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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 surprizelor
legate de structura si de proprietatile lor fizico-chimice, dar ei a aplicatiilor lor importante in
ramuri 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 in
molecula azulena, este legat de ambele aspecte sus-mentionate.
Cateva proprietati fizico-chimice speciale ale acestor derivati le confera o larga gama de utilizari
incepand de la cele clasice de coloranti si terminand cu cele mai moderne, in stocarea datelor sau
transmiterea de date. In cazul derivatilor azoici au fost demonstrate si studiate proprietatile NL
ale acestora, care sunt intensificate de cresterea polaritatii sistemului si de cresterea numarului de
duble 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 altele
posedand un caracter aromatic mai redus si deci mai usor de deformat, precum si introducerea de
grupe polarizante, ca nitro sau amino, determina o crestere semnificativa a coeficentilor mai sus
mentionati.
%
&tilizarea de azoderivati ca produsi de stocare de informatie a fost de asemenea
investigata.
'
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 industria
fotografica
(
sau in tehnologia laserilor. Azoderivatii cu simetrie scazuta au proprietati de cristale
lichide,
)
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 sistemele
azulenice, '.$.1. sinteza intermediarilor. '.$.$. sinteza compusilor. '.$.%. studiul proprietatilor lor
fizico-chimice
1-.%. 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 spre
inelul de ( atomi de carbon realizandu-se, in felul acesta, un se/tet aromatic la fiecare ciclu
azulenic, cel de cinci si de sapte atomi.
_
+
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 deosebire
de hidrocarburile aromatice obisnuite, care necesita grupe donoare de electroni pentru a se implica
in reactiile de cuplare. In acelasi timp, sarurile de diazoniu provenind de la 1-aminoazulene nu
sunt 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 cuplarea
unei 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, izomerii
aminoazobenzenului vor trebui preparati pentru a obtine derivatii bisazoici monoazulenici. Cel
mai usor de obtinut este izomerul para, care rezulta intr-o etapa prin diazotarea anilinei si cuplarea
sarii cu e/cesul de materie prima, urmata de transpozitia triazenei.
NH
2
N N N
H
N N NH
2
1enerarea izomerului meta necesita $ etape indiferent de calea aleasa.
NH
2
NO
2
PhNO
N
NO
2
N Ph
Na
2
S
N
NH
2
N Ph
NH
2
NHAc
PhNO
N
NHAc
N Ph
ClH
N
NH
2
N Ph
In cazul izomerului orto reducerea grupei nitro din pozitia orto nu este posibila si de aceea
singura metoda accesibila ramane cea prin derivatul monoacetilat, accesibil commercial.
NH
2
NHAc
PhNO
N N Ph
NHAc ClH
N N Ph
NH
2
10.1.!. "btinerea #erivatilor monoazulenici
Acesti derivati se vor obtine printr-o reactie de cuplare normala a celor trei izomeri ai
amonoazobenzenului. Acesti izomeri trebuie sa fie suficient de reactivi avand in vedere ca grupa
azo este relativ atragatoare de electroni si activeaza sarurile de diazoniu in reactia de cuplare.
N N Ph
NH
2
N N Ph
N
2
AzR
AcOK
NaNO
2
ClH
N N Ph
N N
R +
R = H, 4,6,8-Me
3
, 3,8-Me
2
-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 ele
si 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 cu
pastrarea azotului descrise in literatura sunt cele cu fenolii.
NH
2
N H
2 N
2
N
2
+ +
2 HSO
4
-
2ste destul de putin probabil ca azulenele sa se cupleze in mediu de acid sulfuric
concentrat datorita instabilitatii lor in medii o/idante si acide. De aceea o modalitate mult mai
sigura 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 izomerul para,
NH
2
NHAc
NaNO
2
HCl
AzH
N
N NHAc
NaNO
2
+ HCl
AzR
di!a"
N
N NH
2
N
N 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 si
cuplarea 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 la
reactii de tip redo/ in care sunt generati radicali liberi.
NH
2
NO
2
NaNO
2
HCl
AzH
N
N NO
2
NaNO
2
+ HCl
AzR
N
N NH
2
N
N N
N
R#
R
R
R
Na
2
S
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 cuplare
cu 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.
NH
2
NH
2
N
N
N
N
NaNO
2
HCl
AzR
R
R
R = H, 4,6,8-Me
3
, 3,8-Me
2
-5-iPr
3intezele devin mai complicate in cazul izomerului orto, unde pot interveni reactii
secundare cu formare de benzotriazoli. Astfel, atat orto-fenilendiamina, cat si derivatul sau
monoacilat formeaza benzotriazoli prin tratare cu nitrit de sodium si acid clorhidric, deci nu se
poate folosi calea pornind de la amina acilata.
NHAc
NH
2
NaNO
2
ClH
N
N
N
R
N H
2
N H
2
NaNO
2
HCl
R = H, Ac
Nici calea care porneste de la orto-nitroanilina nu da rezultatele dorite, intrucat grupa nitro
din pozitia orto nu se reduce curat la amina, ci da produsi de transpozitie. Orto-Fenilendiamina a
putut fi bis diazotata in acid sulfuric concentrat, dar sarea obtinuta este atat de instabila, incat nu
se poate cupla cu pastrarea azotului. De aceea, in aceste cazuri este necesara gasirea altor cai de
sinteza, care sa duca la produsii doriti. astfel de cale ia in considerare obtinerea ftalimidei
fenilendiaminei, diazotarea sa si cuplarea cu azulena. 1rupa protectoare ftaloil se poate indeparta
prin tratare cu hidrazina si apoi se diazotizeaza si se cupleaza cu o alta molecula de azulena. In
acest caz cuplarea va avea loc fara ciclizare, deoarece nu mai e/ista niciun proton disponibil la
azot si inelul ftalimidic este suficient de stabil pentru a nu fi e/pulzat de sarea de diazoniu formata
in pozitia orto.
4
NH
2
NO
2
O
O
O
N
NO
2
O
O
N
NH
2
O
O
N
N
O
O
N
N
2
H
4 NH
2
N N
N
N N
N
HNO
2
AzR#
HNO
2
AzR
R
R
R
R#
H
2
Ni-Ra
10.1.% tu#iul proprietatilor fizice ale #erivatilor sintetizati
+rima parte din aceasta sectiune va debuta cu calculul geometriilor si a densitatilor
electronice ale moleculelor sintetizate prin procedeul 5+AC. 2ste important de stiut daca
izomerul orto este planar sau nu si daca geometria rezultata ii permite sa formeze complecsi cu
metale, ceea ce ar spori imporanta studiului propus de noi. De asemenea substituirea azulenelor cu
metil 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 prin
inlocuirea unui rest fenil cu un radical de azulena sau diferentele ce apar prin disparitia simetriei
moleculelor prin substituirea azulenelor cu alchili. Acest lucru va fi corelat cu efectele push-pull
pe care structura produsilor obtinuti le poate promova. 7aptul prezinta importanta datorita
hiperpolarizabilitatii potentiale a acestor materiale.
atentie deosebita va fi acordata studierii spectrelor electronice. se vor pune in evidenta
influenta 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 indicatii
asupra hiprepolarizabilitatii acestora. De asemenea se vor determina punctele izosbestice acolo
unde e/ista si se vor calcula constantele de bazicitate prin masurarea p8-ului la care apar absorbtii
egale 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 de
cuplare sunt posibile la azulene nesubstituite, substituite cu alchil sau daca in pozitia 1 se afla o
grupa donoare de elecroni care activeaza azulena. Azulenele substituite in pozitia 1 cu grupe
atragatoare 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 si
substituirea sa nu este reversibila. De aceea ea poate fi substituita de o grupa azo in conditii dure
de reactie, la temperaturi ridicate neuzuale pentru reactiile de cuplare.
9

