N-丙基-N-[2-(2,4,6-三氯苯氧基)乙基]氨基甲酰氯分析方法的研究

介绍了N-丙基-N-[2,4,6-三氯苯氧基)乙基]氨基甲酰氯的化学分析法,该方法操作简单,且具有较好的精密度和准确度,可用于N-丙基-N-[2-(2,4,6-三氯苯氧基)乙基]氨基甲酰氯的质量控制分析。     

2-(2,4-二氯苯氧基)-三乙胺的合成

在相转移催化条件下,首先用2,4-二氯苯酚与二氯乙烷反应制得1-氯-2-（2,4-二氯苯氧基）乙烷中间体,然后再与二乙胺反应,合成植物生长调节剂2-（2,4-二氯苯氧基）-三乙胺。其总收率为84．6％,含量为98．0％。     

N-丙基-N-(甲酰氯)-2-(2,4,6-三氯苯氧基)乙胺的分析方法

本文研究了用高效液相色谱法测定N-丙基-N-(甲酰氯)-2-(2,4,6-三氯苯氧基)乙胺的方法。采用Hypersil C18(5μ)键合相填充柱,三元流动相分离,具有可调波长紫外检测器检测,方法的标准偏差为0.321%,变异系数为0.417%,平均回收率为99.1%。方法简便,准确。     

L-乳酸[（2-异亚丙基氨基氧基）乙基]酯的合成研究

以L-乳酸和2-异亚丙基氨基氧基乙醇为原料,经酯化反应合成了L-乳酸[（2-异亚丙基氨基氧基）乙基]酯。实验主要考察了催化剂、带水剂、反应时间、原料配比、催化剂用量等因素的影响,获得了优化的反应条件,L-乳酸酯产率可达83.2%,精酯收率78.5%,产品化学纯度98.5%,ee值99.3%。     

N-[2-(4-氨基苯基)丙基]乙酰胺的合成工艺

以2-苯基丙胺盐酸盐为原料经酸碱中和、酰化、硝化、还原4步合成得到N-[2-(4-氨基苯基)丙基]乙酰胺,探讨了投料方式、还原方法、催化剂等因素对收率的影响,并通过MS、~1H NMR和~(13)C NMR对其结构进行表征。总收率达50%,纯度为97.3%。     

高选择性合成N-(2-丙氧基乙基)-2,6-二乙基苯胺

N-(2-丙氧基乙基)-2,6-二乙基苯胺是除草剂丙草胺的重要中间体,其合成方法有:1)2,6-二乙基苯胺与溴乙基丙基醚或氯代乙基丙基醚反应合成;2)2,6-二乙基苯胺与乙二醇单丙醚直接烷基化反应合成。第1种方法存在着单烷基化选择性不高的问题;而第2种方法需贵金属催化剂及高温、高压等反应条件。芳香胺的N-烷基化还可以通过芳香胺与醛或酮     

4-(2,4-二氯苯氧基)苯酚的合成

4 (2,4 二氯苯氧基)苯酚是一种医药中间体。本文以2,4 二氯苯酚和对氯硝基苯为原料,经过醚化、硝基还原、重氮化及水解等反应合成该中间体,总收率57 6%。产物结构通过薄层色谱、红外光谱、核磁共振光谱进行了表征。     

2-[N-甲基-N-(2-吡啶基)氨基] 乙醇制备条件的优化

2-[N-甲基-N-(2-吡啶基)氨基]乙醇是合成罗格列酮(Rosighitazone)的一种中间体，罗格列酮是新型噻唑烷二酮类胰岛素增敏剂，通过两轮优化设计，实验室小试得到了较好的反应条件．为工业化生产提供了基础数据。     

相转移催化合成2-(2,4-二氯苯氧基)三乙胺

以2,4-二氯苯酚为原料,利用相转移催化剂来制备2-(2,4二氯苯氧基)三乙胺。并以正交实验研究和讨论了反应温度、反应时间、反应物摩尔配比、溶液的酸碱性对醚化实验结果的影响,得到最佳反应条件。对所制备的产物进行表征。通过红外光谱、核磁共振氢谱和元素分析确定了目标化合物的结构。     

2-氨基乙基-二(3-氨基丙基)胺的合成工艺研究

利用氨基乙腈及丙烯腈的亲核加成、氢化反应合成了一种新的不等臂有机多胺化合物 2 -氨基乙基 -二 (3-氨基丙基 )胺。研究了不同工艺条件对反应的影响 ,最佳工艺条件为 :n(丙烯腈 )∶n(氨基乙腈 ) =2 .8～ 3 .0 ,加成温度为 70～ 75℃ ,加成反应时间为 50～ 60h ,催化反应采用复合催化剂 ,m(溶剂 )∶m(物料 )≈ 1 0。两步反应的收率分别为 81 .6 %和 71 .6 % ,用多种谱学手段表征确证了该化合物及其中间产物     

