2,2-二甲基-4-羟基-1,3-苯并二噁茂的合成研究

以2-甲氧基丙烯代替2,2-二甲氧基丙烷为原料合成了2,2-二甲基-4-羟基-1,3-苯并二噁茂。研究了影响反应收率的因素,优化条件为:以二甲苯为溶剂,m(焦性没食子酸)∶m(二甲苯)=1.0∶5.0,n(焦性没食子酸)∶n(2-甲氧基丙烯)=1.00∶1.20,2-甲氧基丙烯滴加温度135℃,滴加时间6 h。优化条件下产物纯度99.2%,收率88.5%,其结构经GC-MS、^(1)H NMR确认。该工艺转化率高、收率高、“三废”少,具有工业化应用前景。

Synthesis and Bioactivity of Novel Aminomethyl-2-(1,2,4-triazol)-4,4-dimethyl-3-pentanone(ol)

Dimethyl-1-(1, 2, 4-triazol) -2- butanone was treated with aqueous formaldehyde to give an additional product, and subsequent elimination by acetic anhydride yielded 4, 4-dimethyl-2-(1, 2, 4-triazol)-1-penten-3-one. Further addition with substituted amines provided a series of (1, 2, 4-triazol)-4, 4-dimethyl-3-pentanone, which were then reduced by KBH4 to obtain a series of (1, 2, 4-triazol)-4, 4-dimethyl-3-pentanol. Their structures were confirmed by 1HNMR and elemental analysis. The results of bioassay showed that the title products possess good fungicidal activities.

Synthesis and Crystal Structure of Trans-4-[(5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.

Effect of 2-butyne-1, 4-diol on silver electrodeposition from 5, 5-dimethyl hydantoin solutions

The effect of 2-butyne-1, 4-diol on silver electrodeposition process from 5, 5-dimethyl hydantoin solutions was investigated by means of cyclic voltammetric measurement, scanning electron microscopy (SEM) and X-ray diffraction (XRD). Cyclic voltammetric studies indicate that the reduction process of silver electrodeposition is influenced by adding 2-butyne-1, 4-diol. Owing to its adsorption on the electrode surface, 2-butyne-1, 4-diol moderately hinders the mass transfer of the silver complexed ions from the bulk solution to the outer limit of the electrode double layer and affects the electrocrystallization step. Scanning electron microscopy analysis reveals that the presence of 2-butyne-1, 4-diol in the electrolyte is beneficial and the silver deposits obtained are smoother, more compact and more leveled. X-ray diffraction analysis of the silver deposits obtained at 0.5 g·L-1 2-butyne-1, 4-diol indicated that the (110) plane is the most preferred plane and is not affected by the presence of 2-butyne-1, 4-diol in the electrolyte.

Synthesis and Crystal Structure of 1,4-Dimethyl-2,5-di{[2’-(3-pyridylmethylamino-formyl)phenoxyl]methyl}benzene Perchlorate

The title compound, 1,4-dimethyl-2,5-di { [2′-（3-pyridylmethylaminoformyl）phenoxyl]- methyl}benzene perchlorate （C36H36Cl2N4O12, Mr = 787.59）, has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal crystallizes in the orthorhombic system, space group Pbca with a = 14.366（4）, b = 15.159（4）, c = 16.443（5）A, V = 3580.9（17）/A3 Z = 4, De = 1.461 g/cm^3, /t = 0.253 mm^-1, F（000） = 1640, R = 0.0618 and wR = 0.1525 for 1615 observed reflections （I 〉 2σ（I））. In the structure of the title compound, a two-dimensional supramolecular layer is formed via intermolecular hydrogen bonding interactions.

Synthesis and Crystal Structure of N1-(2-(4-Bromo-2-nitrophenoxy)-2-dimethyl acyloxymethyl)-5-fluorouracil

The title compound N1-（2-（4-bromo-2-nitrophenoxy）-2-dimethyl acyloxymethyl）-5-fluorouracil（C15H13BrFN3O7, Mr = 446.19） was synthesized and structurally characterized by ^1H-NMR, -（13）C-NMR, ESI-MS and single-crystal X-ray diffraction. The compound crystallizes in triclinic, space group P1, with a = 8.3325（6）, b = 10.1808（13）, c = 11.8194（16） A, α = 73.194（12）, β= 72.351（9）, γ = 89.509（8）o, V = 911.2（2） A^3, Z = 2, T = 300.79（10） K, μ（Cu Kα） = 3.578 mm^-1, Dc = 1.626 g/cm3, F（000） = 448.0, GOF = 1.060, 5723 reflections measured（8.232≤2θ≤139.592°）, 3339 unique（Rint = 0.0184, Rsigma = 0.0254） which were used in all calculations. The final R = 0.0517（I 〉 2s（I）） and wR = 0.1494（all data）. Hydrogen bonds and π-π interactions together stabilize the structure of the molecule. The preliminary biological test shows that the title compound has good antitumor activity against A549 in vitro and lower toxicity to normal cells.