O
O
NH
2
O
2
N
NaNO
2
N
O
N
NO
2
N
O
N
NH
2
NaNO
2
R
N
O
N
N
N
R
AcCl
S"Cl
4 HCl
H
2
Pd
HCl
R = NHAc, OMe, OOCPh
2ste probabil ca acelasi tip de reactie sa poata fi folosit si pe alte tipuri de combinatii si pe
alti izomeri ai nitroanilinelor, in special p-nitroanilina,
MeOOC
O
O
MeO
NH
2
O
2
N
NaNO
2
N
O
N
NO
2
MeO
N
O
N
NH
2
MeO
NaNO
2
R
N
O
N
N
N
R
MeO
AcCl
S"Cl
4 HCl
H
2
Pd
HCl
R = 'r%(a ac)i*a")a $a% $la+ dezac)i*a)are
&tilizarea unor azulene substituite in pozitia 1 pune, totusi, probleme sintezei acestora
deoarece acestia nu sunt produsi comerciali.
Compusii bis azioici sintetizati vor fi caracterizati prin procedeele descrise in capitolul
anterior, studiindu-li-se spectrele de rezonanta magnetica nucleara, precum si cele electronice,
pentru a se evidentia influenta grupelor functionale asupra proprietatilor produsilor.
10.$. inteza #e poliazo#erivati
+rin cresterea numarului de grupe azoice se mareste rezistenta materialului si, in acelasi
timp, i se modifica proprietatile fizice.
Din numarul mare de combinatii posibile intre gruparile fenilen, azulenil si azo au fost
alese cateva combinatii mai accesibile, a caror sinteza ar putea fi realizata in cateva etape, iar un
e/emplu nerestrictiv este reprezentat mai !os,
N N
NH
2
ON NO
2
N N
N N NO
2
N N NH
2
N N
N N
N N N N
Na
2
S
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.
1-
Ne propunem sa e/tindem aceasta preocupare la
derivatii 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# si
azoazulene Az-N:N-C)8'; "p# "1 m5# obtinute prin D+<.
; in C)8(-N:N-
C)8'; "p#
21=$
o/
21=$
red
; in 1-Az-N:N-
C)8'; "p#
21=$
o/
21=$
red
N8$ -.(4% -$.-)'
p5e 1.1$* -1.4(' p5e -.'*( -1.)(-
8 1.%$- -1.*%% 8 -.)$- -1.)*%
pN$ 1.(1* -1.$$4 pN$ -.)'4 -1.$(-
+otentialele sunt masurate fata de cuplul ferocen=feroceniu
627262NC23
6azus A. C., >irzan L.& 3urugiu N. 5., Corbu A. C., Chiraleu 7. Dyes and Pigm. !00', 74(1), $)-%%. 6azus A. C.,
>irzan L., Nae 3., 3urugiu 5. N. Cimpeanu <. J. Heterocyclic Cem. !00$, 4!, 99(-1--'. 6azus A. C., >irzan L.,
Nae 3., Cristian L. Chiraleu 7. Dyes and Pigments !00$, "7, $$%-%%. 6azus A. C., >irzan L., Nae 3., Cristian L.,
Chiraleu 7., 5aganu 5., Cimpeanu <., 0ar?o L. #e$. #o%m. Cim., !00$, 4& ('), '((-)1.
$
Liu @. A., Leng B. N., 7eng A. C., 6en A. 5., ;hou @. Chin. A. Chem. $--%, $1, 9-1(
%
;hu B. Bu 1-3. A. +hDs. Chem. A $--1, 1-(, 9()4-*'.
'
Liu ;. 7., 8ashimoto C., 7u!ishima A. 3cience 199-, %'*, )(4-)-
(
IgnatDev N., Belz->iermann &., Billner 8., 7inze, 5., >ernhardt 2., CucherDna A. >revet +C0 B $--(=-$1))1
A1 din $--(
)
Covshev 2. I., >linov L. 5., 0itov, <. <. &speh. Chim. 19**, '), *(%-9).
*
Catagiri C., guchi E. >revet A+ )--1-$() din 194(
4
2. D. >ergmann, 5. >entar A. rg. Chem. 19(', 19, 1(9'.
9
C. 8afner, A. 3tephan, C. >ernhard Aust. Lieb. Ann. Chem. 19)1, )(-,'$
1-
rezultate 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 molecula
radicali fenilen, fenil si azulenil. Introducerea nucleelor azulenice induce o polarizare si o
polarizabilitate superioare sistemelor similare care cuprind doar grupe aromatice benzenoide prin
cresterea valorii energetice a orbitalilor 85 si scaderea valorii celor L&5. 3inteza
compusilor propusi prezinta elementul de noutate prin aceea ca sarurile de diazoniu ale azulenelor
nu sunt combinatii stabile si de aceea multe din reactiile de cuplare uzuale nu pot fi realizate
utilizand aceste saruri. In aceste conditii materiile prime vor fi sarurile de diazoniu sau bis diazoniu
cu nuclee benzenice, iar componentele de cuplare vor fi azulenele. Azulenele fiind, insa, nucleofili
moderati nu pot cupla cu orice sare de diazoniu. Nici nitrozoderivatii azulenici nu pot fi avuti in
vedere pentru sinteza grupei azo prin reactii de condensare 5ills, deoarece acestia sunt stabili
numai la temperaturi scazute. De asemenea, obtinerea si cuplarea compusilor bis azoici provenind
de la fenilendiamine prezinta o serie de particularitati care trebuie avute in vedere. 3e preconizeaza
ca unele dintre sinteze sa aiba ca materii prime aniline pe care este grefata o grupa potential
generatoare de substituent amino, de e/emplu grupa nitro. Deci studiul sintezei acestor derivati
prezinta interes stiintific si nu este unul de rutina.
$. Al doilea obiectiv il constituie determinarea neechivoca a structurii produsilor obtinuti
si studiul proprietatilor fizico-chimice ale acestora. 3tructura chimica a derivatilor di si poli azoici
permite abordarea unui studiu privind influenta unghiului diedru intre nucleele aromatice asupra
con!ugarii sau eventuala generare de combinatii cu chiralitate anchimerica. In legatura cu
structura produsilor obtinuti va fi studiata si influenta acesteia asupra spectrelor 65N si a celor
electronice. Asa cum s-a amintit mai sus, este de asteptat ca acesti compusi sa prezinte o
polarizare si o plarizabilitate superioare celor monoazoici, prin posibilitatile de con!ugare mult
mai e/tinsa. 2ste foarte probabil ca printre izomerii sintetizati, unii care contin grupe azulenice
diferite sa apara combinatii care sa cristalizeze in sisteme non-centrosimetrice si deci sa posede
bune calitati NL. De asemenea, aceleasi caracteristici de structura pot conferi calitati de cristale
lichide altor materiale din aceasta clasa.
%. Al treilea obiectiv il constituie caracterizarea electrochimica a compusilor sintetizati
folosindu-se atat voltametria ciclica, cat si metoda potentiostatica. 6ezultatele obtinute prin
studiul cineticii de electrod vor fi folosite la elaborarea unor posibile mecanisme de reactie
electrochimice. 3pecificitatea sistemelor propuse consta in prezenta concomitenta a unui pol
reducator de natura azulenica si a unuia relativ o/idant de natura azoica, care pot genera noi
produsi prin reactia cu electrozii. 3e pot anticipa astfel obtinerea de dimeri, oligomeri sau polimeri
cu proprietati electrice interesante. +rodusii sintetizati pe parcursul proiectului pot fi utilizati in
scopuri electrochimice, de e/emplu, acoperiri de electrozi sau generarea unor sisteme de elecroliti
complecsi.
'. &ltimul obiectiv il consitutie faptul ca abordarea unei tematici comple/e si, relativ
complete de cercetare fundamentala de catre cercetatorii tineri, in formare, le da posibilitatea sa
devina cadre de cercetare temeinice, iar o parte din lucrari pot fi dezvoltate in vederea sustinerii
unor teze de doctorat. In plus, de mai multi ani, in colaborare cu institutiile de invatamant
superior, o serie dintre studentii din ultimul an isi efectueaza partea e/perimentala a lucrarii de
diploma la noi in laboratoare. Acelasi lucru este valabil si pentru cei care urmeaza masteratele si
este suficient sa amintim ca aproape toti doctoranzii nostrii si-au desfasurat activitatea
e/perimentala din cadrul masteratului in colectivele noastre. biectivele propuse se incadreaza
intr-o tematica larga, in care colectivele de cercetare au colaborari cu colective din 1ermania,
7ranta si 7inlanda. 6ezultatele acestor cercetari fac de!a obiectul mai multor articole publicate in
reviste 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 de
cromatografierea lor pe coloane de alumina sau silicagel. +entru testarea puritatii sau evaluarea
mersului reactiilor cu produsi incolori se va folosi 8+LC-ul din dotare.
)ontrolul analitic al produsilor obtinuti se va face prin spectroscopia 65N de inalta
performanta, folosindu-se aparate de inalta rezolutie da %-- si '-- 58z. De asemenea se vor
efectua 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 vor
face pe aparate de spectroscopie electronica nou achizitionate, avand performante electronice
deosebite. De asemenea, masurarea p8-ului solutiilor se va efectua cu un p8-metru electronic nou
achizitionat.
tu#iile electroc,imice vor 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 orbitalilor
85 si L&5 precum si in calcule de lungimi de legatura si unghiuri diedre cu a!utorul
programului de mecanica cuantica-5+AC
10.%.-esurse necesare:
10.%.1 -esursa umana
10.%.1.1. Directorul #e proiect
10.%.1.1.1 )ompetenta stiintifica a #irectorului #e proiect
Dr. ing. .irzan /iviu - directorul de proiect,
loc de munca F pozitia - C2N06&L D2 C8I5I2 61ANICA F Costin D. Nenitescu F
>&C&6230I,
C3 II
1. Vechime la locul actual de munca (! ani
2. Domenii de competenta, rezultate semnificative:
tu#iul sintezei c,irale a compusilor naturali. Intre anii 199$-199( s-a studiat sinteza chirala a
6oGuefortinei C la &niversitatea 6ochester-NE, 3&A si s-au preparat sintoane necesare sintezei
unor imunodepresori.
tu#iul reactiilor #e substitutie electrofila si ra#icalica pe nucleul azulenic. Activitatea in tara incepe cu
studiul reactiilor de substitutie electrofila si radicalica pe nucleul azulenic. +rima preocupare a
constat in studierea reactiei de halogenare cu halogenuri metalice pe acest sistem. <or fi
enumerate pe rand o serie de alte preocupari avute de-alungul timpului, Cercetarea reactiei de
diazotare si cuplare pe sisteme heterociclice si azulenice. 6eactiile de obtinere de imine, amine,
amide, imide, carbamati ale azulenei si ale dimerilor acesteia. 6eactiile electrofile competitive pe
derivatii azoici si iminici, continand grupe azulenice si aromatice de tip arilic si heteroarilic.
6educerea si alchilarea N-o/izilor la amine in prezenta grupei azo, dovedind compatibilitatea
dintre grupa N-o/id si nucleul azulenic. btinerea primelor -dicetone continand nucleul azulenic,
deschizand drumul pentru sinteza a numerosi heterocicli cu ( si ) atomi in molecula, cum ar fi,
pirazoli, o/azoli, etc. Insusirea si utilizarea calculelor de mecanica moleculara si mecanica
cuantica in scopul corelarii structurii compsilor chimici cu proprietatilor lor fizico- chimice.
3tudiul mecanismelor de reactie aferente transformarilor chimice cercetate si prezentate mai sus.
&n alt domeniu de interes l-a constituit studiul legaturii structura-deplasari chimice ale protonilor
si atomilor de carbon din spectrele 65N, structura-spectre electronice precum si scindarile
derivatilor de azulena in spectrometrul de masa. In prezent, preocupare principala o constituie
sinteza si proprietatile sarurilor de piriliu, de piraniliu si a piridinelor continand resturi azulenice.
+ana in 1949 a participat la numeroase tehnologii pentru asimilarea unor intermediari necesari
economiei nationale.
3. Articole pulicate cu relevanta pentru acest proiect !selectie")
1.D. L. 3. Eo?otsu!i. B. +. DaileD. A. 3. Cende, L. >irzan. L. Cun H1eneration, direct observation
under matri/ isolation conditions, and ab initio calculations for $-azacDclopenta-$,'-dien-1-oneI
J. Pys. Cem. 199(, **, 1(4*--%.
$.A. C. 6azus. L. >irzan. 3. Nae. 3. A. 6azus. <. Cimpeanu. C. 3tanciu. (zulene-1-azop0ri#ines&
6esursele umane de care dispune Centrul de Chimie rganica F C. D. Nenitescu sunt de un
inalt grad stiintific cu e/perienta indelungata in sinteza organica si caracterizarea fizico-chimica a
compusilor organici. Colectivul de lucru propus pentru realizarea proiectului are e/perienta in
sinteza si caracterizarea compusilor organici. 5a!oritatea membrilor echipei sunt anga!ati ai
Centrului de Chimie rganica - C. D. Nenitescu. &n membru isi elaboreaza teza de doctorat in
cadrul Centrului de Chimie rganica F C.D. Nenitescu
0nt,esis an# 1-al20lation at p0ri#ine moiet0 +ynt. Comm%m. !00!, %$, 4$(-%*.
%. A. C. 6azus, L. >irzan, 3. Nae, L. Cristian and 7. Chiraleu 3(zulene-1-azop0ri#ine 14-oxi#esI
Dyes and Pigments !00$, "7, $$%-%%.
'. A. C. 6azus, L. >irzan, 3. Nae, 5. N. 3urugiu and <. Cimpeanu (zulene-1-azo-!4-t,iazoles.
0nt,esis an# Properties J. Heterocyclic Cem. !00$, 4!, 99(-1--'.
(. A. C. 6azus, L. >irzan, 3. Nae, . L. Lehadus, C. +avel and . Costan (zulenic -2etones.
0nt,esis& properties an# reactions to form five membere# aromatic ,eteroc0cles ,r-i$oc
!005 "/#, *1-4(.
). 2.-5. &ngureanu, A.C. 6azus, L. >irzan, 1. >uica, And 5-3. Cretu 6lectroc,emical tu#0
"f 1-Met,0lazulene ..P./. +ci. /%ll., +eries /, !005, '7(0), 4$-44.
*. Ale/andru C. 6azus, Liviu >irzan& Nina 5irela 3urugiu, Andreea Cristina Corbu and 7ilip
Chiraleu 0nt,eses of (zulen-1-0l-benzot,iazol-!-0l Diazenes Dyes and Pigm. !00', 74(1), $)-
%%.
4. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Cristina Corbu and
Cristian 2nache (zulene-substitute# P0ran0lium alts. 0nt,eses an# Pro#ucts
),aracterization J. Heterocyclic Cem. !007& 40, 9)%-**.
9. 2leonora 5. &ngureanu, Ale/andru. C. 6azus, Liviu >irzan,

