utilizarea compusilor organici bazata pe proprietatile lor fizice

8/10/2019 utilizarea compusilor organici bazata pe proprietatile lor fizice

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ANEXA 3

10. Prezentarea proiectului in limba romana: (Max. 10 pagini)

10.1. Importanta si relevanta continutului stiintific

10. Prezentarea stiintifica

Desi cunoscuti de multa vreme, azoderivatii raman inca in atentia chimistilor datorita surprizelorlegate de structura si de proprietatile lor fizico-chimice, dar ei a aplicatiilor lor importante inramuri de varf ale industriei moderne. Asa cum s-a dovedit si din lucrarile noastre anterioare,1

studiul sintezelor si proprietatilor unor azoderivati mai speciali, cum este cazul celor care contin inmolecula azulena, este legat de ambele aspecte sus-mentionate.Cateva proprietati fizico-chimice speciale ale acestor derivati le confera o larga gama de utilizariincepand de la cele clasice de coloranti si terminand cu cele mai moderne, in stocarea datelor sautransmiterea de date. In cazul derivatilor azoici au fost demonstrate si studiate proprietatile NLale acestora, care sunt intensificate de cresterea polaritatii sistemului si de cresterea numarului deduble legaturi con!ugate prezente "inclusiv azo#. In acest sens, s-a costatat ca bis azo derivatii au

coeficientii , , , mult mai mari decat monoazo derivatii similari.$Calcule de mecanica

cuantica au aratat, de asemenea, ca inlocuirea sistemelor benzenice greu polarizabile cu alteleposedand un caracter aromatic mai redus si deci mai usor de deformat, precum si introducerea degrupe polarizante, ca nitro sau amino, determina o crestere semnificativa a coeficentilor mai susmentionati.%&tilizarea de azoderivati ca produsi de stocare de informatie a fost de asemeneainvestigata.'Acestia se pot folosi, de asemenea, drept coloranti pentru materiale si fibre plastice,pentru producerea de cerneluri si tusuri, pentru colorarea tesaturilor si a hartiei, in industriafotografica(sau in tehnologia laserilor. Azoderivatii cu simetrie scazuta au proprietati de cristalelichide,)iar alte diazene sunt utilizate ca purtatori de sarcina.*

+roiectul este structurat din punct de vedere stiintific in % sectiuni

1.1 Derivati fenilen-bisazozulenici. Aceasta sectiune va cuprinde '.1.1. sinteza materiilor prime'.1.$. obtinerea derivatilor orto-, meta- si para-azulen-fenilenbisazoici simetrici si nesimetrici'.1.%. studiul proprietatilor magnetice, optice si de bazicitate ale acestor combinatii.1.$. Derivati azulen-fenilenbisazoici substituiti cu grupe functiunale polarizante la sistemeleazulenice '.$.1. sinteza intermediarilor '.$.$. sinteza compusilor '.$.%. studiul proprietatilor lorfizico-chimice1.%. Derivati tris si poli azoazulenici '.%.1. sinteze de materii prime '.%.$.sinteza produsilor'.%.%. studiul proprietatilor lor fizico-chimice

10.1. Derivati fenilen-bisazoazulenici

Azulena este o hidrocarbura aromatica polarizata datorita deplasarii unui electron spreinelul de ( atomi de carbon realizandu-se, in felul acesta, un se/tet aromatic la fiecare cicluazulenic, cel de cinci si de sapte atomi.


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_ +

Din acest motiv azulena dobandeste un caracter nucelofil, care se manifesta la ciclul de (

atomi in pozitiile 1 si %, ceea ce ii permite cuplarea cu saruri de diazoniu reactive, spre deosebirede hidrocarburile aromatice obisnuite, care necesita grupe donoare de electroni pentru a se implicain reactiile de cuplare. In acelasi timp, sarurile de diazoniu provenind de la 1-aminoazulene nusunt stabile si nu dau reactii de cuplare decat cu substraturi foarte active cum ar fi beta-naftolul.

Din cele prezentate rezulta ca derivatii bisazoici nu pot fi preparati decat prin cuplareaunei saruri de diazoniu cu nucleu benzenic cu molecule de azulena.

10.1.1. inteza materiilor prime

In ma!oritatea reactiilor de cuplare se pot utiliza intermediari comerciali. 0otusi, izomeriiaminoazobenzenului vor trebui preparati pentru a obtine derivatii bisazoici monoazulenici. Cel

mai usor de obtinut este izomerulpara,care rezulta intr-o etapa prin diazotarea anilinei si cuplareasarii cu e/cesul de materie prima, urmata de transpozitia triazenei.

NH2 N N N

HN N NH

2

enerarea izomerului meta necesita $ etape indiferent de calea aleasa.

NH2

NO2

PhNO

N

NO2

N Ph

Na2S

N

NH2

N Ph

NH2

NHAc

PhNO

N

NHAc

N Ph

ClH

N

NH2

N Ph

In cazul izomerului orto reducerea grupei nitro din pozitia orto nu este posibila si de aceeasingura metoda accesibila ramane cea prin derivatul monoacetilat, accesibil commercial.

NH2

NHAc PhNO

N N Ph

NHAc ClH

N N Ph

NH2

10.1.!. "btinerea #erivatilor monoazulenici

Acesti derivati se vor obtine printr-o reactie de cuplare normala a celor trei izomeri aiamonoazobenzenului. Acesti izomeri trebuie sa fie suficient de reactivi avand in vedere ca grupa


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azo este relativ atragatoare de electroni si activeaza sarurile de diazoniu in reactia de cuplare.

N N Ph

NH2

N N Ph

N2

AzR

AcOK

NaNO2

ClH

N N Ph

N NR+

R = H, 4,6,8-Me3, 3,8-Me2-5-iPr

10.1.$ "btinerea #erivatilor bisazulenici

Acesti derivati pot avea doua resturi identice sau diferite de azulena. In primul caz,teoretic, ar fi mai usoara cuplarea directa a derivatului azulenic cu fenilendiamina bis-diazotata,dar problema care apare este aceea a stabilitatii acestor saruri si a compatibilitatii redo/ dintre elesi azulena.

2ste cunoscut ca para-fenilendiamina se poate bis-diazota doar in medii puternic acide, iar

sarea astfel obtinuta se descompune prin diluare sau neutralizare. 3ingurele reactii de cuplare cupastrarea azotului descrise in literatura sunt cele cu fenolii.

NH2

NH2 N

2N

2

++

2 HSO4-

2ste destul de putin probabil ca azulenele sa se cupleze in mediu de acid sulfuricconcentrat datorita instabilitatii lor in medii o/idante si acide. De aceea o modalitate mult maisigura este cuplarea in trepte pentru care e/ista, in principiu, doua cai de abordare a sintezei. prima cale abordeaza prepararea pornind de la 1,% sau 1,'-acetilaminoaniline si necesita o etapa

intermediara de hidroliza, cum este reprezentata mai !os pentru izomerulpara

NH2

NHAc

NaNO2HCl

AzH

N

N NHAc

NaNO2+ HCl

AzR

di!a"

NN NH

2

NN N

N

R#

R

R R

HCl

R, R# = H, Me3 $a% &%

A doua cale porneste de la p-nitroanilina in care intermediarul obtinut dupa diazotare sicuplarea cu azulene sufera o reducere cu sulfura de sodiu transformand grupa nitro in amino.Aceasta varianta pare, insa, mai riscanta, avand in vedere sensibilitatea derivatilor azulenici lareactii de tip redo/ in care sunt generati radicali liberi.


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NH2

NO2

NaNO2HCl

AzH

N

N NO2

NaNO2+ HCl

AzR

N

N NH2

N

N N

N

R#

R

R R

Na2S

R, R# = H, Me3 $a% &%

In cazul izomerului meta sarea de bis-diazoniu rezultata prin bis diazotarea meta-fenilendiaminei are un caracter o/idant mai redus si are o probabilitate de a da reactii de cuplarecu derivati de azulena mai mare. Chiar si in acest caz, daca se doreste obtinerea de compusi azoici

avand resturi de azulene diferite, singurele accesibile raman sintezele in trepte.

