Umsetzungen mit 1,3-Dichlor-2-methylenpropan,III. Synthesen und Reaktionen von 1,3-Diamino-2-methylenpropanen

Reactions with 1,3-Dichloro-2-methylenepropane. III. Synthesis and Reactions of 1,3-Diamino-2-methylenepropanes 1,3-Bis(dialkylamino)-2-methylenepropanes are obtained by reaction of the chlorination product of isobutene with secondary amines. The synthesis of 1,3-diamino-2-methylenepropane succeeds by Gabrielsynthesis, by reaction of 1,3-diiodo-2-methylenepropane with liquid ammonia and by dehydration of 1,3-diamino-2-methyl-2-propanol, obtained from methallylchloride. The use of 1,3-diamino-2-methylenepropane as a C₃N₂-reagent for the synthesis of heteroalicycles is described.     

1,3-二溴丙酮和1,3-二氨基丙酮盐酸盐的合成

丙酮与溴素(mol比为1:2.03)在冰醋酸存在下发生取代反应,分离提纯后得三种产物。经过IR和NMR分析,可确定主要产物为1,3-二溴丙酮。1,3-二溴丙酮为淡黄色液体(25℃),折光率n_D~(20)为1.553 2。1.3-二溴丙酮与六次甲基四胺成盐物分别在盐酸、乙醇中水解得淡黄色粉状固体。经过IR分析,证明生成物为1,3-二氨基丙酮盐酸盐。     

1，3-二氧戊环

由于 1,4 二烷的致癌性 ,使其在很多领域正在被 1,3 二氧戊环所取代。本文介绍了 1,3 二氧戊环在溶剂、洗涤剂、萃取剂方面广泛的应用 ,同时介绍了它的理化性质和合成方法。     

Cationic copolymerization of 1,3-pentadiene with 1,3-cyclopentadiene

Copolymerizations of 1,3-pentadiene (PD) with 1,3-cyclopentadiene (CPD) initiated by aluminium trichloride were carried out in toluene. The addition of CPD in the PD polymerization system does not affect the molecular weight but greatly increases the softening point of the polymer due to the introduction of cyclic structures. The Gardner color scale of the polymer is also raised by introduction of unsaturated rings of CPD. The copolymerization gives a complete conversion but generates insoluble crosslinked gels at high CPD content due to the high crosslinking reactivity of CPD. The integral intensities of unsaturated protons from PD and CPD segments of the copolymer chain on the ¹H-NMR spectrum give a perfect correlation with the copolymer compositions. The low-conversion experiments were carried out with small amounts of CPD in order to determine the reactivity ratio in this copolymerization system (M₁ = PD and M₂ = CPD). The result of r₁ = k₁₁/k₁₂ = 0.46 demonstrates that CPD has a higher reactivity than PD toward PD growing carbocations, and hence the copolymer shows a higher CPD proportion than the corresponding comonomer. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1883–1887, 1997     

1,4-二苯基-2,3-二二茂铁基-1,3-丁二烯的合成、表征及其电化学性质研究

利用正丁基锂与二氯二茂锆的反应产物二丁基二茂锆(ZrCp2Bu2)与二茂铁苯乙炔的环合、水解等反应,制备出新的标题化合物。采用红外光谱、核磁共振谱、质谱、元素分析等表征手段,对所合成的化合物的组成、结构进行了表征。并利用循环伏安实验中两个二茂铁基电位差的大小,判断出新化合物中两个二茂铁基的相互位置,确定了新分子的基本构型,为二茂铁基-1,3-丁二烯衍生物的合成和分子构型的鉴定提供了新方法。     

1，3－二溴－5，5－二甲基乙内酰脲的合成

考察了反应介质、物料比、反应温度和反应时间对１，３－二溴－５，６－二甲基乙内酰脲合成产率的影响，并确定了最佳合成条件，产率８８％。     

1,3-Dithienium- und 1,3-Dithioleniumsalze. IX. Reaktionen von 1,3-Dithian-2-ylium-tetrafluoroboraten mit C-Nucleophilen

1,3-Dithienium and 1,3-Dithiolenium Salts. IX. Reactions of 1,3-Dithiane-2-ylium Tetrafluoroborates with C-Nucleophiles 1,3-Dithian-2-ylium tetrafluoroborates ( 1 ), which can be easily obtained by variable methods, react in good to excellent yields with variable C-nucleophiles to new geminal disubstituted 1,3-dithianes. The latter compounds are potential precursors of interesting synthetic building blocks. Reactions are described with 2-lithio-1,3-dithianes 2 , sodium cyanide 4 , sodium salts of the nitro alkanes 7 and CH-acids of the type of the 1,3-dicarbonyl compounds 9 . The reduction of 3-oxo-2-(2-phenyl-1,3-dithian-2-yl)-ethoxybutanoat–following a diastereoselective pathway – leads to the Cram product 11 . Further presented is the crystal structure of 2-phenyl-1,3-dithiane-2-ylium tetrafluoroborate ( 1b ).     

