7-氨基-6-硝基苯并二氧化噁二唑(呋咱)的合成、结构表征与性能研究

自行设计了7-氨基-6-硝基苯并二氧化噁二唑(呋咱)(ANBDF)新的合成方法,以1,3,5-三硝基-2,4-二氯苯为原料,经过叠氮化、脱氮环化得到关键中间体6-硝基苯并二氧化嗯二唑(呋咱)(NBDOF),然后利用异常亲核取代反应(VNS)在苯环上引入氨基得到目标化合物ANBDF,总收率为51.0%.中间体和目标产物均通过元素分析、核磁共振、红外光谱等进行了结构表征.优化了VNS反应条件,确定了适宜的条件为:盐酸羟胺为VNS试剂,20～40℃下反应5 h,收率70%.NBDOF与ANBDF的性能对比表明:ANBDF分子中的氨基与硝基形成的氢键,使得分子结构更加紧密,密度增加,热稳定性相当,感度显著降低,爆速提高.实验发现ANBDF没有熔点,分解过程分两步进行.     

3-氨基-4-硝基呋咱和3,3′-二硝基-4，4′-偶氮呋咱的合成研究

3-氨基-4-硝基呋咱（ANF）及其衍生物是一类重要的含能材料．ANF的制备首先以乙二醛、盐酸羟胺和氢氧化钠为原料,经过两步反应制得3,4-二氨基呋咱（DAF）,采用新的氧化体系过氧化氢,甲烷磺酸,钨酸钠混合物（H2O2／CH3SO3H,Na2WO4）代替原氧化体系过氧化氢／硫酸,过硫酸铵混合物[H2O2／H2SO4/（NH4）2S2O8]氧化DAF以67％的产率获得了ANF．然后在单电子氧化体系高锰酸钾,盐酸混合物作用下ANF发生氧化反应以54．7％的产率得到3,3′-二硝基,4,4′-偶氮呋咱（DNAzF）．研究表明过氧化氢,甲烷磺酸,钨酸钠混合物是制备氨基硝基单／多呋咱非常有效的氧化体系．     

5-氯-2-硝基苯胺合成5-氯-苯并氧化呋咱反应的密度泛函研究

利用密度泛函理论(DFT)的B3LYP/6-31G(d,p)计算方法研究了次氯酸钠氧化环化5-氯-2-硝基苯胺合成5-氯-苯并氧化呋咱的反应, 采用连续介质模型(PCM)评估了溶剂效应. 提出两种可能的分步反应通道: (1)氧化、移氢、脱水和环化, (2)移氢、亚氨基氢扭转、氧化、脱水和环化|前者为优势通道. 非极性的CCl₄溶剂有较低的活化能垒, 比极性的乙醇溶剂更有利于5-氯-2-硝基苯胺的合成. 标题反应的机理类似于次氯酸钠氧化邻硝基苯胺合成苯并氧化呋咱, 但其速控步的活化能垒更低, 反应更易进行.     

3-氨基-4-硝基呋咱和3,3’-二硝基-4,4’-偶氮呋咱的合成研究

3-氨基-4-硝基呋咱(ANF)及其衍生物是一类重要的含能材料. ANF的制备首先以乙二醛、盐酸羟胺和氢氧化钠为原料, 经过两步反应制得3,4-二氨基呋咱(DAF), 采用新的氧化体系过氧化氢/甲烷磺酸/钨酸钠混合物(H2O2/CH3SO3H/ Na2WO4)代替原氧化体系过氧化氢/硫酸/过硫酸铵混合物[H2O2/H2SO4/(NH4)2S2O8]氧化DAF以67%的产率获得了ANF. 然后在单电子氧化体系高锰酸钾/盐酸混合物作用下ANF发生氧化反应以54.7%的产率得到3,3’-二硝基- 4,4’-偶氮呋咱(DNAzF). 研究表明过氧化氢/甲烷磺酸/钨酸钠混合物是制备氨基硝基单/多呋咱非常有效的氧化体系.     

3-氨基-4-硝基氧化呋咱含能化合物的设计合成研究

在氧化呋咱环上引入氨基或硝基等功能基团,可提高含能化合物的能量密度和爆炸性能。为了获得更高能量密度的新型含能化合物,本文利用密度泛函理论（DFT）和单、双激发的耦合簇（CCSD）方法探索了以3-酰基叠氮基-4硝基氧化呋咱为起始材料,在二氧六环和水混合溶剂中合成3-氨基-4硝基氧化呋咱的反应机理,给出了反应的势能曲线。结果表明,该反应主要分为两个阶段：3-酰基叠氮基-4硝基氧化呋咱脱N₂后进行Curtious重排产生异氰酸酯;异氰酸酯经水解、羟基扭转、CO₂的脱离形成产物。反应的决速步为CO₂的脱离,能垒为44kcal/mol。因此,加热是实现该合成反应的必要条件。水既绿色环保,又参与反应,是该反应的最佳溶剂。这些结果为3-氨基-4-硝基氧化呋咱的实验合成提供了必要的理论依据。     

3-叠氮基-4-酰氯肟基呋咱的合成及其热稳定性

以3-氨基-4-酰氨肟基呋咱为原料,经重氮化和叠氮化反应合成了新化合物3-叠氮基-4-酰氯肟基呋咱(3),总收率67％.其结构经1H NMR,13C NMR,15N NMR,IR及元素分析表征.热失重法研究结果表明,3具有良好的热稳定性.     

