1,50二叠氮基-3硝-基氮杂戊烷的合成及表征

以吉纳和叠氮化钠为起始原料,经过叠氮化、萃取、洗涤、脱色、过滤以及真空蒸馏等多个步骤合成出1,5-二叠氮基-3-硝基氮杂戊烷（DIANP）;通过红外、核磁及元素分析对产物进行结构表征;并分析测试了其他相关性能;考察了料比、溶媒、温度和时间等对反应的影响。结果表明,合成的最佳条件是：反应物料的质量比为1∶0.59、溶媒DMSO、反应温度80～85℃、反应时间7～8 h,收率不小于80%,纯度不小于98%（LC）。     

1,7-二叠氮基-2,4,6-三硝基-2,4,6-三氮杂庚烷的合成及其性能

以乌洛托品为起始原料,经硝化、氯化、叠氮化反应合成出了1,7-二叠氮基-2,4,6-三硝基-2,4,6-三氮杂庚烷(DATH),总收率为75.3%;测试了DATH的部分理化及爆轰性能,其密度1.71g/cm3,熔点135～137℃,爆速8300m/s(1.64g/cm3),燃烧热10822.02kJ/kg,分解温度192℃,摩擦感度12%(25kg/cm3,66°),撞击感度95%(12kg,25cm)。     

1-氧代-4-叠氮甲基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷的合成

合成了未见文献报道的１－氧代－４－叠氮甲基－２,６,７－三氧杂－１－磷杂双环［２．２．２］辛烷化合物,并用ＩＲ、１ＨＮＭＲ,ＭＳ和元素分析法进行结构鉴定。     

N,N-二甲基叠氮乙基胺合成研究

对2条N,N-二甲基叠氮乙基胺(DMAZ)的合成路线进行了对比研究,制备出纯度99%的DMAZ,产品经FT-IR、GC-MS、1H-NMR表征确认其正确结构。     

1,5-二叠氮基-3-硝基氮杂戊烷的合成及表征

以吉纳和叠氮化钠为起始原料,经过叠氮化、萃取、洗涤、脱色、过滤以及真空蒸馏等多个步骤合成出1,5-二叠氮基-3-硝基氮杂戊烷(DIANP);通过红外、核磁及元素分析对产物进行结构表征;并分析测试了其他相关性能;考察了料比、溶媒、温度和时间等对反应的影响.结果表明,合成的最佳条件是:反应物料的质量比为1∶0.59、溶媒DMSO、反应温度80～85℃、反应时间7～8 h,收率不小于80%,纯度不小于98%(LC).     

叠氮基吡啶及1-吡啶基-1,2,3-三氮唑的合成

叠氮基吡啶是一类重要的有机化合物,其用途十分广泛,可用来构建含氮杂环化合物,合成除草剂等,介绍了叠氮基吡啶和1-吡啶基-1,2,3-三氮唑的合成方法及用途。     

2,2,6,6-四甲基哌啶氮氧自由基的合成

用自制的2，2，6，6-四甲基哌啶采用廉价的二价金属盐—过氧化氢体系，2，2，6，6-四甲基哌啶氮氧自由基；同时对合成的工艺条件作了初步的探索，得到了产率达到80．17％左右的工艺条件，反应温度65℃、滴加时间6h，30％双氧水与2，2，6，6-四甲基哌啶的物质的量比为2．5。     

6-硫-1,2,4-三氮-双环[3.2.0]庚烷-2,4-二烯的合成

以水合肼、硫氰酸盐、多聚甲醛为原料,经过五元环合成、氧化、四元环合成三步反应,合成6-硫-1,2,4-三氮双环[3.2.0]庚烷-2,4-二烯。对合成路线进行了条件优化。最高收率达61.8%。其结构经1H NMR确证。     

2,6-二氨基-1,3二氮杂薁的简便合成

奠系化合物属非苯芳香族系列,其特殊的结构所显示出的生理和药理活性早已引起人们的极大兴趣。其中,1,3-二氮杂奠及其衍生物作为止痛剂、抗发炎药物,液晶化合物,曾进行了较广泛的研究。从结构上看,2,6-二氨基-1,3-二氮杂奠也是合成杂环药物和液晶化合物的有效中间体,本文经偶氮化合物中间体催化氢化合成目标分子,其合成路线如下。     

2,6-二甲基溴苯的合成研究

研究了以间二甲苯为原料经过磺化反应(收率87.7％)、溴代反应(收率92.3％)及去磺化反应(收率96.4％),制得2,6-二甲基溴苯.合成步骤明了,操作简单,提纯方便且有较好收率.     

