Synthesis of 3-Azido-5-amino-1,2,4-triazole

3-Azido-5-amino-1,2,4-triazole was obtained from 3,5-diamino-1,2,4-triazole in two ways: by partial diazotization-substitution directly in the substrate or at its primarily nitrosation, and also with the use of direct or indirect protection of an amino group with subsequent conversion into azido compound followed by deprotection.     

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.     

One-Pot Synthesis of 2-Aryl-4-methyl-3-nitro-2,3-dihydro-1,5-benzothiazepines

Russian Journal of Organic Chemistry -     

3-乙酰基-2,3/2,5-二氢-1,5-苯并硫氮杂卓的选择性合成及其互变异构

研究了温度、时间等因素对合成反应的影响, 发现亚胺型杂卓4和烯胺型杂卓5分别为速度控制产物和平衡控制产物, 并且实现了两种互变异构体的选择性合成. 用核磁共振法研究了溶剂、酸碱度对4, 5互变异构的影响, 发现两种异构体在CD₃OD, DMSO-d₆, C₆D₆以及精制的CDCl₃中比较稳定, 在未精制的CDCl₃中容易发生互变及开环反应, 形成3, 4, 5的平衡混合物, 并以4为主要组分. 4, 5在酸中不稳定, 但在弱碱(吡啶)中能稳定存在. 采用密度泛函理论方法在B3LYP/6-31G基组水平上对四组(八种)不同取代基的上述异构体进行了几何优化和计算. 结果表明, 烯胺型杂卓5比亚胺型杂卓4稳定, 理论计算结果与实验结果基本一致.     

3-叠氮-4-氨基呋咱的合成及其晶体结构

以乙二醛和盐酸羟胺为原料,经加成,闭环和氮化反应制备了新型含能化合物3-叠氮-4-氨基呋咱(AAF),其结构经NMR,IR,X-射线单晶衍射仪及元素分析表征。AAF晶体属单斜晶系,P21/c空间群,晶胞参数为:a=0.5329(16)nm,b=1.0722(3)nm,c=0.8492(2)nm,α=90.00°,β=99.03(2)°,γ=90.00°,V=0.5046(2)nm3,Dc=1.660g.cm-3,Z=4,F(000)=256,μ(MoKα)=0.138mm-1。最终偏离因子R1=0.0768,wR2=0.1983。AAF晶体存在分子间氢键。     

4-取代苯基-2,3-二氢-1,5-苯并硫氮杂(艹卓)-3-乙酸甲酯及其钠盐的合成

以不同取代的苯为原料,经Friedel-Crafts酰基化、酯化、Mannieh反应得到3-亚甲基-4-取代苯基-4-氧代丁酸甲酯(1a～1g),再与2-氨基苯硫酚进行Michael加成和分子内环和,合成了一系列4-取代苯基-2,3-二氢-1,5-苯并硫氮杂草-3-乙酸甲酯并水解了其中的4个化合物,产物的结构经IR,1H NMR,MS和元素分析确证.     

A New Method for Synthesis of Methyl 3—Azido—3—deoxy—2—O—mesyl—5—O—benzoylxylofuranoside

A new method for synthesis of 3-azido-3-deoxyxylofuranoside was described. D-ribose was methylated, then treated with methanesulfonyl chloride to give Ⅱ.Ⅱ was selectively replaced by benzoate at the 5-position to give Ⅲ. All these processes gave good yields. Ⅲ was treated with sodium azide to afford Ⅳ, whose structure was determined by ^1H NMR and ^13C NMR.     

6-叠氮-6-脱氧凝聚多糖的选择性一步合成

由于含氨基或氨基衍生物的多糖对细胞表面及细胞之间的生理功能具有特殊的作用,在研究细胞之间有效作用的促进剂和抑制剂方面具有潜在的应用价值,因而叠氮化多糖作为制备氨基多糖及其衍生物的中间体受到人们的重视,含乙酰氨基的天然多糖（如Chitin）和氨基多糖（如Chitosan）,由于具有抗感染和医治创伤作用,广泛用于医疗领域,含氨基和硫酸酯的多糖肝素有很好的抗凝血作用和降血脂活性,已用于动脉硬化病的治疗,我们发现含乙酰氨基的硫酸化核聚糖具有很高的抗艾滋病毒活性,而且没有抗凝血的副作用。     

A Practical Synthesis of 3-Oximido-substituted-1,5-diazacycloheptane Dihydrochloride

From 3-hydroxyl-1, 5-diazacycloheptane dihydrobromide, we have synthesized a series of new compounds, 3-oximido-substituted-l, 5-diazacycloheptane dihydrochloride, in high yields. The experimental operations are convenient and mild.     