Synthesis, Crystal Structure and Biological Activities of 3-Bromo-5-(4-chlorophenyl)-4-cyanopyrrole-N,N-dimethyl-2-carboxamide

The title compound 3-bromo-5-（4-chlorophenyl）-4-cyanopyrrole-N,N-dimethyl-2-amide（3） was synthesized with 4-bromo-2-（4-chlorophenyl）-5-（trifluoromethyl）-1H-pyrrole-3-carbonitrile（1） and N,N-dimethylformamide（2） by the α-C acylation reaction catalyzed by potassium t-butoxide, and characterized by IR, 1H-NMR and X-ray single-crystal diffraction. It crystallizes in monoclinic, space group P2（1/n）with a = 12.789（2）, b = 13.783（2）, c = 17.980（3） °, β = 109.230（3）°, V = 2992.5 A3, Mr = 352.62, Dc = 1.565 mg/m3, Z = 8, m = 2.924 mm-1, F（000） = 1408, the final R = 0.0424 and w R = 0.0973 for 3518 observed reflections with I 〉 2σ（I）. A total of 23559 reflections were collected, of which 6242 were independent（Rint = 0.0566）. The insecticidal, herbicidal and antibacterial activities of compound 3 were determined, and the experimental results showed that the mortality of 3 at the concentration of 100 ppm on the Fipronil against Linnaeus was 76.6%, the growth inhibition rate of 3 against Cynodon Dactylon under the condition of 100 ppm was 35.8% and the inhibitory activity of 3 at the concentration of 25 ppm against Fusarium graminearum reached 50.9%. Hence, the title compound has the value of further research and application prospect.

Synthesis, Crystal Structure and Fungicidal Activity of (Z)-3,3-Dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one O-2-Chlorobenzyl Oxime Nitrate

The title compound has been synthesized by the reaction of 3,3-dimethyl-1-（1H-1,2,4-triazol-1-yl）butan-2-one oxime with 2-chlorobenzyl chloride, and then treated with 65～68% HNO3. Its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 14.5481（8）, b = 9.3351（5）, c = 13.1911（7） , β = 98.9450（10）°, Z = 4, V = 1769.67（17） 3, Mr = 369.81, Dc = 1.388 g/cm3, S = 1.06, μ = 0.247 mm-1, F（000） = 776, the final R = 0.0352 and wR = 0.0960 for 3069 observed reflections （I 2σ（I））. X-ray crystal structure presents the intramolecular N–H…O hydrogen bond. The packing is nearly parallel without π-π stacking interactions between two adjacent phenyl rings and stabilized by Van der Waals force. The preliminary bioassay shows that the title compound possesses fungicidal activity against Gibberella zeae at the dosage of 25 mg/L.

4-[(Furan-2-ylmethylene)-amino]-1,5-dimethyl-1,2-dihyl-1,2-dihydo-pyrazol-3-one

The title compound （C16H15N3O2, Mr= 281.31） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Schiff base compound is a derivative of 4-aminoantipyrine. As expected, the molecular structure adopts a trans configuration about the C=N double bond. It crystallizes in the monoclinic system, space group P2 1/c with a = 11.150（3）, b = 9.906（3）, c = 13.624（4） A, β = 106.360（4）°, V= 1443.9（7） ,A^3, Z = 4, Dc = 1.294 g/cm^3, F（000） = 592,μ（MoKa） = 0.088 mm ^-1, R = 0.0577 and wR = 0.1214. Of the 5766 total reflections, 2540 were unique. In the molecule there exist two different planes of pyrazoline and O（2）-C（10） phenyl ring, which are approximately coplanar （r.m.s. de deviation from the combined mean plane is 0026 A） with the dihedral angle between them of 6.3°.

六氟磷酸二(2,2’-联吡啶)·(4,4’-二甲基-2,2’-联吡啶)合钌(Ⅱ)的二维核磁共振谱分析

用一维NMR方法研究了电化学发光物质六氟磷酸二(2,2’-联吡啶)·(4,4’-二甲基-2,2’-联吡啶)合钌(Ⅱ)的立体结构,借助二维~1H-~1H COSY和~1H-^(13)C COSY实验技术对其氢谱和碳谱进行了完全的归属,并给出了其氢谱和碳谱的化学位移值.