含氰基二元芳胺固化的酞菁预聚物的合成及表征

以亲核取代反应合成了3种酞菁单体(2,2′-二[4-(3,4-二氰基苯氧基)]丙烷(BAPh)、4,4′-二(3,4-二氰基苯氧基)联苯(BPh)、4,4′-二(3,4-二氰基苯氧基)甲烷(BFPh))和1种含有氰基的高熔点二元芳胺2,6-二(4-氨基苯氧基)苯甲腈(APBN)。通过核磁共振氢谱(1H-NMR)、傅里叶变换红外光谱(FT-IR)、示差扫描量热仪(DSC)和热重分析(TGA)对合成的化合物的化学结构,芳胺和酞菁单体的热聚合行为,不同固化时间预聚物的热性能进行了研究。结果表明,BAPh/APBN和BFPh/APBN体系分别具有宽达101℃与107℃的加工窗口。BFPh型预聚物(固化1 h)比其他2种预聚物具有更高的初始分解温度(390℃下失重5%)、高温残炭率(800℃下61.7%)和固化效率。     

Synthesis of new triisocyanate curatives 2,2-bis(isocyanatomethyl)propyl isocyanate and 4-(isocyanatomethyl)-1,7-heptyl diisocyanate

Summary Two triisocyanate crosslinking agents were synthesized. The 2,2-bis(isocyanatomethyl)-propyl isocyanate was synthesized from 2,2-bis(hydroxymethyl)propanol in three steps via the triazide and the triamine with an overall yield of 20% and >95% purity as determined by NMR. The 4-(isocyanatomethyl)-1,7-heptyl diisocyanate was synthesized from 1,3,5-pentanetricarboxylic acid in six steps with an overall yield of 23.5% and >98% purity as determined by NMR. This synthesis proceeded via the trimethyl ester, the triol, the tris(p-toluenesulfonate), the triazide and the triamine.     

1,3-双(2,6-二异丙基苯基)氯化咪锉嗡的合成

以2,6-二异丙基苯胺与乙二醛为起始原料,合成1,4-双(2,6-二异丙基苯基)-1,4-二氮丁二烯(IPr-1#),随后与多聚甲醛反应,得到1,3-双(2,6-二异丙基苯基)氯化咪锉嗡(IPr.HCl)。考察了反应温度、时间以及料比等条件对反应结果的影响。优化条件后,两步反应可得到含量为98.5%的白色粉末产品,总收率为77.2%。并通过LC-MS、DSC对产物进行表征。     

绿色溶剂法制备2,6-二苦氨基吡啶的研究

采用水作为溶剂,以2,6-二氨基吡啶(DAP)和2,4,6-三硝基氯苯为原料,经N-烷基化反应,制得2,6-二苦氨基吡啶(PAP)。考察了相转移催化剂、反应物配比、缚酸剂用量、反应温度、反应时间等对PAP收率的影响。结果表明,优化工艺条件为:采用AEO9作相转移催化剂,n(三硝基氯苯)∶n(二氨基吡啶)=2.2∶1,n(碳酸氢钠)∶n(二氨基吡啶)=1.83∶1,反应温度95℃,反应时间为5 h。此时2,6-二苦氨基吡啶的得率可达84.6%,熔点315℃,液相色谱分析纯度为97.6%。     

Bis(azidomethyl) oxetane/hydroxyl‐terminated polybutadiene/bis(azidomethyl) oxetane triblock copolymer: Synthesis and characterization

A copolymer consisting of bis(azidomethyl) oxetane and hydroxyl‐terminated polybutadiene was synthesized with different monomer ratios via an activated monomer mechanism. The copolymer thus obtained was characterized with Fourier transform infrared, ¹H‐NMR, molecular weight, and polydispersity measurements. Rhe‐ological and thermal studies were also carried out. The mechanical properties of the gum stock obtained through curing with toluene diisocyanate and crosslinking with pyrogallol at about 50°C were also determined. This was an attempt to combine the useful properties of hydroxyl‐terminated polybutadiene (a nonenergetic binder providing excellent mechanical properties) and poly[bis(azidomethyl) oxetane] (an energetic binder). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis,characterization, and curing of unsaturated polyamides derived from 2,6-di(4-carboxystyryl)pyridine and 2,6-bis(4-carboxybenzylidene) cyclohexanone