Cationic grafting of norbornadiene, indene, and 1,3-cyclohexadiene from PVC

Summary The synthesis of three novel graft copolymers consisting of a PVC backbone fitted with polynorbornadiene (PNbd), polyindene (PInd), polycyclohexadiene (PCHD) branches, i.e., PVC-g-PNbd, PVC-g-PInd, and PVC-g-PCHD, is described. The synthesis strategy was to initiate the grafting of norbornadiene (Nbd), indene (Ind), and 1,3-cyclohexadiene (CHD) by a PVC containing ∼ 1.6 active (tertary and allylic) chlorines in conjunction with Et₂AlCl. The products were characterized by solvent fractionation, molecular weight determination, T_g, and NMR spectroscopy. The effect of temperature on the grafting was investigated in the 20 to −50 °C range. Received: 8 October 2001/ Revised version: 22 April 2002/ Accepted: 23 April 2002     

2-氨基-5-(2-苯基-1,3-硒唑-4-甲硫基)-1,3,4-噻二唑的合成

在氢氧化钾参与下,利用固-液相转移催化法合成了标题化合物,实验考察了不同催化剂、催化剂用量、反应物用量、反应温度对收率的影响,结果表明:以聚乙二醇-400为催化剂,且其物质的量为底物2-苯基-4-氯甲基硒唑的5%,2-苯基-4-硒唑基氯甲烷和2-氨基-5-巯基-1,3,4-噻二唑的物质的量比为1∶1.2,在丙酮中回流,为较佳反应条件,收率可达82.6%,目标物的结构经IR、1HNMR及ESI-MS等方法确证。     

1,3-Dipolar Cycloadditions of 1,1-Difluoroallene,Nitrones, Nitrile-Oxides and Carbonyl Ylides

The 1,3-dipolar cycloadditions of C,N-diphenylnitrone, C-phenyl-N-methylnitrone, triphenylnitrone, mesitylnitrile oxide and tetracyanocarbonyl ylide with 1,1-difluoroallene (DFA) are reported and discussed with respect to regiochemistry. Each of the dipoles adds exclusively to the C₂—C₃, non-fluorine-substituted π-bond of DFA. The nitrones all undergo regiospecific reactions while mesitylnitrile oxide does not. The results are discussed with respect to FMO theory and other factors which can give rise to regiochemical variation.     

1,3-Benzodioxole-Modified Noscapine Analogues: Synthesis,Antiproliferative Activity,and Tubulin-Bound Structure

Since the revelation of noscapine's weak anti-mitotic activity, extensive research has been conducted over the past two decades, with the goal of discovering noscapine derivatives with improved potency. To date, noscapine has been explored at the 1, 7, 6′, and 9′-positions, though the 1,3-benzodioxole motif in the noscapine scaffold that remains unexplored. The present investigation describes the design, synthesis and pharmacological evaluation of noscapine analogues consisting of modifications to the 1,3-benzodioxole moiety. This includes expansion of the dioxolane ring and inclusion of metabolically robust deuterium and fluorine atoms. Favourable structural modifications were subsequently incorporated into multi-functionalised noscapine derivatives that also possessed modifications previously shown to promote anti-proliferative activity in the 1-, 6′- and 9′-positions. Our research efforts afforded the deuterated noscapine derivative 14 e and the dioxino-containing analogue 20 as potent cytotoxic agents with EC₅₀ values of 1.50 and 0.73 μM, respectively, against breast cancer (MCF-7) cells. Compound 20 also exhibited EC₅₀ values of <2 μM against melanoma, non-small cell lung carcinoma, and cancers of the brain, kidney and breast in an NCI screen. Furthermore, compounds 14 e and 20 inhibit tubulin polymerisation and are not vulnerable to the overexpression of resistance conferring P-gp efflux pumps in drug-resistant breast cancer cells (NCI^ADR/RES). We also conducted X-ray crystallography studies that yielded the high-resolution structure of 14 e bound to tubulin. Our structural analysis revealed the key interactions between this noscapinoid and tubulin and will assist with the future design of noscapine derivatives with improved properties.     