NH2

NH2

N

N

N

N

NaNO2HCl

AzR

R

R

R = H, 4,6,8-Me3, 3,8-Me2-5-iPr

3intezele devin mai complicate in cazul izomerului orto, unde pot interveni reactiisecundare cu formare de benzotriazoli. Astfel, atat orto-fenilendiamina, cat si derivatul saumonoacilat formeaza benzotriazoli prin tratare cu nitrit de sodium si acid clorhidric, deci nu sepoate folosi calea pornind de la amina acilata.

NHAc

NH2

NaNO2

ClH N

N

N

R

NH2

NH2

NaNO2

HCl

R = H, Ac

Nici calea care porneste de la orto-nitroanilina nu da rezultatele dorite, intrucat grupa nitrodin pozitia orto nu se reduce curat la amina, ci da produsi de transpozitie. Orto-Fenilendiamina aputut fi bis diazotata in acid sulfuric concentrat, dar sarea obtinuta este atat de instabila, incat nuse poate cupla cu pastrarea azotului. De aceea, in aceste cazuri este necesara gasirea altor cai desinteza, care sa duca la produsii doriti. astfel de cale ia in considerare obtinerea ftalimideifenilendiaminei, diazotarea sa si cuplarea cu azulena. rupa protectoare ftaloil se poate indepartaprin tratare cu hidrazina si apoi se diazotizeaza si se cupleaza cu o alta molecula de azulena. In


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acest caz cuplarea va avea loc fara ciclizare, deoarece nu mai e/ista niciun proton disponibil laazot si inelul ftalimidic este suficient de stabil pentru a nu fi e/pulzat de sarea de diazoniu formatain pozitia orto.4

NH2

NO2

O

O

O

N

NO2

OO

N

NH2

OO

N

N

OO

N

N2H

4 NH2

N NN

N N

NHNO

2

AzR#

HNO2

AzR

RR

R

R#

H2

Ni-Ra

10.1.% tu#iul proprietatilor fizice ale #erivatilor sintetizati

+rima parte din aceasta sectiune va debuta cu calculul geometriilor si a densitatilorelectronice ale moleculelor sintetizate prin procedeul 5+AC. 2ste important de stiut dacaizomerul ortoeste planar sau nu si daca geometria rezultata ii permite sa formeze complecsi cumetale, ceea ce ar spori imporanta studiului propus de noi. De asemenea substituirea azulenelor cumetil in pozitia 4 poate scoate molecula din plan si modifica cromoforul.

3e vor trasa spectrele 65N de proton si de carbon si se vor discuta influentele aparute prininlocuirea unui rest fenil cu un radical de azulena sau diferentele ce apar prin disparitia simetrieimoleculelor prin substituirea azulenelor cu alchili. Acest lucru va fi corelat cu efectele push-pullpe care structura produsilor obtinuti le poate promova. 7aptul prezinta importanta datoritahiperpolarizabilitatii potentiale a acestor materiale.

atentie deosebita va fi acordata studierii spectrelor electronice se vor pune in evidentainfluenta solventului si a p8-ului asupra lungimii de unda a celei mai importante benzi din vizibil.3olvatocromismul produsilor obtinuti va fi tratat cu toata atentia in ideea de a decela indicatiiasupra hiprepolarizabilitatii acestora. De asemenea se vor determina punctele izosbestice acolounde e/ista si se vor calcula constantele de bazicitate prin masurarea p8-ului la care apar absorbtiiegale intre forma acida si bazica a compusului.

10.! Derivati fenilen bis(azoazulenici) substituiti la azulena cu grupe functionale.

Azulenele sunt la limita capacitatii de cuplare cu saruri normale de diazoniu. 6eactiile decuplare sunt posibile la azulene nesubstituite, substituite cu alchil sau daca in pozitia 1 se afla ogrupa donoare de elecroni care activeaza azulena. Azulenele substituite in pozitia 1 cu grupeatragatoare de electroni nu vor cupla in conditii normale. 0otusi se cunosc si e/ceptii, de e/emplu,o grupa acetil are o mobilitate mai ridicata ca grupa fugace electrofila decat protonul sisubstituirea sa nu este reversibila. De aceea ea poate fi substituita de o grupa azo in conditii dure


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de reactie, la temperaturi ridicate neuzuale pentru reactiile de cuplare.9

OO

NH2

O2N

NaNO2

N

O

N

NO2

N

O

N

NH2

NaNO2

R

N

O

N N

NR

AcCl

S"Cl4 HCl

H2

Pd

HCl

R = NHAc, OMe, OOCPh

2ste probabil ca acelasi tip de reactie sa poata fi folosit si pe alte tipuri de combinatii si pealti izomeri ai nitroanilinelor, in special p-nitroanilina

MeOOC

OO

MeO NH2

O2N

NaNO2

N

O

N

NO2

MeO

N

O

N

NH2

MeO NaNO2

R

N

O

N NN R

MeO

AcCl

S"Cl4 HCl

H2

Pd

HCl

R = 'r%(a ac)i*a")a $a% $la dezac)i*a)are

&tilizarea unor azulene substituite in pozitia 1 pune, totusi, probleme sintezei acestoradeoarece acestia nu sunt produsi comerciali.

Compusii bis azioici sintetizati vor fi caracterizati prin procedeele descrise in capitolulanterior, studiindu-li-se spectrele de rezonanta magnetica nucleara, precum si cele electronice,

pentru a se evidentia influenta grupelor functionale asupra proprietatilor produsilor.

10.$. inteza #e poliazo#erivati

+rin cresterea numarului de grupe azoice se mareste rezistenta materialului si, in acelasitimp, i se modifica proprietatile fizice.

Din numarul mare de combinatii posibile intre gruparile fenilen, azulenil si azo au fostalese cateva combinatii mai accesibile, a caror sinteza ar putea fi realizata in cateva etape, iar un


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e/emplu nerestrictiv este reprezentat mai !os

N N

NH2

ON NO2

N N

N N NO2

N N NH2

N N

N N

N N N N

Na2S NaNO

2

AzH

HCl

10.% tu#iul unor potentiale re#ox ale acestor combinatii

In cadrul laboratorului nostru au fost studiate potentialele de reducere si o/idare a

numeroase combinatii azoice ale azulenelor.1Ne propunem sa e/tindem aceasta preocupare laderivatii bisazoici si poliazoici in vederea stabilirii de posibile reactii redo/ pe aceste sisteme.

+otentiale de o/idare si reducere a catorva azobenzeni p-substituiti C)8(-N:N-C)8'; "p# siazoazulene Az-N:N-C)8'; "p# "1 m5# obtinute prin D+irzan L., Nae 3., Cristian L.,

Chiraleu 7., 5aganu 5., Cimpeanu revet + )-1$() din 194(

42. D. >ergmann, 5. >entar . rg. Chem. 19(', 19, 1(9'.


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9. 8afner, A. 3tephan, C. >ernhard ust. Lieb. Ann. Chem. 19)1, )(,'$

1rezultate nepublicate inca

10.!. "biectivele proiectului

+roiectul pe care il propunem are in vedere cateva obiective stiintifice importante si de actualitate.1. +rimul obiectiv il constituie elaborarea unui procedeu pentru sinteza unor compusi

apartinand unei noi clase si anume clasa derivatilor bis si poliazoici, care contin in molecularadicali fenilen, fenil si azulenil. Introducerea nucleelor azulenice induce o polarizare si opolarizabilitate superioare sistemelor similare care cuprind doar grupe aromatice benzenoide princresterea valorii energetice a orbitalilor 85 si scaderea valorii celor L&5. 3intezacompusilor propusi prezinta elementul de noutate prin aceea ca sarurile de diazoniu ale azulenelornu sunt combinatii stabile si de aceea multe din reactiile de cuplare uzuale nu pot fi realizateutilizand aceste saruri. In aceste conditii materiile prime vor fi sarurile de diazoniu sau bis diazoniucu nuclee benzenice, iar componentele de cuplare vor fi azulenele. Azulenele fiind, insa, nucleofilimoderati nu pot cupla cu orice sare de diazoniu. Nici nitrozoderivatii azulenici nu pot fi avuti invedere pentru sinteza grupei azo prin reactii de condensare 5ills, deoarece acestia sunt stabilinumai la temperaturi scazute. De asemenea, obtinerea si cuplarea compusilor bis azoici provenindde la fenilendiamine prezinta o serie de particularitati care trebuie avute in vedere. 3e preconizeazaca unele dintre sinteze sa aiba ca materii prime aniline pe care este grefata o grupa potentialgeneratoare de substituent amino, de e/emplu grupa nitro. Deci studiul sintezei acestor derivatiprezinta interes stiintific si nu este unul de rutina.

