2-氨基-3-硝基吡啶和2-氨基-5-硝基吡啶的CI-MS-MS分析

二氨基-3-硝基吡啶和2_氨基-5-硝基吡啶的EI—MS质谱图接近，单纯通过Ⅱ-MS质谱图较难区分这两种异构体，作者以甲烷为反应气对2-氨基-3-硝基吡啶和2-氨基-5-硝基吡啶进行化学电离，并利用离子阱质谱的串联质谱技术在离子阱内以He作碰撞气进行碰撞诱导裂解，所得的CI—MS—MS质谱图表明，两者之间存在明显的差别，可用于2-氨基-3-硝基吡啶和2-氨基一5一硝基吡啶的鉴别。     

2-氨基-3-硝基吡啶和2-氨基-5-硝基吡啶的EI/MS/MS分析

2 氨基 3 硝基吡啶和2 氨基 5 硝基吡啶的一级质谱图接近,单纯通过一级质谱图较难区分这两种异构体,利用离子阱质谱的串联质谱技术对2 氨基 3 硝基吡啶和2 氨基 5 硝基吡啶在离子阱内以He作碰撞气进行碰撞诱导裂解,所得的二级质谱图表明,两者之间存在明显的差别,可用于2 氨基 3 硝基吡啶和2 氨基 5 硝基吡啶的鉴别。     

5-氮杂吲哚的合成工艺研究

本文以3-甲基-4-硝基氮氧化吡啶为起始原料,经两步反应合成5-氮杂吲哚。通过单因素实验法研究了温度、N,N-二甲基甲酰胺(DMF)、N,N-二甲基甲酰胺二甲缩醛(DMA)、铁粉等因素对反应的影响。较佳工艺条件下,产品按3-甲基-4-硝基吡啶氮氧化物计总收率为88.57%,较文献[1,2]提高了6%。通过熔点测定、1H NMR对最终产物进行了结构表征。此工艺的优点在于操作简单,反应时间短,成本低,收率高,适合于工业化生产。     

一种有效制备2-氨基-3,5-二硝基-6-氯吡啶及其衍生物的方法

研究了2-氨基-3,5-二硝基-6-氯吡啶(4)及其衍生物的制备新方法.以廉价易得的2,6-二氯吡啶(1)为起始原料,通过硝化、氨化、硝化反应步骤得到中间体2-氨基-3,5-二硝基-6-氯吡啶(4),再与氨、叠氮化钠等亲核试剂反应分别得到2-氨基-3,5-二硝基吡啶-6-取代衍生物5~7.研究表明该方法具有原料便宜易得、后处理操作简单和产品纯度高等优点.     

5-氨基-6-硝基-[1,2,5]噁二唑并[3,4-b]吡啶-1-氧化物的合成新方法

以2,6-二氯吡啶为起始原料, 经肼基化、还原、硝化、Nietzki-Dietschy环合4步反应得到5-氨基-6-硝基-[1,2,5]噁二唑并[3,4-b]吡啶-1-氧化物。 结合反应机理讨论了还原、硝化、Nietzki-Dietschy环合反应的影响因素,获得了合成5-氨基-6-硝基-[1,2,5]噁二唑并[3,4-b]吡啶-1-氧化物的最佳工艺条件,目标产物的总收率为59.2%。 用1H NMR、MS和IR谱对5-氨基-6-硝基-[1,2,5]噁二唑并[3,4-b]吡啶-1-氧化物的结构进行了表征。     

4-氯-2-甲基吡啶并[3,2-d]嘧啶的合成

吡啶并嘧啶类衍生物具有较好的生物活性,4-氯-2-甲基吡啶并[2,3-d]嘧啶是一种重要的医药中间体,已报道的合成方法成本较高且操作繁琐,不适合工业化生产.本文以2-氯-3-硝基吡啶为起始原料,经取代、还原、环合等5步反应得到目标化合物,产物结构经1 H NMR,13C NMR和MS确证,总收率为33％.该路线具有成本低、反应条件温和、后处理简单、副产物少、收率较高等优点,是一条适合工业化生产的合成路线.     

1-(4-硝基苯基)-3-(5-溴-吡啶)-三氮烯的合成及其与镍显色反应的研究

三氮烯试剂是测定镉、汞、锌、镍、铜等金属离子的高灵敏显色试剂[1~3],其中含氮杂环的三氮烯试剂的显色效果更佳[4~6]。为改善试剂的分析性能,提高此类试剂的灵敏度和选择性,合成了未见报道的1-(4-硝基苯基)-3-(5-溴-吡啶)-三氮烯(NPBPDT),并对其与镍的显色反应进行了研究。结     

2-氨基-6-甲氧基-3-硝基吡啶的合成

以2-氯-5-硝基吡啶为原料,经甲氧基化反应得2-甲氧基-5-硝基吡啶(2),2再与液氨/高锰酸钾进行氨化反应制得2-氨基-6-甲氧基-3-硝基吡啶,总收率77%。     

3-甲氧基-5-氯-2,6-二硝基吡啶的合成及晶体结构

以3,5-二氯吡啶为原料, 通过取代、硝化合成了3-甲氧基-5-氯-2,6-二硝基吡啶, 由X射线单晶衍射, IR, ¹H NMR, MS及元素分析对其进行了表征. 晶体结构分析表明, 化合物为单斜晶系, 空间群P2₁/n, 晶胞参数a＝0.66490(13) nm, b＝1.0842(2) nm, c＝1.2715(3) nm, β＝95.55(3)°, V＝0.9123(3) nm³; Z＝4, D_c＝1.701 g•cm^－3; F(000)＝472; μ＝0.426 mm^－1.     

