Synthesis And Structure Of Novel Amidine Ligands & Recognition Of Biomolecular By Porphyrin And Metalloporphyrin

The research work consists of two parts: (i) Syntheses and characters of novel amidine ligands and amidometals; (ii) Recognition of biomolecules (purine, ammo acids, serum albumin, and pyridine) by hematoporphyrin and metallohematoporphyrin.Part one1 .The history and the developments of the type of amidine ligands and amidometals arereviewed,(l)Syntheses and struetures or l-azzalyl ligands(η³)and β-diketiminato(η⁵)metal complexes;(2)The progresses of amidometals and imines in organic synthesis andcatalysis;(3)The developments of amidometals and imines in catalytic reactions of olefinpolymerization.2 .The part work focusing on the characters of the substitution and the addition reactions ofN,N-diketiminatopropionitrile with potassium tert-butoxide or diisopropylamino-lithium.Three novel complexes were synthesized and charaeterized.2.1 The seetion deseribes synthetie and stnjetural studies leading to the novel nitrogenousheterocyclic organic compound N,n-dimethyl-3-cyano-4-amino-1,2,5,6-tetrahydro-pyrdinium chloride 2b.The compound was characterized by NMR,element analysis andsingle crystal X-ray diffraction.Unusual features of the reaetions leading to 2b are(1)thatthe substitution of N,N- diketiminatoProPionitrile by potassium tert-butoxide,then a 1,2addition reaction between the earbanion and another N,N-diketiminatopropionitrile leadingto{N(R)₂CH₂C(H)(CN)C(CH₂CH₂NR₂)(NK),(R=CH₃)2a.(2)2a was hydrolyzed,and extractedby CH₂Cl2,the related reaction 15 an elimination of dimethylamine.2.2 The section 15 eoneemed with synthetie and struetural studies onthe2.2 The seetion is concemed with synthetic and structural studies on the LINC{CH2CH2N(RQ)C(H)(CN)CH2N(R)2,(R=CH3)2c((from N,N- diketiminato-propionitrile and lithium disiopropylamino):theN(R)ZCHZC(H)(CN)C(NSiMe3)(CH2CH2NR2),(R(H3),2d(from 2c and trimethyl一chlorosilane);and an unusual two-eoordinate lithiumeomPlex Li{N(5 iMe3)CZCHZN(CH3)2}2e.(rrom 2d and butyl lithium).The reaetion meehanism was diseussed.2.3 The seCtion relates to syntheses from N,N- diketiminato-propionitrile,potassiumtert-butoxide and a Zr(IV)saltl of a novel nitrogenous heterocyelie organie comPound2,6-di(N,N-dimethylaminoethyl)-3,5-dicyano-2,3,4,5-tetrahydro-pyridine 2f. The eompound 2fwas eharaeterized by element analysis and single erystalX-ray diffraetion stodles.Thereaetion meehanism was diseussed.The reaction eondition and reagents see Sehemel3.The part deals with th。reaetions of[LIN(siMe3)C(BuL)CH(SIMe3)]2(l一azzalyl)3a withtransition metals salts,Fe(II),Co(II),Ni(II),and Ti(IV).The (R=siMe3)(3b)and co[N(R))C(Bu)(CHR]2(R=siMe3) Complexes(3C)and a coupling coupound[N(R)e(Bu)CH(R)]2(3d)were synthesized(seheme2);The eomplexes 3b,3c and 3d werecharacterized by NMR,element analysis and single erystal X.ray diaction studies.Seheme 1:The synthetic route of eompounds 2a-2f. Reagents and conditions:(1)KoBu,,hexane,24h,o(2)H2O,1h,room temp.;(3)CH2Cl2,24h,room temp:(4)LDA,hexane or thf, 24h,ca.0℃:(5)Me3SiCL,thf, 12h,ca.0℃,:(6)LiBun,hexane or thf, 12h,ca.0℃:(7)KoBu,,hexane,24h,ca.o℃,ZrCl4,24h,ca-78℃.sehemeZ:The synthetie route of mpounds 3a-3d.ents and eondirions:(l)Bu,CN,Et20,Zh,ca.ooC;(2)NIC12 or TICI;,hexane,24h,ca一78aC;(3)CoC12 or FeC12,hexane,24h,ea-78℃Partl4.The Progresses of Porphyrin and metalloPorphyrin were reviewed in the molecularreeognition,Probe,d 50 on.5.The metal eomPlexes of hematoporphyrin were synthesized.The interactions ofbiomoleeular with hematoPorphyrin and metalloPorphn were studied in detail.And themeehanisms vvere diseussed.5·1 The metai eomPlexes(Zn,Cu,Co,Ni)ofhematoPorphnweresynthesized.Hematopo hn(HP)has five eharacteristie peaks in UV-visible region(one in Soret band,the others in Q band).While the metal Porphn(MHP)was formed,the peak in Soret bandwas remarkable blue shift or red shift,and only two peaks left in Q band.The...