N-（3-氯-4-（3-氟苯甲氧基）苯基）-6-碘喹唑啉-4-胺盐酸盐的合成

以2-氯-4-硝基苯酚为原料,经Williamson反应得3-氯-4-（3-氟苯甲氧基）硝基苯,硝基还原后与4-氯-6-碘喹唑啉缩合得到抗肿瘤药物拉帕替尼的重要中间体N-（3-氯-4-（3-氟苯甲氧基）苯基）-6-碘喹唑啉-4-胺盐酸盐,总收率约62％。中间体及目标产物结构经1HNMR和MS得以证实。     

一种黑色可逆热致变色染料的合成及表征

研究了黑色可逆热致变色染料2′-(2-氯苯氨基)-6′-二丁氨基荧烷(Ⅰ)的合成及表征。以邻氯苯胺、对苯二酚为原料,合成2-氯-4-羟基二苯胺(Ⅱ)。以间硝基苯酚为原料,经酚羟基保护、硝基还原、氨基烷基化反应、脱保护、与邻苯二甲酸酐反应合成N,N-二正丁基-4-氨基-2-羟基-2′-甲酸二苯甲酮(Ⅲ)。化合物Ⅱ与化合物Ⅲ反应合成目标产物Ⅰ,总收率56.2%,纯度99.54%(HPLC),其结构经~1HNMR、~(13)CNMR证实。     

N-(2-氟-4-氯-5-环戊氧基苯基)氨基甲酸乙酯的合成

环戊口恶草酮是一种新型口恶唑啉二酮类除草剂,N-(2-氟-4-氯-5-环戊氧基苯基)氨基甲酸乙酯是合成该除草剂的重要中间体之一.本文以5-硝基-2-氯-4-氟苯酚为原料,经催化加氢还原、烷基化反应等合成了N-(2-氟-4-氯-5-环戊氧基苯基)氨基甲酸乙酯.该方法操作简便,四步总收率达56.7%.     

染料中间体2-氨基-5-硝基苯甲酸的合成

本文以两条合成路线制备了染料中间体2-氨基-5-硝基苯甲酸。路线一首先利用对硝基苯胺与水合三氯乙醛、盐酸羟胺反应先制得对硝基（N-肟基乙酰）苯胺,再用浓硫酸关环生成5-硝基靛红,最后用过氧化氢氧化,制得2-氨基-5-硝基苯甲酸。路线二以靛红为原料,经发烟硝酸硝化到5-硝基靛红,再用过氧化氢氧化得2-氨基-5-硝基苯甲酸。两条路线产物的总收率分别为27.3％和61.2％,其结构经IR和1HNMR表征得以确认。     

4-氯-2-氨基苯酚的合成

本文研究了2,5-二氯硝基苯水解合成4-氯-2-硝基苯酚.在催化剂存在下,水合肼催化还原合成4-氯-2-氨基苯酚,目标产物纯度大于99.0％,收率达92％.     

2-氨基-4-氯-5-硝基苯酚的生产工艺

以2-氨基-4-氯苯酚为原料。经乙酰化、闭环、硝化、碱解和酸化合成2-氨基-4-氯-5-硝基苯酚,精制品总收率为64％。     

2,3,5,6-四氨基吡啶及其（2-羟基）对苯二甲酸复合盐的合成

为了制备高纯度与高收率的2,3,5,6-四氨基吡啶/2-羟基对苯二甲酸复合盐（TH盐）,通过以2,6-二氨基-3,5二硝基吡啶（DADNP）为原料催化加氢还原制得2,3,5,6-四氨基吡啶盐酸盐（TAPH）。反应在55～60℃的氢气氛围下,以甲醇为溶剂,Pd/C为催化剂制得纯度99.4%的TAPH,收率82.1%。制成的盐酸盐再和2-羟基对苯二甲酸（HTA）钠盐在氮气氛围的保护下合成2,3,5,6-四氨基吡啶/2-羟基对苯二甲酸复合盐（TH盐）单体,结构经过13C-NMR、MS和FT-IR表征分析,结果表明是目的产物,纯度达98%以上。     

2-氨基-5-硝基噻唑的合成研究

以乙酸乙烯酯为原料,经氯化、水解与硫脲环合反应制备2-氨基噻唑,收率91％。将其在硫酸体系中,经成盐-硝化“一锅法”合成2-氨基-5-硝基噻唑。当反应物n（2-氨基噻唑）:n（硫酸）:n（硝酸）=1∶4∶1.05,30℃反应4小时,硝化产物收率为81％。     

2,6-二氯-4-氨基苯酚的合成方法

[目的]筛选出合成2,6-二氯-4-氨基苯酚的最佳工艺条件.[方法]2,6-二氯-4-硝基苯酚经加氢反应合成2,6-二氯-4-氨基苯酚,并对其合成及提纯工艺进行优化.[结果]最优反应条件下,产品纯度≥99.5％,反应总收率≥93％.[结论]优化了2,6-二氯-4-氨基苯酚合成及提纯工艺,产品收率高且易分离,适合工业化生...     

