含取代噁唑结构的新型吡唑肟衍生物的合成与生物活性

为了发现具有良好生物活性的吡唑肟化合物,以唑螨酯为先导化合物,在吡唑肟中引入取代噁唑结构,设计并制备了20个未见文献报道的新型吡唑肟衍生物,利用1H NMR,13C NMR和元素分析确证了目标产物的结构.生物活性测试结果显示,部分目标化合物在500和100μg/mL浓度下对粘虫或蚜虫表现出优良的杀虫活性,其中5-(3-氟苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9j)、5-(4-氟苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9k)、5-(4-叔丁基苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9r)和5-(4-甲氧基苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9s)在浓度为100μg/mL时对粘虫的防治效果均达100%,5-(4-溴苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氟苯基)噁唑-2-基]甲基}肟(9g)和9s在浓度为100μg/mL时对蚜虫的杀灭活性均为100%.此外,化合物9s在500μg/mL时对朱砂叶螨的防治效果为70%.     

侧链接有噁二唑的硅氧烷嵌段聚对苯乙烯撑衍生物的合成及其性能研究

在强碱条件下,单体2-(4-辛氧基苯基)-5-[4-(2,5-二溴甲基苯氧基)苯基]-1,3,4-噁二唑和二甲基二对溴甲基苯氧基硅烷发生Gilch脱卤聚合反应,成功合成了一种新型的侧链接有噁二唑的硅氧烷嵌段聚对苯乙烯撑衍生物(8),其结构经FT-IR表征。用UV-Vis,FL和DSC研究了8的光学性能和热稳定性。结果表明,8的热稳定性较单体有所改善;最大发射峰在480 nm。     

双核铕(Ⅲ)配合物的合成及选择性激发

成功地合成一种新的四齿配体2,5-二(4-((2-吡啶-1氢-苯并[d]嘧唑)甲基)苯基)-1,3,4-噁二唑(L),并且将该配体作为第二配体合成出双核Eu3+配合物[Eu(TTA)3]2L(TTA二2-噻吩三氟甲基乙酰丙酮),配合物[Eu(TTA)3]2L的结构用红外光谱,吸外-可见吸收光谱进行了充分表征.为了讨论配...     

N-杂环甲基2-(4-杂芳氧基苯氧基)丙酰胺的合成及除草活性

以2-(4-羟基苯氧)丙酸为原料,设计合成了16个新的手性N-杂环甲基2-(4-杂芳氧基苯氧基)丙酰胺化合物,其化学结构经核磁共振、色谱-质谱、红外光谱及元素分析确证.初步生物活性测定结果表明,合成的化合物在2.25×103g/ha剂量时对单子叶杂草马唐(Digitaria sanguinalis)、稗草(Echinochloa crus-galli)及狗尾草(Setaria viridis)等均具有90%以上的活性;进一步活性及作物安全性测试表明,化合物(R)-(+)-N-[(6-氯吡啶-3-基)甲基]-2-[4-(3-氯-5-三氟甲基吡啶-2-基氧基)苯氧基]丙酰胺(2b)的除草活性高于噁唑酰草胺,且对水稻茎叶处理安全,同时对水稻田主要杂草千金子的活性远高于氰氟草酯;化合物的除草活性与立体构型有关,R构型为活性构型.     

新型酰基脲类Raf激酶抑制剂的合成及其抗肿瘤活性

以4-氯吡啶甲酸为原料,经6步反应制得两个中间体——取代基-4-【{2-[5-(三氟甲基)-1H-咪唑-2-基]吡啶-4-基}氧基】苯胺(7a和7d);7分别与取代苯甲酰基异硫氰酸酯反应,合成了6个新型的酰基脲类Raf激酶抑制剂(9a~9f),其结构经1H NMR和ESI-MS表征。用MTT法考察了9a~9f对人胃癌细胞株(BGC823)的抑制活性。结果表明:N-【3-氟-4-{2-[5-(三氟甲基)-1H-咪唑-2-基]吡啶-4-氧基}苯基】-4-氯苯甲酰硫脲(9c)和N-【4-{2-[5-(三氟甲基)-1H-咪唑-2-基]吡啶-4-氧基}苯基】-3-(吡啶-3-基)丙烯酰硫脲(9d)的抑制活性较好。在用药量为100μg时,9c和9d对BGC823的抑制率分别为66.86%和63.60%,与索拉非尼药效接近(70.97%)。     

双枝[1,3,4]-噁二唑衍生物的合成与荧光性质

通过Wittig反应和Heck反应合成了三个双枝噁二唑衍生物: N-{{{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}-4-苯基}二苯胺(BBOD-2), N,N-双{{{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}-4-苯基}苯胺(BBOD-3), N,N,N-三{4-{2-{3,5-二-[5-(4-叔丁基苯基)-1,3,4-噁二唑-2]-苯基}-E-乙烯基}苯基}胺(BBOD-4). 化合物结构经过红外光谱、核磁共振谱、质谱和熔点确证, 测定了它们在不同溶剂中的紫外光谱和单光子荧光光谱. BBOD-1, BBOD-2, BBOD-3, BBOD-4在二氯甲烷中的最大吸收峰分别位于295, 390, 398和408 nm; 最大发射峰分别为360, 486, 483和487 nm. 讨论了Stokes位移与溶剂极性的关系.     

