2—羟基—4,5—二烷氧基苯乙酮合成的新方法

2-羟基-4,5-二烷氧基苯乙酮是合成色酮和黄酮的重要中间体文献报道的Ⅰ～Ⅳ等四个化合物的合成均是以2,4-二羟基苯乙酮为起始物,经烷基化得到2-羟基-4-烷氧基苯乙酮,再经 Elbs 氧化引入5位羟基得Ⅰ及Ⅱ,再次烷基化得Ⅲ及Ⅳ。即:     

L-精氨酸席夫碱钴(Ⅱ)配合物的合成及结构研究

以2,4-二羟基苯甲醛-L-精氨酸席夫碱为配体,合成了钴(Ⅱ)的配合物.通过元素分析、TG-DTA、IR及电子光谱研究了配合物的组成和结构.     

新型Salen双肟化合物及其钴配合物的合成与表征

以3,5-二溴-2-羟基苯甲醛及1,4-二胺氧丁烷、1,3-二胺氧丙烷、1,2-二胺氧乙烷为原料,在无水乙醇溶剂中合成了3种新型的Salen双肟化合物。以Salen双肟化合物及乙酸钴为原料,合成了一种过渡金属Co配合物。采用IR、元素分析、1H NMR及TG-DTA等手段对化合物作了表征。结果表明,所合成的新型Salen双肟化合物与钴(Ⅱ)离子有较强的配位能力。     

N-2,4-二羟基苯甲醛甘氨酸-水合铜(Ⅱ)的合成

<正> N-2,4-二羟基苯甲醛甘氨酸在分析化学中可作为显色剂和络合剂,N-2,4-二羟基苯甲醛甘氨酸-水合铜在化学工业上可用于一些金属的防腐剂、还可作为抗病毒剂、抗霉菌剂。近来发现具有显著抗癌活性。吴自慎等采用直接合成方法,就是将2,4-二羟基苯甲醛、甘氨酸,铜(Ⅱ)离子直     

2,4-二磺酸基苯甲醛含量的测定

本文介绍了一种测定2,4-二磺酸基苯甲醛含量的方法.2,4-二磺酸基苯甲醛与亚硫酸氢钠加成反应生成4-(羟基磺酸基甲基)苯-1,3-二磺酸,再与碳酸氢钠共热释放出亚硫酸氢钠,然后用碘量法测亚硫酸氢钠含量,从而分析2,4-二磺酸基苯甲醛的含量.     

新型含氟席夫碱配合物的合成与表征

目前抗肿瘤药物的需求依然非常急迫,有研究表明,含氟配合物具有良好的生物活性。本文选择了2-氨基-4-三氟甲基苯甲酸与2,4-二羟基苯甲醛进行缩合,并选择邻菲罗啉作为第二配体,合成了六种新型的含氟席夫碱配合物,为未来研究新型抗肿瘤药物提供可行性方向。     

肉桂酰香豆素-7-酚酯的合成及其荧光性能

以2,4-二羟基苯甲醛为起始原料经过Knoevehgel反应、内酯化反应和酰化反应合成肉桂酰香豆素-7-酚酯。使用HNMR、红外、紫外可见光谱对所合成的催化剂进行表征,并对所合成的化合物进行荧光测试,测试结果表明所合成化合物荧光的λ_（max）位于406 nm。     

中间体2,4-二羟基苯乙酮合成工艺研究

介绍了合成2,4-二羟基苯乙酮的工艺路线：在催化剂的作用下,由原料间苯二酚和冰醋酸经付-克反应合成2,4-二羟基苯乙酮。最佳反应条件为：冰醋酸用量12 g、催化剂用量16 g、反应时间1.5 h、反应温度135℃。产品经紫外、红外、熔点和Rf值鉴定为2,4-二羟基苯乙酮。     

在改性HY分子筛催化剂上甲基叔丁基醚与苯酚合成步丁基苯酚的研究

甲基叔丁基醚(MTBE)作为烷基化剂,以改性HY分子筛为催化剂,在常压连续流动固定床反应器上,对苯酚烷基化合成对叔丁基和2,4-二叔丁基苯酚(2,4-DTBP)的反应规律进行了较为系统的研究.以不同改性物及其含量改性HY分子筛可调变其表面酸量、酸分布及孔道尺寸,从而改变催化剂的反应活性及产物选择性.苯酚与MTBE烷基化反应主要在中等强度和弱的B酸中心上进行.催化剂表面的酸量和酸分布不但影响活性,同时影响2,4-DTBP的选择性.对10种单组分氧化物改性的HY分子筛催化剂研究表明,每种改性物均存在一个最佳含量,P2O5改性后HY催化剂的性能最优越.苯酚的转化率达99.60%,2,4-DTBP选择性达63.90%.这一结果是目前分子筛用催化剂合成2,4-DTBP的最好结果,具有潜在的应用前景.     