2,6-二氯-4-氨基苯酚的合成

[目的]制备新型农药氟啶脲和氟铃脲的高纯度中间体2,6-二氯-4-氨基苯酚。[方法]采用2,6-二氯苯酚为原料,在溶剂中硝化合成2,6-二氯-4-硝基苯酚,再在自制的催化剂存在下水合肼催化还原合成2,6-二氯-4-氨基苯酚,探讨合成过程的影响因素。[结果]实验确定了最佳反应条件,得到了纯度大于99.0%的目标产物。[结论]该工艺具有收率高、操作简单、安全可靠的特点,可为工业化生产提供参考。     

Synthesis and characterization of new hyperbranched poly(ether ketones) with various number of phenylene units

A new series of AB₂ type monomers with aromatic thio and various number of phenylene units were prepared. Three series of AB₂ type monomers, 4-thio-3′,5′-bis(4-fluorobenzal)biphenyl 1, 4-thio-3′′,5′′-bis(4-fluorobenzal)-p-terphenyl 2 and 4-thio-3′′′,5′′′-bis(4-fluorobenzal)-p-quarterphenyl 3 were synthesized in a stepwise manner starting from 3,5-bis(4-fluorobenzoyl)phenol 4 by repeating a series of conversions of the hydroxy group to the triflate, cross-coupling reaction of the triflate with (p-methoxythiophenyl)boronic acid, reduction of carbonyl groups followed by conversion of methylthio to thio group. Three kinds of hyperbranched poly(ether ketones) were prepared by the polymerization of the these three AB₂ type monomers. All compounds were characterized by elemental analysis, thermal analysis, ¹H and ¹³C NMR spectrometry.     

D_4阳离子开环聚合

介绍了用于八甲基环四硅氧烷（以下简称写Ｄ＿４）阳离子开环聚合的高真空微型聚合实验技术，以及Ｄ＿４在三氟甲基磺酸（简称ＴｆｏＨ）和三氟甲基磺酸苄基二甲基硅酯（简写ＴＰＯＳ）组成的引发体系下进行开环聚合取得的初步结果。在Ｄ＿４转化率低于２０％时，反应产生的主要是Ｄ＿５—Ｄ＿（１２）环体副产物。三种引发体系由于活性中心不同，导致聚合反应速度和分子量的差异。     

Gel electrolytes based on crosslinked tetraethylene glycol diacrylate/poly(ethylenimine) systems

Gel electrolytes were prepared by crosslinking low molecular weight poly(ethylenimine) (PEI) with tetraethylene glycol diacrylate (TEG) in the presence of 2-methoxyethyl ether (diglyme) and lithium triflate (LiTf). Impedance and infrared (IR) spectroscopies were used as complimentary tools for studying the mode of ion conduction in these gel electrolytes. Ionic conductivity measurements for all samples tested exhibited significant LiTf and diglyme composition dependency. The maximum ionic conductivity at 20 °C was 2×10⁻⁴ S/cm with moderate LiTf and high diglyme compositions. The calculated molal concentration of non-ionically bound ‘free’ triflate ion was found to vary directly with ionic conductivity with the highest molality ‘free’ triflate samples yielding the highest ionic conductivity. Lithium ion interactions with the triflate ion, diglyme and the crosslinked polymer matrix were observed with IR spectroscopy. A lower frequency shoulder on the v_s(CO) vibrational mode increases in intensity as LiTf composition is increased. Curve fitting and molar calculations suggest that over 85% of the total lithium ions available are coordinated to the TEG carbonyl at dilute LiTf compositions.     

The first carboranyl bis(adenosine diphosphate) (CBADP): a synthetic investigation

The synthesis of the first carboranyl bis(adenosine diphosphate) (CBADP) (5) was achieved in three steps. The first step involved the reaction of o-carborane dianion, 1, with methyl dichlorophosphate to yield 2. Reagent 4 was synthesized by the reaction of bis-benzoyl-protected adenosine with phosphoryl chloride, followed by the protection of the free hydroxyl group in the product, 3, with methyl triflate. The final step converged both 2 and 4 into the title compound, CBADP (5).     