Two new series of heat-curable polyamides were prepared utilizing the unsaturated dicarboxylic acids 2,6-di(4-carboxystyryl)pyridine (DCSP) and 2,6-bis(4-carboxybenzylidene)cyclohexanone (BCBC) as starting materials. They were prepared from the condensation of 4-carboxybenzaldehyde with a half molar amount of 2,6-dimethylpyridine or cyclohexanone, respectively. The dicarboxylic acids reacted with various aromatic diamines, utilizing triphenyl phosphite and pyridine as condensing agents, to yield polyamides. In addition, two model diamides were prepared by condensing the dicarboxylic acids with aniline. Characterization of starting materials, polyamides, and model compounds was accomplished by IR and ¹H–NMR spectroscopy. The curing behavior of polyamides was investigated by DTA. Upon heat-curing, the unsaturated polyamides were crosslinked through their olefinic bonds to afford insoluble, heat-resistant resins. The thermal stability of the resins was evaluated by TGA and isothermal gravimetric analysis (IGA). The cured resins were stable up to 310–322°C in N₂ or air and afforded anaerobic char yield of 57–69% at 800°C.     

Synthesis, characterization and olefin polymerization studies of iron(II) and cobalt(II) catalysts bearing 2,6-bis(pyrazol-1-yl)pyridines and 2,6-bis(pyrazol-1-ylmethyl)pyridines ligands

The complexes Py(PzR₃)₂MCl₂ (R = H, Me; M = Fe, Co) and Py(CH₂PzR₃)₂MCl₂ (R = H, Me; M = Fe, Co) have been synthesized, characterized and used in the ethylene polymerization. Treatment of these iron and cobalt complexes with methylaluminoxane (MAO) as cocatalyst leads to active ethylene polymerization catalysts that produced linear polyethylene. In general, iron catalysts were more active than cobalt analogs. The steric and electronic effects of the ligands were study over the catalytic activity toward ethylene polymerization. Complexes with small substituents groups (R = H) on the pyrazolyl ring, increase the catalytic activity in comparison to complexes with bigger substituents groups (R = CH₃). Additionally, complexes with methylene groups placed between pyridine and pyrazole rings of ligands have less catalytic activity than complexes without the methylene group (CH₂). The presence of methyl groups (R = CH₃) in iron and cobalt complexes allow to obtain polyethylene with molecular weights higher than the one obtained with complexes without these methyl groups. Additionally, complexes with methylene groups present between pyridine and pyrazole rings generate polyethylenes with molecular weight higher than the ones produced with complexes without these methylene groups.     

4-叔丁基-2,6-二(4-吗啉甲基)苯酚的合成

在碱催化条件下,以对叔丁基酚为底物,与甲醛和吗啉进行Mannich反应,制备了4 叔丁基2, 6 二(4 吗啉甲基)苯酚。最佳工艺条件为: 80℃回流反应8h,w(NaOH) =10%的水溶液进行催化,收率83 8%。并通过红外光谱、核磁共振氢谱和碳谱对目标产物进行了结构表征。     

Synthesis and transition metal coordination of 2-(azidomethyl) phenyl isocyanide

The reaction of 2-(chloromethyl)phenyl formamide, 2-(CH₂Cl)C₆H₄NHCHO, with NaN₃ in DMSO at room temperature affords 2-(azidomethyl)phenyl formamide, 2-(CH₂N₃)C₆H₄NHCHO (1), which is then dehydrated to 2-(azidomethyl)phenyl isocyanide, 2-(CH₂N₃)C₆H₄NC, (2) upon reaction with SOCl₂ in DMF at low temperature. The coordination ability of the isocyanide 2 has been tested towards some Pt(II), Pd(II) and W(0) metal complexes to yield derivatives of the type [PtCl₂(CNC₆H₄-2-CH₂N₃)₂], [PdCl₂(CNC₆H₄-2-CH₂N₃)(PPh₃)] and [W(CO)₅(CNC₆H₄-2-CH₂N₃)], respectively.