植物生长调节剂2-(2,4-二氯苯氧基)三乙胺的合成新方法

以2,4 二氯苯酚为原料,采用相转移催化剂,经过醚化、胺化反应合成了2 (2,4 二氯苯氧基)三乙胺,总收率大于80%。研究了反应物的摩尔配比、反应时间及反应温度对2,4 二氯苯酚和二溴乙烷的醚化反应的影响,优惠工艺条件为:2,4 二氯苯酚与1,2 二溴乙烷配比为1∶30(mol/mol),反应温度80℃、反应时间10h。通过红外光谱、核磁共振氢谱和元素分析确定了目标化合物的结构。     

新型植物生长调节剂2-(2,4-二氯苯氧基)三乙胺的合成与应用

采用二氯乙烷为原料合成了植物生长调节剂２－ （２,４－ 二氯苯氧基）三乙胺,总收率达６０ ％ ～６８％ 。田间试验表明,该调节剂对大豆具有增强光合作用、使植株矮化、促进分枝、增花增荚的作用。大豆产量增加８．０ ％ ～１６．４ ％ 。     

N,N-二甲基-2-(2,4-二氯苯氧基)乙酰胺的制备

以2,4-二氯苯氧乙酸为原料,制备了标题化合物。经优化反应条件,使得标题化合物的收率达83%以上,其结构经IR1、HNMR和MS分析进行了表征。     

Controlling the ethylene polymerization parameters in iron pre-catalysts of the type 2-[1-(2,4-dibenzhydryl-6-methylphenylimino)ethyl]-6-[1-(arylimino)ethyl] pyridyliron dichloride

The ligand series 2-[1-(2,4-dibenzhydryl-6-methylphenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridines and the iron(II) chloride complexes thereof have been synthesized and characterized by elemental and spectroscopic analyses. The molecular structures of C1 and C2, determined by single-crystal X-ray diffraction analysis, confirmed a pseudo-square-pyramidal geometry at the iron center. Upon treatment with either MAO or MMAO, all iron pre-catalysts possessed good thermo-stability and exhibited high activities [up to 5.22 × 10⁷ g mol^?1(Fe) h^?1] toward ethylene polymerization, producing highly linear polyethylene products. Optimization of the reaction parameters gave polyethylenes with narrow molecular weight distributions, indicating that single-site active species were formed; the molecular weights of the resultant polyethylenes could also be controlled.     

氯化1-{2-[双(2-氨基乙基)氨基]乙基}吡啶离子液体的合成及在ATRP反应中的应用

采用N-烷基化方法将二乙烯三胺（DETA）接枝到氯化1-氯乙基吡啶离子液体[CePy]Cl上,合成了离子液体氯化1-{2-[双（2-氨基乙基）氨基]乙基}吡啶（[N₃Py]Cl）,通过FTIR、¹H NMR和MS等测试手段对合成离子液体的结构进行了表征。采用循环伏安法对离子液体配合物[N₃Py]Cl/CuBr和有机配合物PMDETA/CuBr的氧化还原电位（E_1/2）进行测试,结果表明：合成的离子液体[N₃Py]Cl和CuBr形成配合物的氧化还原电势为E_1/2=-0.541V,比常用的有机配合物PMDETA/CuBr（E_1/2=-0.142V）具有更低的氧化还原电势。将离子液体[N₃Py]Cl与CuBr配位形成催化体系,在离子液体[AMIM]Cl中催化甲基丙烯酸甲酯（MMA）的原子转移自由基聚合（ATRP）反应。结果表明,当配体、催化剂和溶剂的用量分别为n（CuBr）=0.19mmol、n（[N₃Py]Cl）=1.13mmol、n（[AMIM]Cl）=0.02mol,反应温度60℃,反应时间4h时,单体转化率高达75%,分子量分布较窄（M_w/M_n=1.24）,ATRP反应具有明显的可控性能。     

2-[1-(2,6-Dibenzhydryl-4-chlorophenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridyliron(II) dichlorides: Synthesis,characterization and ethylene polymerization behavior

