芳香查尔酮衍生物的合成、理论计算及三阶非线性光学性质

合成了2种新的具有潜在应用价值的非线性光学(NLO)有机材料芳香查尔酮衍生物1-(呋喃-2-基)-3-(4-甲氧基苯基)丙烯酮(1)和1-(噻吩-2-基)-3-(4-甲氧基苯基)丙烯酮(2),并对其进行了NMR、IR和HR-MS结构表征。 采用4f相位相干成像技术测定了化合物1和2的三阶NLO性质并确定了相关参数:脉冲宽度4 nm,激光波长440 nm,化合物1:非线性吸收系数β=5.5×10^-10 m/W,非线性折射系数n₂=-2.1×10^-17 m²/W,三阶非线性极化率χ⁽³⁾=1.58×10^-11 esu;化合物2:β=-2.4×10^-10 m/W,n₂=0.3×10^-17 m²/W,χ⁽³⁾=0.50×10^-11 esu;并测定了紫外光谱和DSC曲线。 采用密度泛函方法计算了化合物1和2的轨道能量和极化率,结果表明电子转移能在分子内部进行,说明比较易于极化,展示了良好的非线性光学性质。     

1-(芘-1-基)-3-(4-甲氧基苯基)丙烯酮的合成及三阶非线性光学性质

合成了一种新的有机非线性光学(NLO)材料1-(芘-1-基)-3-(4-甲氧基苯基)丙烯酮(PMPAK),通过¹H NMR、IR、HR-MS和元素分析表征其结构。 以Nd:YAG-Laser System作为光源,激光波长450 nm,脉冲宽度4 ns(FWHM),采用4f相位相干成像技术测定了PMPAK的三阶NLO性质并确定了相关参数:非线性折射率n₂=-1.84×10^-16 m²/W,非线性吸收系数β=2.53×10^-9 m/W,非线性极化率χ⁽³⁾=1.137×10^-10 esu。     

1-(芘-1-基)-3-(苯并噻吩-3-基)丙烯酮的合成和三阶非线性光学性质研究

合成1种查尔酮衍生物1-(芘-1-基)-3-(苯并噻吩-3-基)丙烯酮(PBTAK),经IR,1 H NMR,13C NMR和HR-MS对其结构进行表征.采用4f相位相干成像技术测定了它的三阶非线性光学性质并确定了相关参数:脉宽为4nm,激光波长为460nm,非线性吸收系数β=0.23×10~(-9) m/W,非线性折射率n2=-0.50×10~(-16) m~2/W,三阶非线性极化率χ~((3))=9.37×10~(-21) C;同时测定了紫外光谱、荧光光谱和DSC曲线.运用密度泛函方法计算了PBTAK的分子轨道能量和极化率,结果表明电子转移能在分子内部进行,显示出良好的非线性光学活性.     

D-π-A-π-D型双查尔酮衍生物的合成和三阶非线性光学性质

合成一种新颖的D-π-A-π-D型双查尔酮衍生物2,6-二[3-(4-甲氧基苯基)]丙烯酰基吡啶,经IR,~1H NMR和HR-MS对其结构进行表征,采用4f相位相干成像技术测定了它的三阶NLO性质并确定了相关参数:脉宽4ns,激光波长450nm,非线性吸收系数β=0.9×10~(-9) m/W,非线性折射率n_2=-0.42×10~(-16) m~2/W,三阶非线性极化率χ~((3))=4.10×10~(-19) m~2/V~2;并测定了紫外光谱和DSC曲线.     

1-二茂铁基-3-[(9-乙基)咔唑-3-基]丙烯酮的合成及三阶非线性光学性质

合成了一个新的非线性光学(NLO)有机材料1-二茂铁基-3-[(9-乙基)咔唑-3-基]丙烯酮(FCAK),并通过NMR、IR、MS和元素分析等技术手段进行了表征。 采用粉末Nd∶YAG激光技术测定了标题化合物的三阶非线性光学性质并确定了相关参数。 激光脉冲为4 ns时,非线性折射率n₂=-3.5×10^-18 m²/W,非线性吸收系数β=-2.7×10^-11 m/W,三阶非线性极化率χ⁽³⁾=2.04×10^-12 esu,三阶非线性分子超极化率γ=1.1×10^-30 esu。 激光脉冲为21 ps时,n₂=0.55×10^-18 m²/W,β=-0.6×10^-11 m/W,χ⁽³⁾=3.4×10^-13 esu,γ=0.13×10^-30 esu。     