1eorge >uica, 5ariana Cretu and
2nache Cristian 6lectroc,emical c,lorination of azulenic #erivatives. Insig,t into mec,anism
of ano#ic oxi#ative c,lorination 1lectrocimica ,cta !007& "(& *9'-4-%.
1-. Ale/andru C. 6azus, Liviu >irzan, Andreea Corbu, ana ;aharia and Cristian 2nache
0nt,esis an# Properties of %-($-ubstitute# azulen-1-0l)-!&7-#ip,en0l-p0ri#ines ,r-i$oc
!007, 1(, 1$1-1$9.
11. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Corbu,

7ilip
Chiraleu and Cristian 2nache (zulene-substitute# P0ri#ines an# P0ri#inium alts. 0nt,esis
an# tructure. 1. (zulene-substitute# p0ri#ines J. Heterocyclic Cem& !00', 44, $'(-$(-.
1$. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Corbu,

7ilip
Chiraleu and Cristian 2nache

(zulene-substitute# P0ri#ines an# P0ri#inium alts. 0nt,esis
an# tructure. !. (zulene-substitute# p0ri#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-azop0ri#ine& s0nt,esis-al20lation A. C. 6azus, L. >irzan, 3tefania Nae,
<ictorita 0ecuceanu, +oster la al-$)-lea 3impozion National de Chimie, Calimanesti-Caciulata,
<ilcea 6omania, '-) oct. !000
$. .iazulene-reactii A. C. 6azus, 3tefania Nae, L. >irzan +oster la al-$4-lea 3impozion
National de Chimie, Calimanesti-Caciulata, <ilcea 6omania, '-) oct. !00!
%. 1-(azulen-1-il)-!-(benzotiazol-!-il) #iazene. 3inteza si proprietati A. C. 6azus, L.
>irzan, 3. Nae, N. 5. 3urugiu, A. Negoescu si <. Cimpeanu- a @@<III-a Conferinta Nationala de
Chimie )-4 ct. !00%& Calimanesti-Caciulata
'. aruri #e piri#iniu si bis-piri#iniu substituite cu !-(azulen-1-il)etene. sinteza&
proprietati& utilizari 1/". A. C. 6azus, L. Cristian, L. >irzan, 3. Nae, . Costan si C. 2nache- a
@@<III-a Conferinta Nationala de Chimie )-4 ct. !00%, Calimanesti-Caciulata
(. 6tu#e 8lectroc,imi9ue #e compos8s azul8ni9ues& 2.-5.&ngureanu, A. 6azus, A. Ion,
C. 6abagiu-6oman, L. >arzan, 5. Cretu, AournJes dK2lectro-chimie $--(, ( - 4 !uillet !005, 3aint
5alo, 7rance, 0hLme $ 2lectrochimie 5olJculaire et >ioelJctrochimie.
). -e#ox be,avior of some azulene #erivatives& 2.-5.&ngureanu, A. C. 6azus, L.
>arzan, 5. Cretu, 1. >uica, 6omanian International Conference of ChemistrD and Chemical
2ngineering 6ICCC2 1', 31--C-$., !007
*. 6lectroc,emical stu#0 of azulene #erivatives b0 c0clic an# #ifferential pulse
voltametr0 2.-5. &ngureanu, L. >arzan, A. C. 6azus, 5. 3. Cretu, 7. 5. 0ugurel, +D-4,
Conferinta Nationala Chimia, !007, HvidiusI Constanta
4. Mec,anisme #e ,alogenation electroc,imi9ue #es composes azuleni9ues 2.-
5.&ngureanu, A. C. 6azus, L. >arzan, 1. >uica, Le Guatrieme colloGue franco-romain de chimie
appliGue, $4 Auin-$ Aulliet !007, Clemont-7errand, 7rance
9. inteza unor saruri #e piraniliu si a unor piri#ine substituite in pozitia % cu
ra#icali azulen-1-il Ale/andru C. 6azusM, Liviu >irzan, ana Lehadus, Claudia +avel, Liliana
Cristian, ana ;aharia si Cristian 2nache, +oster la al-$9-lea 3impozion National de Chimie,
Calimanesti-Caciulata, <ilcea 6omania, %-(, oct. !007
1-. Discassion about mass spectra of %-azulen-1-0l-!&7-#imet,0lp0ri#inium
perc,lorates C. 6azus, L. >irzan, . Lehadus, C. +avel, C. 2nache, +oster la al-$9-lea 3impozion
National de Chimie, Calimanesti-Caciulata, <ilcea 6omania, %-(, oct. !007
11. 6tu#es electroc,imi9ue appli9uees aux !-:(6)-azulen-1-0l#iazen0l;-1&$-
benzot,iazoles 2. 5. &ngureanu, 5. 3. Cretu, A. C. 6azus, L. >irzan, +oster at the 1'th 2dition
of the Conference of 5icrosensors, 5icroactuators and 5icrosDstems, LDon, 7rance, Aune 1--1',
!00'
%. E&perienta acumulata in pro'rame nationale si internationale
-eactii #e substitutie pe sisteme azulenice. <alogenarea, participant, 5C0, octombrie
-decembrie 199). aprilie - noiembrie 1994
-eactii #e oxi#are ale unor compusi azulenici, participant, 5C0, octombrie 199*-
noiembrie 1994
tu#iul unor materiale pornin# #e la sisteme nesaturate ,omo si ,eteroatomice care
contin grupe azulenil, participant, AN30I, martie 1999- noiembrie $---
tu#iul sintezei si al comportarii unor pro#usi azulenici care contin #uble legaturi in
molecula, participant, AN30I, noiembrie 1999-octombrie $--1
Derivati #e 1&14-biazulena& sinteze& proprietati& importanta aplicativa a #omeniului,
participant, 52C, octombrie $--1- decembrie $--$
)ontributii la stabilirea structurii si a reactivitatii unor compusi azulenici cu
proprietati #e transmitere neliniara a luminii, participant, CNC3I3, iulie -decembrie $--$
1-+inilazulene substituite = o noua clasa #e sintoni utilizabili pentru generarea unor
molecule complexe si a unor materiale cu proprietati #e transmitere neliniara a luminii
(1/") si proprietati electroc,imice superioare, participant, 11'---, 52C, noiembrie $--%-
noiembrie $--(
inteza si stu#iul unor materiale azulen-1-azo-,eterociclice cu ,iperpolarizabilitate
inalta& participant, CNC3I3, iunie $--'-noiembrie $--'
)ompusi ,eteroaromatici stabilizati prin substitutie cu azulene. inteze& stu#iul
proprietatilor lor fizico-c,imice si electroc,imice& utilizari in te,nica transmiterii neliniare a
luminii (1/"), participant, 4-----, 52C, octombrie $--(-prezent
(. Alte mentiuni:
- 5embru al asociatiilor profesionale, 3ocietatea ChimiNtilor din 6omOnia
- +remiul II la limpiada Internationala de Chimie- Leningrad 19*9.
- 6eferent la Aournal of rganic ChemistrD, DDes and +igments si 0he Chemical 2ducation
Aournal.
10.%.1.1.!. )ompetenta manageriala a #irectorului #e proiect
Crd"a)r%l de (riec) are experienta $i abilitatea de a administra ac)i*i)a)ile $i
+%'e)%l (riec)%l%i c",r- (la"i,icarii.
10.%.1.!. 6c,ipa #e cercetare
/ista membrilor ec,ipei #e cercetare: "7ara directorul de proiect#
1r.
crt.
1ume si prenume
(nul
nasterii
>itlul #i#actic
stiintific ?
Doctorat
? ?
emnatura
1 6azus Ale/andru
Constantin
19%* C3 I DA
$ 0ecuceanu <ictorita 19*% C+ III DA
% 2nache Cristian 19*- Cercetator Doctorand
' Cristea 5ihaela 194- Asistent
cercetare
Doctorand
( Dragu Andreea 194( Asistent
cercetare
Doctorand
? /a 3>itlu #i#actic@stiintificA completati cu una din variantele:
Profesor @ )onferentiar @ /ector @ (sistent @ ) I @ ) II @ ) III @ )ercetator
?? /a 3DoctoratA completati cu una din variantele: D( @1* @ Doctoran#
10.%.1.!.1. )ercetatori cu experienta
.
6xecutant 1 : (lexan#ru )onstantin -azus F Dr. Ing.,
<echime la locul de munca actual, '' ani
1. E&perienta profesionala: 'enerala si in domeniu
- 19(9 - 19)- 2nginer stagiar - 7abrica medicamente 3IN07A65
Descriere, H+roductie medicamenteI
- 19)- - 19)$ 3enolog se4 de sector F 7abrica medicamente 3IN07A65
Descriere, H+roductie medicamenteI
- 19)$ F 19)' 2nginer F Centrul de Chimie rganica F C. D. Nenitescu, >ucuresti.
Descriere, H3olvolize in sisteme ciclopropilcarbinilice.I
- 19)' - 19)4 Cercetator +tiinti4ic F Centrul de Chimie rganica F C. D. Nenitescu, >ucuresti.
Descriere, H3olvolize in sisteme ciclopropilcarbinilice.I
- 19)4 - 1949 Cercetator Principal 222 F Centrul de Chimie rganica F C. D. Nenitescu,
>ucuresti.
Descriere, H6eactii de alchilare 7riedel-Crafts.I
- 1949 - 1991 Cercetator Principal 22 F Centrul de Chimie rganica F C. D. Nenitescu, >ucuresti.
Descriere, HChimia compusilor azulenici.I
- 1991 F prezent Cercetator Principal 2 F Centrul de Chimie rganica F C. D. Nenitescu,
>ucuresti.
Descriere, HChimia compusilor azulenici.I
2. E&perienta in domeniu) Activitate de peste 1( ani in studierea influentei sistemului azulenic
asupra unor structuri din care acesta face parte, caracterizarea compusilor obtinuti si reflectarea
con!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 de
compusilor azulenici nou sintetizati. &nele dintre procedee si rezultate au facut obiectul unor
publicatii specifice. Activitate de cercetare de peste '( ani in domeniile sintezei compusilor
organici, a caracterizarii lor, a studierii proprietatilor fizico-chimice si a determinarii unor
mecanisme de reactie, activitate recompensata prin premiul Academiei 6omane. Are peste 4-
lucrari 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/./23/.
2. Procedeu de preparare a clorurii acidului dicloracetic.0re*e) RSR 35 61/ di" //.18./281
3. Procedeu de preparare a clorurii acidului dicloracetic. 0re*e) RSR 33 263 di" 18.18./28/
4. Procedeu de preparare a clorurii acidului dicloracetic.0re*e) RSR 38 125 di" 18.18./28/
5. Procedeu pentru prepararea 1-fenil-4-etiloctan-1,3-dionei. 0re*e) RSR 21 46/ di" /5.15./286
6. Procedeu pentru purificarea glucoheptonatului de sodiu. 0re*e) RSR /1/ 548 di" 24.12./221.
3. Procedeu catalitic pentru prepararea 5-alchil-salicilaldehidelor. 0re*e) R-a" /12 463 di" 31./1
/221.
#. +ucrari semnificative pulicate:
/. A.C. Raz%$, 4. 5er)hei-er, 6. 0adea a"d A.-M . &la)z, Solol!tic "ehaiour of Strained S!stems.
