2-(二硝基亚甲基)-4,5-咪唑烷二酮与甲醇的反应研究

以2-甲基咪唑为原料合成2-(二硝基亚甲基)-4,5-咪唑烷二酮(1), 收率为33.9% (16.8%文献值), 首次采用低碳液态醇实现1的开环反应, 产物为FOX-7. 对反应条件进行了优化, 对比了甲醇、甲酸、氨水三种亲核试剂的开环效果, 开环试剂为甲醇时, FOX-7收率为94.6%, 高于文献值(87.4%). 研究了1的络合性能, 合成了1的甲醇加合物2并进行了结构表征. 对开环反应机理和乙二酰脲的形成机理进行了探讨.     

Synthesis and thermal behavior of 4,5-dihydroxyl-2-(dinitromethylene)-imidazolidine (DDNI)

A novel energetic material, 4,5-dihydroxyl-2-(dinitromethylene)-imidazolidine (DDNI), was synthesized by the reaction of FOX-7 and glyoxal in water at 70 °C. Thermal behavior of DDNI was studied with DSC and TG-DTG methods, and presents only an intense exothermic decomposition process. The apparent activation energy and pre-exponential factor of the decomposition reaction were 286.0 kJ mol⁻¹ and 10^31.16 s⁻¹, respectively. The critical temperature of thermal explosion of DDNI is 183.78 °C. Specific heat capacity of DDNI was studied with micro-DSC method and theoretical calculation method, and the molar heat capacity is 217.76 J mol⁻¹ K⁻¹ at 298.15 K. The adiabatic time-to-explosion was also calculated to be a certain value between 14.54 and 16.34 s. DDNI presents lower thermal stability, for its two ortho-hydroxyl groups, and its thermal decomposition process becomes quite intense.     

Synthesis,Crystal Structure and Thermal Behavior of 4,5-Dimethoxy-2-(dinitromethylene)imidazolidine

A new energetic material, 4,5-dimethoxy-2-(dinitromethylene)imidazolidine(DMDNI), was synthesized by the reaction of 4,5-dihydroxyl-2-(dinitromethylene)-imidazolidine(DDNI) and methanol, and structurally characterized by single crystal X-ray diffraction. DMDNI crystallized in triclinic space group P, with crystal data a=0.4324(4) nm, b=1.3599(11) nm, c=1.7503(14) nm, α=77.406(14)°, β=84.494(15)°, γ=87.976(14)°, V=0.9997(14) nm³, Z=4, μ＝0.140 mm^-1, F(000)=488, D_c=1.556 g/cm³, R₁=0.0773 and wR₂=0.1574. Thermal decomposition of DMDNI was studied, and its thermal decomposition process was divided into two stages. The first stage was a mel- ting process and the second stage was an exothermic decomposition process. The enthalpy, apparent activation energy and pre-exponential constant of the exothermic decomposition reaction are -491.5 J/g, 142.3 kJ/mol and 10^14.24 s^-1, respectively. The critical temperature of thermal explosion is 162.47℃. DMDNI has a lower thermal stability than DDNI but it is close to that of 4,5-diacetoxyl-2-(dinitromethylene)-imidazolidine(DADNI).     

2-(2-Furyl)-1(3)H-imidazo[4,5-f]quinoline. Synthesis and electrophilic substitution reactions

2-(2-Furyl)-1(3)H-imidazo[4,5-f]quinoline was synthesized by the Weidenhagen reaction of quinoline-5,6-diamine with furfural. Its alkylation with methyl iodide in the system KOH-DMSO gave two isomeric N-methyl derivatives, 2-(2-furyl)-1-methyl-1H- and 2-(2-furyl)-3-methyl-3H-imidazo[4,5-f]quinolines, the latter prevailing. 2-(2-Furyl)-3-methyl-3H-imidazo[4,5-f]quinoline was brought into electrophilic substitution reactions: bromination, nitration, formylation, acylation, sulfonation. Depending on the reaction conditions, electrophilic attack could be directed at both furan ring and quinoline fragment.     

