ｏ＾２－４（「Ｃｕ２（Ｌ１）２（ｏｘ）」，１），ＡｃＯ＾－（「Ｃｕ２（ＡｃＯ）（Ｌ２）２」ＢＦ４，２）和酚氧（「Ｃｕ２９Ｌ３０２」（ＣｌＯ４）２，３）为桥基的双核铜配合物，并测定了１的复配合物「Ｃｕ２（Ｌ１）２（ｏｘ）」「Ｆｅ（ＯＨ）２（Ｈ２Ｏ）４」ＣｌＯ４．Ｈ２Ｏ及２和３的晶体结构。     

2—（6—硝基—2—苯并噻唑偶氮）—5—二甲氨基苯甲酸与铜显色反应的研…

本研究了２－（６－硝基－２－苯并噻唑偶氮）－５－二甲氨基苯甲酸（６－ＮＯ２－ＢＴＡＭＢ）与铜的显色反应。结果表明，在ｐＨ２．０￣４．５的乙醇水溶液中６－ＮＯ２－ＢＴＡＭＢ与铜形成一种稳定的蓝绿色络合物，其最大吸收波长位于６５０ｎｍ处，表观摩尔吸收系数为７．７５×１０＾４Ｌ·ｍｏｌ＾－１·ｃｍ＾－１，络合物的组成为６－ＮＯ２－ＢＴＡＭＢ∶Ｃｕ＝１∶１，铜浓度在０￣１０μｇ／１０ｍｌ范围内服从比尔定     

碳基铁—硫醇（硫酚）—格氏试剂体系与芳酰氯反应的研究：…

通过Ｆｅ３（ＣＯ）１２、硫醇（硫酚）和ＥｔＭｇＢｒ所形成的络盐［（μ－ＣＯ）（μ－ＲＳ）Ｆｅ２（ＣＯ６）》－Ｍｇ＾＋Ｂｒ与氯代芳酰氯的原位反应，合成了通式为（μ－ＲＳ）（μ－ｏ－ＣｌＣ６Ｈ４ＣＯ）Ｆｅ２（ＣＯ６）和（μ－ＲＳ）（μ－ｍ－ＣｌＣ６Ｈ４ＣＯ）Ｆｅ２（ＣＯ）６（Ｒ＝ｎ－Ｂｕ，ｔ－Ｂｕ，Ｐｈ）的６个新桥芳酰基铁硫配合物，并用Ｃ／Ｈ分析、ＩＲ和＾１ＨＮＭＲ表征了它们的结构。     

溶胶—凝胶合成（Mg,Ca）O—SiO2：Eu^3＋,Bi^3＋发光体及其发光行为

以Ｍｇ（ＮＯ３）２，Ｃａ（ＮＯ３）２，Ｅｕ（ＮＯ３）３，Ｂｉ（ＮＯ３）３和Ｓｉ（ＯＣ２Ｈ５）４为反应物，采用溶胶－凝胶法，在比较低的温度，首次合成０．７０１ｍｏｌＭｇＯ－０．１７５ｍｏｌＣａＯ－１．２５ｍｏｌＳｉＯ２：０．０６ｍｏｌＥｕ＾３＋，０．００２ｍｏｌＢｉ＾３＋（加入Ｌｉ＾＋作为电荷补偿剂）发光体，得到了最佳合成条件，研究了由溶胶向凝胶转变和凝胶向发光晶体的转变过程，探讨了发光体在不同激光     

CaAl2B2O7：Eu的振动光谱和发光特性

采用高温固相反应法,合成了ＣａＡｌ２Ｂ２Ｏ７：Ｅｕ磷光体。测定了ＣａＡｌ２Ｂ２Ｏ７：Ｅｕ的振动光谱,结果表明ＢＯ３的振动吸收位于１４００－１６００ｃｍ＾－１区域内,ＡｌＯ６的吸收位于５１９ｃｍ＾－１。     

