Synthesis of 3,11-Dioxatetracyclo[6.3.0.02,6.05,9]undecanes and 3,5,7-Trioxapentacyclo[7.2.1.02,8.04,11.06,10]dodecane

The synthesis of 3,11-dioxatetracyclo[6.3.0.0^2,6.0^5,9]undecanes has been accomplished from furans in a short sequence by iodine-induced cyclization reaction. The application of iodine-induced cyclization reaction for the synthesis of 3,5,7-trioxapentacyclo[7.2.1.0^2,8.0^4,11.0^6,10]dodecane itself was also demonstrated.     

Synthesis of Novel Triacetal Trioxa-Cage Compounds by Ozonolysis of Bicyclo[2.2.1]Heptenes and Bicyclo[2.2.2]Octenes

Several novel triacetal trioxa-cage compounds 11a-11g, 13, 15, 17 and 19 are synthesized in a short sequence. Ozonolysis of bicyclo[2.2.1]heptenes 4a-4c, 8a-8c, 10a, 10b and 14 in dichloromethane at ?78 °C followed by reduction with dimethyl sulfide gave triacetal oxa-cages 11a-11g, 13 and 15 in moderate yields, respectively. Ozonolysis of bicyclo[2.2.2]octenes 16 and 18 under the same reaction conditions gave triacetal oxa-cages 17 and 19 in moderate yields, respectively.     

吸热型碳氢燃料五环[6.3.1.02,7.03,5.09,11]十二烷的催化合成

吸热型碳氢燃料是为解决高超音速飞行器冷却难题而研制的一类新型燃料[1].其最突出的优点是作为性能优良燃料的同时,还能满足飞行器的冷却要求,可减小飞行器的体积和质量,提高飞行速度,是高超音速飞行器的理想燃料.其冷却及燃烧原理是:大分子碳氢燃料在进入燃烧室前吸收飞行系统产生的热量气化、再裂解为小分子,产物进入燃烧室燃烧并释放出吸收的热量,从而在对系统冷却的同时提高了能源的利用率,减少了高超音速飞行器的负载,满足了燃烧室壁面和机身温度控制等要求.因此,吸热型碳氢燃料已成为各国研发的热点,但目前研究多限于原油调配燃料的催化裂解和脱氢,对新燃料的合成报道较少[2,3].……     

Chemical Transformations of 4,6-Dimethyl-2β-hydroxy-8-oxo-3,5,7-trioxatetracyclo[7.2.1.04,11.06,10]dodecane

Reactions of 4,6-dimethyl-2β-hydroxy-8-oxo-3,5,7-trioxatetracyclo-[7.2.1.0.^4,11.0^6,10]dodecane 1 with nucleophiles have been studied. Reaction of 1 with alcohols, triethylsilane, allyltrimethylsilane, and methylthiotrimethylsilane in CH₂Cl₂ in the presence of TiCL₄, gave the substitution products 2,7a, 7b, and 7c in 80-90% yields. The substitution reaction took place chemoselectively on the hemiacetal group of I. Reaction of 1 with cyanotrimethylsilane in CH₂C1₂ in the presence of TiCL₄, gave compound 8 and the rearranged product 9. The structure of 9 was proven by X-ray analysis.     

Synthesis and properties of 1,4,9-triazaspiro[5,5]undecane and 3,7,11-triazaspiro[5,6]dodecane

Bromination of 1-methylpiperidine-4-carboxaldehyde gave 4-bromo-1-methylpiperidine-4-carboxaldehyde hydrobromide which was used to synthesize 1,4,9-triazaspiro[5,5]undecane and 3,7,11-triazaspiro[5,6]dodecane. Cyanoethylation and alkylation with various alkyl halides gave their mono- and di-substituted derivatives. The side chain nitrile group was reduced and the hydrazide was obtained from the ester analog.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1673–1676, December, 1986.     

Tricyclo[4.2.2.22,5] dodecane and Tricyclo [4.2.2.12,5]undecane. Preliminary communication

A synthesis of tricyclo [4.2.2.2^2,5]dodecane ( 19 ), a novel tricyclic C₁₂H₂₀ compound, is described. The key intermediate ketone 13 was prepared either from the C₁₀-photodimer 1 of cyclopentadienone or the C₁₁-cycloaddition products 11 and 12 . 13 was also transformed to tricyclo [4.2.2.1^2,5]undecane ( 8 ).     