#he "enzo$b%bic!clo$3.1.&%hex-'-en-4-!l cation, 7e)rahedr" 8e))er$, 1()5, 22-23, /322-/812.
2. S.A. O$adchii, 4.9. Ma-a):%; ,
4.&. Sh%+i", A.C. Raz%$, <. 0ar)ha a"d =$. Ar*a: *!cloprop!lal+!l *ations of a Spiro$',4%heptane
S!stem, Russ. Chem. Bull., 1((4, 43, 2134-2138.
3. &. 9,)i-e, P. &. 8acri!, K. Na;a)a"i a"d A. C. Raz%$ Push-Pull ,zulene-"ased *hromophores -ith
.onlinear /ptical Properties Tetrahedron Lett., 1((0, 39, 6853-56.
4. A. C. Raz%$ S!ntheses of Pol!c!clic *ompounds b! /xidatie *oupling of ,zulene-1-azo-arenes
J. Chem. Soc., Perkin Trans., 1, '&&&, 28/-288.
5. A. C. Raz%$, C. Ni)% /xidatie benz!lic substitution of azulene-1-azo142-meth!lbenzene3s, J. Chem.
Soc., Perkin Trans., /, '&&&, 282-224.
6. A. C. Raz%$, C. Ni)%, S. Car*aci, 8. 0irza", S.A. Raz%$, M. P( a"d 8. 7ar; S!nthesis and reactions
of .-1azulen-1-!lmeth!lene3ar!lamines >. Chem. Soc., Perkin Trans., 1, '&&1, /223-/233.
3. A. C. Raz%$, 8. 0irza", S. Nae, 8. Cri$)ia", 6. Chirale% a"d 4. Ci-(ea"%, ,zulene-1-azop!ridine 12-
oxides Des and P!m., '&&3, "#, 223-233.
8.. A. C. Raz%$, C. Ni)%, 4. 7ec%cea"% a"d 4. Ci-(ea"%, '-Substituted 1azulen-1-!l3ethenes $ur. J. %r!.
Chem., '&&3, 411/-41/1.
2. 8. Cri$)ia", 9. Sa$a;i, P. 8. 8acri!, 0. ?""adie%, 9. A$$el+er'h$, K. Cla:$ a"d A. C. Raz%$, 4onating
Strenght of ,zulene in 5arious ,zulen-1!l Substituted *ationic 4!es6 ,pplication in .onlinear
/ptics. Chem &ater., '&&4, 1', 3543-355/.
/1.. A. C. Raz%$, C. Ni)%, C. Pa*el, C.-A. Ci%c%le$c%, 4. Ci-(ea"%, C. S)a"ci% a"d P. P. P@er, /xidation
of 1-142-substituted phen!l3-'-14-meth!lphen!l3diazene7 benz!lic substitution versus *-azo bond
brea+ing Canad. J. Chem., '&&5, 83, 244-251.
//. <.-M. A"'%rea"%, A. C. Raz%$, 8. 0irza", &. 0%ica, M. Cre)% a"d C. <"ache 8lectrochemical
chlorination of azulene deriaties. 9nsight into the mechanism of anodic oxidatie chlorination
$lectrochimica (cta, '&&:, 52, 324.
,. -emru al .ocietatii de /himie din 0omania
%. +ista comunicari stiintifice relevante pentru proiect
1.-eactii #e ubstitutie in Pozitia .enzilica la )ompusi (zulen-1-azo-(%4-metilbenzenici)
ubstituiti la Brupa azulenil. &niversitatea 0ehnica Darmstadt-7acultatea de Chimie
rganica,.Darmsta#t, 1CCD. /onferinta.
$. )ompusi cu legaturi #uble ,omolitice si ,eterolitice substituite cu azulene si arene.
inteze& proprietati& utilizari. Al @@<I-lea 3impozion National de Chimie. Calimanesti-
Caciulata. -m. +ilcea, !000. /onferinta
%. 6lectroc,emical an# ),emical "xi#ation of Derivatives of (zulene. N.D. 0otir, A.C. 6azus,
C. Nitu, C. Lete and 3. Lupu, 0he 194
th
5eeting of H0he 2lectrochemistrD 3ocietDI8Datt 6egencD
+hoeni/. ct., !000. 3&A. /omunicare.
'.6lectroc,emical .e,aviour of ome #erivatives of azulene. N. D. 0otir, A. C. 6azus, C. Nitu,
C. Lete and 3. Lupu, >unsen ColloGuium, 3eptember, !00! F Dresden. +oster. /on'res
(. )omparative tu#0 of ),emical an# 6lectroc,emical "xi#ation of ome (zulene
Derivatives. C. Lete, 1. +alleschi, C. Nitu, 5 >adea and A.C. 6azus, 0he 4
th
International
3Dmposium on Cinetics in AnalDtical ChemistrD, 6ome, ItalD, $--'.
(. E&perien*a acumulat1 2n pro'rame na*ionale si interna*ionale
-eactii #e substitutie pe sisteme azulenice. <alogenarea, director proiect, 5C0,
octombrie -decembrie 199). aprilie - noiembrie 1994
-eactii #e oxi#are ale unor compusi azulenici, director proiect, 5C0, octombrie 199*-
noiembrie 1994
tu#iul unor materiale pornin# #e la sisteme nesaturate ,omo si ,eteroatomice care
contin grupe azulenil, director proiect, AN30I, martie 1999- noiembrie $---
tu#iul sintezei si al comportarii unor pro#usi azulenici care contin #uble legaturi in
molecula, director proiect, AN30I, noiembrie 1999-octombrie $--1
Derivati #e 1&14-biazulena& sinteze& proprietati& importanta aplicativa a #omeniului&
director proiect, 52C, octombrie $--1- decembrie $--$
)ontributii la stabilirea structurii si a reactivitatii unor compusi azulenici cu
proprietati #e transmitere neliniara a luminii& director proiect, CNC3I3, iulie -decembrie
$--$
1-+inilazulene substituite = o noua clasa #e sintoni utilizabili pentru generarea
unor molecule complexe si a unor materiale cu proprietati #e transmitere neliniara a
luminii (1/") si proprietati electroc,imice superioare& director proiect, 11'---, 52C,
noiembrie $--%-noiembrie $--(
inteza si stu#iul unor materiale azulen-1-azo-,eterociclice cu
,iperpolarizabilitate inalta& director proiect, CNC3I3, iunie $--'-noiembrie $--'
)ompusi ,eteroaromatici stabilizati prin substitutie cu azulene. inteze& stu#iul
proprietatilor lor fizico-c,imice si electroc,imice& utilizari in te,nica transmiterii
neliniare a luminii (1/")& director proiect, 4-----, 52C, octombrie $--(-prezent
enzori electroc,imici inovativi pentru analize clinice si #e me#iu& responsabil proiect&
$-----, 52C, august $--)-prezent
6xecutant !: +ictorita >ecuceanu F dr. in chimie
1. E&perienta profesionala:
- i%lie /222 B ia"%arie 2111 (sistent cercetare stiinti)ica sta!iar - Centrul de Chimie rganica F C. D.
Nenitescu, >ucuresti.
Descriere, H3intezO organicaI
- ianuarie $--- F septembrie $--' ,sistent cercetare stiinti4ica - Centrul de Chimie rganica F C.
D. Nenitescu, >ucuresti.
Descriere, HChimia compusilor azuleniciI
- septembrie $--' F prezent Cercetator stiinti4ic - Centrul de Chimie rganica F C. D. Nenitescu,
>ucuresti.
Descriere, HChimia compusilor azuleniciI
2. E&perienta in domeniu) Din momentul anga!arii in cadrul Centrului de Chimie rganica HC.D.
NenitescuI, la 1 iulie 1999, a activat in cadrul colectivului condus de Dr. Ing. A.C. 6azus.
biectul activitatii sale in cadrul colectivului a constat, la inceput, in sinteza de materii prime
pentru obtinerea de compusi noi din clasa azulenelor. 5etoda de lucru este originala, constituind
subiectul unui articol aparut intr-o revista de interes international. +e parcursul cercetarilor, a
contribuit la elaborarea unei metode noi de sinteza pentru compusii vinil-azulenici, metoda ce se
incadreaza in asa numita Hchimie verdeI, in acord cu normele de protectia mediului inco!urator.
Intre anii 1999 si $--( a participat la realizarea mai multor cercetari finantate prin 1ranturi
acordate de Academia 6omana si de 5inisterul Cercetarii si 0ehnologiei. Din luna mai a anului
$--' a preluat sarcina de elaborare a actelor necesare contractarii diverselor programe nationale
de finantare a cercetarii fundamentale, de tipul 1ranturilor CNC3I3 si a programelor C2623. In
luna decembrie a anului $--) si-a sustinut public teza de doctorat cu titlul H1-"Azulen-1-il#etene-
$-substituite. Influenta substituentilor asupra sintezei, mecanismului acesteia si asupra unor
trasaturi caracteristice ale produsilorI. Conducator stiintific Dr. Ing. Ale/andru C. 6azus.
3. +ucrari pulicate:
1. 1,1-"iazulene 4eriaties. S!ntheses and ;eactions, A.C. Raz%$, 8. 0irza", S. Nae, C. Ni)%, 4.
7ec%cea"%, 4. Ci-(ea"%, (rki*ok, '&&' CiiD, /42-/53.
'. *onsiderations on the <ragmentations of some substituted ,zulenes in the =ass Spectrometer
A.C. Raz%$, 8. 0irza", P. 6ili(, M. ?a"ila, 4. 7ec%cea"%, 8. Cri$)ia", M. P(e$c%, Re*. Chim. '&&', "3+1,-,
64/-46.
3. '-Substituted1,zulen-1->l38thenes A.C. Raz%$, C. Ni)%, 4. 7ec%cea"%, 4. Ci-(ea"%, $uro.ean
Journal o) %r!anic Chemistr, '&&3, /3, 461/-46/1.
4. #he *oupling *apacit! /f 4iazotized .-Substituted ,minop!ridines - , =echanical ?uantum
,pproach A.C. Raz%$, 8. 0irza", S. Nae, 4. 7ec%cea"%, 8. 7ar;, Re*ue Roumaine de Chimie, '&&3,
40+3D, /2/-/26.
5. Path-a!s for the solent-free condensation bet-een Schiff bases and meth!lenic compounds
A.C. Raz%$, C. Ni)%, 4. 7ec%cea"% a"d 8. 0irza", Re*ue Roumaine de Chimie, '&&5, ",C2-/1D, 322-336.
#. +ista comunicari stiintifice relevante pentru proiect
/. ,zulen-1-azopiridine. Sinteza alchilare.A. C. Raz%$, 8. 0irza", S. Nae a"d 4. 7ec%cea"%,
Al EE49-lea Si-(zi" Na)i"al de Chi-ie. Cali-a"e$)i-Caci%la)a, 2111.
2. *ondensarea unor baze Schiff azulenice cu compusi cu metilen acti pentru obtinerea unor
inilazulene. A.C. Raz%$, S. Nae, C. Ni)%, 4. 7ec%cea"%, C. Pa*el, O. =aharia $i 4. Ci-(ea"%,
A EE4999-a C",eri")a Na)i"ala de Chi-ie, 6-8 c)-+rie 2114, 4alcea.
10.%.1.!.!. )ercetatori in formare
In echipa de lucru sunt inclusi si tineri cercetatori, urmarindu-se promovarea acestora si elaborarea
unor teze de doctorat de inalta valoare stiintifica,
1. 61()<6 )ristian F cercetator, doctorand
Lucrari publicate,
1. 3Dnthesis and +roperties of '-"%P-3ubstituted azulen-1P-Dl#-$,)-diphenDl-pDridines. A. C.
6azus, L. >irzan, Andreea Corbu and C. 2nache, ,r-i$oc, !007, 1$1-1$9.
$. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Corbu,