1—N—（苯并咪唑—1—乙酰基）—4—苯基—3—氨基硫脲金属配合物的合成及结…

合成了新配体１－Ｎ－（苯并咪唑－１－乙酰基）－４－苯基－３－氨基硫脲（ＢＰＭＳ），将其与Ｍｎ（Ⅱ），Ｃｏ（Ⅱ），Ｎｉ（Ⅱ），Ｃｕ（Ⅱ），Ｃｄ（Ⅱ），Ｚｎ（Ⅱ），ＵＯ２（Ⅱ）等金属的醋酸盐反应，合成了７个新配合物，所有化合物均经元素分析，ＩＲＨＮＭＲ和热重分析等表征，红外光谱表明，配体以四齿方式通过烯醇式羰基氧还子，烯醇式硫羰基硫原子以及Ｃ＝Ｎ＾１和Ｃ＝Ｎ＾２的氮原子与金属配位。     

二［氧合—二（4—二茂铁基苯甲酸二烷基锡（Ⅳ））］配合物？…

合成了｛［（ｎ－Ｂｕ）２Ｓｎ（４－Ｆｃ－Ｃ６Ｈ４ＣＯＯ）］２Ｏ｝２（１）和｛［ｎ－Ｏｃｔ）２Ｓｎ（４－Ｆｃ－Ｃ６Ｈ４ＣＯＯ）］２Ｏ｝２（２）（Ｆｃ＝ｆｅｒｒｏｅｎｙｌ两组新的配合物,对其进行了元素分析,并用ＩＲ,ＮＭＲ（＾１Ｈ,＾１３Ｃ,＾１１９Ｓｎ）进行了谱学表征,单晶Ｘ射线衍射法测定表明,配合物１的晶体属单斜晶系,Ｐ２１／ｃ空间群,晶胞参数ａ＝１．２９８８（１）ｎｍ,ｂ＝２．６５５（１）ｎｍ,     

2—取代—1,7—二氧螺（4.4）壬—8—酮的合成研究

分别用Ｋ２ＣＯ３，１，５－二氮双环（４．３．０）壬－５－烯（ＤＢＮ）和四丁基氟化铵（ＴＢＡＦ）等碱催化３－（３－羟基丙基）－γ－丁烯酸内酯的分子内Ｍｉｃｈｅａｌ加成反应合成了２－取代－１，７－二氧螺（４．４）壬－８－酮     

New cholesteric liquid‐crystal epoxy resins derived from 6‐hydroxy‐2‐naphthoic acid

Liquid‐crystalline epoxy resins were synthesized from 6‐hydroxy‐2‐naphthoic acid, which was used as a mesogenic component, with phenylhydroquinone or isosorbide and via a further reaction with (6‐bromo‐1‐hexyl)glycidylether, which was used as a flexible spacer. In this way, phenylhydroquinone‐bis‐6‐[6‐(glycidyloxy)hexyloxy]2‐naphthoate (Gly A) and isosorbide‐bis‐6‐[6‐(glycidyloxy)hexyloxy]2‐naphthoate (Gly B) were obtained. Nematic elastomers were obtained by the crosslinking of Gly A with 2,4‐diaminotoluene (DAT) and 1,10‐decanedicarboxylic acid (SA). The liquid‐crystalline behavior was investigated with differential scanning calorimetry, polarizing light microscopy, and X‐ray diffractometry. Cholesteric mesophases were produced by the blending of different ratios of Gly A and Gly B, and these blends were then crosslinked with SA to produce nematic mesophases. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2847–2858, 2001     

The cocrystal of 3‐hydroxy‐2‐naphthoic acid and 4,4′‐bipyridine

4,4′‐Bipyridine cocrystallizes with 3‐hydroxy‐2‐naphthoic acid in a 1:2 ratio to give a centrosymmetric three‐component supra­molecular adduct, namely 3‐hydroxy‐2‐naphthoic acid–4,4′‐bipyridine (2/1), C₁₁H₈O₃·0.5C₁₀H₈N₂, in which 4,4′‐bipyridine is located on an inversion center. The pyridine–carboxylic acid heterosynthon generates an infinite one‐dimensional hydrogen‐bonded chain viaπ–π inter­actions between naphthyl and 4,4′‐bipyridine groups. The one‐dimensional chains are further assembled into a three‐dimensional network by weak C—H⋯π inter­actions between pyridyl and naphthyl rings, and C—H⋯O inter­actions between 3‐hydroxy‐2‐naphthoic acid mol­ecules.     