Synthesis of 1,5-diaryl-3-tetrazolylformazans

Several 1,5-diphenyl-3-tetrazolylformazans were synthesized by reaction of 1,5-diaryl-3-cyanoformazans with sodium azide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1679–1681, December, 1977.     

Synthesis of trans-thienyl-3-ethoxycarbonyl-2,3-dihydro[1,5]benzothiazepin-4(5H)-ones

A series of trans-thienyl-3-ethoxycarbonyl-2,3-dihydro[1,5]benzothiazepin-4(5H)-ones 6-8 was synthesized from thienylmethylidenemalonates 3a-3c and 2-aminobenzenethiol 3d in the presence of triethylamine hydrochloride at 160°. The [1,5]benzothiazepines 6-8 were alkylated using 2-dimethylaminochloroethane, 3-dimethylaminochloropropane and 3-(N-piperidino)chloropropane in order to obtain the corresponding 5-aminoalkylbenzothiazepinones 9-14 .     

新型2,3-二氢-3-芳亚甲基-4-芳基-1,5-苯并硫氮杂革的合成及表征

在盐酸和乙醇存在下,苯乙酮、多聚甲醛以及N,N-二甲基甲酰胺进行Mannich反应,得到了Mannich碱;将其和1,2,4-三唑在水中反应,得到含有1,2,4-三唑的苯丙酮;然后,在哌啶和甲苯存在下,苯丙酮和苯甲醛进行羟醛缩合,得到一系列含有1,2,4-三氮唑的查尔酮;最后,在三氟乙酸的催化下,查尔酮和邻氨基硫酚发生亲核取代反应,然后脱水缩合,合成了一系列2,3-二氢-3-芳亚甲基-4-芳基-1,5-苯并硫氮杂革.其结构经IR,1H NMR,MS及元素分析确证.     

Synthesis of 4-Pyridyl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones

4-Pyridyl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones were obtained by the condensation of ethyl nicotinoyl- or isonicotinoylacetates with o-phenylenediamine. Alkylation of the pyridylbenzodiazepinones with ethyl iodide under phase-transfer catalysis conditions occurred at the amide nitrogen of the heterocycle, whereas in nitromethane it occurred at the nitrogen of the pyridine substituent. Bromination with N-bromosuccinimide occurred at position 3 of the heterocycle. Pyridyldibenzodiazepinones underwent thermal rearrangement to derivatives of vinylbenzimidazole.     

Synthesis of 4-styryl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones

4-Styryl-2,3-dihydro-1H-1,5-benzodiazepin-2-ones were synthesized and their structure was established by means of PMR spectra and mass spectroscopy.Dnepropetrovsk State University Named in Honor of 300th Anniversary of the Reunion of Ukraina and Russia, Dnepropetrovsk 320625. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1560–1562, November, 1987.     

3-Phenylazo-4-methyl-2,3-dihydro-1,5-benzodiazepin-2-ones

The corresponding azo derivatives, which exist primarily in the azo form, are formed in the reaction of 2,3-dihydro-1,5-benzodiazepin-2-ones with diazonium cations. The hydrazone form of these compounds is possible in solutions of acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1558–1560, November, 1978.     

2-叠氮基-1,1-二硝基乙基取代苯衍生物的合成

详细研究了2-叠氮基-1,1-二硝基乙基取代苯衍生物的合成方法。由苯基二硝基甲烷钾盐经羟甲基化,磺酰酯化和叠氮化得到目标化合物:3-硝基-(2-叠氮基-1,1-二硝基乙基)苯(4b),4-硝基-(2-叠氮基-1,1-二硝基乙基)苯(4c),m-二(2-叠氮基-1,1-二硝基乙基)苯(10)和p-二(2-叠氮基-1,1-二硝基乙基)苯(15)。     

Synthesis and properties of 2,2,4-trisubstituted 2,3-dihydro-1H-1,5-benzodiazepines

General conditions for the condensation of acetylarenes with o-phenylenediamine hydrochloride, leading to the formation of 2,4-diaryl-2-methyl-2,3-dihydro-1H-1,5-benzodiazepines, have been worked out. It has been shown that this reaction is an equilibrium one, that the equilibrium is extremely sensitive to the amount of water in the reaction medium, and that the process takes place with the formation of bisazomethines as intermediates. The UV, IR, and PMR spectra and the dipole moments of the heterocyclic compounds obtained are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 126–131, January, 1984.