7ilip
Chiraleu and Cristian 2nache Azulene-substituted +Dridines and +Dridinium 3alts.
3Dnthesis and 3tructure. 1. Azulene-substituted pDridines J. Heterocyclic Cem, $--*, 44,
$'(-$(-.
%. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Corbu,

7ilip
Chiraleu and Cristian 2nache

Azulene-substituted +Dridines and +Dridinium 3alts. 3Dnthesis
and 3tructure. $. Azulene-substituted pDridinium salts J. Heterocyclic Cem $--*, 44, $(1-
$)-.
$. )-I>6( Mi,aela F asistent cercetare- Centrul de Chimie rganica F C.D. Nenitescu
Lucrari publicate,
1.1,%-Dipolar cDcloaddition reactions of 1-"%-nitrophenacDl#-1,1--phenanthrolinium N-Dlide
Qith activated al?Dnes 7. Dumitrascu, C. Draghici, 5. 6. Caira, A. >adoiu, L. >arbu, 5. Cristea
,r-i$oc, !005 "/#, 1)(-1*%
$. 3Dnthesis and @-raD 3tructure of a neQ +DrroloR1,$-bS-pDridazine Derivative 5. 6. Caira, 7.
Dumitrascu, C. Draghici, D. Dumitrascu, 5. Cristea 5olec%les, !005& 1!, %)--%)).
% Azulene Derivatives 3oluble In +olar 3olvents. 1-"Azulen-1-Dl#-$-"0hien-$- or %-Dl#-2thenes
Ale/andru C. 6azus, Liviu >irzan, <ictorita 0ecuceanu, 5ihaela Cristea,
Alina Nicolescu and Cristian 2nache #e$.#o%m,Cim., in print
%. D-(B* (n#reea F asistent cercetare - Centrul de Chimie rganica F C.D. Nenitescu
,cti$itatile la care $or participa, s%nt in con4ormitate c% cele pre$a6%te in plan%l de reali6are al
proiect%l%i) vor participa la obtinerea informatiilor din literatura pentru tema propusa, la obtinerea
de cantitati de materii prime necesare pentru etapele urmatoare, la sinteza derivatilor bisazoici
monoazulenici, a derivatilor bisazoici meta si para biazulenici, a derivatilor bisazoici orto
biazulenici, a derivatilor bisazoici biazulenici functionalizati, precum si la sinteza derivatilor
bisazoici triazulenici functionalizati
10.%.! (lte resurse
10.%.!.1. -esurse financiare
/biectie@,ctiitati ;esurse
umane
1om x luna3
Re$%r$e %-a"eF-a)eriale
A+re*ieriG CP B crd"a)r
(riec)
< /...4 B e!ec%)a") /...4
;esurse
financiare de la
buget
1;/.3
8#,P, 9 '&&)@3 luni
Documentare sinteza #e materii primeE
incercari preliminare
) persoane T
-.() luni
C+ F stabilire
responsabilitati in cadrul
proiectului
<B 15'C@!00!
1"1.1.#, )1%-)
'"*.1.#, %----
1%"1'.1%#, 4)9'
Completarea documentarii asupra informatiilor
e/istente in literature in legatura cu tema
propusa
C+ , 21, 2$, 2%, 2', 2( F
documentare
btinerea de cantitati de materii prime necesare
pentru etapele urmatoare
2$, 2%, 2', 2( F obtinere
materii prime
Analizarea si caracterizarea materiilor prime C+, 21, 2$, 2% F analizarea
si caracterizare materii prime
6>(P( II = !00D @ % luni
"btinerea #erivatilor bisazoici monoazulenici
) persoane T
-.*( luni
C+ F stabilire
responsabilitati in cadrul
obiectivului
<B 15'C@!00!
1"1.1.#, 1%---
'"*.1.#, 1-----
1%"1'.1%#, $----
3inteza derivatilor bisazoici monoazulenici 2$, 2', 2( F sinteza materii
prime
Caracterizarea produsilor obtinuti
corelarea spectrelor &<-<I;, 35 si 65N cu
structura bis azo derivatilor obtinuti
C+, 21, 2$, 2% F
caracterizare produsi
3tudii electrochimice C+, 21 F studii
electrochimice
6>(P( III = !00D @ ' luni
"btinerea #erivatilor bisazoici #iazulenici
(izomerii meta si para)
) persoane T
1.%1 luni
C+ F stabilire
responsabilitati in cadrul
obiectivului
<B 15'C@!00!
1"1.1.#, 1'%-'*
1%"1'.1.#, %---
1%"1'.$.#, )---
1%"1'.%.#, %(---
1%"1'.1%#, 1$9(%
3inteza derivatilor bisazoici meta si para
biazulenici
2$, 2%, 2', 2( F obtinere
produsi
Caracterizarea produsilor obtinuti
corelarea spectrelor &<-<I;, 35 si 65N cu
structura bis azo derivatilor obtinuti
C+, 21, 2$, 2% F
caracterizare produsi
3tudii electrochimice C+, 21 F studii
electrochimice
6>(P( I+ = !00C @ 5 luni
"btinerea #erivatilor bisazoici #iazulenici
(izomerul orto) ) persoane T
-.9% luni
C+ F stabilire
responsabilitati in cadrul
obiectivului
<B 15'C@!00!
1"1.1.#, 41*'1
'"*.1.#, (----
1%"1'.1%#, 14$(9
3inteza derivatilor bisazoici orto biazulenici 2$, 2%, 2', 2( F obtinere
produsi
Caracterizarea produsilor obtinuti
corelarea spectrelor &<-<I;, 35 si 65N cu
structura bis azo derivatilor obtinuti
C+, 21, 2$, 2% F
caracterizare produsi
3tudii electrochimice C+, 21 F studii
electrochimice
6>(P( + = !00C @ ' luni
"btinerea #erivatilor bisazoici #iazulenici
functionalizati
) persoane T
1.%1 luni
C+ F stabilire
responsabilitati in cadrul
obiectivului
<B 15'C@!00!
1"1.1.#, 1'%-'*
1%"1'.1.#, %---
1%"1'.$.#, )---
1%"1'.%.#, %(---
1%"1'.1%#, 1$9(%
3inteza derivatilor bisazoici biazulenici
functionalizati
2$, 2%, 2', 2( F obtinere
produsi
Caracterizarea produsilor obtinuti
corelarea spectrelor &<-<I;, 35 si 65N cu
structura bis azo derivatilor obtinuti
C+, 21, 2$, 2% F
caracterizare produsi
3tudii electrochimice C+, 21 F studii
electrochimice
6>(P( +I = !00C @ 5 luni
"btinerea #erivatilor trisazoici azulenici
C+ F stabilire
responsabilitati in cadrul
<B 15'C@!00!
( persoane T
-.9% luni
obiectivului
1"1.1.#, 1-$1*)
1%"1'.1%#, 1'4$'
3inteza derivatilor trisazoici monoazulenici 2$, 2%, 2', 2( F obtinere
produsi
Caracterizarea produsilor obtinuti
corelarea spectrelor &<-<I;, 35 si 65N cu
structura tris azo derivatilor obtinuti
C+, 21, 2$, 2% F
caracterizare produsi
3tudii electrochimice C+, 21 F studii
electrochimice
6>(P( +II = !010 @ 5 luni
+alorificarea aspectelor #e noutate ale
rezultatelor cercetarii
) persoane T
-.9% luni
C+ , 21, 2$, 2%, 2', 2( F
diseminare rezultate
<B 15'C@!00!
1"1.1.# )1%-)
1%"1'.1.#, 1(--
1%"1'.$.#, %---
1%"1'.%.#, 1*(--
1%"1'.1%#, 1))9'
Diseminarea rezultatelor prin publicarea
nationala sau internationala a rezultatelor
10.%.!.!. Infrastructura #isponibila
In vederea realizarii e/perimentelor necesare derularii proiectului Centrul de Chimie rganica
dispune de urmatoarele echipamente si facilitati pentru e/perimentare ,
spectrometru 65N >ruc?er Avance '--,
1
8 F 65N , '-- 58z.
1%
C F 65N , 1--.)$ 58z ,
uzura medie (U,
cromatograf 1C-7I33N3 <IC 9--,
spectrofotometru &<-<I3, stabilitate V-.---% A=h la (-- nm. lungime de unda 19--11-- nm.
banda spectrala V $nm, achizitionat in $--(,
lichid cromatograf "8+LC#, coloana analitica LC 11$-=LC 11(-. cuptor de termostatare
coloane, autosempler, achizitionat in $--(,
autoclave, etuve,
bOi de ultrasunete,
pompe de vid avansat,
agitatoare, termostate=criostate,
aparaturO de sticlO specificO laboratoarelor de chimie organicO,
aparaturO de multiplicare Ni Wndosariere documente.
6eXea de computere Ni echipamente periferice, con/iune IN026N20.
ANEXA 3
11. Prezentarea proiectului in limba engleza: (Max. 10 pagini)
11. Although ?noQn for a long time, azoderivatives still remain in the attention of the chemists
due to the une/pected results lin?ed Qith their structure and their phDsico-chemical properties
important for some top industrial branches.
As it Qas proved from our previous papers,
1
the studD of the sDnthesis and properties of some
special azoderivatives hoQ is the case of those that contain an azulene in the molecule is lin?ed
both on scientific interest and industrial applications. 3ome peculiar phisDco-chemical
properties enable them to be used in manD fields starting Qith that classical ones, as dDes and
finishing Qith most up to date ones in data stoc?ing and transmission. In the case of the azo
derivatives, Qas proved that their NL properties are enhanced bD the increasing of the sDstem
polaritD and of the length of the chromophore, as a result of the increasing of the number of
con!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 the
replacement of the benzene sDstem, Qhich are hardlD polarizable Qith others that possess a
diminished 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 mentioned
coefficients.
%
0he utilization of the azoderivatives as stoc?ing products has also been
investigated.
'
0hese can be used also as dDes for materials and plastic fibers, for in?
manufacture and stamp in?s, for the photographic industrD
(
or in the laser technologies.
Azoderivatives Qith loQ sDmmetrD have liGuid crDstal properties
)
and other diazenes are useful
as charge carriers.
*
0he pro!ect is structured in three sections,
11.1 +henDlene bisazoazulene derivatives. 0his section contains, '.1.1. the preparation of roQ
materials. '.1.$. the preparation of o-, m-, or p-phenDlene-bisazoazulenes Qith a sDmmetric or
an asDmmetric structure. '.1.%. the studD of the magnetic, optic or acid-base properties of these
combinations.
11.$. +henDlene bis azoazulenes derivatives containing polarizating functional groups at
azulenes moieties. '.$.1. the preparation of the roQ materials. '.$.$. the preparation of the
azulenic compounds. '.$.%. the studD of their phisico-chemical properties.
11.%. 0ris and polD azoazulenic derivatives, '.%.1. the preparation of the roQ materials. '.%.$ the
preparation of the azulenic compounds. '.%.%. the studD of their phisico-chemical properties.
11.1 P,en0lene bis azoazulenes #erivatives
Azulene is an aromatic hDdrocarbon Qhich is polarized due to the transition of an
electron toQard the five-atom ring for achieving an aromatic se/tet at both cDcles.
_
+
0herefore azulenes acGuires a nucleophilic character Qhich appears at five-membered
ring at the positions 1 and % Qhich permit its coupling Qith reactive diazonium salts contrarD to
the benzenoid aromatic hDdrocarbons that need activation electron donor groups for azo
coupling reactions. At the same time, the diazonium salts obtained from 1-azulenamines are not
stable and give azo coupling reactions onlD Qith verD reactive substrates such as -naphthol.
As a conclusion, it can be postulated that the azulenic bisazoic derivatives can be
prepared onlD bD coupling a diazonium salt possessing a benzenic core Qith an azulenic
molecule.
11.1.1. >,e preparation of t,e roF materials
7or the ma!oritD of the coupling reactions commercial reagents are used.
0he generation of bis azoderivatives containing onlD one azulenic moietD into the
molecule reGuires the sDnthesis of amino-azobenzene isomers. 0he easiest to be obtained is the
para-isomer Qhich results in one "or tQo# step bD the aniline diazotization folloQed bD
coupling of the resulted diazonium salt Qith an e/cess of the aniline and in sit% transposition of
the generated triazene.

