Surface Chirality (4,13) - Substituted Ring Imitation Imidazoline Synthesis Of Research

The Nobel Prize of chemistry was awarded to Grubbs and the other two scientists in honor of the great contributions that they did in the study of olefin metathesis in 2005. And the most effective catalyst of olefin metathesis is the Ruthenium catalyst system based upon N-heterocyclic carbene. The complexes derived from imidazoliums, imidazoliniums and transition metals have been employed in the formations of C-C, C-H, C-N and C-O. Paracyclophane is a planar chiral compound which becomes the most remarkable characteristic of it. This characteristic has been attracting the interest of scientists more and more. A series of novel complexes derived from planar chiral paracyclophane and N-heterocyclic carbene can represent much special character that different from neither the paracyclophane nor the N-heterocyclic carbene. So the synthesis of these complexes will have great and profound meaning.The primary content of this thesis is as follows:The first part is preparation of [2, 2] paracyclophane. [2,2]paracyclophane was obtained from para-methylbenzyl-(N,N,N-trimethyl) ammonium chloride and sodium hydroxide in dimethyl sulphoxide by Hofmann elimination.The second part is preparation of (Rp)-(-)-4-amino [2, 2] paracyclophane. By the nitration, reducation and resolution of [2, 2] paracyclophane, this material can be accessed.The third part is preparation of (4Sp, 13Rp)-(-)-4-amino-13-bromo [2, 2] paracyclophane. It was obtained by the nitration, bromination, reducation and resolution.Then (-)-4-amino-13-bromo-[2,2]paracyclophane was changed into (Sp)-(+)-4-amino[2,2]paracyclophane under Pd-DPPF catalysis, the absolute configuration was confirmed by comparison of its specific rotation with the reported value.So it can be concluded that the optical form is (4Sp,13Rp), named(4Sp,13Rp)-(-)-4-amino-13-bromo-[2,2]paracyclophane.The fourth part is that (4Sp,13Rp)-(-)-4-amino-13-(3-methoxyphenyl)-[2,2] paracyclophane,(4Sp,13Rp)-(-)-4-amino-13-phenyl-[2,2]paracyclophane,(4Sp, 13Rp)-(-)-4-amino-13-(a-naphthyl)-[2,2]paracyclophane and (4Sp,13Rp)-(-)-4- amino -13-(2-methylol-phenyl)-[2,2]paracyclophane was obtained by Suzuki cross coupling from (4Sp,13Rp)-(-)-4-amino-13-bromo[2,2]paracyclophane with 3-methoxyphenyl boronic acid, phenylboronic acid, 1-naphylboronic acid, and 2-methoxyphenylboronic acid.The fifth part is that diimines were obtained by the reactions of glyoxal and the fourth compounds done before.The sixth part is that diimines were reduced to the diamines with sodium borohydride and 20% hydrosulfonic acid, N,N'-bis (4Sp, 13Rp- (-) - (13-bromo) -4-[2, 2]paracyclophane)diamide was also reduced to the corresponding diamine with borane. N,N'-bis (4Sp, 13Rp- (-) -13-(2-hydroxylphenyl)-4-[2, 2]paracyclophane) diamine can be obtained by demethylation reaction.The seventh part is that six new chiral dicyclophane dihydroimidazolium tetrafluoroborates were gained from the diamine, triethyl orthofonnate and ammonium tetrafluoroborate.The eighth part is that we want to get imidazolium. The mixture of dimine and paraformaldehyde was heated to 100℃ in toluene, and then the 2,4-dioxane saturated with hydrochloride was added to get the imidazolium. The reaction can be carried out in 2, 4-dioxane by added chloromethyl methyl ether at room temperature or in dichloromethane using trifluorence methyl sulfonic sliver and chloromethyl-ethyl ether to produce imidazolium trifluoromethyl sulfonate. But, no aim products can be got.The ninth part is that by the reaction of (4Sp, 13Rp)-(-)-4-amino-13-bromo [2, 2] paracyclophane and dimethyl sulphate as methylation reagent, passium carbonate as base, (4Sp, 13Rp)- (+)-4-dimethylamino- 13-bromo [2, 2] paracyclophane was obtained. then (4Sp, 13 Rp)-(+)-4-dimethylamino-13 -bromo[2,2]paracyclophane reacted with diarylphosphine chloride through Grignard reagent or n-butyllithium, in order to perform phosphatization reaction, reacted with triarylphosphine to give (4Sp, 13Rp)-(+)-4-dimethylamino-[2, 2] paracyclophane ,but we didn't get the aim product with diarylphosphine chloride. The tenth part is that (4Sp, 13Rp)-(+)-4-hydroxy-13-bromo-[2,2]paracyclophane was got by treatment of (4Sp, 13Rp)-(-)-4-amino-13-bromo-[2, 2] paracyclophane, acetic anhydride and acetic acid with solid sodium nitrite, and followed by hydrolysis with passium hydroxide. (4Sp, 13Rp)-(+)-4-hydroxy -13-bromo-[2, 2] paracyclophane reacted with dimethyl sulphate and passium carbonate as base to give (4Sp, 13Rp)-(+)-4-methoxy -13-bromo-[2, 2] paracyclophane. The product formed by metalation with Grignard reagent or n-butyllithium reacted with diarylphosphine chloride in order to perform phosphatization reaction, the aim products were not found.The eleventh part is that using oxalyl chloride and 2, 4, 6-trimethylphenylamine we get single acetyl chloride. Then it reacted with (4Sp, 13Rp)-(-)-4-amino-13-bromo-[2, 2] paracyclophane, we get the mixed diamide. Next, it was reduced by borane to give the mixed diamine. We want to let the mixed diamine to react with 2-methoxylphenylboric acid in Suzuki reaction, but, it didn't work, the initial material was recovered. We get the new mixed dihydroimidazolium tetrafluoroborate from the mixed diamine, triethyl orthoformate and ammonium tetrafluoroborate.The innovation of this thesis is as follows:1. Seven novel compounds were obtained in this thesis: seven diamines2. Seven novel compounds were obtained in this thesis:Using the upper diamine we get the seven new dihydroimidazolium tetrafluoroborates.