新型含吡啶环结构的吡唑肟酯类衍生物的合成与生物活性研究

为了寻找具有较好生物活性的吡唑类衍生物,通过活性亚结构拼接的方法,设计制备了一系列未见文献报道的含取代吡啶结构的吡唑肟酯化合物.通过~1HNMR、~(13)CNMR和元素分析对目标化合物的结构进行了表征.初步的生物活性测试结果显示,部分化合物表现出一定的杀虫活性.在测试浓度为500μg/mL时,有7个化合物对粘虫的杀灭活性可达60%~100%,6个化合物对蚜虫的杀死率可达50%~90%.当测试浓度降为100μg/mL时,1,3-二甲基-5-(4-氯苯氧基)吡唑-4-甲醛-O-(2-氯吡啶-3-甲酰基)肟(5f)和1,3-二甲基-5-(4-甲基苯氧基)吡唑-4-甲醛-O-(2-氯吡啶-3-甲酰基)肟(5j)对蚜虫仍表现出一定的杀虫活性,其杀死率均为50%.1,3-二甲基-5-(3-氟苯氧基)吡唑-4-甲醛-O-(2-氯吡啶-3-甲酰基)肟(5b)和5f在测试浓度为500μg/mL时对褐飞虱的杀死率均为100%.另外,1,3-二甲基-5-(4-氟苯氧基)吡唑-4-甲醛-O-(2-氯吡啶-3-甲酰基)肟(5c),1,3-二甲基-5-(3-氯苯氧基)吡唑-4-甲醛-O-(2-氯吡啶-3-甲酰基)肟(5e),1,3-二甲基-5-(4-三氟甲氧基苯氧基)吡唑-4-甲醛-O-(2-氯吡啶-3-甲酰基)肟(5i)和5j对人肝癌(Hep G2)细胞株显示出明显的抗肿瘤活性,其IC_(50)值分别为2.6,4.6,1.8和1.1μmol/L.     

1,3,4-噁二唑三氮烯衍生物的合成及生物活性测定

利用拼合原理,将具有生物活性的三氮烯结构与1,3,4-噁二唑结构相拼合,设计合成了11个未见报道的1,3,4-噁二唑三氮烯衍生物.所合成化合物经1H NMR,IR和HRMS得到表征.用四甲基偶氮唑盐(MTT)法法评价了该类化合物对胃癌细胞(MGC803)和前列腺癌细胞(PC-3)的抑制作用,结果显示化合物2-[4-(3,3-二甲基三氮烯-1-基)苯基]-5-(4-甲氧基苯基)-1,3,4-噁二唑(b4)、2-[4-(3,3-二甲基三氮烯-1-基)苯基]-5-(2-甲氧基苯基)-1,3,4-噁二唑(b9)、2-[4-(3,3-二甲基三氮烯-1-基)苯基]-5-(3,4-甲叉二氧基苯基)-1,3,4-噁二唑(b10)、2-[4-(3,3-二甲基三氮烯-1-基)苯基]-5-(吡啶-4-基)-1,3,4-噁二唑(b11)对前列腺癌细胞的抑制作用强于典型三氮烯药物达卡巴嗪(DTIC),其IC50值分别为74.145,87.790,87.327和104.875μmol/L,而对胃癌细胞则几乎没有抑制作用.采用微量肉汤稀释法测试了该类化合物对大肠埃希菌(E.coli.)和金黄葡萄球菌(S.aureus)的抑制作用,结果显示这类化合物对这两种细菌并没有表现出抑制作用.     

新型二唑类4-氨基喹唑啉衍生物的合成及其抗肿瘤活性

N-(3-氯-4-氟苯胺基)-7-(3-氯丙氧基)-6-甲氧基喹唑啉-4-胺与一系列取代二唑类化合物经取代反应合成了6个新型的二唑类4-氨基喹唑啉衍生物(3a~3f),其结构经1H NMR,13C NMR,IR及元素分析表征。用MTT法初步测定了3a~3f对前列腺癌细胞(PC-3)和人乳癌细胞(Bcap-37)的抑制率。结果表明:N-(3-氯-4-氟苯基)-6-甲氧基-7-{3-[5-(4-硝基苯基)-1,3,4-噻二唑-2-巯基]丙氧基}喹唑啉-4-胺和N-(3-氯-4-氟苯基)-7-{3-[5-(4-氯苯基)-1,3,4-噁二唑-2-巯基]丙氧基}-6-甲氧基喹唑啉-4-胺在用药量为10μmol·L-1时对PC-3的抑制率分别为66.8%和72.2%。     

1,3,4-噁二唑键联二芳基乙烯化合物的合成及性质

将1,3,4-噁二唑基团引入二芳基乙烯分子中, 合成了2种新的二芳基乙烯类光致变色化合物1-氰基-2-(2H-5-苯基-1,3,4-噁二唑)-1,2-二(2,4,5-三甲基-3-噻吩)乙烯(3)和1,4-二{[1-氰基-2-(2H-5-苯基-1,3,4-噁二唑)-1,2-二(2,4,5-三甲基-3-噻吩)乙烯]-1,3,4-噁二唑}苯(4). 通过IR, NMR, MS和元素分析对化合物进行了结构表征, 并研究了其UV-Vis吸收、荧光发射、动力学特性和抗疲劳性质. 实验结果表明, 化合物[STHZ]3[STBZ]和[STHZ]4[STBZ]具有良好的光致变色性质, 光致变色闭环反应为零级反应, 开环反应为一级反应.     

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%.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.