NH
2
N N N
H
N N NH
2
0he sDnthesis of meta- isomer needs tQo steps indifferentlD of selected route.
NH
2
NO
2
PhNO
N
NO
2
N Ph
Na
2
S
N
NH
2
N Ph
NH
2
NHAc
PhNO
N
NHAc
N Ph
ClH
N
NH
2
N Ph
7or the orto isomer, the reduction of the nitro group is not selective and therefore the
single accessible QaD remains that using the mono acetDlated derivative commerciallD
accessible.
NH
2
NHAc
PhNO
N N Ph
NHAc ClH
N N Ph
NH
2
11.1.!. >,e preparation of p,en0lene bisazoazulenic #erivatives
0he proposed derivatives possess tQo identical or different azulenic moieties. In the first
case, theoreticallD, Qould be easier the direct coupling of the azulenic derivative Qith diazotized
phenDlenediamines. 0he stabilities of these salts and also of their redo/ compatibilities Qith
azulenes, hoQever, rises some problems.
It is ?noQn that p-phenDlenediamine can be bis diazotized onlD in strong acidic media
and the obtained bis diazonium salt decomposes at dilution or neutralization. 0here Qere
reported until noQ onlD its azo coupling reactions Qith phenols.
NH
2
N H
2 N
2
N
2
+ +
2 HSO
4
-
0he coupling Qith azulenes in a sulfuric acid medium seems to be prohibited due to
their loQ stabilitD in strong o/idant and acidic media. 0here are tQo possible QaDs for solving
this problem namelD, "a# starting from 1,% or 1,'-acetDlaminoaniline Qith a hDdrolDtic step, as
presented beloQ for the for para-isomer.
NH
2
NHAc
NaNO
2
HCl
AzH
N
N NHAc
NaNO
2
+ HCl
AzR
di!a"
N
N NH
2
N
N N
N
R#
R
R
R
HCl
R, R# = H, Me3 $a% &%
"b# 0he other route consists in m- or p-nitroanilines diazotization, coupling of the intermediate
salt Qith azulenes and the reduction of the nitro group to amine Qhich finallD is diazotized and
coupled. 0his QaD seems, hoQever, hazardous if Qe consider the sensibilitD of the azulene
derivatives at the reducing media Qhen free radicals are generated.
NH
2
NO
2
NaNO
2
HCl
AzH
N
N NO
2
NaNO
2
+ HCl
AzR
N
N NH
2
N
N N
N
R#
R
R
R
Na
2
S
R, R# = H, Me3 $a% &%
0he bis diazonium salt resulted from m-phenDlenediamine bD bis diazotization has a
loQer o/idant character and, therefore has a greater possibilitD to succesfullD couple Qith
azulene derivatives. 2ven in this case, if asDmetric derivatives are desired Qith tQo different
substituted azulenic moieties the single possible sDnthetical QaD ramains the above analDsed
stepQise route.
NH
2
NH
2
N
N
N
N
NaNO
2
HCl
AzR
R
R
R = H, 4,6,8-Me
3
, 3,8-Me
2
-5-iPr

0he sDntheses become more complicated for the o- isomer Qhere secondarD reactions
are possible Qith benzotriazole formation. 0hus, both o-phenDlenediamine and its
monoacetDlated derivative generate benzotriazoles bD treating Qith sodium nitrite and
hDdrochloric acid, therefore, the N-acetDlaminoaniline can not be used as starting material for
this target.
NHAc
NH
2
NaNO
2
ClH
N
N
N
R
N H
2
N H
2
NaNO
2
HCl
R = H, Ac
0he QaD starting Qith o-nitroaniline also fails because the nitro group in orto position
cannot be cleanlD reduced to amine and onlD transposition products results. o-
+henDlenediamine could be bis diazotized in concentrated sulfuric acid the generated salt
hoQever 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, the
generation of o-"N-phthalimido#-aniline, its diazotization folloQed bD the coupling of the
resulting diazonium salt Qith azulenes. 0he protecting group, phthaloDl can be removed bD
treating the product Qith hDdrazine and than the neQ amine can be diazotized and coupled Qith
another molecule of an azulene derivative. In this case the coupling Qill ta?e place Qithout
cDclization because there is no nitrogen proton remained to be replaced bD azo group and the
phthalimidic group is stable enough to not be opened bD the attac? of the diazonium ion.
4