3,6-双(3′-氨基呋咱-4-基)-1,4-二氧杂-2,5-二氮杂环己-2,5-二烯的合成及晶体结构

以3-氨基-4-酰胺肟基呋咱(AAOF)为原料合成出了含能化合物3-氨基-4-酰氯肟基呋咱(ACOF)。用稀碱3%~5%Na2CO3水溶液处理,ACOF脱去一分子HCl生成不稳定中间体3-氨基-4-氰基呋咱的氧化物(ACFO),随后发生歧化反应,生成3,4-二(氨基呋咱基)氧化呋咱(BAFF)及其异构体3,6-双(3′-氨基呋咱-4-基)-1,4-二氧杂-2,5-二氮杂环己-2,5-二烯(BADDD)。用IR、MS1、H NMR1、3C NMR和元素分析对ACOF的分子结构进行了表征。分子和晶体结构测试表明,BADDD是一具有新颖化学分子结构的化合物。     

氨基呋咱氧化为氨基硝基呋咱的合成研究

研究开发了将氨基呋咱转化为氨基硝基呋咱新的高收率氧化方法. 采用甲烷磺酸为介质, 以过氧化氢、碱或碱土金属和胺为基的氧化物(如钨酸钠或过硫酸铵)混合物的新氧化体系[H2O2/CH3SO3H/Na2WO4或(NH4)2S2O8]代替以硫酸为介质的过氧化氢和过硫酸铵混合物氧化体系, 分别对3,4-二氨基呋咱(DAF)、3,3’-二氨基-4,4’-氧化偶氮呋咱(DAAF)和3,3’-二氨基-4,4’-偶氮呋咱(DAAzF)进行氧化, 以高于65%的产率获得了3-氨基-4-硝基呋咱(ANF)和3-氨基-3’-硝 基-4,4’-氧化偶氮呋咱(ANAF), 并以15%的收率合成得到新化合物3-氨基-3’-硝基-4,4’-偶氮呋咱(ANAzF). 研究表明甲烷磺酸/过氧化氢/碱或碱土金属和胺为基的氧化物混合物是制备同时含有氨基和硝基基团的系列呋咱化合物非常有效的氧化体系.     

3,4-二氨基呋咱基氧化呋咱异构体的合成与表征

将含能化合物3-氨基-4-氯肟基呋咱(ACOF)在低温下用稀碱处理后发生过渡中间体3-氨基-4-氰基呋咱氧化物(ACFO)的二聚关环反应合成了新型呋咱类含能化合物3,4-二氨基呋咱基氧化呋咱异构体(DAFF iso-m er),产率达66.3%。培养了DAFF isom er的单晶。用四圆单晶X-射线衍射仪,1H NMR,13C NMR,IR,MS及元素分析对其结构进行了表征。结果表明:DAFF isom er晶体属三斜晶系,空间群P-1,分子呈平面构型,层状晶体内存在分子内和分子间氢键,晶胞堆积层间不存在氢键。     

3，6-双（3’-氨基呋咱-4-基）-1，4-二氧杂-2，5-二氮杂环己-2，5-二烯的合成及晶体结构

以3-氨基-4-酰胺肟基呋咱（AAOF）为原料合成出了含能化合物3-氨基-4-酰氯肟基呋咱（ACOF）。用稀碱3％～5％Na2CO3水溶液处理，ACOF脱去一分子HCl生成不稳定中间体3-氨基-4-氰基呋咱的氧化物（ACFO），随后发生歧化反应，生成3，4-二（氨基呋咱基）氧化呋咱（BAFF）及其异构体3，6-双（3’-氨基呋咱-4-基）-1，4-二氧杂-2，5-二氮杂环己-2，5-二烯（BADDD）。用IR、MS、^1H NMR、^13C NMR和元素分析对ACOF的分子结构进行了表征。分子和晶体结构测试表明，BADDD是一具有新颖化学分子结构的化合物。     

Chemistry of Diamantane Part II. Synthesis of 3,5-Disubstituted Derivatives

Although chemical¹ and microbiological² methods for functionalisation of one or more of the bridgehead positions of diamantane are available, there have been no reports of substitution reactions at the methylene positions apart from that of the preparation of diamantanone (1)¹ by sulphuric acid oxidation of the hydrocarbon. There are three structural arrangements possible for a non-bridgehead disubstituted diamantane, but the synthetic route described here leads exclusively to 3,5-disubstituted derivatives.