$. Al doilea obiectiv il constituie determinarea neechivoca a structurii produsilor obtinutisi studiul proprietatilor fizico-chimice ale acestora. 3tructura chimica a derivatilor di si poli azoicipermite abordarea unui studiu privind influenta unghiului diedru intre nucleele aromatice asupracon!ugarii sau eventuala generare de combinatii cu chiralitate anchimerica. In legatura custructura produsilor obtinuti va fi studiata si influenta acesteia asupra spectrelor 65N si a celorelectronice. Asa cum s-a amintit mai sus, este de asteptat ca acesti compusi sa prezinte opolarizare si o plarizabilitate superioare celor monoazoici, prin posibilitatile de con!ugare multmai e/tinsa. 2ste foarte probabil ca printre izomerii sintetizati, unii care contin grupe azulenicediferite sa apara combinatii care sa cristalizeze in sisteme non-centrosimetrice si deci sa posedebune calitati NL. De asemenea, aceleasi caracteristici de structura pot conferi calitati de cristalelichide altor materiale din aceasta clasa.

%. Al treilea obiectiv il constituie caracterizarea electrochimica a compusilor sintetizatifolosindu-se atat voltametria ciclica, cat si metoda potentiostatica. 6ezultatele obtinute prinstudiul cineticii de electrod vor fi folosite la elaborarea unor posibile mecanisme de reactieelectrochimice. 3pecificitatea sistemelor propuse consta in prezenta concomitenta a unui pol


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reducator de natura azulenica si a unuia relativ o/idant de natura azoica, care pot genera noiprodusi prin reactia cu electrozii. 3e pot anticipa astfel obtinerea de dimeri, oligomeri sau polimericu proprietati electrice interesante. +rodusii sintetizati pe parcursul proiectului pot fi utilizati inscopuri electrochimice, de e/emplu, acoperiri de electrozi sau generarea unor sisteme de elecroliticomplecsi.

'. &ltimul obiectiv il consitutie faptul ca abordarea unei tematici comple/e si, relativcomplete de cercetare fundamentala de catre cercetatorii tineri, in formare, le da posibilitatea sadevina cadre de cercetare temeinice, iar o parte din lucrari pot fi dezvoltate in vederea sustineriiunor teze de doctorat. In plus, de mai multi ani, in colaborare cu institutiile de invatamantsuperior, o serie dintre studentii din ultimul an isi efectueaza partea e/perimentala a lucrarii dediploma la noi in laboratoare. Acelasi lucru este valabil si pentru cei care urmeaza masteratele sieste suficient sa amintim ca aproape toti doctoranzii nostrii si-au desfasurat activitateae/perimentala din cadrul masteratului in colectivele noastre. biectivele propuse se incadreazaintr-o tematica larga, in care colectivele de cercetare au colaborari cu colective din ermania,7ranta si 7inlanda. 6ezultatele acestor cercetari fac de!a obiectul mai multor articole publicate inreviste de prestigiu sau comunicate la simpozioane si congrese.

10.$. Meto#ologia cercetarii

+roiectul implica atat activitati e/perimentale cat si teoretice.ctivitatea experimentala consta in obtinerea materiilor prime precum si a azoderivatilor

continand resturi azulenice in molecula. 2a consta in sinteza chimica a acestor compusi urmata decromatografierea lor pe coloane de alumina sau silicagel. +entru testarea puritatii sau evaluareamersului reactiilor cu produsi incolori se va folosi 8+LC-ul din dotare.ontrolul analitic al produsilor obtinuti se va face prin spectroscopia 65N de inaltaperformanta, folosindu-se aparate de inalta rezolutie da % si ' 58z. De asemenea se vorefectua spectre de masa prin procedeul 23I, cel mai adecvat pentru molecule relativ mari si polare.tu#iile #e *+-+iz- curbele pentru determinarea izosbesticilor compusilor nou sintetizati se vorface pe aparate de spectroscopie electronica nou achizitionate, avand performante electronicedeosebite. De asemenea, masurarea p8-ului solutiilor se va efectua cu un p8-metru electronic nouachizitionat.tu#iile electroc,imicevor fi e/ecutate partial la &niversitatea +olitehnica >ucuresti si partial in

cadrul institutului. Catedra de la &niversitate poseda aparatura moderna in acest domeniu.Partea teoretica se bazeaza pe corelari de potentiale de o/idare si reducere cu energiile orbitalilor85 si L&5 precum si in calcule de lungimi de legatura si unghiuri diedre cu a!utorulprogramului de mecanica cuantica-5+AC


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nt,esis an# -al2lation at pri#ine moiet+ynt. Comm%m. !00!, %$, 4$(-%*.%. A. C. 6azus, L. >irzan, 3. Nae, L. Cristian and 7. Chiraleu 3zulene-1-azopri#ine 14-oxi#esDyes and Pigments !00$, "7, $$%-%%.'. A. C. 6azus, L. >irzan, 3. Nae, 5. N. 3urugiu and irzan& Nina 5irela 3urugiu, Andreea Cristina Corbu and 7ilipChiraleunt,eses of zulen-1-l-benzot,iazol-!-l DiazenesDyes and Pigm. !00', 74(1), $)-%%.4. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Cristina Corbu andCristian 2nache zulene-substitute# Pranlium alts. nt,eses an# Pro#ucts,aracterizationJ. Heterocyclic Cem.!007& 40, 9)%-**.

9. 2leonora 5. &ngureanu, Ale/andru. C. 6azus, Liviu >irzan,

eorge >uica, 5ariana Cretu and2nache Cristian 6lectroc,emical c,lorination of azulenic #erivatives. Insig,t into mec,anismof ano#ic oxi#ative c,lorinationlectrocimica cta !007& "& *9'-4%.1. Ale/andru C. 6azus, Liviu >irzan, Andreea Corbu, ana ;aharia and Cristian 2nachent,esis an# Properties of %-($-ubstitute# azulen-1-l)-!&7-#ip,enl-pri#ines ri$oc

!007, 1, 1$1-1$9. 11. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Corbu, 7ilipChiraleu and Cristian 2nache zulene-substitute# Pri#ines an# Pri#inium alts. nt,esisan# tructure. 1. zulene-substitute# pri#inesJ. Heterocyclic Cem& !00', 44,$'(-$(.1$. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Corbu, 7ilip

Chiraleu and Cristian 2nache zulene-substitute# Pri#ines an# Pri#inium alts. nt,esis

an# tructure. !. zulene-substitute# pri#inium salts J. Heterocyclic Cem !00', 44, $(1-$).#. $atent

1. +rocedeu catalitic pentru prepararea (-alchil-salicilaldehidelor. >revet 6oman 1$ ')%din %.1 199.5. Comunicari stiintifice la conferine cu volume publicate

1. zulene-1-azopri#ine& snt,esis-al2lationA. C. 6azus, L. >irzan, 3tefania Nae,irzan, 3. Nae, N. 5. 3urugiu, A. Negoescu si


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5alo, 7rance, 0hme $ 2lectrochimie 5olJculaire et >ioelJctrochimie.). e#ox be,avior of some azulene #erivatives& 2.-5.&ngureanu, A. C. 6azus, L.

