Synthesis of β-Aminoketones of the Adamantane Series

4-(1-Adamantyl)-1-aminobutan-3-one hydrochlorides were synthesized by the Mannich reaction of (1-adamantyl)acetone with paraformaldehyde and secondary amine hydrochlorides (diethylamine, dibenzylamine, piperidine). Analogous reactions of 1-adamantyl(methyl)amine with acetone, p-hydroxyacetophenone, and methyl 2-thienyl ketone gave 1-[(1-adamantyl)methylamino]propan-3-one hydrochlorides.     

1-取代哌啶-4-酮肟醚的合成与杀菌活性测定

以取代苄胺或苯乙胺为起始原料, 依次经Michael 加成, Dieckmann缩合, 水解脱羧, 肟化和醚化等多步反应合成了11个未见文献报道的1-取代哌啶-4-酮肟醚5a～5k. 目标化合物的结构经元素分析, IR, 1H NMR和MS测定确证. 初步杀菌活性测试表明, 部分化合物有较好的杀菌活性.     

磷钨酸铜绿色催化合成缩醛(酮)及其催化活性测定

合成了绿色杂多酸盐催化剂磷钨酸铜;将环己酮、苯甲醛同乙二醇、1,2-丙二醇的缩合反应作为探针反应,测定了催化剂的催化活性,比较系统地考察了催化剂用量、物料配比、反应时间、带水剂用量等因素对反应产率的影响.结果表明:在底物醛(酮)用量0.2 mol、醛(酮)/乙二醇(1,2-丙二醇)摩尔比1.0/1.5、催化剂用量0.5 g、带水剂环己烷用量18 mL、一定温度下回流反应2.0 h,1,4-二氧螺[4,5]癸烷产率为83.3%,3-甲基-1,4-二氧螺[4,5]癸烷产率为89.7%,2-苯基-1,3-二氧环戊烷产率为66.7%,4-甲基-2-苯基-1,3-二氧环戊烷产率为78.5%.     

Phloretamide及其衍生物的合成与抗氧化活性

以3-(4-羟基苯基)丙烯酰胺（Phloretamide）为先导化合物,取代苯丙烯酸为原料,经取代反应和酰胺化反应制得苯丙烯酰胺类化合物(2a~2d); 2经氢化还原反应合成了4个Phloretamide衍生物(3a~3d); 1, 2和3经去甲基化反应分别制得〖WTHZ〗〖STHZ〗1e, 2e~2f和3e~3f〖STBZ〗〖WTBZ〗。其中,3-(3,4,5-三羟基苯基)丙烯酰胺(2f), 3-(2,3,4-三羟基苯基)丙酰胺(3e)和3-(3,4,5-三羟基苯基)丙酰胺(3f)为新化合物,其结构经¹H NMR, ¹³C NMR和ESI-MS表征。初步抗氧化活性测定结果表明：c为10 μmol·L^-1时,2b, 2f和3f具有较好的自由基清除活性,其清除率分别为66.8%, 59.8%和69.4%,均优于阳性对照咖啡酸,咖啡酸苯乙酯和Vc。     

Rhenium(V) complexes with thiolato and dithiolato ligands: synthesis, structures, and monomerization reactions