基于1-甲基-2,4-苯二脲路径的尿素法合成甲苯-2,4-二氨基甲酸甲酯反应研究

采用尿素法合成甲苯-2,4-二氨基甲酸甲酯(TDC)是一条绿色的工艺路线。其反应路径之一是以1-甲基-2,4-苯二脲(TBU)为中间产物,即2,4-二氨基甲苯(TDA)与尿素反应生成TBU,TBU再与甲醇反应得到TDC。首先对该路径进行了热力学分析,然后分别对两步反应进行了研究。对于TBU合成反应,适宜溶剂和催化剂分别为环丁砜(CBS)和乙酸锌;适宜反应条件为:反应温度130℃,反应时间7 h,n(TDA):n(Zn(OAc)2):n(Urea):n(CBS)=1:0.05:3.5:10。此时TDA转化率为54.3%,TBU选择性为73.3%。对于TDC合成反应,基于液相色谱-质谱和气相色谱分析结果,确定了反应组分。适宜的反应条件为:反应温度140℃,反应时间5 h,反应压力1.1 MPa,甲醇与TBU摩尔比为110:1。在该反应条件下,TBU转化率为100%,TDC选择性为60.4%。

食用香料2,4,5-三甲基噁唑和4-乙基-2,5-二甲基噁唑的合成

分别以丙氨酸和2-氨基丁酸为起始原料,经Dakin-West和Robinson-Gabriel两步反应合成2,4,5-三甲基噁唑和4-乙基-2,5-二甲基噁唑两种食用香料。考察催化剂、原料物质的量比、反应温度、反应时间、环化缩合剂种类等因素的影响,确定2,4,5-三甲基噁唑的较佳合成工艺:第一步Dakin-West反应,丙氨酸与乙酸酐的物质的量之比1:11,二甲基氨基吡啶和无水乙酸钠作催化剂(二甲基氨基吡啶用量为丙氨酸物质的量的10%、无水乙酸钠用量为丙氨酸物质的量的2.5倍),130℃反应5h,得产物Ⅰ(α-乙酰氨基酮);第二步Robinson-Gabriel反应,以多聚磷酸为环化脱水剂,产物Ⅰ与PPA物质的量比1:4,150℃反应2h,得产物Ⅱ。产物Ⅱ减压蒸馏纯化得2,4,5-三甲基噁唑,两步反应的总产率为30.5%。按上述条件合成4-乙基-2,5-二甲基噁唑,两步反应的总产率为28.8%。2,4,5-三甲基噁唑和4-乙基-2,5-二甲基噁唑均具有烤香、清香香气特征。产品结构通过质谱、红外光谱和核磁共振进行确认。本合成工艺路线以氨基酸为原料,具有原料易得、操作简单、产品香气纯正的优点,具有较好的工业化开发前景。

1-[(4,6-二甲基-2-嘧啶)偶氮]-2-萘酚的合成及其与钴Ⅱ的显色反应

合成了新显色剂 1 [( 4 ,6 二甲基 2 嘧啶 )偶氮 ] 2 萘酚 (DMPAN) ,并研究了该试剂的性质及其与钴显色反应的条件。结果表明 :试剂的离解常数 pka=7 4,λmax=374 0nm ,在 pH6 2 2的磷酸盐缓冲介质中 ,试剂与钴形成红色 1∶1络合物 ,其最大吸收波长λmax=42 6nm ,络合比Co2 +∶R =1∶1 ,摩尔吸光系数ε=2 66× 1 0 4 ,钴量在 0～ 1 2 μg/mL范围内遵守比尔定律 ,在掩蔽剂作用下 ,可不经分离直接用于含钴样品的分析 ,结果满意。

SO_4^(2-)/Ce-TiO_2光催化降解二甲基二氯乙烯基磷酸酯

以钛酸四丁酯 (Ti(OBu) 4 )、Ce(NO3 ) 3 、H2 SO4为主要原料 ,采用溶胶 凝胶法制备了SO2 -4/Ce TiO2 光催化剂 ,用XRD、IR、BET、XPS、TG DTA等测定技术对所制得的试样进行了表征 ,并将其用于光催化降解二甲基二氯乙烯基磷酸酯的稀释液。结果表明 ,SO2 -4/Ce TiO2 中TiO2 以锐钛矿晶型存在 ,并且具有超强酸特征 ,当n(Ce) /n(TiO2 ) =0 0 0 5 ,c(H2 SO4) =0 5mol/L时 ,焙烧温度为 5 0 0℃是最佳制备条件 ,其光催化降解性能较Ce TiO2 有明显提高。