新型双手性二羟基配体的合成及其在不对称加成反应中的应用

以(R)-(+)-2-乙酰基-2′-三氟甲磺酸酯基-1,1′-联萘为原料合成双手性二羟基配体,并将其与四异丙氧钛络合形成手性催化剂,应用于苯甲醛与二乙基锌的不对称加成反应中,能得到产率为85.8%,ee值最高为61.5%的产物。     

Coordination polymers, 4. Electrical properties of some bisphenolic chelate polymers

The electrical properties of Ni(II) and Cu(II) chelate polymers of bis(2,4-dihydroxybenzaldehyde), bis(2,4-dihydroxyacetophenone), bis(2,4-dihydroxybenzophenone), bis(2,4-dihydroxybenzaldehyde)ethylenediimine, bis(2,4-dihydroxyacetophenone)-ethylenediimine, bis(2,4-dihydroxybenzophenone)ethylenediimine and bis(2,4-dihydroxyacetophenoneimine) and aromatic acid chlorides have been studied. The chelate polymers with the most rigid structure were found to have the highest conductivities.     

聚酰胺-胺树状分子锡配合物催化性能研究

通过固相合成的方法将聚酰胺-胺树状大分子PAMAM担载于大孔硅胶上,并对其外围分别用对羟基苯甲醛、2,4-二羟基苯甲醛和邻羟基苯甲醛进行修饰,再与SnCl2.2H2O反应形成三类共计9种不同代数树状高分子锡配合物。将该类配合物用作质量分数30%双氧水氧化酮的Baeyer-Villiger(B-V)反应的催化剂,考察其催化活性,结果表明,在该类配合物作用下,2-金刚烷酮、环戊酮、环己酮、4-甲基环己酮、4-叔丁基环己酮、3-甲基-2-戊酮和4-甲基-2-戊酮都可以发生B-V氧化反应而转化为相应的酯和内酯,底物的转化率(75%～99%)和产物选择性(95%～100%)都较高。比较了不同载体(氯球、纤维素、壳聚糖、硅胶)、不同配体的金属锡配合物对B-V催氧化反应的催化效果,研究发现,载体、配体和金属担载量对配合物的催化活性均有不同程度的影响。其中,硅胶为最好的载体,而邻羟基苯甲醛为最好的配体。     

Synthesis and electronic spectra of 3-hetaryl substituted coumarin derivatives 7-hydroxy-2H-chromen-2-on and 9-hydroxy-2H-benzo(f)chromen-2-on

The synthesis of 3-hetaryl substituted coumarin derivatives [7-hydroxy-2H-chromen-2-on and 9-hydroxy-2H-benzo(f)chromen-2-on] containing a hydroxyl group by reacting 2,4-dihydroxybenzaldehyde and 2,4-dihydroxynaphtaldehydes with 2-cyanomethylbenzothiazole, 2-cyanomethylbenzimidazole, 1-methyl-2-cyanomethylbenzimidazole and 2-cyanomethyl-4-phenylthiazole is presented. The absorption and steady-state fluorescence characteristics of the synthesised 3-hetaryl substituted 7-hydroxy-2H-chromen-2-on and 9-hydroxy-2H-benzo(f)chromen-2-on in a solution of ethanol and at different pH values are studied to assess their possible application as fluorescent probes for use in molecular biology and medicine.     

Pellioditis pellio: Substituted phenolic compounds as chemoattractants

Vanillin, vanillic acid, and other related compounds are chemoattractants either for nematodes or arthropods. We tested vanillin, vanillic acid, and 2,4-dihydroxybenzaldehyde in an in vitro bioassay system for their ability to attractPellioditis pellio males and females. Females were not attracted to any of the three compounds tested. Males responded to vanillin and vanillic acid, but not to 2,4-dihydroxybenzaldehyde. Males responded to vanillin and vanillic acid when these compounds were present at 10^–5 M concentration. Vanillin at 10^–3 and 10^–7 M concentrations was not attractive.     