When treated with sodium azide in cold methanesulphonic acid diamantanone (1) underwent a Schmidt fragmentation-recyclisation reaction of the type described by Sasaki et al.,³ yielding a compound which was not isolated but which was presumed to be the keto-mesylate (2) since treatment of the reaction mixture with sodium hydroxide caused a second fragmentation and the final product was the unsaturated acid (3) in 41% yield. The structure of the acid is based on the spectral data and on subsequent chemical transformations. The normal Schmidt rearrangement product, which is probably a mixture of the two possibilities (4) and (5), was also isolated in 50% yield. The unsaturated acid was readily recyclised under acidic conditions. Use of 96% sulphuric acid resulted in the formation of the lactone (6), but use of hot 50% sulphuric acid furnished 5ax-hydroxydiamantan-5-one (7) as the preponderant product (82%). That the hydroxyl-group occupied the axial config-     

Intramolecular reactions of benzylic azides with ketones: competition between Schmidt and Mannich pathways.

The Lewis acid-promoted reactions of benzylic azides with ketones can proceed by two major pathways. The azido-Schmidt reaction involves simple addition of azide to the ketone followed by rearrangement and ring expansion. In addition, benzylic azides can undergo prior rearrangement to afford iminium ions that can subsequently participate in a Mannich reaction. A series of ketones containing an alpha CH2(CH2)nCH(N3)Ph substituent (n = 1-3) was prepared to investigate the dependence of products on ketone ring size and tether length. For all ketones examined, good yields of bicyclic lactams arising from intramolecular Schmidt reaction were obtained when a four-carbon linker was used (n = 1 in the above formulation), but Mannich products predominated for the longer tethers examined (n = 2, 3).     

Synthesis of 3,4‐dihydro‐1(2H)‐isoquinolinonesxs

Approaches toward the preparative‐scale synthesis of target 3,4‐dihydro‐1(2H)‐isoquinolinones 1–3 are presented. Compounds 1 and 2 were prepared via a Schmidt rearrangement on easily obtained indanone precursors, but in low overall yield. A better method to make this class of compounds is exemplified by the large‐scale synthesis of 2 via a Curtius rearrangement sequence. Thus, high‐temperature thermal cyclization of an in situ formed styryl isocyanate from precursor 8 in the presence of tributylamine gave the corresponding 1(2H)‐isoquinolinone ( 9 ). Catalytic hydrogenation of 9 provided the desired 3,4‐dihydro‐5‐methyl‐1(2H)‐isoquinolinone ( 2 ) in 65 % overall yield. Similar reduction of a commercially available 5‐hydroxy‐1(2H)‐isoquinolinone precursor 10 followed by an O ‐alkylation/amination sequence gave target 3 in good overall yield. The route proceeding via the Curtius rearrangement is recommended for large scale synthesis of other 3,4‐dihydro‐1(2H)‐isoquinolinones. Only when deactivating substituents or sensitive functionality within the benzenoid ring render the high temperature ring closure of the intermediate isocyanate inefficient might a Schmidt rearrangement protocol be the method of choice.     

Synthesis of 3-alkyl-8-substituted- and 4-hydroxy-8-substituted-2,3,4,5-tetrahydro-1H-2-benzazepines

Based on the Schmidt reaction and an iodolactone ring expansion reaction, two different synthetic routes to substituted 2,3,4,5-tetrahydro-1H-2-benzazepines were developed. The Schmidt reaction on 2,3-dihydro-2H-1-naphthalenone ( 1 ) gave 3 , the product resulting from the alkyl group migration, as the major product instead of the tetrazole 2. This prompted the investigation of the Schmidt reaction on aromatic ketones 8 and 12. The product 9 due to alkyl group migration was the major product of the Schmidt reaction on 2-methyl-3,4-dihydro-2H-1-naphthalenone ( 8 ). The β-keto diester 12 gave a mixture of decarb-oxylated lactams after the Schmidt reaction. In this case, the lactam 13 resulting from the migration of the aromatic ring dominated over the other lactam 14. When lactam 14 was subjected to nitration, a single regioisomer was produced and transformed to the bromo alcohol 19. The other approach was based on the single pot ring expansion of the iodolactone 22 to the lactam 23 in the presence of methanolic ammonia. The iodolactone 22 was readily prepared from 2-allylbenzoic acid.     