2-羟基和4-羟基-3,5-二硝基吡啶铅盐的热行为、分解机理、非等温分解反应动力学及其在推进剂中的应用

在程序升温条件下 ,用DSC ,TG ,慢速裂解 /傅里叶红外 ,研究了 2 羟基 3 ,5 二硝基吡啶铅盐 ( 2HDNPPb)和 4 羟基 3 ,5 二硝基吡啶铅盐 ( 4HDNPPb)的热行为、机理和动力学参数 ,提出了它们的热分解机理 ,计算了热爆炸临界温度 ,考察了它们对RDX改性双基推进剂的催化效果 .结果表明 :2HDNPPb和 4HDNPPb主放热分解反应的表观活化能和指前因子值分别为 2 5 2 .3 4kJ·mol-1,10 19.3 0 s-1和 187.3 9kJ·mol-1,10 13 .74s-1.由加热速率 β→ 0的DSC曲线的初始温度 (Te)和峰温 (Tp)算得 2HDNPPb和 4HDNPPb的热爆炸临界温度值分别为 3 2 7.64 ,3 3 6.5 7和 3 2 3 .90 ,3 3 3 .96℃ .2HDNPPb的热稳定性优于4HDNPPb .0 .1MPa时 ,它们的放热分解过程动力学方程可表示为 :　　对 2HDNPPb　　dα/dT =10 2 0 .48( 1-α) [-ln( 1-α) ] 3 /5e-3 .0 3 51× 10 4 /T　　对 4HDNPPb　　dα/dT =10 15.0 0 ( 1-α) [-ln( 1-α) ] 2 /3 e-2 .2 53 9× 10 4 /T对含RDX改性双基推进剂 ,它们都具有催化燃烧和降低压力指数的作用 .2HDNPPb的催化效果明显优于 4HDNPPb .羟基在分子中所处的不同位置是影响热稳定性和催化效果的主要因素     

Reactions of 3-nitro-1,2,4-triazole derivatives with alkylating agents. 5. Selective synthesis of 1,4-dialkyl-and 1,4,5-trialkyl-3-nitro-1,2,4-triazolium salts from 1-alkyl-and 4,5-dialkyl-3-nitro-1,2,4-triazoles and dialkyl sulfates

Interaction of N₍₁₎-alkyl-substituted 3-nitro-5-R-1,2,4-triazoles with dialkyl sulphates proceeds selectively and results in the respective salts of 1,4-dialkyl-, 1,4,5-trialkyl-3-nitro-1,2,4-triazoliums. The reaction of N₍₄₎-alkyl-substituted 3-nitro-5-R-1,2,4-triazoles yields the mixtures of the salts of 1,4-dialkyl-, 1,4,5-trialkyl-3-nitro-1,2,4-triazoliums and 1,4-dialkyl-, 1,3,4-trialkyl-1,2,4-triazol-5-ones with predominance of quaternary salts. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 927–934, June, 2007.     

Reaction Of 3-Nitro-1,2,4-triazolederivatives with Alkylating Agents. 1. Alkylation in the Presence of Alkali

Alkylation of 3-nitro-1,2,4-triazole and 5-methyl-3-nitro-1,2,4-triazole with dialkyl sulfates or alkyl halides in the presence of alkali proceeds with a low selectivity for the alkylating agent with the formation of two regioisomers at the N₍₁₎ and N₍₂₎ atoms of the heterocycle. Depending on the reaction conditions the proportion of the N₍₂₎ isomer was 14.6-33.8%. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1020–1025, July, 2005.     

AGNTO的制备和分子结构

通过3-硝基-1,2,4-三唑-5-酮（NTO）与氨基胍重碳酸盐反应制备NTO氨基胍盐,并用X射线衍射、元素分析、红外光谱对其进行了表征.晶体属于单斜晶系,空间群为P21/n.晶体学参数为：a=0.67870(10)nm, b=2.7915(4)nm, c=1.2739(2)nm; β =96.930(10) V=2.3959(6)nm3, Z=12, Dc=1.698 g•cm －3, μ( Mo K )=1.47 cm －1, F(000)=1272.晶体结构经全矩阵最小二乘法修正,最终偏离因子R=0.0352, wR =0.0718.该盐是一种具有广泛应用前景的产气剂材料.     