The new compound {(PhS)(2)ReO(mu-SPh)}(2), 1, was synthesized from Re(2)O(7) and PhSH and then used as the synthon for a number of hitherto unknown oxorhenium(V) compounds. Reactions between dithiols and 1 (2:1 ratio) afford {PhSReO(dt)}(2), where the dithiols, dtH(2), are 1,2-ethanedithiol (edtH(2)), 1,3-propanedithiol (pdtH(2)), 1,3-butanedithiol (pdtMeH(2)), 1,2-benzenedithiol (bdtH(2)), 2-(mercaptomethyl)thiophenol (mtpH(2)), and 2-mercaptoethyl sulfide (mesH(2)). Similar reactions carried out with a 3:1 ratio of dtH(2) to 1 afford [(ReO)(2)(dt)(3)], dt = edt, pdt. When NEt(3) was introduced prior to the 3:1 reaction between edtH(2) and 1, a compound containing an anionic complex was isolated, [PPh(4)][ReO(edt)(2)]. The new compounds were characterized analytically, spectroscopically, and crystallographically. The Re-O groups in two of the compounds, 1 and {ReO(mu-SPh)(bdt)}(2), exist in rare anti orientations; the others adopt the more familiar syn geometry, as discussed. Selected monomerization reactions of {PhSReO(dt)}(2) were also carried out: {PhSReO(dt)}(2) + 2L = 2[PhSReO(dt)L]. The rate for L = 4-phenylpyridine is given by v = {k(a)[L] + k(b)[L](2)} x [{PhSReO(dt)}(2)], as it is for the reactions of {MeReO(dt)}(2); for all of these compounds, the reaction proceeds nearly entirely by the third-order pathway. Values of k(b)/L(2) mol(-2) s(-1) at 25.0 degrees C are 5.8 x 10(2) (mtp), 2.97 x 10(3) (pdt), 4.62 x 10(5) (edt), and 3.87 x 10(5) (bdt). The rate law for the reactions of {PhSReO(dt)}(2) with L = PAr(3) is v = k(a)[L]/{1 + kappa[L]} x [{PhSReO(dt)}(2)]. For PPh(3), values at 25.0 degrees C of k(a)/L mol(-1) s(-1) (kappa/L mol(-1)) for {PhSReO(dt)}(2) are 9.64 x 10(-2) (1.87) for mtp, 3.43 x 10(-2) (0.492) for pdt, 1.91 (1.42) for edt, 1.84 x 10(-2) (0.82) for bdt, and 1.14 x 10(3) (10.6) for 1. Mechanisms are proposed that are consistent with the data obtained and with earlier work.     

2,4-二氧代-1,3,2-苯并二氮磷杂环己烷与■C=C■及CS_2加成反应的研究

本文研究了2,4-二氧代-1,3,2-苯并二氮磷杂环己烷的磷氢键对β-硝基苯乙烯、丙烯酸酯、丙烯腈及二硫化碳的加成反应,共合成了18个新的加成产物.发现通过选用不同的碱或控制碱的用量.可选择性的进行加成或开环反应.由X衍射证实:在加成产物的结构中,环外P-C键构象因受磷杂环船式构象影响,以邻位交叉式(A)为主.     

2,6-二(5-烷基水杨基)-4-烷基苯酚的合成

以自制的正构长链烷基酚为原料与多聚甲醛在碱性催化剂下进行羟甲基化反应,生成2,6-二羟甲基-4-烷基苯酚,再与另两分子烷基酚在固体超强酸催化下进行缩合反应生成2,6-二(5-烷基水杨基)-4-烷基苯酚,用核磁共振氢谱和碳谱、红外光谱和元素分析对产物进行了结构鉴定,探讨了催化剂、反应物料配比、反应时间等条件对产物产率的影响.另外根据上述反应路线,以工业品壬基酚和多聚甲醛为原料,经羟甲基化反应、缩合反应合成了2,6-二(5-壬基水杨基)-4-壬基苯酚.上述两种结果表明,选用SO24-/SnO2固体超强酸作催化剂,2,6-二羟甲基-4-烷基苯酚和烷基酚的配比为1:2,140℃反应2h,产率达到95%.     

Synthesis, structures, and optical properties of cadmium iodide/phenethylamine hybrid materials with controlled structures and emissions

A new type of organic-inorganic hybrid materials based on cadmium iodide (CdI2) and phenethylamine (PEA) has been synthesized and characterized. The reaction of CdI2 with PEA in a 1:2 molar ratio yields a four-coordinate hybrid material CdI2(PEA)2 (1) with extended 1D (CdI2)n chains, while the reaction of CdI2 with PEA in a 1:4 molar ratio produces a six-coordinate hybrid material CdI2(PEA)4 (2) with a discrete linear structure of CdI2 moiety. By introducing a trace amount of Na2S to the reaction for CdI2(PEA)2, we obtained a new compound [CdI2(PEA)2](CdS)0.038 (3) with uniformly doped CdS nanoparticles. Steady and transient photoluminescence studies reveal that compounds 1 and 2 exhibit bright blue (465 nm) and green (512 nm) fluorescent emissions in solid state at room temperature, respectively, while compound 3 gives a broad and complex emission ranging from 450 to 700 nm. Theoretical studies of electronic structures were carried out using density functional theory in order to gain a good understanding of the luminescent behaviors of these hybrid materials.     

