RUTHENIUM-MEDIATED NUCLEOPHILIC AROMATIC SUBSTITUTION OF HALOGENS ON BENZENE SYSTEMS: SYNTHESIS OF 1,3,5-TRIAMINOBENZENES

 
 
 
 

RUTHENIUM-MEDIATED NUCLEOPHILIC AROMATIC SUBSTITUTION OF HALOGENS ON BENZENE SYSTEMS: SYNTHESIS OF 1,3,5-TRIAMINOBENZENES

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dc.contributor.advisor Pearson, Anthony J. en_US
dc.contributor.author Serve', Brian J. en_US
dc.date.accessioned 2008-07-10T14:29:40Z
dc.date.available 2008-07-10T14:29:40Z
dc.date.created 2006 en_US
dc.date.issued 2008-07-10T14:29:40Z
dc.identifier.uri http://rave.ohiolink.edu/etdc/view?acc_num=case1152813193 en_US
dc.identifier.uri http://hdl.handle.net/2374.OX/16481
dc.description A method for the synthesis of unsymmetrical peralkylated 1,3,5-triaminobezenes was developed. The strategy consists of sequential ruthenium-mediated nucleophilic aromatic substitution to install two secondary amines and a palladium-catalyzed amination for the third. 1,3,5-Trichlorobenzene was metallated with [(CH3CN)3RuCp]PF6 in 51% yield. It was discovered that [(CH3CN)3RuCp]PF6 is not completely consumed in the reaction and the material causes an unusual decomposition of the resulting mono-substituted Ru-complex under SNAr conditions. Recrystallization and chromatography were ineffective at removing [(CH3CN)3RuCp]PF6; however, it was discovered that acetone destroys the precursor leaving (1,3,5-trichlorobenzene)RuCpPF6 intact. Two sequential nucleophilic aromatic substitution reactions were performed using the non-coordinating solvent, methylene chloride, and the heterogeneous base, sodium carbonate. It was found that SNAr conditions would not substitute the third chloro group. With each successive substitution the Ru-complex becomes less reactive towards SNAr requiring higher temperatures as forcing conditions, which prematurely decomplexes the arene. The synthesis was completed by photolytically cleaving the metal and performing a palladium-catalyzed amination on the final chloro group. The method successfully synthesized 1,3,5-tripyrrolidinobenzene and unsymmetric 1-morpholino-3-piperidino-5-pyrrolidinobenzene in 23% yield over five steps for the latter. en_US
dc.format application/pdf en_US
dc.format 81p. en_US
dc.rights unrestricted en_US
dc.rights Copyright and permissions information available at the source archive en_US
dc.subject Triaminobenzenes en_US
dc.subject (1,3,5-trichlorobenzene)RuCpPF6 en_US
dc.title RUTHENIUM-MEDIATED NUCLEOPHILIC AROMATIC SUBSTITUTION OF HALOGENS ON BENZENE SYSTEMS: SYNTHESIS OF 1,3,5-TRIAMINOBENZENES en_US
dc.type Electronic Thesis or Dissertation en_US
dc.degree.name PhD en_US
dc.degree.level doctoral en_US
dc.degree.discipline Chemistry en_US
dc.degree.grantor Case Western Reserve University en_US
dc.contributor.publisher Case Western Reserve University / OhioLINK en_US

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