| Cage-like hydrocarbons are an important class of organic compounds with spatialstructure and unique properties, and they have a wide range of applications in the high-energy fuel, medicinal, fine chemicals, materials, and many other fields. Therefore, thepaper studied on the synthesis of cage-like hydrocarbons and the direct C-H functiona-lization and got some new research results.Pentacyclo[5.4.0.02,6.03,10.05,9]undecane (PCU) has a high density and high heat ofcombustion, it could be used as high-energy fuel additives. In order to improve theconventional synthetic process, pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione (PCUD)was synthesized by the one-pot reaction of cyclopentadiene and benzoquinone in a highyield. Due to the high toxicity, high risk, inconvenient operation of high concentrationhydrazine hydrate, lower concentration hydrazine hydrate was used as Wolff-Kishner-Huang reduction reagents in this paper. Then the affect on reduction reaction of the amountof alkali, hydrazine hydrate and reaction time were studied by means of orthogonalexperiment, and the optimum conditions were determined as: n(KOH): n(PCU)=8:1,n(N2H4·H2O): n(PCU)=4:1and reaction time4h. This methodology overcomesshortcomings of conventional synthesis such as severe conditions, low yield and poorselectivity.The direct Csp3-H functionalization, which dramatically simplifies synthetic routes,has been drawing extensive interest in the feld of synthesis. In the paper, the amination ofcage-like alkanes catalyzed by Lewis acid-polyhalogenated methane was studied, and aconversion of Csp3-H to Csp3-N was achieved by one-step. The effects of Lewis acids,polyhalogenated methane, temperature, time and substrates molar ratio was studied, and theoptimum conditions of synthesizing monosubstituted cage-like hydrocarbons were obtainedas: AlBr3(2eq), CBr4(1eq), adamantane (1eq), azole/amine (1eq), temperature (0oC) andreaction time (1h). It is a general and simple method for the direct amination ofadamantanes, norbane and PCU, meanwhile a series of amination products of azoles,arylamines or heteroarylamines were obtained. With adjusting the molar ratio of catalystsand substrate,1,3-diaminated adamantane were synthesized in one step, the optimumconditions were determined as: AlBr3(4eq), CBr4(2eq), adamantane (1eq), azole/amine(2eq), temperature (0oC) and reaction time (1h). When studying the amination of N-phenyl-urea and adamantane, we found that thisconversion did not give the expected amination product, but Csp2-Csp3coupling compound.The ureido group was first directing group, but meta alkylation product was obtained by thecatalyst of Lewis acid-polyhalomethane. In view of this, the meta-directing effects of amidegroups for the reaction of N-acetylaniline and adamantane catalyzed by Lewisacid-polyhalomethane under the conditions were studied. The optimal conditions ofsynthesizing meta-adamantyl-N-acetylaniline were determined as: AlBr3(2eq), CBr4(1eq),adamantane (1eq), acetylaniline (1eq), temperature (20oC) and reaction time (1h). Thesame ones of synthesizing meta-diadamantyl-N-acetylaniline were determined as: AlBr3(5eq), CBr4(2.5eq), adamantane (2.5eq), acetylaniline (1eq), temperature (20oC) andreaction time (1h). The possible mechanism maybe the cation complex of polyhalomethanecation and acetylaniline was the key factor of changing positioned effects of amide groups.The expanded research showed that carboxamido, propionamide, ureido, thiourea all hadmeta-directing effect.The paper also found that solid phase grinding technology could be used for theamination of cage-like alkanes Csp3-H achieved under the catalysed of AlX3-CX4in theabsence of a solvent. Compared with the reaction in solution, a substoichiometric amountof polyhalomethane-AlX3could play an efficient role under the grinding condition.Meanwhile, microwave technology could promote direct amination reaction of cage-likealkanes catalyzed by super electrophilic catalyst ZrCl4-CBr4, and the optimal conditions ofmicrowave-assisted synthesis of azole or arylamine substituted adamantane were obtained.The structures of cage-like hydrocarbons and derivatives, which have been synthesized,were characterized by IR, MS, NMR and elemental analysis. Partically, the structure of1,3-ditriazolyl-adamantane was determined by X-ray crystallography, and its crystal densityis1.400g/cm3. It is proved that the density of adamantanes could be increased byintroduction of azoles into adamantane. |
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