芘基查尔酮的合成及三阶非线性光学性质

合成了一种新的具有潜在应用价值的非线性光学(NLO)有机材料1-(芘-1-基)-3-(4-二甲氨基苯基)丙烯酮(PMAK),并通过 NMR、IR、MS和元素分析等技术手段进行了表征。 采用溶液Nd:YAG激光技术测定了PMAK的三阶非线性光学性质并确定了相关参数。 纳秒实验结果:折射率n₂=-3.5×10^-17 m²/W,吸收系数β=7.0×10^-10 m/W,极化率χ⁽³⁾=2.54×10^-11 esu,分子超极化率γ=3.44×10^-30 esu;皮秒实验结果:n₂=-2.8×10^-18 m²/W,β=8.3×10^-11 m/W,χ⁽³⁾=2.49×10^-12 esu,γ=3.33×10^-31 esu。     

基于二茂铁的两个查尔酮衍生物的合成及超快三阶非线性光学响应

二茂铁是合成新颖有机功能材料的基本单元之一。 本文设计并合成了两个基于二茂铁的同分异构查尔酮衍生物:1-二茂铁基-3-(噻吩-2-基)丙烯酮(a)和1-二茂铁基-3-(噻吩-3-基)丙烯酮(b)。 采用超快激光Z-扫描技术(脉宽180 fs,波长532 nm)测定了化合物a和b的三阶非线性光学性质。 结果表明,化合物a吸收系数β=-2.1×10^-12 m/W,折射率n₂=1.9×10^-19 m²/W,分子超极化率γ=5.37×10^-32 esu;化合物b:β=-1.2×10^-13 m/W,n₂=2.0×10^-19 m²/W,γ=4.48×10^-32 esu。 说明在飞秒激光激发下,电荷转移能够在化合物a和b分子内部快速进行,二者均具有优异的超快三阶非线性光学响应。 在B3LYP/6-311+G(d,p)理论水平下,计算了化合物a和b分子轨道能量、极化率和各基团在前线分子轨道中的占有率。 理论计算结果显示,二茂铁基团在化合物a和b前线分子轨道中占有率分别为97%和98%,对两化合物的非线性光学性能起主导作用。     

苯并[b]萘并[2'''',3'''':5,6][1,4]二噻英并[2,3-i]噻蒽-5,7,9,14,16,18-六酮的合成及其三阶非线性光学性能

以1,4-萘醌为原料,合成了含硫的醌构稠杂环化合物苯并[b]萘并[2',3':5,6][1,4]二噻英并[2,3-i]噻蒽-5,7,9,14,16,18-六酮(4),其结构经1H NMR和IR确证.采用波长为800 nm,脉宽为80 fs的Ti:Sapphire飞秒激光,运用双光束简并四波混频法测定了4的三阶非线性光学性能,结果表明,4的三阶非线性光学极化率χ(3),非线性折射率n2,分子二阶超极化率γ和响应时间分别为2.89×10-13 esu, 5.31×10-12 esu, 3.14×10-31 esu和101 fs.并分析了4的分子结构对其三阶非线性光学性能的影响.     

1,4-双(4-吡啶基甲基苯基醚)(C18H18N2O2)与SCN^-形 成的超分子化合物[H2 (C18H18N2O2)](SCN)2的合成、结构 及其在溶液中的三阶非线性光学性质

超分子化合物[H2(C18H18N2O2)](SCN)由Fe(NO3)3·9H2O,KSCN和1,4-双(4-吡啶基甲基苯基醚)反应得到。通过X射线衍射仪测得该化合物是通过N┈H—N,S┈H—C(C5H5N)及S┈H—C(亚甲基CH2)三种氢键而形成的二维平面网状结构。用Z扫描法对该超分子在DMF溶液中的三阶非线性光学性质进行研究,发现它具有强的三阶非线性折射性能,三阶非线性超极化率X^(3)=6.27×10^-12esu.     

两种Ni(Ⅱ)配合物的合成及三阶非线性光学性能

合成了两种新的Ni(Ⅱ)配合物,用UV、IR、MS和元素分析进行了表征。采用飞秒激光,运用简并四波混频法,研究了Ni(Ⅱ)配合物在非共振状态下的三阶非线性光学性能。它们的三阶非线性光学极化率χ(3)为3.21×10-13 esu和3.58×10-13 esu,非线性折射率n2为5.89×10-12 esu和6.58×10-12 esu,分子二阶超极化率γ为3.21×10-31 esu和3.57×10-31 esu,响应时间τ为54 fs和59 fs。探索了配合物的分子结构对三阶非线性光学性能的影响。结果表明具有大的高度离域的π电子共轭体系是获得较大三阶非线性光学性能的关键。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.