Synthesis of 4-(1-Adamantyl)- and 4-(1-Adamantylmethyl)-substituted Halothiazoles

1-Adamantyl bromomethyl ketone and 1-adamantylmethyl chloromethyl ketone react with potassium thiocyanate in dimethylformamide to give the corresponding thiocyanatoketones which cyclize under the influence of HCl into 4-(1-adamantyl) and 4(-adamantylmethyl)chlorothiazole respectively. 4-(1-Adamantyl)-2-amino-5-bromothiazole and its N-derivative were synthesized by the reaction of 1-adamantyl dibromomethyl ketone with thioureas and N-substituted thiourea in acetonitrile.     

Spontaneous hydrolysis reactions of cis- and trans-beta-methyl-4-methoxystyrene oxides (Anethole oxides): buildup of trans-anethole oxide as an intermediate in the spontaneous reaction of cis-anethole oxide

Rates and products of the reactions of trans- and cis-beta-methyl-4-methoxystyrene oxides (1 and 2) (anethole oxides) and beta,beta-dimethyl-4-methoxystyrene oxide (3) in water solutions in the pH range 4-12 have been determined. In the pH range ca. 8-12, each of these epoxides reacts by a spontaneous reaction. The spontaneous reaction of trans-anethole oxide (1) yields ca. 40% of (4-methoxyphenyl)acetone and 60% of 1-(4-methoxyphenyl)-1, 2-propanediols (erythro:threo ratio ca. 3:1). The spontaneous reaction of cis-anethole oxide is more complicated. The yields of diol and ketone products vary with pH in the pH range 8-11, even though there is not a corresponding change in rate. These results are interpreted by a mechanism in which 2 undergoes isomerization in part to the more reactive trans-anethole oxide (1), which subsequently reacts by acid-catalyzed and/or spontaneous reactions, depending on the pH, to yield diol and ketone products. The buildup of the intermediate trans-anethole oxide in the spontaneous reaction of cis-anethole oxide was detected by (1)H NMR analysis of the reaction mixture. Other primary products of the spontaneous reaction of 2 are (4-methoxyphenyl)acetone (73%) and threo-1-(4-methoxyphenyl)-1,2-propanediol (ca. 3%). The rates and products of the spontaneous reaction of 2 and its beta-deuterium-labeled derivative were determined, and the lack of significant kinetic and partitioning deuterium isotope effects indicates that the isomerization of 2 to ketone and to trans-anethole oxide must occur primarily by nonintersecting reaction pathways.     

Synthesis of acyclic and macrocyclic analogs of Di-, Tri-, and tetranucleotides

Compounds consisting of two or three uracil fragments were synthesized by reaction of methyl-substituted uracil sodium salts with 1-(6-bromohexyl)-3,6-dimethyluracil or 1,6-dibromohexane. Treatment of these compounds with paraformaldehyde gave the corresponding pyrimidinophanes and acyclic compounds in which the uracil fragments are linked through methylene bridges. Uracil derivatives having no substituent on N³ were synthesized by reactions of silylated uracils with 1,3-bis(6-bromohexyl)uracil or 4,4′-(6-bromohexyloxy)diphenylmethane. The acyclic compound was converted into pyrimidinophane containing uracil fragments with N³H groups. A trinucleotide analog including uracil and two adenine fragments was synthesized from 1,3-bis(6-bromohexyl)uracil.     

S-烃基-1-烃基-3-[4-(苯并咪唑-2-巯基)苯基]异硫脲的合成及其iNOS抑制活性

以2-巯基苯并咪唑(1)为原料,经缩合和还原得到2-(4-氨基苯硫基)苯并咪唑(3),再与异硫氰酸苯甲酰酯或异硫氰酸烃基酯反应得到取代硫脲(5和7),最后与卤代烃反应得到20个新的S-烃基-1-烃基-3-[4-(苯并咪唑-2-巯基)苯基]异硫脲化合物(6和8),其结构经IR,¹HNMR,MS及元素分析确证.初步的药理试验表明,20个目标化合物均有不同程度的iNOS抑制活性,其中化合物6b,8d和8f的iNOS抑制活性与阳性对照药氨基胍相当.     