One-pot synthesis of cobalt-salen catalyst immobilized in silica by sol–gel process and applications in selective oxidations of alkanes and alkenes

Salen ligand prepared from 1,2-phenylenediamine and 2-hydroxy-3(3-triethoxysilyl-propyl)-benzaldehyde has been used as cobalt-chelate for the immobilization of the catalytic site by a one-pot synthesis method. Sol–gel hydrolysis and polycondensation of this chelate with 10 equivalents of tetraethyl orthosilicate produced the heterogeneous catalyst. This catalyst is active in selective molecular oxygen oxidations of cyclohexane, cyclohexene, toluene, styrene and anthracene in the presence of butyraldehyde at room temperature.     

α-Zirconium phosphate supported metal–salen complex: synthesis,characterization and catalytic activity for cyclohexane oxidation

Metal–salen intercalated α-zirconium phosphate, abbreviated as {α-ZrP·M(Salen), where M = Fe(III) and Mn(II)} was synthesized insitu by the flexible ligand method. The structure of resulting compounds was characterized by BET surface area, powder X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, thermogravimetric analysis and UV–visible spectroscopy. The catalytic activity of α-ZrP·M(Salen) was tested for the oxidation of cyclohexane using dry tert-butylhydroperoxide as an oxidant. In the oxidation reaction, cyclohexane was oxidized to cyclohexanol (A), cyclohexanone (K) and some unidentified products. It was found that the reactivity of α-ZrP·Fe(Salen) is greater than α-ZrP·Mn(Salen) in the oxidation reaction. Influence of various reaction parameters viz. reaction temperature, catalyst concentration, substrate to oxidant molar ratio was studied using α-ZrP·Fe(Salen) catalyst to obtain maximum conversion (29.30%) of cyclohexane. The catalyst was reused for five cycles without significant loss of catalytic activity.     

手性salen配合物合成及应用研究进展

简述了Salen配合物的合成以及在不对称催化中的应用。     

聚甲基乙撑碳酸酯的研究进展

综述了聚甲基乙撑碳酸酯(PPC)的合成、改性等方面的研究进展,并对其市场应用前景进行了分析。合成PPC的催化体系主要有锌催化剂、双金属催化剂、稀土催化体系、Salen(MX)催化剂、金属卟啉类催化剂等,其中锌类催化剂催化活性最高,Salen（MX）复合物的二元或双官能团催化体系效率最高。PPC的改性方法主要有交联共聚、溶液共混和熔融共混。最后,指出PPC在我国具有广阔的市场前景。     

Discrete versus In Situ‐Generated Aluminum‐Salen Catalysts in Enantioselective Cyanosilylation of Ketones: Role of Achiral Ligands

The monometallic species {Salen}AlX (X=Me, 2a , b ; X=Cl, 4a , b ; O‐i‐Pr, 5a,b ) and open bimetallic species {Salen}[AlMe₂]₂ ( 3a , b ) that result from binary combinations between an aluminum precursor [trimethylaluminum, dimethylaluminum chloride, aluminum tris(isopropoxide)] and a diprotio {Salen}H₂ pro‐ligand 1a , b ( a =1R,2R‐cyclohexyl‐salen; b =1R,2R‐diphenylethylene‐salen) have been isolated. The crystal structures of 3b , 4b and of μ‐oxo species [{diphenylethylene‐salen}Al]₂O ( 6b ) are reported. The discrete species 2 – 5a,b have been individually evaluated in the asymmetric cyanosilylation of acetophenone. It is shown that, in several cases, these discrete catalysts display dramatically different performances than the catalyst systems in situ‐generated from the binary combinations. The influence of the achiral ligand X on both the enantioselectivity and activity of the cyanosilylation reaction has been investigated, resulting in the definition of a highly active and productive hexafluoro‐2‐propoxide‐based catalyst for a variety of aryl alkyl ketones (TON up to 470, TOF up to 140 h⁻¹ at −20 °C for acetophenone).     

三种溴酚类中间体化合物的合成与分析

本文以香兰素为原料,经过脱甲基反应、溴代反应,采用不同的反应条件分别制取和分离得到了3-溴-4,5-二羟基苯甲醛(1)、2,3-二溴-4,5-二羟基苯甲醛(2)、2,5-二溴-3,4-二羟基苯甲醛(3),并进行了IR、HNMR谱图表征。反应条件温和,产率分别为69.8%,26%,29%。这三种化合物可用于溴酚类海洋药物合成的中间体。