2-甲基-1,3-氧硫杂环戊烷和2-丙基-1,3-氧硫杂环戊烷的合成

以对甲苯磺酸为催化剂 ,巯基乙醇与乙醛、丁醛 (量比为 1.0∶1.1)在苯中共沸脱水 ,合成两种目标产物 :2 甲基 1,3 氧硫杂环戊烷、2 丙基 1,3 氧硫杂环戊烷。其产率分别为 81%和 88% ,质量分数分别为 99%和 98%。经红外光谱、色谱、质谱、核磁共振谱检测 ,确证了产物结构。此方法简便易行 ,产率较高     

取代1,3-二苯基-1,3-丙二酮的合成与抗氧化性能

以取代芳酮和取代芳酯为原料,经克莱森反应合成了5个取代1,3-二苯基-1,3-丙二酮。采用正交实验优化1,3-二(4-甲氧基苯基)-1,3-丙二酮较佳的工艺条件:以甲苯为溶剂,NaNH2作催化剂,n(对甲氧基苯乙酮)∶n(对甲氧基苯甲酸甲酯)∶n(氨基钠)=1∶4∶5,微波辐射功率320 W,反应时间45 min,收率为72.1%。合成的产物结构经IR与1HNMR光谱进行了结构表征,用HPLC测定其含量。对UV光谱有良好的吸收及对猪油有较好的抗氧化作用。     

Electrosynthesis using a fluoride ion mediator. Part V: Fluoride ion mediated anodic methoxylation and acetoxylation of thiazolidines, 1,3-oxathiolanes, and 1,3-dithiolanes

Anodic methoxylation and acetoxylation reactions of five membered cyclic sulfides such as thiazolidines, 1,3-oxathiolanes and 1,3-dithiolanes, which have been reported to not always undergo the Pummerer reaction, were successfully carried out by using a fluoride ion mediator.     

Crystallization kinetics of the pure triacylglycerols glycerol-1,3-dipalmitate-2-oleate,glycerol-1-palmitate-2-oleate-3-stearate,and glycerol-1,3-distearate-2-oleate

Crystallization kinetics of the three main components of cocoa butter, the triacylglycerols POP, POS, and SOS (where P, O, and S stand for palmitic, oleic, and stearic acids, respectively) were studied by combined differential scanning calorimetry and polarized light microscopy. The morphologies, nucleation kinetics, growth kinetics, and phases of the grains formed were identified with this system. The experimental data, as well as two different models to simulate crystallization and to predict behavior of the pure triacylglycerols, are presented. The first model is based on a macroscopical approach to solidification by using time-temperature-transformation (TTT) diagrams and the additivity principle. It allows prediction of the proportion of the different phases formed for any given thermal path imposed on the sample once the TTT diagram is known for the product. It is illustrated for SOS at constant cooling rates and is compared with experimental results. The second model directly simulates growth of the spherulites in the sample by using nucleation and growth rates that are determined experimentally. It provides a view of the structure as it would be observed with a microscope and shows evolution of the heat released in the sample. Isothermal solidification of POP at 15°C is displayed. The experiment and the model are in good agreement.     

2-异戊酰基-1，3-茚二酮铕（Ⅲ）配合物的合成、表征及其荧光性质的研究

合成了标题化合物,并用红外光谱、紫外光谱、元素分析和热重-差热分析及荧光光谱对配合物进行了组成确定和表征.荧光分析结果表明配体能够激发Eu3+的电偶极跃迁而发红光,配合物具有很好的荧光性能,是一种潜在的红色发光材料.     

1,3-二(二苯基氯硅烷基)-2,2,4,4-四苯基环二硅氮烷的合成及液晶性表征

用1,3-二(二甲基氯硅烷基)-2,2,4,4-四甲基环二硅氮烷与二苯基二氯硅烷反应,得1,3-二(二苯基氯硅烷基)-2,2,4,4-四苯基环二硅氮烷,用甲苯与正辛烷提纯化合物,熔点200～206℃,收率75%～78%。产品经IR和1H NMR确证了结构,用示差扫描量热法(DSC)与偏光显微镜分析,发现该化合物具有液晶性,属于热致型液晶,显示六方相。经教育部科技查新工作站(L03)2007年11月22日出具的第2007236号《科技查新报告》证实,在国内文献中未见关于1,3-二(二苯基氯硅烷基)-2,2,4,4-四苯基环二硅氮烷液晶性表征的相关报道。