>arzan, 5. Cretu, . >uica, 6omanian International Conference of Chemistr and Chemical2ngineering 6ICCC2 1', 31-$., !007

*. 6lectroc,emical stu# of azulene #erivatives b cclic an# #ifferential pulse

voltametr 2.-5. &ngureanu, L. >arzan, A. C. 6azus, 5. 3. Cretu, 7. 5. 0ugurel, +D-4,Conferinta Nationala Chimia, !007, Hvidius Constanta

4. Mec,anisme #e ,alogenation electroc,imi9ue #es composes azuleni9ues 2.-5.&ngureanu, A. C. 6azus, L. >arzan, . >uica, Le Guatrieme colloGue franco-romain de chimieappliGue, $4 uin-$ ulliet !007, Clemont-7errand, 7rance

9. inteza unor saruri #e piraniliu si a unor piri#ine substituite in pozitia % cura#icali azulen-1-il Ale/andru C. 6azusM, Liviu >irzan, ana Lehadus, Claudia +avel, LilianaCristian, ana ;aharia si Cristian 2nache, +oster la al-$9-lea 3impozion National de Chimie,Calimanesti-Caciulata, irzan, . Lehadus, C. +avel, C. 2nache, +oster la al-$9-lea 3impozion

National de Chimie, Calimanesti-Caciulata, irzan, +oster at the 1'th 2ditionof the Conference of 5icrosensors, 5icroactuators and 5icrosstems, Lon, 7rance, une 1-1',!00'

%. E&perienta acumulata in pro'rame nationale si internationale eactii #e substitutie pe sisteme azulenice.


13/37

- 5embru al asociatiilor profesionale 3ocietatea Chimitilor din 6omOnia- +remiul II la limpiada Internationala de Chimie- Leningrad 19*9. - 6eferent la ournal of rganic Chemistr, Des and +igments si 0he Chemical 2ducationournal.

10.%.1.1.!. ompetenta manageriala a #irectorului #e proiectCrd"a)r%l de (riec) are experienta$i abilitatea de a administraac)i*i)a)ile $i

+%'e)%l (riec)%l%i c"r (la"iicarii.

10.%.1.!. 6c,ipa #e cercetare

/ista membrilor ec,ipei #e cercetare: "7ara directorul de proiect#

r.

crt.ume si prenume

nul

nasterii

>itlul #i#actic

stiintific ?

Doctorat

??

emnatura

1 6azus Ale/andruConstantin

19%* C3 I DA

$ 0ecuceanu ucurestiDescriere H3olvolize in sisteme ciclopropilcarbinilice. - 19)4 - 1949 Cercetator Principal 222 F Centrul de Chimie rganica F C. D. Nenitescu,>ucuresti


14/37

Descriere H6eactii de alchilare 7riedel-Crafts.

- 1949 - 1991 Cercetator Principal 22F Centrul de Chimie rganica F C. D. Nenitescu, >ucurestiDescriere HChimia compusilor azulenici.

- 1991 F prezent Cercetator Principal 2 F Centrul de Chimie rganica F C. D. Nenitescu,

>ucurestiDescriere HChimia compusilor azulenici.

2. E&perienta in domeniu Activitate de peste 1( ani in studierea influentei sistemului azulenicasupra unor structuri din care acesta face parte caracterizarea compusilor obtinuti si reflectareacon!ugarii azulenei cu restul moleculei in proprietatile fizice si chimice, mecanisme de reaeactie.Au fost utilizate procedee de analiza fizico-chimica in scopul caracterizarii complete a sute decompusilor azulenici nou sintetizati. &nele dintre procedee si rezultate au facut obiectul unorpublicatii specifice. Activitate de cercetare de peste '( ani in domeniile sintezei compusilororganici, a caracterizarii lor, a studierii proprietatilor fizico-chimice si a determinarii unormecanisme de reactie, activitate recompensata prin premiul Academiei 6omane. Are peste 4lucrari publicate in reviste de prestigiu, conferinte tinute in tara si strainatate, peste ' participari

la simpozioane din tara si strainatate.3. )revete de inven*ii/. Procedeu de preparare a dietil-zincului. 0re*e) RSR 53 582 di" 22.1/.//.2. Procedeu de preparare a clorurii acidului dicloracetic.0re*e) RSR 5 61/ di" //.18./813. Procedeu de preparare a clorurii acidului dicloracetic.0re*e) RSR 63 di" 18.18./8/4. Procedeu de preparare a clorurii acidului dicloracetic.0re*e) RSR 8 15 di" 18.18./8/5. Procedeu pentru prepararea 1-fenil-4-etiloctan-1,3-dionei. 0re*e) RSR 1 46/ di" /5.15./866. Procedeu pentru purificarea glucoheptonatului de sodiu.0re*e) RSR /1/ 548 di" 24.1./1.. Procedeu catalitic pentru prepararea 5-alchil-salicilaldehidelor. 0re*e) Ra" /12 463 di" 31./1/1.

#. +ucrari semnificative pulicate:/. A.C. Raz%$, . er)heier, . 0adea a"d A.-M . &la)z, Solol!tic "ehaiour of Strained S!stems.#he "enzo$b%bic!clo$3.1.&%hex-'-en-4-!l cation, 7e)rahedr" e))er$, 1()5, 22-23, /-/812.

2. S.A. O$adchii, .9. Maa):%; ,

.&. Sh%+i", A.C. Raz%$, . Chem. Soc., Perkin Trans., 1, '&&1, /22-/233.

. A. C. Raz%$, . 0irza", S. Nae, . Cri$)ia", . Chirale% a"d . Ci(ea"%, zulene-1-azop!ridine 12-oxidesDes and P!m., '&&3, "#, 223-233.

8.. A. C. Raz%$, C. Ni)%, . 7ec%cea"% a"d . Ci(ea"%, '-Substituted azulen-1-!lethenes$ur. J. %r!.Chem., '&&3,411/-41/1.

. . Cri$)ia", 9. Sa$a;i, P. . acri!, 0. ?""adie%, 9. A$$el+er'h$, K. Cla:$ a"d A. C. Raz%$, onatingStrenght of zulene in arious zulen-1!l Substituted *ationic !es6 pplication in onlinear


15/37

/ptics. Chem &ater., '&&4, 1', 3543-355/.

/1.. A. C. Raz%$, C. Ni)%, C. Pa*el, C.-A. Ci%c%le$c%, . Ci(ea"%, C. S)a"ci% a"d P. P. P@er, /xidationof 1-42-substituted phen!l-'-4-meth!lphen!ldiazene7 benz!lic substitution versus *-azo bondbrea+ing Canad. J. Chem., '&&5,83, 244-251.

//.


16/37


17/37

10.%.1.!.!. ercetatori in formare

In echipa de lucru sunt inclusi si tineri cercetatori, urmarindu-se promovarea acestora si elaborarea

unor teze de doctorat de inalta valoare stiintifica1. 6irzan, Claudia +avel, ana Lehadus, Andreea Corbu,7ilipChiraleu and Cristian 2nacheAzulene-substituted +ridines and +ridinium 3alts. 3nthesis

and 3tructure. $. Azulene-substituted pridinium saltsJ. Heterocyclic Cem $*, 44,$(1-$).$. I>6 Mi,aelaF asistent cercetare- Centrul de Chimie rganica F C.D. Nenitescu

Lucrari publicate 1.1,%-Dipolar ccloaddition reactions of 1-"%-nitrophenacl#-1,1-phenanthrolinium N-lideQith activated al?nes 7. Dumitrascu, C. Draghici, 5. 6. Caira, A. >adoiu, L. >arbu, 5. Cristeari$oc, !005"/#, 1)(-1*% $. 3nthesis and @-ra 3tructure of a neQ +rroloR1,$-bS-pridazine Derivative 5. 6. Caira, 7.Dumitrascu, C. Draghici, D. Dumitrascu, 5. Cristea5olec%les, !005&1!,%)-%)). % Azulene Derivatives 3oluble In +olar 3olvents. 1-"Azulen-1-l#-$-"0hien-$- or %-l#-2thenesAle/andru C. 6azus, Liviu >irzan,