4-羟基吡啶-2,6-二甲酸二甲酯合成工艺研究

考察了以吡啶-2，6-二甲酸为原料，经酯化、吡啶环自由基亲核取代合成4-羟甲基吡啶-2，6-二甲酸二甲酯的工艺路线，并对吡啶-2，6-二甲酸二甲酯羟甲基化的反应工艺条件进行了优化。结果表明，将9．8g（44mmol）吡啶-2，6-二甲酸二甲酯溶于60mL 30％（V）硫酸和75mL甲醇混合溶液中，同时等速滴加40．8mL（400mmol）30％过氧化氢溶液和含15．2g（100mmol）硫酸亚铁的饱和溶液，反应温度控制在30～50℃，目标产物产率可达65．8％，经液相色谱测定产物的纯度大于98％，其结构经由核磁氢谱（^1H-NMR），红外分析（IR）和元素分析得以表征。

2,6-二甲基-4-(2-氯苯基)-1,4-二氢-3,5-吡啶二羧酸二甲酯对大鼠野百合碱性肺动脉高压的防治作用

用野百合碱（ＭＣＴ）复制大鼠慢性肺动脉高压（ＰＨ）病理模型，探讨钙拮抗剂２，６－二甲基－４－（２－氯苯基）－１，４－二氢－３，５－吡啶二羧酸二甲酯（ＤＣＤＤＰ）对ＰＨ的防治作用．ＤＣＤＤＰ５，５０，５００μｇ·ｋｇ－１ｉｐ，每日１次，连续２８ｄ；ＭＣＴ６０ｍｇ·ｋｇ－１在第１次给ＤＣＤＤＰ后３０ｍｉｎｓｃ．观察肺血流动力学指标变化，血浆和肺匀浆中内皮素样免疫反应物（ｉｒ－ＥＴ），一氧化氮（ＮＯ）含量，超氧化物歧化酶（ＳＯＤ）活性和丙二醛（ＭＤＡ）含量的改变．三种不同剂量的ＤＣＤＤＰ分别使平均肺动脉压从４．５±０．９ｋＰａ（ＭＣＴ组）降至３．２±０．２，３．５±０．６和３．８±０．９ｋＰａ，肺血管阻力从１１８±１７ｋＰａ·ｍｉｎ－１·Ｌ－１（ＭＣＴ组）降至６５±１６，６８±１８和７６±１８ｋＰａ·ｍｉｎ－１·Ｌ－１（Ｐ＜０．０１），提示在本实验剂量范围内，中，低剂量ＤＣＤＤＰ防治效果似较好．ＤＣＤＤＰ不影响ＭＣＴ性ＰＨ时血浆和肺匀浆中ｉｒ－ＥＴ的改变，但可显著升高肺匀浆中ＮＯ的含量和ＳＯＤ活性，使肺匀浆中ＭＤＡ含量降至正常，这可能是其降低肺动脉压的机理之一．

2,5-二甲基-4-羟基-3(2H)呋喃酮的合成

以乙酰丙酮(1)为原料,经电解氧化偶联,Paal-Knorr闭环,Baeyer-Villiger氧化,水解等步骤,合成了一种重要的杂环香料,2,5-二甲基-4-羟基-3(2H)呋喃酮(6)。

一锅法合成4′-羟基-2,2′:6′,2″-三联吡啶

在无水乙醇中,以乙醇钠为碱、2-乙酰吡啶与碳酸二甲酯为原料合成1,3,5-三酮中间体,不经纯化,继续与氨水发生关环反应,一锅法合成了4′-羟基-2,2′:6′,2″-三联吡啶,收率50%.此方法文献少见报道,合成步骤简单,产品易于纯化,收率较高.对反应收率受反应溶剂、碱性条件、反应温度、反应时间的影响进行了讨论.

2-乙氧羰基-3-溴-4-甲基-5-甲酰基吡咯的制备

以2-乙氧羰基-3-溴-4,5-二甲基吡咯为原料,合成了托尼卟吩A的重要中间体2-乙氧羰基-3-溴-4-甲基-5-甲酰基吡咯,考察了不同氧化剂、温度及时间对产物收率的影响。结果表明,当以硝酸铈铵为氧化剂,且它与反应物的摩尔比为4.2∶1,反应温度为0℃,反应时间为1.5 h时,产物的收率达到最高值94.2%。

2,6-二烷基-4-溴苯胺的合成及表征

以液溴为溴化试剂,分别与2,6-二甲基苯胺、2,6-二异丙基苯胺反应,通过控制反应温度和时间,物料滴加方式,合成了2,6-二甲基-4-溴苯胺和2,6-二异丙基-4-溴苯胺,产率分别为67%和61%。通过1HNMR对目标产物进行结构表征。