Syntheses of aromatic polyketones and aromatic polyamide

High molecular weight aromatic polyketones were prepared from p- and m-phenoxybenzoic acid in polyphosphoric acid by heating the reaction mixture at 100°C. High molecular weight aromatic polyamide was derived from the polyketone obtained through Schmidt reaction or Beckmann rearrangement. The polyamide obtained by Schmidt reaction was found to have some regularity in an arrangement of its repeating units. The thermal stability of the polyketone and the polyamide were good.     

柠檬醛及中间体的合成

以异戊烯醛和异戊烯醇为原料,经异戊烯酸催化缩醛化反应得到3-甲基-2-丁烯醛二异戊烯基缩醛,再经磷酸二氢铵催化消除反应得到顺/反-异戊二烯基-3-甲基丁二烯醚,并进一步热重排获得柠檬醛。研究了缩醛化反应条件和消除反应条件对转化率的影响。结果表明,以0.3%异戊烯酸为酸性催化剂,70～75℃共沸脱水反应8 h,异戊烯醛的单程转化率达到63%～64%,处理后可得含量为97.5%的3-甲基-2-丁烯醛二异戊烯基缩醛,收率96.8%;以0.2%～0.5%磷酸二氢铵为催化剂,100～130℃,2.66 kPa下反应并及时将反应产物蒸出,处理后得到含量为95.9%的顺/反-异戊二烯基-3-甲基丁二烯醚,收率97.0%。顺/反-异戊二烯基-3-甲基丁二烯醚在120～130℃重排反应1 h,其反应产物柠檬醛含量97.5%,收率90.2%。     

钼酸催化简便合成D－葡萄庚酮糖

本文首次报道了在三氧化钼水溶液体系下催化碳链重排合成D-葡萄庚酮糖的简便方法。首先以D-甘露糖为原料在碘催化下进行异丙叉保护,产率90％;接着在碱催化下与甲醛水溶液亲核加成反应,在C-2上引入羟甲基侧链,产率40％;然后在酸性条件下异丙叉脱保护,产率92％;最后在三氧化钼水溶液催化下碳链重排合成葡萄庚酮糖,产率56％（总产率18％）。另外对2-C-羟甲基-D-甘露糖和葡萄庚酮糖的乙酰化产物进行了核磁氢谱表征。该方法原料易得,缩短了反应步骤,避免了昂贵金属试剂的使用,有较好的应用前景。     

Comparison of one-step and two-step methods of polyimidization and substitution effect in the synthesis of new poly(ester-imide)s with bulky pendent group

New naphthalene-ring containing ester diamines, as new monomers for the preparation of polyimides were synthesized via two successive reactions. Nucleophilic reaction of 3,5-dinitrobenzoylchloride with 1-naphthol and 2-naphthol in the presence of sodium hydroxide led to the preparation of 1- and 2-(3,5-dinitrobenzoyloxy)naphthalene, respectively. Next step was reduction of them by hydrazine hydrate/Pd-C to produce 1- and 2-(3,5-diaminobenzoyloxy)naphthalene. All the prepared compounds were characterized by common spectroscopic methods. These ester containing aromatic diamines with pendent naphthalene group were used to prepare soluble polyimide copolymers via two different methods: catalyzed one-step high-temperature polycondensation in m-cresol, and two-step polycondensation in NMP and subsequent chemical dehydration. The obtained poly(ester-imide)s were characterized and their properties were studied. One-step and two-step methods for the preparation of five-membered ring polyimides were compared. Polymers prepared through one-step method showed higher yield and inherent viscosities and therefore better physical properties.     

Studies on the benzo[1,2]cyclohepta[3,4,5-d,e]isoquinoline ring system

The syntheses of various oxidation states of the novel benzo[1, 2]cyclohepta[3, 4, 5-d, e]-isoquinoline ring system is described. The ring system was obtained by the Schmidt rearrangement, with exclusive alkyl migration, of 1, 6, 7, 11b-tetrahydro - 2H - dibenz-[cd,h]azulen-2-one and by a Bischler-Napieralski reaction of suitable derivatives of 10, 11-dihydro-5H-dibenzo[a, d]cycloheptene - 5 - methylamine. 4, 5, 10, 11 - Tetramethoxy derivatives of the new ring system were best prepared by a Pictet-Spengler reaction of the appropriate amine.     

胡椒酸己二胺的合成

以胡椒碱为起始原料,与KOH反应生成胡椒酸钾盐,经酸化后制得胡椒酸(2); 2与乙醇经酯化反应制得胡椒酸乙酯(3); 3与己二胺在金属钠催化下经氨解反应合成了胡椒酸己二胺(4),其结构经¹H NMR, ¹³C NMR和IR确证。合成4的最佳反应条件为：催化剂用量2 wt%, n(3):n(己二胺)=0.6, m(乙醇):m(3)=2.5,于65～75 ℃反应48 h,收率83.5%。该工艺在微型实验基础上放大十倍,收率大于79%。