赖诺普利关键中间体的合成研究

以3-苯甲酰丙烯酸乙酯（BZ）和三氟乙酰赖氨酸（LA1）为原料,在三氟甲磺酸三正丁胺盐催化作用下,经迈克尔加成反应、氢化还原反应合成赖诺普利关键中间体N2-（1-乙氧羰基-3-苯丙基）-N6-三氟乙酰基-L-赖氨酸（LA2）,总收率为38.8%。LA2加成物立体选择性可达到84：16。该方法具有操作简单,收率高,是一条适合工业化生产的合成路线。     

Electroseparation of zinc(II) from uranium(III) prepared by reduction of uranium(IV) with zinc amalgam in dimethylformamide

Journal of Applied Electrochemistry - The Electroseparation of zinc(II) from a solution of uranium(III) generated by the reduction of uranium(IV) triflate (U(OTf)4) with zinc amalgam (Zn(Hg)) was...     

Facile Routes to Manganese(II) Triflate Complexes

Manganese(II) chloride reacts with trimethylsilyl triflate (TMS(OTf) where OTf = (-)OSO(2)CF(3)) in a 1:1 mixture of acetonitrile and tetrahydrofuran, and after recrystallization affords the linear coordination polymer [Mn(II)(CH(3)CN)(2)(OTf)(2)](n). Each distorted octahedral manganese(II) center in the polymeric chain has trans-acetonitriles and the remaining equatorial coordination positions are occupied by the bridging triflate anions. Dissolving [Mn(II)(CH(3)CN)(2)(OTf)(2)](n) in equal volumes of acetonitrile and pyridine followed by recrystallization with diethyl ether yields trans-[Mn(II)(C(5)H(5)N)(4)(OTf)(2)]. The distorted octahedral geometry of the manganese center features monodentate trans-triflate anions and four equatorial pyridines. Exposure of either [Mn(II)(CH(3)CN)(2)(OTf)(2)](n) or [Mn(II)(C(5)H(5)N)(4)(OTf)(2)] to water readily gives [Mn(II)(H(2)O)(6)](OTf)(2). XRD reveals hydrogen-bonding interactions between the [Mn(II)(H(2)O)(6)](2+) cation and the triflate anion. All three of these species are easily crystallized and provide convenient sources of manganese(II) for further synthetic elaboration.     

Polymerization of 2-phenyl-aziridine

Summary The ring-opening polymerization of 2-phenyl aziridine was studied with several catalyst systems: boron trifluoride etherate, chlorhydric acid, perchloric acid, dimethyl sulfate and methyl triflate. The corresponding polyamine was obtained as a pale yellow solid with a number average molecular weight around 2,000–3,000.A kinetic study is discussed in the case of perchloric acid and methyl triflate.     

Two‐component photoresists containing thermally crosslinkable photoacid generators

Bis{4‐[2′‐(vinyloxy)ethoxy]phenyl}‐4‐methoxyphenylsulfonium triflate (TPS‐2VE‐Tf) and tris{4‐[2′‐(vinyloxy)ethoxy]phenyl}sulfonium triflate (TPS‐3VE‐Tf) were synthesized as thermally crosslinkable photoacid generators (PAGs) and used in a two‐component chemically amplified photoresist system. The photoresist films formulated with poly(p‐hydroxystyrene) (PHS) as a binder polymer and a thermally crosslinkable PAG are insolubilized in aqueous base by prebaking due to the thermal crosslinking reaction between PHS and the PAG. The insolubilization temperature of the resists and conversion of vinyl ether groups are greatly influenced by the PAG concentration and prebaking temperature, respectively. Upon exposure to deep UV and subsequent postexposure bake, the crosslinks are cleaved by photogenerated acid, leading to effective solubilization of the exposed areas. Photoresists containing TPS‐2VE‐Tf and TPS‐3VE‐Tf exhibited sensitivities of 12 and 45 mJ/cm², respectively. Positive‐tone images were obtained using a 2.38 wt% aqueous tetramethylammonium hydroxide developer.     

Silver Triflate‐Catalyzed or Electrophile‐Mediated Tandem Reaction of N′‐(2‐Alkynylbenzylidene)hydrazides with Dimethyl Acetylenedicarboxylate

Different outcomes were generated under different conditions for the tandem reactions of N′‐(2‐alkynylbenzylidene)hydrazides with dimethyl acetylenedicarboxylate (DMAD) catalyzed by silver triflate or in the presence of electrophiles. The unexpected isoquinoline‐based azomethine ylides were obtained when the reaction was catalyzed by silver triflate or in the presence of bromine, while the fused 1,2‐dihydroisoquinolines were afforded when iodine was employed in the above tandem reactions.