18/37

/biectie@ctiitati ;esurseumane

om x luna

Re$%r$e %a"eFa)erialeA+re*ieriG CP B crd"a)r

(riec)< /...4 B e!ec%)a") /...4

;esursefinanciare de la

buget;/

8#P 9 '&&)@3 luni

Documentare sinteza #e materii primeE

incercari preliminare

) persoane T.() luni

C+ F stabilireresponsabilitati in cadrul

proiectuluiP II = !00 @ % luni

"btinerea #erivatilor bisazoici monoazulenici

) persoane T.*( luni

C+ F stabilireresponsabilitati in cadrulobiectivului


19/37

( persoane T

.9% luni

obiectivului

1"1.1.# 1$1*)

1%"1'.1%# 1'4$'

3inteza derivatilor trisazoici monoazulenici 2$, 2%, 2', 2( F obtinereprodusi

Caracterizarea produsilor obtinuti

corelarea spectrelor &ruc?er Avance ', 18 F 65N ' 58z 1% C F 65N 1.)$ 58z ,uzura medie (U,cromatograf C-7I33N3


20/37

11. Although ?noQn for a long time, azoderivatives still remain in the attention of the chemistsdue to the une/pected results lin?ed Qith their structure and their phsico-chemical propertiesimportant for some top industrial branches.As it Qas proved from our previous papers,1the stud of the snthesis and properties of some

special azoderivatives hoQ is the case of those that contain an azulene in the molecule is lin?edboth on scientific interest and industrial applications. 3ome peculiar phisco-chemicalproperties enable them to be used in man fields starting Qith that classical ones, as des andfinishing Qith most up to date ones in data stoc?ing and transmission. In the case of the azoderivatives, Qas proved that their NL properties are enhanced b the increasing of the sstempolarit and of the length of the chromophore, as a result of the increasing of the number ofcon!ugated double bonds present "including azo#. 0herefore, it Qas observed that bis azo

derivatives have the , , , coefficients much higher than those registered for the

corresponding mono azo compounds.$0he Guantum mechanics have also shoQn that both thereplacement of the benzene sstem, Qhich are hardl polarizable Qith others that possess adiminished aromatic character and are therefore easier to be polarized, and the introduction of

polarizing groups as nitro or amino induce a significant increase of the above mentionedcoefficients.% 0he utilization of the azoderivatives as stoc?ing products has also beeninvestigated.' 0hese can be used also as des for materials and plastic fibers, for in?manufacture and stamp in?s, for the photographic industr( or in the laser technologies.Azoderivatives Qith loQ smmetr have liGuid crstal properties)and other diazenes are usefulas charge carriers.*

0he pro!ect is structured in three sections11.1 +henlene bisazoazulene derivatives. 0his section contains '.1.1. the preparation of roQmaterials '.1.$. the preparation of o-, m-, orp-phenlene-bisazoazulenes Qith a smmetric oran asmmetric structure '.1.%. the stud of the magnetic, optic or acid-base properties of thesecombinations.

11.$. +henlene bis azoazulenes derivatives containing polarizating functional groups atazulenes moieties '.$.1. the preparation of the roQ materials '.$.$. the preparation of theazulenic compounds '.$.%. the stud of their phisico-chemical properties.11.%. 0ris and pol azoazulenic derivatives '.%.1. the preparation of the roQ materials '.%.$ thepreparation of the azulenic compounds '.%.%. the stud of their phisico-chemical properties.11.1 P,enlene bis azoazulenes #erivatives

Azulene is an aromatic hdrocarbon Qhich is polarized due to the transition of anelectron toQard the five-atom ring for achieving an aromatic se/tet at both ccles.

_ +

0herefore azulenes acGuires a nucleophilic character Qhich appears at five-memberedring at the positions 1 and % Qhich permit its coupling Qith reactive diazonium salts contrar tothe benzenoid aromatic hdrocarbons that need activation electron donor groups for azocoupling reactions. At the same time, the diazonium salts obtained from 1-azulenamines are not

stable and give azo coupling reactions onl Qith ver reactive substrates such as -naphthol.

As a conclusion, it can be postulated that the azulenic bisazoic derivatives can beprepared onl b coupling a diazonium salt possessing a benzenic core Qith an azulenic


21/37

molecule.11.1.1. >,e preparation of t,e roF materials

7or the ma!orit of the coupling reactions commercial reagents are used.0he generation of bis azoderivatives containing onl one azulenic moiet into the

molecule reGuires the snthesis of amino-azobenzene isomers. 0he easiest to be obtained is the

para-isomer Qhich results in one "or tQo# step b the aniline diazotization folloQed bcoupling of the resulted diazonium salt Qith an e/cess of the aniline and in sit%transposition ofthe generated triazene.

NH2 N N N

HN N NH

2

0he snthesis of meta-isomer needs tQo steps indifferentl of selected route.

NH2

NO2

PhNO

N

NO2

N Ph

Na2S

N

NH2

N Ph

NH2

NHAc

PhNO

N

NHAc

N Ph

ClH

N

NH2

N Ph

7or the ortoisomer, the reduction of the nitro group is not selective and therefore thesingle accessible Qa remains that using the mono acetlated derivative commerciall

accessible.NH

2

NHAcPhNO

N N Ph

NHAc ClH

N N Ph

NH2

11.1.!. >,e preparation of p,enlene bisazoazulenic #erivatives

0he proposed derivatives possess tQo identical or different azulenic moieties. In the firstcase, theoreticall, Qould be easier the direct coupling of the azulenic derivative Qith diazotizedphenlenediamines. 0he stabilities of these salts and also of their redo/ compatibilities Qithazulenes, hoQever, rises some problems.

It is ?noQn thatp-phenlenediamine can be bis diazotized onl in strong acidic mediaand the obtained bis diazonium salt decomposes at dilution or neutralization. 0here Qerereported until noQ onl its azo coupling reactions Qith phenols.

NH2

NH2 N

2N

2

++

2 HSO4-


22/37

0he coupling Qith azulenes in a sulfuric acid medium seems to be prohibited due totheir loQ stabilit in strong o/idant and acidic media. 0here are tQo possible Qas for solvingthis problem namel "a# starting from 1,% or 1,'-acetlaminoaniline Qith a hdroltic step, aspresented beloQ for the for para-isomer.

NH2

NHAc

NaNO2HCl

AzH

NN NHAc

NaNO2+ HCl

AzR

di!a"

N

N NH2

N

N NN

R#

R

R R

HCl

R, R# = H, Me3 $a% &%

"b# 0he other route consists in m- orp-nitroanilines diazotization, coupling of the intermediatesalt Qith azulenes and the reduction of the nitro group to amine Qhich finall is diazotized andcoupled. 0his Qa seems, hoQever, hazardous if Qe consider the sensibilit of the azulenederivatives at the reducing media Qhen free radicals are generated.

NH2

NO2

NaNO2HCl

AzH

N

N NO2

NaNO2+ HCl

AzR

N

N NH2

N

N N

N

R#

R

R R

Na2S

R, R# = H, Me3 $a% &%

0he bis diazonium salt resulted from m-phenlenediamine b bis diazotization has a

loQer o/idant character and, therefore has a greater possibilit to succesfull couple Qithazulene derivatives. 2ven in this case, if asmetric derivatives are desired Qith tQo differentsubstituted azulenic moieties the single possible snthetical Qa ramains the above analsedstepQise route.


23/37

NH2

NH2

N

N

N

N

NaNO2HCl

AzR

R

R

R = H, 4,6,8-Me3, 3,8-Me2-5-iPr

0he sntheses become more complicated for the o-isomer Qhere secondar reactionsare possible Qith benzotriazole formation. 0hus, both o-phenlenediamine and itsmonoacetlated derivative generate benzotriazoles b treating Qith sodium nitrite andhdrochloric acid, therefore, the N-acetlaminoaniline can not be used as starting material forthis target.

NHAc

NH2

NaNO2

ClH N

N

N

R

NH2

NH2

NaNO2

HCl

R = H, Ac

0he Qa starting Qith o-nitroaniline also fails because the nitro group in ortopositioncannot be cleanl reduced to amine and onl transposition products results. o-+henlenediamine could be bis diazotized in concentrated sulfuric acid the generated salthoQever is in such degree unstable that can not be coupled Qith azo group preservation.