A series of 2-[1-(2,6-dibenzhydryl-4-chlorophenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridine ligands (L1–L5) as well as the ligand 2,6-bis[1-(2,6-dibenzhydryl-4-chloro-phenylimino)ethyl]pyridine (L6) were synthesized and reacted with FeCl₂·4H₂O to afford the iron(II) dichloride complexes [LFeCl₂] (Fe1–Fe6). All new compounds were fully characterized by elemental and spectroscopic analysis, and the molecular structures of the complexes Fe1, Fe2 and Fe4 were determined by single-crystal X-ray diffraction, which revealed a pseudo-square-pyramidal geometry at iron. Upon activation with either MAO or MMAO, all iron pre-catalysts exhibited very high activity in ethylene polymerization with good thermal stability. To the best of our knowledge, the current system showed the highest activity amongst iron bis(imino)pyridine pre-catalysts reported to-date. The polymerization parameters were explored to determine the optimum conditions for catalytic activity, which were typically found to be 2500 eq. Al to Fe at 60 °C in the presence of MMAO, and 80 °C in the presence of MAO. The resultant polyethylene possessed a narrow molecular polydispersity index (PDI) consistent with the formation of single-site active species.     

5,10,15-三苯基-20-{间-[2-(5,10,15-三苯基-20-间胺苯卟啉基)]胺苯基}邻苯二甲酰基卟啉及其双金属钯配合物的合成与表征

报道了标题化合物（α-PhACBTPP）其双金属钯配合物的合成,并通过紫外可见光谱、红外光谱、核磁共振氧谱和元素分析等手段进行了结构表征。     

2-溴-3-{4-[2-(5-乙基-2-吡啶基)-乙氧基]苯基}丙烯酸甲酯的合成

以5－乙基－2吡啶基乙醇为起始原料,与对氟硝基苯缩合,Pd/C催化加氢,得4－[2－（5－乙基－2－吡啶基）－乙氧基]苯胺,再经重氮化和桑德迈尔反应,制得2－溴－3－{4－[2－（5－乙基－2－吡啶基）－乙氧基]苯基}丙烯酸甲酯,总收率为65．6％,最终产物经IR和NMR结构确证。     

Phase behavior for the poly[2-(2-ethoxyethoxy)ethyl acrylate] and 2-(2-ethoxyethoxy)ethyl acrylate in supercritical solvents

Pressure-composition (p, x) isotherms were obtained for the carbon dioxide + 2-(2-ethoxyethoxy)ethyl acrylate [2-(2-EE)EA] system at five temperatures (313.2 K, 333.2 K, 353.2 K, 373.2 K, and 393.2 K) and pressure up to 22.86 MPa. The carbon dioxide + 2-(2-EE)EA system exhibits type-I phase behavior with a continuous mixture critical curve. The experimental results for carbon dioxide + 2-(2-EE)EA mixtures are correlated using the Peng–Robinson equation of state (PR-EOS) using mixing rule including two adjustable parameters. The critical property of 2-(2-EE)EA is estimated with the Joback–Lyderson method.Experimental data up to 485 K and 206.6 MPa are reported for binary and ternary mixtures of poly(2-(2-ethoxyethoxy)ethyl acrylate) [P(2-(2-EE)EA)] + carbon dioxide + 2-(2-EE)EA, P(2-(2-EE)EA) + carbon dioxide + dimethyl ether (DME), P(2-(2-EE)EA) + carbon dioxide + propylene and P(2-(2-EE)EA) + carbon dioxide + 1-butene systems. High-pressure cloud-point data are also reported for P(2-(2-EE)EA) in supercritical carbon dioxide, propane, propylene, butane, 1-butene, and DME at temperature to 474 K and a pressure range of (8.45–206.6) MPa. Cloud-point behavior for the P(2-(2-EE)EA) + carbon dioxide + 2-(2-EE)EA system were measured in changes of the pressure–temperature (p, T) slope and with 2-(2-EE)EA mass fraction of 0.0 wt%, 5.9 wt%, 14.9 wt%, 30.3 wt% and 60.2 wt%. With 0.650 2-(2-EE)EA to the P(2-(2-EE)EA) + carbon dioxide solution, the cloud point curves take on the appearance of a typical lower critical solution temperature boundary. The P(2-(2-EE)EA) + carbon dioxide + (0.0–46.6) wt% DME systems change the (p, T) curve from upper critical solution temperature region to lower critical solution temperature region as the DME mass fraction increases. Also, the impact by propylene and 1-butene mass fraction for the P(2-(2-EE)EA) + carbon dioxide + propylene and 1-butene system is measured at temperatures to 454 K and a pressure range of (75.7 to 119.6) MPa.