Domino Reaction for the Synthesis of Highly Functionalized Triazatricyclo[6.2.2.01,6]dodecane

A simple and highly efficient protocol has been developed for the synthesis of triazatricyclo[6.2.2.0^1,6]dodecane-9,12-dione (TATCD) derivatives. Use of metal hydroxide catalyst in the presence of protic solvent plays a key role in these reaction transformations. Mechanistic studies specify that the proposed mechanism proceeds only via aldol reaction, condensation, cyclization, and dehydration to form the desired product. This current protocol provides several advantages such as use of a readily available precursor, consumption of less energy, short reaction time, moderate to good yields, and convenient workup.     

Synthesis and Crystal Structure of 2,6,8,12-Tetraacetyl- 2,4,6,8,10,12-hexaazatetracyclo[5.5.0.05,9.03,11]dodecane

1 INTRODUCTION Hexanitrohexaazaisowurtzitane (HNIW or CL-20),the fourth generation in energetics, is the most power-ful explosive available for military applications inboth plastic bonded explosive (PBX) compositionsand propellant. To date, a number of nitrolyzable pre-cursors to CL-20 have been investigated, includingisowurtzitane cages substituted with acetyl, formyland nitroso groups and partly unsubstituted cages.Only the synthetic route of CL-20 using 2,6,8,12-te-traacetyl-2,4,6…     

A Novel Synthesis of Imidazo[1,2-c]pyrimidines

A new method for the preparation of imidazo[1,2-c]pyrimidines is described.     

Synthesis of tricyclo[6.2.2.0]dpdecane and tricyclo[6.3.1.0]dodecane ring systems involving intramolecular cyclisation of diazomethyl ketones

2,8-Dimethyltricyclo[6.2.2.0^1,6]dodeca-2,5-diene-4,9-dione ( ), 2,9-dimethyltricyclo [6.3.1.0^1,6]dodeca-2,5-diene-4,10-dione ( ) and 2-methyltricyclo[6.3.1.0^1,6]dodeca-2,5-diene-4,10-dione ( ) have been synthesised for entry into the ring systems of a few tetracyclic diterpenes.     

新型色满酮并环己烷螺环氧化吲哚类化合物的合成

以色酮 氧化吲哚合成子与硝基苯乙烯,在催化剂DBU作用下,在二氯甲烷中发生Michael/Michael加成环化反应,合成了9个未见文献报道的新型色满酮并环己烷螺环氧化吲哚类化合物3a~3i产率72%~87%, dr值4/1~2/1, 其结构经¹H NMR, ¹³C NMR和HR-MS（ESI-TOF）表征确定。     

新型甾体类吡唑并[1,5-a]嘧啶化合物的合成

以雄烯二酮为原料,制得16E-苯亚甲基甾体衍生物（1）; 1和3-氨基吡唑反应合成了D-环吡唑并[1,5-a]嘧啶基修饰的雄烯二酮类衍生物,收率达72%,其结构经¹H NMR, ¹³C NMR和HR-MS(ESI)表征。     

硫代丁内酯拼接吡唑啉酮双螺环化合物的合成

以3-异硫氰酸酯取代的硫代丁内酯1为合成子,在有机催化剂DABCO作用下,与各种取代的吡唑啉酮烯烃2发生Michael加成与环化反应,获得了9个未见文献报道的新型硫代丁内酯拼接吡唑啉酮双螺环化合物3a～3i,产率70%～77%,dr 2/1～9/1,其结构经¹H NMR,¹³C NMR和HR-MS(ESI-TOF)表征,通过单晶进一步确定了化合物3c的构型。该类化合物含有螺环丁内酯和螺环吡唑啉酮生物活性骨架,对医药行业具有重要的潜在价值。     

新型富勒烯-吖啶二酮衍生物的合成

通过环加成、水解和酯化三步反应在富勒烯上引入吖啶二酮结构合成了一种新型的富勒烯-吖啶二酮衍生物,其结构经UV,1H NMR,13C NMR,IR和MS表征。