Synthesis of naphthalene and indene precursors to naphthoic and indenoic acids

As part of ongoing research to investigate structural requirements for lactate dehydrogenase inhibition by highly substituted naphthoic and indenoic acids, certain naphthalene and indene precursors to those types of compounds are required. Described here are efficient preparations of 1-naphthoic acid precursors 6-benzyl-2,3-dimethoxy-1-propylnaphthalenes, including compounds with substituted benzyl groups and 7-benzyl-2,3-dimethoxy-1-propylnaphthalene. Also described are the syntheses of indenoic acid precursors 2-benzyl-5,6-dimethoxy-7-propyl-1H-indenes, including compounds with substituted benzyl groups. These compounds were made from the key intermediates 6,7-dimethoxy-5-propyl-1-tetralone, 6,7-dimethoxy-8-propyl-1-tetralone, and 5,6-dimethoxy-4-propyl-1-indanone.     

Template-Assembled Synthetic Proteins (TASP). Cyclic Templates with Incorporated Turn-Inducing Mimics

The 8-amino-5,6,7,8-tetrahydronaphth-2-oic acid ( 1 ), 8-(aminomethyl)-5,6,7,8-tetrahydronaphth-2-oic acid ( 2 ), and 8-(aminomethyl)naphth-2-oic acid ( 3 ) were synthesized in their protected forms as turn-inducing dipeptide mimics. Two of them ( 2 and 3 ) were incorporated into a novel type of cyclic, peptide-based structures (see 21 and 34 – 36 ) designed as templates for the synthesis of TASP molecules.     

Synthesis of mono- and difluoronaphthoic acids

Aryl carboxamides are useful structural units found in several biologically active compounds. Unlike their benzoic acid counterparts, fluorinated versions of naphthoic acids are relatively unknown. In connection with a recent project, we needed viable syntheses of several mono- and difluorinated naphthoic acids. Herein we describe the synthesis of 5-, 6-, 7-, and 8-fluoro-1-naphthalenecarboxylic acids and 5,7-, 5,8-, 6,7-, and 4,5-difluoro-1-naphthalenecarboxylic acids. The 5-fluoro derivative 1was obtained from the corresponding 5-bromo compound via electrophilic fluorination of the lithio-intermediate. The rest of the monofluoro (2, 3, and 4) and the difluoro acids (5, 6, and 7) were prepared by a new, general route which entailed the elaboration of commercial fluorinated phenylacetic acids to 2-(fluoroaryl)glutaric acids with differential ester groups; selective hydrolysis to a mono acid, intramolecular Friedel-Crafts cyclization, and aromatization furnished the target structures. An alternative process to assemble a naphthalene skeleton is also presented for the difluoro acids 5 and 6. Finally, 4,5-difluoro-1-naphthalenecarboxylic acid (8) was prepared expeditiously from 1,8-diaminonaphthalene by adapting classical reactions.     

The Reaction of 2-Aminoethyl- and 3-Aminopropyl-substituted Heterocycles with 2-Formyl-1,3-cyclanediones and 4-Oxo-3,1-benzoxazines

The reaction of 2-formyl-1,3-cyclohexanedione, its 5,5-dimethyl, 5-phenyl and 5-(2-furyl) derivatives and of 2-formyl-1,3-indanedione and dehydroacetic acid with histamine, 3-(1-imidazolyl)propylamine, 3-(4-morpholyl)propylamine, 3-(2-pyrrolidon-1-yl)propylamine, 2-(1-piperazinyl)ethylamine, tryptamine, and 2-(aminomethyl)pyridine gave fifteen 2-aminomethylene derivatives. The reaction of these amines with 2-methyl-4-oxo-3,1-benzoxazine gave the 3-substituted 2-methyl-4(3H)-quinazolinones and with 4-oxo-2-phenyl-3,1-benzoxazine the monosubstituted N-benzoylanthranilic acid amides.     