Synthesis of aromatic polyethers by Scholl reaction. V. Synthesis and polymerization of 1,3-bis[4-(1-naphthoxy) benzoyl]benzene, 1,4-bis[4-(1-naphthoxy)benzoyl]benzene,bis[4-(1-naphthoxy)phenyl]methane, 1,3-bis[4-(1-naphthoxy) phenylmethyl]benzene,and 1,4-bis-[4-(1-naphthoxy)phenylmethyl]benzene

This article describes the synthesis and the cation-radical polymerization (Scholl reaction) of 1,3-bis[4-(1-naphthoxy) benzoyl] benzene ( 6 ) and 1,4-bis[4-(1-naphthoxy) benzoyl]- benzene ( 7 ) initiated by FeCI₃. This polymerization produced poly(ether ether ketone ketone)s (PEEKK) of number average molecular weight (M?_n) up to 5400 g/mol. The synthesis of bis[4-(1-naphthoxy) phenyl] methane ( 8 ), 1,3-bis[4-(1-napthoxy) phenylmethyl] benzene ( 9 ), and 1,4-bis[4-(1-naphthoxy) phenylmethyl] benzene ( 10 ) are also described. Polyethers of M?_n up to 15400 g/mol at a FeCl₃/monomer molar ratio of 2/1 were obtained. An increased polymerizability of the monomers 9 and 10 containing two CH₂ groups versus that of the corresponding monomers containing two carbonyl groups ( 6 and 7 ) was observed. This enhanced polymerizability was explained based on the increased nucleophilicity of monomers 9 and 10 .     

Synthesis and electrochemical behavior of inclusion complexes based on β-cyclodextrin and alkylaromatic compounds: Electrochemical carboxylation of the β-cyclodextrin-1-(4-isobutylphenyl)ethylchloride inclusion complex on a glassy-carbon cathode in anhydrous dimethylformamide

Inclusion complexes of β-cyclodextrin with alkylaromatic compounds β-cyclodextrin-1-(4-isobutylphenyl)ethylchloride in the “guest-host” molar ratio of 1 : 2 and β-cyclodextrin-methyl-(4-isobutylphenyl)ketone in the “guest-host” molar ratio of 1 : 1, are synthesized, isolated, and characterized. It is shown that preparative electrocarboxylation of the inclusion complex β-cyclodextrin-1-(4-isobutylphenyl)ethylchloride on a glassy-carbon cathode with a dissolving magnesium anode in dimethylformamide affords S-forms of 2-(4-isobutylphenyl)propionic acid (S-Ibuprofen) in a high enantiomeric excess (97%). In addition to the acid, a dimer and a hydride form from the corresponding intermediates.     

8-5’新木脂素类化合物的合成方法研究

对羟基桂皮酸甲酯和阿魏酸甲酯分别在氧化银催化下发生自由基仿生氧化偶联反应, 合成得苯并二氢呋喃环结构化合物1, 1经甲基化反应得2. 1a和1和2分别在无水碳酸钾、10%氢氧化钠水溶液等不同的碱性条件下进行反应, 获得了11个苯并二氢呋喃环开环产物, 即8-5’新木脂素类化合物3a～9b, 实现了由苯并二氢呋喃新木脂素向8-5’新木脂素的转变, 也为合成芪类化合物提供了一种新方法. C-8位上的吸电子基团如酯基的影响使苯并二氢呋喃环易在碱性条件下开环形成8-5’新木脂素类化合物．所合成化合物的结构由MS, IR, 1H NMR和13C NMR进行了表征.     

Photodecarbonylation of dibenzyl ketones and trapping of radical intermediates by copper(II) chloride in frozen aqueous solutions