Reactions of 3-nitro-1,2,4-triazoles with alkylating agents. 3. Alkylation of a neutral heterocycle by diethyl sulfate

The reaction of 3-nitro-5-R-1,2,4-triazoles with diethyl sulfate gives 1-ethyl-3-R-5-nitro-, 4-ethyl-3-nitro-5-R-1,2,4-triazoles, 1,4-diethyl-, 1,4-diethyl-3-methyl-1,2,4-triazol-5-ones, and 1,4-diethyl-3-nitro-5-R-1,2,4-triazolium salts. When compared with the use of dimethyl sulfate as alkylating agent the ethylation products have a markedly increased fraction of triazolones (up to 30–37%) and a somewhat lowered yield of nitrotriazolium salts (up to 6–10%). The reaction time is increased by an order. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1378–1381, September, 2006.     

Molecular and crystal structures of 5,7-dichloro-4-nitro-2,1,3-benzoxadiazole and products of its reactions with secondary amines

The molecular and crystal structures of 5,7-dichloro-4-nitro-2,1,3-benzoxadiazole and products of its reactions with hexamethyleneimine and dimethylamine were established by X-ray diffraction analysis. The molecular structures and the systems of hydrogen bonds in the crystals of these compounds are discussed.     

The Benzoylation of 6-Methyluracil and 5-Nitro-6-methyluracil

6-Methyluracil and 5-nitro-6-methyluracil react with variable molar quantities of benzoyl chloride in acetonitrile-pyridine at room temperature to give I-N, 3-N-dibenzoyl-6-methyluracil 3b and l-N-benzoyl-5-nitro-6-methyluracil 4b. The reactive rates of debenzoylation of 3b and 4b were investigated.     

Electrochemical reduction of 5-halo-5-nitro-1,3-dioxanes and 2-halo-2-nitro-1,3-propanediols

The character of the first stage of reduction of 5-X-5-nitro-1,3-dioxanes 1—10 and 2-X-2-nitro-1,3-propanediols 11 and 12 is independent of the nature of halogen (X = Br, Cl) and substituents in position 2 of the dioxane cycle. The transfer of two electrons to a molecule of compound 1—12 is accompanied by the anionoid elimination of halogen and formation of the anion of nitronic acid. The high mobility of halogen is mainly due to the acceptor nitro group capable of further transformations in the -position to halogen. The direction of further reduction involving the electron transfer to electrochemically active groups in the aromatic fragment of the molecule is determined by the nature of these groups. Chloro-, bromo-, and iodophenyl-substituted derivatives 4, 5, and 8—10 are reduced as typical halobenzenes. In the case of nitrophenyl-substituted compounds 3 and 7, the dioxane cycle opens to form dianions of p- and m-nitrobenzaldehydes along with the reduction of the nitroso group through the stages of formation of the radical anion and radical anion of the nitroso group. The radical anions of the nitro and nitroso derivatives were identified by ESR.     

气相色谱法测定DIANP纯度标准物质中有机杂质

建立了气相色谱法测定1,5-二叠氮基-3-硝基氮杂戊烷纯度标准物质中微量二氯甲烷、二甲基亚砜、1-羟基-5-叠氮基-3-硝基-3-氮杂戊烷含量的方法.样品以四氢呋喃作为溶剂进行溶解,采用RTX-1毛细管色谱柱(30 m×0.32 mm,5μm)和程序升温进行分离,外标法定量.线性相关系数(r)为0.999 0～0.99...     

4-氨基-5-硝基-1,3-二氟苯重氮化反应机理研究

以4-氨基-1,3-二氟苯、乙酸酐和浓硝酸等为原料,合成了4-乙酰基-5-硝基-1,3-二氟苯,并且采用FT-IR和^1H NMR对产物进行了表征．采用量子化学方法,探讨了重氮化反应过程中重氮盐形成的微观机理,采用密度泛函理论（Density Functional Theory）在B3LYP／6．311G^＊＊水平下搜索得到反应路径,并对各中间体、过渡态和产物进行几何优化、振动频率分析和标准热力学函数计算;反应路径经过IRC验证．在MP2／6．311G^＊＊水平上对所有中间体、过渡态和产物进行更精确的能量校对．     

3-硝基-1,3,4-三唑-5-酮金属(Li,Na, Pb,Cu)盐的制备反应热动力学

在常压、298.15 K条件下, 用RD496-2000微量热仪开展了3-硝基-1,3,4-三唑-5-酮(NTO)金属(Li, Na,Pb, Cu)盐制备反应的热动力学研究, 得到了反应过程中的热力学参数(活化焓、活化熵和活化自由能), 速率常数和动力学参数(活化能、指前因子和反应级数), 还得到了在25-40℃范围内NTO金属(Li, Na, Pb, Cu)盐制备反应过程的反应焓. 结果表明, NTO金属(Li, Na, Pb, Cu)盐的制备反应较容易发生. 基于Hess定律, 得到了Δ_fH_m⁰ (Li(NTO)·2H₂O, aq, 298.15 K)和Δ_fH_m⁰ (Na(NTO)·H₂O, aq, 298.15 K)的值.