Insecticidal Activity of Some New Amidophosphoric Acid Esters Containing Substituted Pyridine Moieties

Some new amidophosphoric acid esters containing substituted pyridine moieties were synthesized by the reaction of O-aryl, O-ethyl phosphoryl chlorides with 3-(aminomethyl)pyridine and 5-(aminomethyl)-2-chloropyridine. Characterization was done by ¹H NMR, ³¹P{¹H} NMR, IR, MS, and elemental analyses. The results of preliminary bioassay showed that the new compounds possess good insecticidal activity against aphides.     

Synthesis of Naturally Occurring Rubilactone,Mollugin, and Dihydromollugin of Rubia cordifolia

Rubilactone ( 1 ), dihydromollugin ( 2 ), and mollugin ( 3 ) are naturally occurring products found in Rubia cordifolia, which is a famous Chinese herb with anti tumor, viral inhibition and other activities. Synthetic studies were carried out in these naphthoic acid esters starting from 1,4‐dihydroxy‐2‐naphthoic acid. In this study, we finished the synthesis of rubilactone which has not been reported before and also synthesized dihydromollugin and mollugin with better yields with different approaches compared to those previously reported in the literature.     

合成E-10-羟基-2-癸烯酸的新方法

以1,8-辛二醇（1）为起始原料,经4步反应合成了（E）-10-羟基-2-癸烯酸,其结构经¹H NMR, ¹³C NMR和MS确证。考察了乙酰氯、缚酸剂种类及其用量［r=n（1）: n（乙酰氯）: n（缚酸剂）］对8-乙酰氧基-1-辛醇（2）收率的影响以及反应温度、三乙胺滴加温度、低温停留时间对8-乙酰氧基辛醛（3）收率的影响。结果表明：以三乙胺为缚酸剂,r=1.0 : 1.1 : 2.0时,2产率达78%;反应温度为-65 ℃、三乙胺滴加温度低于-50 ℃、低温反应3 h, 3产率达97%。     

萘甲酸功能化聚砜的制备及其与Eu(Ⅲ)稀土离子配合物的荧光发射特性

以1,4-二氯甲氧基丁烷(BCMB)为氯甲基化试剂,使聚砜(PSF)氯甲基化(CM),形成氯甲基化聚砜(CMPSF),然后用6-羟基-2-萘甲酸(HNA)使CMPSF的氯甲基与HNA的酚羟基之间发生亲核取代反应,将萘甲酸(NA)配基键合在聚砜侧链,制得了功能化改性的聚砜NAPSF。采用红外光谱和核磁共振氢谱对其结构进行了表征。考察了主要因素对CMPSF与HNA之间亲核取代反应的影响规律,分析了反应机理,优化了反应条件。结果表明,CMPSF与HNA之间取代反应的速率与亲核试剂HNA的浓度无关,遵循SN1的反应机理;使用极性较强的溶剂二甲亚砜,有利于亲核取代反应的进行;在适宜条件下,CMPSF的氯甲基转化率可达96%,NA的键合量为1.68 mmol/g。将NAPSF与Eu(Ⅲ)离子配位,制得了聚合物-稀土配合物NAPSF-Eu(Ⅲ),它不仅发射出Eu3+离子的特征荧光,而且对Eu3+离子的荧光发射显示出很强的敏化作用。萘甲酸功能化的大分子配基NAPSF对Eu3+离子的敏化作用,远强于苯甲酸(BA)功能化的大分子配基BAPSF对Eu3+离子的敏化作用。