This paper presents a quantitative and qualitative study of the Norrish type I reaction of dibenzyl ketone (DBK) and 4-methyldibenzyl ketone (MeDBK), producing the benzyl radicals and consequently recombination products, in frozen aqueous solutions over a broad temperature range (-80 to 20 degrees C). This work extends previous research on the cage effects in various constrained media to provide information about the dynamics and reactivity of the photochemically generated intermediates at the grain boundaries of ice matrix. As the temperature of aqueous solutions decreases, the solute concentrations become high at layers covering ice crystals, causing efficient molecular segregation. The cage effect experiments have shown that diffusion of the benzyl radicals within such reaction aggregates is still remarkably efficient at temperatures below -50 degrees C, independently of the initial ketone concentration in the range of 10(-6)-10(-4) mol L(-1). In addition, the study of trapping the benzyl radicals formed in situ by CuCl2 was used as a qualitative probe of heterogeneous bimolecular reactions in the frozen aqueous matrix and on its surface. Molecules of both solutes were found to be segregated from the ice phase to the same location and underwent chemical reactions within diffusion and intermediates lifetimes limits. Understanding the fundamental physicochemical processes in ice is unquestionably important in related environmental or cosmochemical investigations.     

Study on the alkylation reaction of guanine and N-acetylguanine and the synthesis of 1''''-C alkylated carba-DHPG analogues

The alkylation reaction of guanine and N-acetylguanine with model compounds such as isopropyl bromide or 4-heptyl tosylate were studied. The reaction conditions such as temperature, solvent, base, and catalyst were examined for their effects on the reaction rate, and the yield and regioselectivity of the coupling reaction. The highest yield was obtained by using DMSO as the solvent. The reaction proceeded in a homogenous manner to give higher yield of 9-N and 7-N substituted product in a mole ratio of 1:1. The ratio could be raised to 2:1 if dibenzo-18-crown-6 was used as a catalyst. Using the above procedure, three carba-DHPG analogues bearing different 1'-C alkyl side chains were synthesized.     

Chemische und pharmakologische Studien über Derivate des Benzo[de]chinolins. II. 10.Mitteilung über natürliche und synthetische Isochinolinderivate

Chemical and Pharmacological Studies on Derivatives of Benzo[de]quinoline, II Spirocompounds of type V ( 12–18 ) were synthesized by a carbenium ion cyclization reaction of the intermediates 7 and 11 , respectively. 7 was prepared from 2-oxocyclopentanepropionic acid via 1, 2 , and 4–6; 11 from the same starting material via 1, 2 , and 8–10 . - The spiro[7H-benzo[de]quinolin-7,1′-cyclohexan]-2′-one 27 and other compounds of type VI could be synthesized from the (1-isoquinolinyl)ethyl-cyclohexanone 25: 25 is hydroxylated to the hydroxyketone 26 ; treatment of 26 with a mixture of sulfuric acid and oleum gives 27 . The structure of 27 has been proved by transformation into the known spirocyclohexane 33 . - Aporphine analogues of type VII ( 38, 39 ) were synthesized from the cyclic ketone 34 via either the formylketone 35 and its methyl vinyl ketone adducts 36 and 37 or the methyl ethynyl ketone adduct 40 . Compound 40 has also been cyclized to the 10-hydroxy-aporphine 42 . 9 compounds of the types mentioned have been screened for hypotensive action in rats, and partly in cats and dogs. Only compound 13 · HCl proved to be (moderately) active in rats and dogs.     

Regioselective nucleophilic addition to carbonyl ylide intermediates: a novel diastereoselective synthesis of cycloalkyl fused furan-3-ones

[structures: see text] A range of cis-fused hexahydro-1-benzofuran-3(2H)-one or tetrahydro-2H-cyclopenta[b]furan-3(3aH)-one ring systems was synthesized by the rhodium(II) acetate catalyzed reaction of alpha-diazo carbonyl compounds in the presence of various oxygen, nitrogen, and sulfur nucleophiles. A double-nucleophilic addition was possible by using an excess of alpha-diazo ketone. These reactions proceeded with complete diastereoselectivity, and the stereochemistry was confirmed by the single-crystal X-ray analysis. This process discloses the first example of tandem cyclization-nucleophilic addition reaction.     

Photochemical and thermal bergman cyclization of a pyrimidine enediynol and enediynone

[reaction: see text] Novel 10-membered pyrimidine enediynes (3 and 4) were synthesized in seven and eight steps, respectively. These compounds were compared for their abilities to undergo Bergman cyclization both thermally and photochemically. Alcohol 3 readily cyclized both thermally and photochemically in (i)PrOH, while ketone 4 only showed efficient thermal cyclization. Both compounds were also shown to cleave dsDNA under the appropriate conditions.