Synthesis of 1-(2-hydroxyphenyl)-2,4-imidazolidinedione derivatives through cyclic transformations of ethyl 2-oxo-3(2H)-benzoxazoleacetate derivatives

A series of ethyl 2-oxo-3(2H)-benzoxazoleacetate derivatives 2 have been synthesized. By reaction with ammonia, primary amines or hydrazine, these compounds 2 were transformed into 1-(2-hydroxyphenyl)-2,4-imidazolidinedione derivatives 4, 5 and 6 , respectively. Some of these new hydantoins 4 , treated with phosphorus oxychloride, gave 3H-2-oxoimidazo[2,1-b]benzoxazole derivatives 9 . Ethyl 2-oxo-3(2H)-benzoxazolepropionate ( 10 ) was prepared by a Michaël reaction of ethyl acrylate with 2-benzoxazolone ( 1a ). With 10 , no cyclic transformation was observed in the presence of ammonia or alkylamine.     

2-(2-Furyl)-5,6-dihydro-1(3)H-acenaphtho[4,5-d]imidazole. Synthesis and electrophilic substitution reactions

2-(2-Furyl)-5,6-dihydro-1(3)H-acenaphtho[4,5-d]imidazole was synthesized by the Weidenhagen reaction of acenaphthene-4,5-diamine with furfural. Alkylation of the title compound with methyl iodide in KOH-DMSO gave isomeric 1- and 3-methyl derivative, the latter being the major product. 2-(2-Furyl)-3-methyl-5,6-dihydro-3H-acenaphtho[4,5-d]imidazole was subjected to electrophilic substitution reactions (bromination, nitration, formylation, acylation, and sulfonation. Depending on the conditions, electrophilic attack was directed at the furan ring or acenaphthene fragment or both these.     

Synthesis of 4,5-diaryl-2-(n-methyl-3-carbazolyl)- and 4,5-diaryl-2-(n-methyl-1,2,3,4-tetrahydro-7-carbazolyl) imidazoyl radicals

A number of imidazoles were obtained by the reaction of substituted benzils with aldehydes of the carbazole series. Chlorobenzene solutions of the imidazoles take on a green coloration on oxidation with lead dioxide. The presence of free radicals in these solutions is confirmed by the ESR spectra and by the reaction with hydroquinone, diphenylamine, carbazole, and ,-diphenyl--picrylhydrazine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1550–1551, November, 1971     

5-(4-羟基苯基)-2,4-咪唑啉二酮酯类化合物的合成及其生物活性

在模拟AdSS酶天然抑制剂结构合成5-(4-羟基苄基)-2,4-咪唑啉二酮酯系列化合物的基础上,为优化其结构,以5-(4-羟基苯基)-2,4-咪唑啉二酮为中间体,合成了28个未见文献报道的5-(4-羟基苯基)-2,4-咪唑啉二酮羧酸酯类化合物,它们的结构均经IR,1HNMR和元素分析表征.初步生物活性测试表明目标化合物5-(4-羟基苯基)-2,4-咪唑啉二酮对叔丁基苯甲酸酯(2i)和2-噻吩酸酯(3b)在浓度200μg/mL时对拟南芥生长抑制率达70%..     

STRUCTURE OF 3-(IMIDAZOLIDIN-2-YLIDENE)-4,5-DIMETHYL-4,5-DIHYDRO-2(3H)-FURANONE, C_9H_(14)O_2N_2

<正> Mr=182.25, Orthorhombic, Pna21, a=10.698(4), b=9.779(4), c=8.872(5)A, Z=4, V=928.1(7)A3, Dx=1.3 Mgm-3, λ(MoKα)=0 . 71069A, μ(MoKα) = 1.0cm-1, F(000)=392, room temperature, R=0.034 for 637 reflections. The lactone ring and imidazolidine ring are twisted mutually by 12.3°. The two methyl groups are in cis positions relative to the lactone ring. There exist intramolecular and intermolecular hydrogen bonds in the structure.