NH
2
NO
2
O
O
O
N
NO
2
O
O
N
NH
2
O
O
N
N
O
O
N
N
2
H
4 NH
2
N N
N
N N
N
HNO
2
AzR#
HNO
2
AzR
R
R
R
R#
H
2
Ni-Ra
11.1.%. >,e stu#0 of t,e p,0sical properties of t,e s0nt,esize# #erivatives
0he first part of this section Qill start Qith the calculation of the geometries and of the
electronic densities of the sDnthesized molecules using 5+AC program. It is important to
?noQ if the orto isomer is planar or not and if the resulted geometrD alloQs it to form
comple/es Qith metals ions, Qhich Qould increase the impact of our studD. At the same time,
the substitution of azulenes Qith methDl at the position 4 could hinder the co planaritD of
azulene Qith the entire molecule and therefore could change the chromophore.
All the compounds Qill be characterized bD N56 proton and carbon spectra. 0he
influences of the phenDl replacement Qith azulene moieties or the differences induced bD the
disappearance of the molecule sDmmetrD bD azulene substitution Qith al?Dl groups Qill be
studied. 0hese facts Qill be also correlated Qith push-pull effects generated bD the structures of
the sDnthesized compounds. 0his fact is important due to the potential hDperpolarizabilitD of
these materials.
A special attention Qill be accorded to the studD of the electronic spectra. It Qill be
observed the influence of the solvent and of the p8 on the Qave length for the most important
band in visible region. 0he solvatochromism of the obtained products Qill be treated verD
carefullD for finding signs of their hDperpolarizabilitD. 0here Qill be determined also the
isosbestic points Qhere theD e/ist and Qill be calculated the bazicitD constants of the
azoderivatives bD measuring the p8 in Qhich are present eGual concentrations "absorptions# of
acidic and basic form of compounds.
11.! P,en0lene bis(azoazulenes) #erivatives substitute# at azulene Fit, functional groups
Azulenes are on the limit of the coupling capacitD of the normal diazonium salts. 0he
coupling reactions are possible Qith the unsubstituted azulenes, substituted Qith al?Dl or if at
position 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 acetDl group has a higher mobilitD as
electrophilic leaving group than the proton has and more of that its substitution is not reversible
as in the case of proton. 0herefore, it can be substituted bD an azo group in severe reaction
conditions, at high temperatures unusual for normal coupling reactions.
9
O
O
NH
2
O
2
N
NaNO
2
N
O
N
NO
2
N
O
N
NH
2
NaNO
2
R
N
O
N
N
N
R
AcCl
S"Cl
4 HCl
H
2
Pd
HCl
R = NHAc, OMe, OOCPh
It is possible that this reaction QaD to be also used for other derivatives as described
beloQ,
MeOOC
O
O
MeO
NH
2
O
2
N
NaNO
2
N
O
N
NO
2
MeO
N
O
N
NH
2
MeO
NaNO
2
R
N
O
N
N
N
R
MeO
AcCl
S"Cl
4 HCl
H
2
Pd
HCl
R = 'r%(a ac)i*a")a $a% $la+ dezac)i*a)are
0he use of the substituted azulenes at position 1 needs the sDnthesis of the roQ materials
because these azulenes are not commerciallD available.
0he sDnthesized bis azocompounds Qill be characterized bD the procedure described in
the previous chapter. It Qill be studied their magnetic resonance spectra and mainlD electronic
spectra for emphasizing the influence of the functional groups on the phDsical properties of the
products.
11.$ >,e preparation of pol0azo#erivatives
>D increasing the number of the azoic groups the mechanical properties of the material
is enhanced and at the same time the phDsical properties are modified, usuallD a bathochromic
shift could be observed.
0here are a high number of possible polDazoderivatives containing azulene, phenDlene
and azo groups. 0herefore, some more accessible combinations Qere considered, Qhose
sDnthesis could be realized in several steps using the intermediates alreadD prepared. 8ere is
presented one e/ample,
N N
NH
2
ON NO
2
N N
N N NO
2
N N NH
2
N N
N N
N N N N
Na
2
S
NaNO
2
AzH
HCl
11.%. >,e stu#0 of re#ox potentials of t,ese combinations
ur team in collaboration Qith the &niversitD +olDtehnica >ucharest has studied the
reduction and o/idation potentials of numerous azoic derivatives of azulenes. Be propose to
e/tend this studD also to the bis azoderivatives and polDazoderivatives to determine the possible
redo/ reactions on these sDstems. 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 bD D+<.
1-
; in C)8(-N:N-
C)8'; "p#
21=$
o/
21=$
red
; in 1-Az-N:N-
C)8'; "p#
21=$
o/
21=$
red
N8$ -.(4% -$.-)'
p5e 1.1$* -1.4(' p5e -.'*( -1.)(-
8 1.%$- -1.*%% 8 -.)$- -1.)*%
pN$ 1.(1* -1.$$4 pN$ -.)'4 -1.$(-
+otentials are measured using ferocen=feroceniu couple.
6azus A. C., >irzan L.& 3urugiu N. 5., Corbu A. C., Chiraleu 7. Dyes and Pigm. !00', 74(1), $)-%%. 6azus A.
C., >irzan L., Nae 3., 3urugiu 5. N. Cimpeanu <. J. Heterocyclic Cem. !00$, 4!, 99(-1--'. 6azus A. C., >irzan
L., Nae 3., Cristian L. Chiraleu 7. Dyes and Pigments !00$, "7, $$%-%%. 6azus A. C., >irzan L., Nae 3., Cristian
L., Chiraleu 7., 5aganu 5., Cimpeanu <., 0ar?o L. #e$. #o%m. Cim., !00$, 4& ('), '((-)1.
$
Liu @. A., Leng B. N., 7eng A. C., 6en A. 5., ;hou @. Chin. A. Chem. $--%, $1, 9-1(
%
;hu B. Bu 1-3. A. +hDs. Chem. A $--1, 1-(, 9()4-*'.
'
Liu ;. 7., 8ashimoto C., 7u!ishima A. 3cience 199-, %'*, )(4-)-
(
IgnatDev N., Belz->iermann &., Billner 8., 7inze, 5., >ernhardt 2., CucherDna A. >revet +C0 B
$--(=-$1))1 A1 din $--(
)
Covshev 2. I., >linov L. 5., 0itov, <. <. &speh. Chim. 19**, '), *(%-9).
*
Catagiri C., guchi E. >revet A+ )--1-$() din 194(
4
2. D. >ergmann, 5. >entar A. rg. Chem. 19(', 19, 1(9'.
9
C. 8afner, A. 3tephan, C. >ernhard Aust. Lieb. Ann. Chem. 19)1, )(-,'$
1-
rezultate 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 sDnthesis of some compounds
belonging to a neQ class, that of bis- and polD- azoderivatives Qhich contain in their molecules
phenDlene, phenDl and azulene-1-Dl radicals. 0he introduction of the azulenic moieties induces
a superior polarization than those observed for similar sDstems that have onlD benzenoide
aromatic groups bD increasing the energetic values of the 85 orbitals and decreasing those
of L&5 orbitals. 0he sDnthesis of the proposed compounds presents the noveltD element due
to the fact that the diazonium salts of azulenes are not stable compounds and therefore manD of
the usual coupling reactions can not be realized using these salts. In these conditions the roQ
materials must be the diazonium or tetrazonium salts Qith benzene nuclei and the coupling
components Qill be the azulene derivatives. 8oQever, azulenes being moderate nucleophiles
can not also couple Qith anD diazonium salts. Neither nitrosoderivatives of azulenes can be
considered for the generation of the azo compounds due to their loQ stabilitD, being obtained
onlD at loQ temperatures. 0he preparation and the coupling of the bis azo compounds generated
from phenDlenediamine presents also a series of peculiarities Qhich must be considered. Be
believe that some of the sDnthesis should have as starting materials anilines on Qhich is lin?ed a
substituent able to easilD generate an amino group. for e/ample a nitro group. 3o, the studD of
the sDnthesis of these derivatives presents scientific interest and is not a cosmetic sDnthetic
route.
$.0he second ob!ective is the unambiguous determination of the structures of the obtained
products and the studD of their phDsico-chemical properties. 0he chemical structure of the di-
and polD- azoderivatives ma?es possible a studD regarding the influence of the dihedral angle
betQeen the aromatic nuclei on the the con!ugation or the eventuallD generation of an
anchimeric chiral combination. 6egarding the structure of the obtained products Qill be also
studied its influence both on the N56 and electronic spectra. As has been alreadD mentioned
above, it is li?elD that these compounds to present a superior polarization and polarizabilitD than
those of monoazo compounds due to the enhanced con!ugation possibilities on a higher number
of pi atoms. It is also verD li?elD that betQeen the sDnthesized isomers, some of them that
contain different azulenic groups to shoQ up combination that could crDstallize in
noncentrosDmmetric sDstems and, therefore, to possess good NL properties. 0he same
structural characteristics can also generate the liGuid crDstal Gualities to some other materials
from the same class.
%.0he third ob!ective is the electrochemical characterization of the sDnthesized compounds
using both cDclic voltammetrD and potentiostatic method. 0he results obtained bD the studD of
the electrode ?inetic Qill be used to the elaboration of some possible mechanism of the
electrochemical reactions. 0he specificitD of the proposed sDstems consists in the concomitant
presence of a reducing pole belonging to an azulene derivative and of a relativelD o/idant one
represented bD the azo group, Qhich could generate neQ products bD interacting Qith the
electrodes. It can be anticipated the preparation of dimmers, oligomers or polDmers Qith
interesting electric properties. 0he sDnthesized products during this pro!ect can be utilized in
electrochemical purposes, for e/ample, electrode coverings or the generation of some sDstems
of comple/ electrolDtes.
'.0he last ob!ective is the fact that the beginning of a comple/ themes and relativelD complete
of fundamental research bD the Doung researcher in formation Qill give them the possibilitD to
become good research specialists and a part of the papers can be developed toQard the
sustaining of a doctoral theses. 5ore of that, for several Dears, in collaboration Qith the
institutions of superior education, a part of the students from the last Dear of studD ma?e their
e/periments for their diplomas in our labs. 0he same thing is valuable and for those Qho are
folloQing their 53 programs and is sufficient to remember that almost all our +h-D. students
Qor? their e/perimental part of their 53 dissertations in our teams. 0he proposed ob!ectives
harmonize Qith those of our collaborators from 2uropean countries such as 1ermanD, 7rance or
7inland. 0he results of these previous researches have been alreadD published in manD
prestigious chemical !ournals or presented at sDmposia and congresses
11.$ -esearc, met,o#olog0
0he pro!ect contains both e/perimental and theoretical parts.
6xperimental activit0 consists in the preparation of the starting materials and of the target
products-bisazoderivatives containing azulenic moieties into the molecules. It involves both the
chemical sDnthesis of the chemical compounds and the column chromatographD on alumina or
silica gel for their purification. 7or the testing of the puritD or the folloQing of the reactions
"usuallD for uncolored reagents# Qill be used our 8+LC apparatus.
(nal0tic control of the obtained products Qill be done bD high performance N56
spectroscopD using high resolution apparatus of %-- 58z and '-- 58z. Also, 53 spectra Qill
be done using 23I procedure, Qhich is the most adeGuate for our relativelD big and polar
molecules.
*v-+iz stu#ies- the curves for the determination of the isosbestiGues of the neQ sDnthesized
compounds Qill be realized on devices for electronic spectra bought recentlD bD our team that
have high resolutions. Also, the p8-measurement of the solutions Qill be done using a brand
neQ device bought from rion CompanD.
6lectroc,emical stu#ies Qill be e/ecuted partiallD at the &niversitD +olDtehnica >ucharest and
partiallD in our group after the acGuisition of a potentiostat. 0he &niversitD 2lectrochemical
Department possesses modern apparatus for electrochemical characterization of the compounds.
>,e t,eoretical part is based on correlations of o/idation and reduction potentials Qith the
L&5 and 85 energies and on calculus of bond lengths and dihedral angles Qith the help
of the Guantum mechanical program-5+AC.
11.%. 1ecessar0 resources
11.%.1. <uman resources
0he Institute of rganic ChemistrD-Costin Nenitescu possesses a Qell trained personal, highlD
scientificallD educated and having a long e/perience in the organic sDnthesis and phDsico-
chemical characterization of the organic compounds. 0he research team proposed for the pro!ect
elaboration is e/perimentated in the sDnthesis and characterization of organic compounds. 0he
ma!oritD of the team members are researchers in the Institute of rganic ChemistrD-C. D.
Nenitescu. 8oQever, one member is not Qor?ing here but is Qor?ing at its +hD thesis in our
institute.
11.%.1.1. ProGect manager
11.%.1.1.1. cientific competence of t,e proGect manager
Dr. eng. /iviu .irzan-pro!ect manager,
Qor?ing place-IN30I0&02 7 61ANIC C825I306E-C. D. N2NI023C&->&C8A6230
position, C3 II
1. Hears of service at actual For2ing place-(! Dears
!. )ompetence fiel#s& significantl0 results:
>,e stu#0 of total c,iral s0nt,esis of natural pro#ucts. >etQeen 199$ and 199( it Qas
studied the total chiral sDnthesis of 6oGuefortine C at 6ochester &niversitD, NeQ Eor?, &3A
and also some chiral sDnthons Qere prepared for the sDnthesis of some immunitD depressives.
>,e stu#0 of t,e electrop,ilic an# ra#icalic substitution reactions on azulenic nucleus. 0he
first preoccupation consisted in the studD of the halogenation reaction Qith the metallic halides
on this sDstem. b# 0he studD of the diazotization and coupling reaction on heterocDclic and
azulenic sDstems. c# 6eactions for preparation of the imines, amines, amides, carbamates of
azulenes and its dimers. d# 6eduction and al?Dlation N-o/ides to amines in the presence of an
azo group proving the compatibilitD betQeen an N-o/id function and an azulene moietD. e# 0he
preparation of the first -di?etones containing an azulenic group open the road for the sDnthesis
of numerous heterocDcles Qith ( or ) atoms into the molecule, such as pDrazols, o/azoles, etc
that possess azulene in their structure. f# sDnthesis of pDrDlium, pDridinium salts and pDridines
containing azulene moieties. g# Correlation of the chemical properties Qith Guantum
mechanical data and Qith nucleophilic reactivitD inde/es. h# 0he studD of the reaction
mechanism regarding above transformations. i# 0he studD of the correlation betQeen structure
and chemical shifts of protons and carbon atoms and the splitting of the azulenic derivatives in
the mass spectrometers. I participated at numerous technologies for the assimilation of
intermediates needed for national chemical industrD till 1949.
3. Articles pulished 3ith relevance for this pro4ect !selection"
1.A. C. 6azus. L. >irzan. 3. Nae. 3. A. 6azus. <. Cimpeanu. C. 3tanciu. (zulene-1-
azop0ri#ines& 0nt,esis an# 1-al20lation at p0ri#ine moiet0 +ynt. Comm%m. !00!, %$,
4$(-%*.
$. A. C. 6azus, L. >irzan, 3. Nae, L. Cristian and 7. Chiraleu (zulene-1-azop0ri#ine 14-
oxi#es Dyes and Pigments !00$, "7, $$%-%%.
%. A. C. 6azus, L. >irzan, 3. Nae, 5. N. 3urugiu and <. Cimpeanu (zulene-1-azo-!4-
t,iazoles. 0nt,esis an# Properties J. Heterocyclic Cem. !00$, 4!, 99(-1--'.
'. A. C. 6azus, L. >irzan, 3. Nae, . L. Lehadus, C. +avel and . Costan (zulenic -2etones.
0nt,esis& properties an# reactions to form five membere# aromatic ,eteroc0cles ,r-i$oc
!005 "/#, *1-4(.
(. 2.-5. &ngureanu, A.C. 6azus, L. >irzan, 1. >uica, And 5-3. Cretu 6lectroc,emical
tu#0 "f 1-Met,0lazulene ..P./. +ci. /%ll., +eries /, !005, '7(0), 4$-44.
). Ale/andru C. 6azus, Liviu >irzan& Nina 5irela 3urugiu, Andreea Cristina Corbu and 7ilip
Chiraleu 0nt,eses of (zulen-1-0l-benzot,iazol-!-0l Diazenes Dyes and Pigm. !00', 74(1),
$)-%%.
*. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Cristina Corbu
and Cristian 2nache (zulene-substitute# P0ran0lium alts. 0nt,eses an# Pro#ucts
),aracterization J. Heterocyclic Cem. !007& 40, 9)%-**.
4. 2leonora 5. &ngureanu, Ale/andru. C. 6azus, Liviu >irzan,

