Synthesis Of N-Aryl-N'-(4, 13)-Disubstituted [2.2]Paracyclophanyl Dihydroimidazolium Salts

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 used in the formation of C-C,C-H,C-N,and C-O,respectively.[2.2]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[2.2]paracyclophane and N-heterocyclic carbene can represent much special character that differs from either the[2.2] paracyclophane or the N-heterocyclic carbene.In order to develop the asymmetric catalyst and asymmetric catalytic reaction,the research of N-heterocyclic carbenes bearing chiral[2.2]paracyclophanes have the significant 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(4Sp,13Rp)-(-)-4-amino-13-bromo[2,2] paracyclophane.It was obtained by the nitration,bromination,reduction and resolution.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 third part is preparation of(4Sp,13Rp)-(-)-4-amino-13-(α-naphthyl)[2,2] paracyclophane,(4Sp,13Rp)-(-)-4-amino-13-(2-methoxyphenyl)[2,2]paracyclophane. It was obtained by the Suzuki cross coupling from(4Sp,13Rp)-(-)-4-amino-13-bromo [2,2]paracyclophane with 1-naphylboronic acid or 2-methoxyphenylboronic acid.The fourth part is preparation of N,N'-bis[(4Sp,13Rp)-(-)-13-(2-methoxyphenyl) -4-[2,2]paracyclophanyl]ethylene-1,2-diamine.Treatment of(4Sp,13Rp)-(-)-4-amino -13-(2-methoxyphenyl)[2,2]paracyclophane with glyoxal gaved the desired diimine, which was reduced to the diamines with sodium borohydride and 20%hydrosulfonic acid.The fifth part is synthesis of N,N'-bis[(4Sp,13Rp)-(-)-13-(2-methoxyphenyl) -4-[2,2]paracyclophanyl]-4,5-dihydroimidazolium chloride.It was synthesis by trirethyl orthoformate and ammonium chloride,but no expected product was isolated.The sixth part is preparation of asymmetric oxamides.Starting from oxalyl chloride and aromatic amines,oxo-arylamino acetyl chlorides were obtained,and then reacted with(4Sp,13Rp)-(-)-4-amino-13-R[2,2]paracyclophanes to produce the mixed diamides.They are N-(4Sp,13Rp-(-)-13-(2-methoxyphenyl)-4-[2,2] paracyclophanyl)- N'-(2,6-isopropylphenylamino)oxamide,N-(4Sp,13Rp-(-)-13-(α-naphthyl)-4-[2,2] paracyclophanyl)-N'-(2,6-isopropylphenylamino)oxamide,N-(4Sp ,13Rp-(-)-13-bromo-4-[2,2]paracyclophanyl)-N'-(2,6-isopropylphenylamino)oxam ide,N-(4Sp,13Rp-(-)-13-(2-methoxyphenyl)-4-[2,2]paracyclophanyl)-N'-(2,4,6-trimethylphenylamino) oxamide,N-(4Sp,13Rp-(-)-13-(α-naphthyl)-4-[2,2]paracyclophan yl)-N'-(2,4,6-trimethylphenylamino)oxamide.The seventh part is synthesis of asymmetric dihydroimidazolium tetrafluoroborates. The mixed diamides were reduced by borane to give corresponding mixed diamine. Then,the new asymmetric dihydroimidazolium tetrafluoroborates were obtained from the mixed diamine,triethyl orthoformate and ammonium tetrafluoroborate.The innovation of this thesis is as follows:1.(4Sp,13Rp)-(-)-4-amino-13-bromo[2,2]paracyclophane were obtained by the resolution of a mixture of diastereomeric N-(4-amino-13-bromo[2,2]paracyclophanyl) (1R)-Camphor-10-Sulfonyl amides for the first time.2.Five novel asymmetric oxamides were obtained in this thesis.3.Five novel dihydroimidazolium tetrafluoroborates were obtained in this thesis...