0herefore, other paths must be found to lead to the desired products as for e/ample, thegeneration of o-"N-phthalimido#-aniline, its diazotization folloQed b the coupling of theresulting diazonium salt Qith azulenes. 0he protecting group, phthalol can be removed btreating the product Qith hdrazine and than the neQ amine can be diazotized and coupled Qithanother molecule of an azulene derivative. In this case the coupling Qill ta?e place Qithoutcclization because there is no nitrogen proton remained to be replaced b azo group and thephthalimidic group is stable enough to not be opened b the attac? of the diazonium ion.4


24/37

NH2

NO2

O

O

O

N

NO2

OO

N

NH2

OO

N

N

OO

N

N2H

4 NH2

N NN

N N

NHNO

2

AzR#

HNO2

AzR

RR

R

R#

H2

Ni-Ra

11.1.%. >,e stu# of t,e p,sical properties of t,e snt,esize# #erivatives

0he first part of this section Qill start Qith the calculation of the geometries and of the

electronic densities of the snthesized molecules using 5+AC program. It is important to?noQ if the orto isomer is planar or not and if the resulted geometr alloQs it to formcomple/es Qith metals ions, Qhich Qould increase the impact of our stud. At the same time,the substitution of azulenes Qith methl at the position 4 could hinder the co planarit ofazulene Qith the entire molecule and therefore could change the chromophore.

All the compounds Qill be characterized b N56 proton and carbon spectra. 0heinfluences of the phenl replacement Qith azulene moieties or the differences induced b thedisappearance of the molecule smmetr b azulene substitution Qith al?l groups Qill bestudied. 0hese facts Qill be also correlated Qith push-pull effects generated b the structures ofthe snthesized compounds. 0his fact is important due to the potential hperpolarizabilit ofthese materials.

A special attention Qill be accorded to the stud of the electronic spectra. It Qill beobserved the influence of the solvent and of the p8 on the Qave length for the most importantband in visible region. 0he solvatochromism of the obtained products Qill be treated vercarefull for finding signs of their hperpolarizabilit. 0here Qill be determined also theisosbestic points Qhere the e/ist and Qill be calculated the bazicit constants of theazoderivatives b measuring the p8 in Qhich are present eGual concentrations "absorptions# ofacidic and basic form of compounds.11.! P,enlene bis(azoazulenes) #erivatives substitute# at azulene Fit, functional groups

Azulenes are on the limit of the coupling capacit of the normal diazonium salts. 0hecoupling reactions are possible Qith the unsubstituted azulenes, substituted Qith al?l or if atposition 1 there is one electron donor group Qhich activates azulene. 0he azulenens substituted

at position 1 Qith electron QithdraQing groups Qill not couple in normal conditions. 8oQever,there are ?noQn some e/ceptions. 7or e/ample, an acetl group has a higher mobilit aselectrophilic leaving group than the proton has and more of that its substitution is not reversibleas in the case of proton. 0herefore, it can be substituted b an azo group in severe reactionconditions, at high temperatures unusual for normal coupling reactions.9


25/37

OO

NH2

O2N

NaNO2

N

O

N

NO2

N

O

N

NH2

NaNO2

R

N

O

N N

NR

AcCl

S"Cl4 HCl

H2

Pd

HCl

R = NHAc, OMe, OOCPh

It is possible that this reaction Qa to be also used for other derivatives as describedbeloQ

MeOOC

OO

MeO NH2

O2N

NaNO2

N

O

N

NO2

MeO

N

O

N

NH2

MeONaNO

2

R

N

O

N NN

RMeO

AcCl

S"Cl4 HCl

H2

Pd

HCl

R = 'r%(a ac)i*a")a $a% $la dezac)i*a)are

0he use of the substituted azulenes at position 1 needs the snthesis of the roQ materialsbecause these azulenes are not commerciall available.

0he snthesized bis azocompounds Qill be characterized b the procedure described inthe previous chapter. It Qill be studied their magnetic resonance spectra and mainl electronicspectra for emphasizing the influence of the functional groups on the phsical properties of theproducts.11.$ >,e preparation of polazo#erivatives

> increasing the number of the azoic groups the mechanical properties of the materialis enhanced and at the same time the phsical properties are modified, usuall a bathochromicshift could be observed.

0here are a high number of possible polazoderivatives containing azulene, phenleneand azo groups. 0herefore, some more accessible combinations Qere considered, Qhosesnthesis could be realized in several steps using the intermediates alread prepared. 8ere ispresented one e/ample


26/37

N N

NH2

ON NO2

N N

N N NO2

N N NH2

N N

N N

N N N N

Na2S NaNO2

AzH

HCl

11.%. >,e stu# of re#ox potentials of t,ese combinations

ur team in collaboration Qith the &niversit +oltehnica >ucharest has studied thereduction and o/idation potentials of numerous azoic derivatives of azulenes. Be propose toe/tend this stud also to the bis azoderivatives and polazoderivatives to determine the possibleredo/ reactions on these sstems. In the folloQ table Qe e/emplifies some electrochemical data

/idation and reduction potentials of some p-substituted azobenzenes C)8(-N:N-C)8'; "p#and azoazulenes Az-N:N-C)8'; "p# "1 m5# obteined b D+irzan L., Nae 3., Cristian

L., Chiraleu 7., 5aganu 5., Cimpeanu revet + )-1$() din 194(

42. D. >ergmann, 5. >entar . rg. Chem. 19(', 19, 1(9'.

9. 8afner, A. 3tephan, C. >ernhard ust. Lieb. Ann. Chem. 19)1, )(,'$

1rezultate nepublicate inca

11.!. ProGect obGectives

0he pro!ect that Qe propose considers several important scientific and actual ob!ectives.1.0he first ob!ective is the elaboration of a procedure for the snthesis of some compoundsbelonging to a neQ class, that of bis- and polazoderivatives Qhich contain in their moleculesphenlene, phenl and azulene-1-l radicals. 0he introduction of the azulenic moieties inducesa superior polarization than those observed for similar sstems that have onl benzenoidearomatic groups b increasing the energetic values of the 85 orbitals and decreasing thoseof L&5 orbitals. 0he snthesis of the proposed compounds presents the novelt element due

to the fact that the diazonium salts of azulenes are not stable compounds and therefore man ofthe usual coupling reactions can not be realized using these salts. In these conditions the roQmaterials must be the diazonium or tetrazonium salts Qith benzene nuclei and the couplingcomponents Qill be the azulene derivatives. 8oQever, azulenes being moderate nucleophilescan not also couple Qith an diazonium salts. Neither nitrosoderivatives of azulenes can beconsidered for the generation of the azo compounds due to their loQ stabilit, being obtainedonl at loQ temperatures. 0he preparation and the coupling of the bis azo compounds generatedfrom phenlenediamine presents also a series of peculiarities Qhich must be considered. Bebelieve that some of the snthesis should have as starting materials anilines on Qhich is lin?ed asubstituent able to easil generate an amino group for e/ample a nitro group. 3o, the stud ofthe snthesis of these derivatives presents scientific interest and is not a cosmetic snthetic

route.$.0he second ob!ective is the unambiguous determination of the structures of the obtainedproducts and the stud of their phsico-chemical properties. 0he chemical structure of the di-and polazoderivatives ma?es possible a stud regarding the influence of the dihedral anglebetQeen the aromatic nuclei on the the con!ugation or the eventuall generation of ananchimeric chiral combination. 6egarding the structure of the obtained products Qill be alsostudied its influence both on the N56 and electronic spectra. As has been alread mentionedabove, it is li?el that these compounds to present a superior polarization and polarizabilit thanthose of monoazo compounds due to the enhanced con!ugation possibilities on a higher numberof pi atoms. It is also ver li?el that betQeen the snthesized isomers, some of them thatcontain different azulenic groups to shoQ up combination that could crstallize in

noncentrosmmetric sstems and, therefore, to possess good NL properties. 0he samestructural characteristics can also generate the liGuid crstal Gualities to some other materialsfrom the same class.%.0he third ob!ective is the electrochemical characterization of the snthesized compoundsusing both cclic voltammetr and potentiostatic method. 0he results obtained b the stud ofthe electrode ?inetic Qill be used to the elaboration of some possible mechanism of theelectrochemical reactions. 0he specificit of the proposed sstems consists in the concomitantpresence of a reducing pole belonging to an azulene derivative and of a relativel o/idant onerepresented b the azo group, Qhich could generate neQ products b interacting Qith theelectrodes. It can be anticipated the preparation of dimmers, oligomers or polmers Qithinteresting electric properties. 0he snthesized products during this pro!ect can be utilized in

electrochemical purposes, for e/ample, electrode coverings or the generation of some sstemsof comple/ electroltes.'.0he last ob!ective is the fact that the beginning of a comple/ themes and relativel completeof fundamental research b the oung researcher in formation Qill give them the possibilit tobecome good research specialists and a part of the papers can be developed toQard thesustaining of a doctoral theses. 5ore of that, for several ears, in collaboration Qith theinstitutions of superior education, a part of the students from the last ear of stud ma?e theire/periments for their diplomas in our labs. 0he same thing is valuable and for those Qho arefolloQing their 53 programs and is sufficient to remember that almost all our +h-D. studentsQor? their e/perimental part of their 53 dissertations in our teams. 0he proposed ob!ectivesharmonize Qith those of our collaborators from 2uropean countries such as erman, 7rance or

7inland. 0he results of these previous researches have been alread published in manprestigious chemical !ournals or presented at smposia and congresses


27/37

11.$ esearc, met,o#olog

0he pro!ect contains both e/perimental and theoretical parts.6xperimental activit consists in the preparation of the starting materials and of the targetproducts-bisazoderivatives containing azulenic moieties into the molecules. It involves both thechemical snthesis of the chemical compounds and the column chromatograph on alumina orsilica gel for their purification. 7or the testing of the purit or the folloQing of the reactions"usuall for uncolored reagents# Qill be used our 8+LC apparatus.naltic control of the obtained products Qill be done b high performance N56spectroscop using high resolution apparatus of % 58z and ' 58z. Also, 53 spectra Qill


28/37

be done using 23I procedure, Qhich is the most adeGuate for our relativel big and polarmolecules.*v-+iz stu#ies- the curves for the determination of the isosbestiGues of the neQ snthesizedcompounds Qill be realized on devices for electronic spectra bought recentl b our team thathave high resolutions. Also, the p8-measurement of the solutions Qill be done using a brand

neQ device bought from rion Compan.6lectroc,emical stu#ies Qill be e/ecuted partiall at the &niversit +oltehnica >ucharest andpartiall in our group after the acGuisition of a potentiostat. 0he &niversit 2lectrochemicalDepartment possesses modern apparatus for electrochemical characterization of the compounds.>,e t,eoretical part is based on correlations of o/idation and reduction potentials Qith theL&5 and 85 energies and on calculus of bond lengths and dihedral angles Qith the helpof the Guantum mechanical program-5+AC.

11.%. ecessar resources

11.%.1. &C8A6230

position C3 II1. Hears of service at actual For2ing place-!ears!. ompetence fiel#s& significantl results:

>,e stu# of total c,iral snt,esis of natural pro#ucts. >etQeen 199$ and 199( it Qasstudied the total chiral snthesis of 6oGuefortine C at 6ochester &niversit, NeQ Eor?, &3Aand also some chiral snthons Qere prepared for the snthesis of some immunit depressives.>,e stu# of t,e electrop,ilic an# ra#icalic substitution reactions on azulenic nucleus . 0hefirst preoccupation consisted in the stud of the halogenation reaction Qith the metallic halideson this sstem. b# 0he stud of the diazotization and coupling reaction on heterocclic andazulenic sstems. c# 6eactions for preparation of the imines, amines, amides, carbamates ofazulenes and its dimers. d# 6eduction and al?lation N-o/ides to amines in the presence of an

azo group proving the compatibilit betQeen an N-o/id function and an azulene moiet. e# 0hepreparation of the first -di?etones containing an azulenic group open the road for the snthesis

of numerous heteroccles Qith ( or ) atoms into the molecule, such as prazols, o/azoles, etcthat possess azulene in their structure. f# snthesis of prlium, pridinium salts and pridinescontaining azulene moieties. g# Correlation of the chemical properties Qith Guantummechanical data and Qith nucleophilic reactivit inde/es. h# 0he stud of the reactionmechanism regarding above transformations. i# 0he stud of the correlation betQeen structureand chemical shifts of protons and carbon atoms and the splitting of the azulenic derivatives in


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the mass spectrometers. I participated at numerous technologies for the assimilation ofintermediates needed for national chemical industr till 1949.

3. Articles pulished ith relevance for this pro4ect !selection"1.A. C. 6azus L. >irzan 3. Nae 3. A. 6azus irzan, 3. Nae, L. Cristian and 7. Chiraleu zulene-1-azopri#ine 14-oxi#esDyes and Pigments !00$, "7, $$%-%%.%. A. C. 6azus, L. >irzan, 3. Nae, 5. N. 3urugiu and irzan, 3. Nae, . L. Lehadus, C. +avel and . Costan zulenic -2etones.nt,esis& properties an# reactions to form five membere# aromatic ,eteroccles ri$oc!005"/#, *1-4(. (. 2.-5. &ngureanu, A.C. 6azus, L. >irzan, . >uica, And 5-3. Cretu 6lectroc,emicaltu# "f 1-Met,lazulene .P./. +ci. /%ll., +eries /, !005, '7(0),4$-44.). Ale/andru C. 6azus, Liviu >irzan& Nina 5irela 3urugiu, Andreea Cristina Corbu and 7ilip

Chiraleunt,eses of zulen-1-l-benzot,iazol-!-l DiazenesDyes and Pigm. !00', 74(1),$)-%%.*. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Cristina Corbuand Cristian 2nache zulene-substitute# Pranlium alts. nt,eses an# Pro#ucts,aracterizationJ. Heterocyclic Cem.!007& 40, 9)%-**.4. 2leonora 5. &ngureanu, Ale/andru. C. 6azus, Liviu >irzan,eorge >uica, 5ariana Cretuand 2nache Cristian 6lectroc,emical c,lorination of azulenic #erivatives. Insig,t intomec,anism of ano#ic oxi#ative c,lorinationlectrocimica cta !007& "& *9'-4%.9. Ale/andru C. 6azus, Liviu >irzan, Andreea Corbu, ana ;aharia and Cristian 2nachent,esis an# Properties of %-($-ubstitute# azulen-1-l)-!&7-#ip,enl-pri#ines ri$oc

!007, 1, 1$1-1$9.

1. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Corbu,

7ilipChiraleu and Cristian 2nache zulene-substitute# Pri#ines an# Pri#inium alts.nt,esis an# tructure. 1. zulene-substitute# pri#inesJ. Heterocyclic Cem& !00', 44,

$'(-$(.11. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Corbu, 7ilip

Chiraleu and Cristian 2nache zulene-substitute# Pri#ines an# Pri#inium alts.nt,esis an# tructure. !. zulene-substitute# pri#inium salts J. Heterocyclic Cem!00', 44,$(1-$).#. $atent

1. Cataltic procedure for the preparation of (-al?l-saliclaldehides. +atent 61$')% from %.1 199.. 5he list of the scientific communications that are relevant for the pro4ect

1. zulene-1-azopri#ine& snt,esis-al2lationA. C. 6azus, L. >irzan, 3tefania Nae,irzan, 3. Nae, N. 5. 3urugiu, A. Negoescu si


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de Chimie )-4 ct. $', Calimanesti-Caciulata'. Pri#inium an# bis-pri#inium salts substituite# Fit, !-(azulen-1-l)et,enes.

nt,esis& properties& uses as /" materials. A. C. 6azus, L. Cristian, L. >irzan, 3. Nae, .Costan si C. 2nache- a @@arzan, A. C. 6azus, 5. 3. Cretu, 7. 5. 0ugurel, +D-4,Conferinta Nationala Chimia, $), vidius Constanta

4. Mec,anisme #e ,alogenation electroc,imi9ue #es composes azuleni9ues 2.-5.&ngureanu, A. C. 6azus, L. >arzan, . >uica, Le Guatrieme colloGue franco-romain de

chimie appliGue, $4 uin-$ ulliet $), Clemont-7errand, 7rance9. >,e snt,esis of some pranlium salts an# of some pri#ine substitute# in %position Fit, azulen-1-l ra#icals Ale/andru C. 6azusM, Liviu >irzan, ana Lehadus,Claudia +avel, Liliana Cristian, ana ;aharia si Cristian 2nache, +oster la al-$9-lea 3impozionNational de Chimie, Calimanesti-Caciulata, irzan, . Lehadus, C. +avel, C. 2nache, +oster la al-$9-lea3impozion National de Chimie, Calimanesti-Caciulata, irzan, +oster at the 1'th2dition of the Conference of 5icrosensors, 5icroactuators and 5icrosstems, Lon, 7rance,

une 1-1', $*%. E&perience accumulated in national and international pro'rams ubstitution reactions on azulenic sstems.


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>,e snt,esis an# t,e stu# of some azulen-1-azo-,eterocclic materials Fit, ,ig,

,perpolarizabilit&participant, CNC3I3, une $'-november $'


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3tage at IC '' ears1. Beneral experience:

19(9-19) 3tagier engineer F3IN07A65 +lant Fdrugs production19)-19)$ 0echnolog chief sector as above19)$-19)' Ingineer- Centre of rganic Chemistr-solvolsis in ccloproplcarbinl sstems

19)'-19)4 3cientific researcher -as above19)4-1949 3enior researcher III -as above-7riedel-Crafts al?lation reactions1949-1991 3enior researcher II-as above- 0he chemistr of azulenes1991-present 3enior researcher I -as above2. E&perience in the pro4ect field:7or more than 1( ears, Dr. 6azus put the accent on the stud of the influence of the of theazulenic sstem on some structures from Qhich it belongs characterization of the compoundsobtained and the reflection of the azulene con!ugation Qith the rest of the molecules in theirphisico-chemical properties. 0here have been used procedures of phisico-chemical analsis inthe scope to completel characterize hundreds of neQ snthesized azulenic compounds. 3ome ofthe procedures and results have made the sub!ect of specific publications. 8e has a prestigious

research activit Qhich covers '( ears in the fields of the snthesis of the organic compounds,of their characterization and of the stud of their phsico-chemical properties and for thedetermination of some reaction mechanisms, activit reQarded b the prize of the 6omanianAcadem. 8e has 4 papers published in prestigious !outrnals, conferences both in our countrand above, more than ' participations to the smposia hold in 6omania and abroad.3.$atents1.+rocedure for preparation of diethlzinc +atent 6(%(4$ from 19*1$.+rocedure for the preparation of the dichloroacetic acid chloride +atent 6*()1 from 194%. +rocedure for the preparation of the dichloroacetic acid chloride +atent 6**9)% from 1941' +rocedure for the preparation of the dichloroacetic acid chloride +atent 6*49( from 1941(. +rocedure for preparation of 1-phenl-'-ethloctan-1,%-dione. +atent 69')1 from 194)

). +rocedure for the purification of sodium glucoheptonate +atent 611('4 from 199*. Cataltical procedure for the preparation of (-al?l-saliclaldehdes +atent 61$')% from199.#. i'nificantl8 pulished papers:/. A.C. Raz%$, . er)heier, . 0adea a"d A.-M . &la)z, Solol!tic "ehaiour of Strained S!stems.#he "enzo$b%bic!clo$3.1.&%hex-'-en-4-!l cation, 7e)rahedr" e))er$, 1()5, 22-23, /-/812.

2. S.A. O$adchii, .9. Maa):%; ,

.&. Sh%+i", A.C. Raz%$, . Chem. Soc., Perkin Trans., 1, '&&1, /22-/233.

. A. C. Raz%$, . 0irza", S. Nae, . Cri$)ia", . Chirale% a"d . Ci(ea"%, zulene-1-azop!ridine 12-


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oxidesDes and P!m., '&&3, "#, 223-233.

8.. A. C. Raz%$, C. Ni)%, . 7ec%cea"% a"d . Ci(ea"%, '-Substituted azulen-1-!lethenes $ur. J.%r!. Chem., '&&3,411/-41/1.

. . Cri$)ia", 9. Sa$a;i, P. . acri!, 0. ?""adie%, 9. A$$el+er'h$, K. Cla:$ a"d A. C. Raz%$, onatingStrenght of zulene in arious zulen-1!l Substituted *ationic !es6 pplication in onlinear

/ptics. Chem &ater., '&&4, 1', 3543-355/./1.. A. C. Raz%$, C. Ni)%, C. Pa*el, C.-A. Ci%c%le$c%, . Ci(ea"%, C. S)a"ci% a"d P. P. P@er,/xidation of 1-42-substituted phen!l-'-4-meth!lphen!ldiazene7 benz!lic substitution versus*-azo bond brea+ing Canad. J. Chem., '&&5,83, 244-251.

//.


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,perpolarizabilit, pro!ect manager, CNC3I3, une $'-november $'i)ucharestDescription Hrganic snthesis- !anuar $ F september $' #esearc assistant - Centre of rganic Chemistr F C. D.Nenitzescu, >ucharestDescription H0he chemistr of azulenes- september $' F present +cientiic researcer - Centre of rganic Chemistr F C. D.Nenitzescu, >ucharest

Description H0he chemistr of azulenes!. 6xperience in t,e proGect fiel#:

Dr. 0ecuceanu has e/perience in snthesis of derivatives of azulenes, Qhich is starting materialsfor another neQ compound. 0he pathQa to obtain this compound is one original. 3he ta?e partto the elaboration of a neQ Qa to obtain vinl-azulenes compounds, method in agrees QithHgreen chemistr, Qho Qants to protect the environment. In December $) she sustains inpublic her +h. D. H$-3ubstituted-1-"azulen-1-l#ethene. 0he substituents influence to snthesis,mechanism of reaction and products proprieties, under supervision of Dr. 2ng. Ale/andru C.6azus.%. ignificantl publis,e# papers:

1. 1&1-iazulene Derivatives. nt,eses an# eactions& A.C. 6azus, L. >irzan, 3. Nae, C.

Nitu,


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11.%.1.!.!. Houng esearc,ers

In our Qor?ing team are included also oung researchers, loo?ing after their promovation andthe elaboration of a high level +hD thesis

1. 6nac,e ristian-researcher, +h. D. student+ublished papers

1. 3nthesis and +roperties of '-"%P-3ubstituted azulen-1P-l#-$,)-diphenl-pridines. A. C.6azus, L. >irzan, Andreea Corbu and C. 2nache, Ar?ivoc, !007, 1$1-1$9.$. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Corbu,7ilip

Chiraleu and Cristian 2nache Azulene-substituted +ridines and +ridinium 3alts.3nthesis and 3tructure. 1. Azulene-substituted pridinesJ. Heterocyclic Cem, $*, 44,$'(-$(.%. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Corbu,7ilipChiraleu and Cristian 2nacheAzulene-substituted +ridines and +ridinium 3alts.3nthesis and 3tructure. $. Azulene-substituted pridinium saltsJ. Heterocyclic Cem$*, 44,$(1-$).$. ristea Mi,aela-research assistant-Institute of rganic Chemistr C. D. Nenitzescu

+ublished papers 1.1,%-Dipolar ccloaddition reactions of 1-"%-nitrophenacl#-1,1-phenanthrolinium N-lide Qith activated al?nes 7. Dumitrascu, C. Draghici, 5. 6. Caira, A. >adoiu, L. >arbu, 5.Cristeari$oc, !005(),1)(-1*% $. 3nthesis and @-ra 3tructure of a neQ +rroloR1,$-bS-pridazine Derivative 5. 6.Caira, 7. Dumitrascu, C. Draghici, D. Dumitrascu, 5. Cristea5olec%les,!005, 1!, %)-%)). % Azulene Derivatives 3oluble In +olar 3olvents. 1-"Azulen-1-l#-$-"0hien-$- or %-l#-2thenes Ale/andru C. 6azus, Liviu >irzan,


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/bAectis@ctiities Buman;esourcesom x luna

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spectra Qith the structure of the obtained bis azo

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