1eorge >uica, 5ariana Cretu
and 2nache Cristian 6lectroc,emical c,lorination of azulenic #erivatives. Insig,t into
mec,anism of ano#ic oxi#ative c,lorination 1lectrocimica ,cta !007& "(& *9'-4-%.
9. Ale/andru C. 6azus, Liviu >irzan, Andreea Corbu, ana ;aharia and Cristian 2nache
0nt,esis an# Properties of %-($-ubstitute# azulen-1-0l)-!&7-#ip,en0l-p0ri#ines ,r-i$oc
!007, 1(, 1$1-1$9.
1-. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Corbu,

7ilip
Chiraleu and Cristian 2nache (zulene-substitute# P0ri#ines an# P0ri#inium alts.
0nt,esis an# tructure. 1. (zulene-substitute# p0ri#ines J. Heterocyclic Cem& !00', 44,
$'(-$(-.
11. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Corbu,

7ilip
Chiraleu and Cristian 2nache

(zulene-substitute# P0ri#ines an# P0ri#inium alts.
0nt,esis an# tructure. !. (zulene-substitute# p0ri#inium salts J. Heterocyclic Cem
!00', 44, $(1-$)-.
#. $atent)
1. CatalDtic procedure for the preparation of (-al?Dl-salicDlaldehides. +atent 61-$
')% from %-.1- 199-.
,. 5he list of the scientific communications that are relevant for the pro4ect
1. (zulene-1-azop0ri#ine& s0nt,esis-al20lation A. C. 6azus, L. >irzan, 3tefania Nae,
<ictorita 0ecuceanu, +oster la al-$)-lea 3impozion National de Chimie, Calimanesti-Caciulata,
<ilcea 6omania, '-) oct. $---
$. .iazulene-reactions A. C. 6azus, 3tefania Nae, L. >irzan +oster la al-$4-lea
3impozion National de Chimie, Calimanesti-Caciulata, <ilcea 6omania, '-) oct. $--$
%. 1-(azulen-1-il)-!-(benzotiazol-!-il) #iazene. 3Dntesis and properties. A. C. 6azus, L.
>irzan, 3. Nae, N. 5. 3urugiu, A. Negoescu si <. Cimpeanu- a @@<III-a Conferinta Nationala
de Chimie )-4 ct. $--', Calimanesti-Caciulata
'. P0ri#inium an# bis-p0ri#inium salts substituite# Fit, !-(azulen-1-0l)et,enes.
0nt,esis& properties& uses as 1/" materials. A. C. 6azus, L. Cristian, L. >irzan, 3. Nae, .
Costan si C. 2nache- a @@<III-a Conferinta Nationala de Chimie )-4 ct. $--', Calimanesti-
Caciulata
(. 6tu#e 8lectroc,imi9ue #e compos8s azul8ni9ues& 2.-5.&ngureanu, A. 6azus, A.
Ion, C. 6abagiu-6oman, L. >arzan, 5. Cretu, AournJes dK2lectro-chimie $--(, ( - 4 !uillet
$--(, 3aint 5alo, 7rance, 0hLme $ 2lectrochimie 5olJculaire et >ioelJctrochimie.
). -e#ox be,avior of some azulene #erivatives& 2.-5.&ngureanu, A. C. 6azus, L.
>arzan, 5. Cretu, 1. >uica, 6omanian International Conference of ChemistrD and Chemical
2ngineering 6ICCC2 1', 31--C-$., $--)
*. 6lectroc,emical stu#0 of azulene #erivatives b0 c0clic an# #ifferential pulse
voltametr0 2.-5. &ngureanu, L. >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, 1. >uica, Le Guatrieme colloGue franco-romain de
chimie appliGue, $4 Auin-$ Aulliet $--), Clemont-7errand, 7rance
9. >,e s0nt,esis of some p0ran0lium salts an# of some p0ri#ine substitute# in %
position Fit, azulen-1-0l ra#icals Ale/andru C. 6azusM, Liviu >irzan, ana Lehadus,
Claudia +avel, Liliana Cristian, ana ;aharia si Cristian 2nache, +oster la al-$9-lea 3impozion
National de Chimie, Calimanesti-Caciulata, <ilcea 6omania, %-(, oct. $--)
1-. Discassion about mass spectra of %-azulen-1-0l-!&7-#imet,0lp0ri#inium
perc,lorates C. 6azus, L. >irzan, . Lehadus, C. +avel, C. 2nache, +oster la al-$9-lea
3impozion National de Chimie, Calimanesti-Caciulata, <ilcea 6omania, %-(, oct. $--)
11. 6tu#es electroc,imi9ue appli9uees aux !-:(6)-azulen-1-0l#iazen0l;-1&$-
benzot,iazoles 2. 5. &ngureanu, 5. 3. Cretu, A. C. 6azus, L. >irzan, +oster at the 1'th
2dition of the Conference of 5icrosensors, 5icroactuators and 5icrosDstems, LDon, 7rance,
Aune 1--1', $--*
%. E&perience accumulated in national and international pro'rams
ubstitution reactions on azulenic s0stems. <alogenation, participant, 5C0, ctober
-December 199). April - November 1994
"xi#ation reactions of some azulenic compoun#s, participant, 5C0, ctober 199*-
november 1994
>,e stu#0 of some materials starting from unsaturate# ,omo an# ,eteroatomic
s0stems F,ic, contain azulen0l groups, participant, AN30I, march 1999- November $---
>,e stu#0 of t,e s0nt,esis an# of t,e be,avior of some azulenic pro#ucts F,ic,
contain #ouble bon#s in t,e molecule, participant, AN30I, November 1999-october $--1
Derivatives of 1&14-biazulena& s0nt,esis& properties& applicative importance of t,e
fiel#, participant, 52C, ctober $--1- December $--$
)ontributions to t,e establis,ing of t,e structure an# of t,e reactivit0 of some
azulenic compoun#s Fit, nonlinear lig,t transmission properties, participant,
CNC3I3, AulD -December $--$
ubstitute# 1-v0n0lazulenes = a neF class of s0ntons useful for t,e generation of
some complex molecules an# of some materials Fit, nonlinear lig,t transmission
properties (1/") an# superior electroc,emical properties& participant, 11'---, 52C,
November $--%-november $--(
>,e s0nt,esis an# t,e stu#0 of some azulen-1-azo-,eteroc0clic materials Fit, ,ig,
,0perpolarizabilit0& participant, CNC3I3, Aune $--'-november $--'
<eteroaromatic compoun#s stabilize# b0 substitution Fit, azulene moieties.
0nt,esis& stu#0 of t,eir p,0sico-c,emical an# electroc,emical properties& use# in t,e
tec,ni9ue of nonlinear lig,t transmission (1/"), participant, 4-----, 52C, ctober
$--(-present
(. 6ther mentions:
75ember of the professional associations, 0he 3ocietD of the Chemist from 6omania
-3econd prize at the International ChemistrD lDmpiad-Leningrad, 6ussia 19*9
-6eferee for the Aournal of rganic ChemistrD, DDes and +igments and 0he Chemical
2ducation Aournal.
11.%.1.1.!. Managerial competence of t,e proGect manager
0he pro!ect manager has the e/perience and abilitD to administrate the activities and the budget
conform to the planning.
11.%.1.!. -esearc, team
>,e list of t,e researc, team: "Qithout pro!ect manager#
1r.
crt.
/ast an# Iirst 1ame
Hear of
birt,
cientific
title ?
P,D
? ?
ignature
1
6azus Ale/andru
Constantin
19%* C3 I E23
$
0ecuceanu <ictorita 19*% C3 III E23
%
2nache Cristian 19*- 3cientific
researcher
+hD student
'
Cristea 5ihaela 194- 6esearch
assistant
+hD student
(
Dragu Andreea 194( 6esearch
assistant
+hD student
11.%.1.!.1 6xperimentate# researc,ers
Participant 1: Dr. eng. (lexan#ru ). -azus
3tage at IC, '' Dears
1. Beneral experience:
19(9-19)- 3tagier engineer F3IN07A65 +lant Fdrugs production
19)--19)$ 0echnolog chief sector as above
19)$-19)' Ingineer- Centre of rganic ChemistrD-solvolDsis in cDclopropDlcarbinDl sDstems
19)'-19)4 3cientific researcher -as above
19)4-1949 3enior researcher III -as above-7riedel-Crafts al?Dlation reactions
1949-1991 3enior researcher II-as above- 0he chemistrD of azulenes
1991-present 3enior researcher I -as above
2. E&perience in the pro4ect field:
7or more than 1( Dears, Dr. 6azus put the accent on the studD of the influence of the of the
azulenic sDstem on some structures from Qhich it belongs, characterization of the compounds
obtained and the reflection of the azulene con!ugation Qith the rest of the molecules in their
phisico-chemical properties. 0here have been used procedures of phisico-chemical analDsis in
the scope to completelD characterize hundreds of neQ sDnthesized azulenic compounds. 3ome of
the procedures and results have made the sub!ect of specific publications. 8e has a prestigious
research activitD Qhich covers '( Dears in the fields of the sDnthesis of the organic compounds,
of their characterization and of the studD of their phDsico-chemical properties and for the
determination of some reaction mechanisms, activitD reQarded bD the prize of the 6omanian
AcademD. 8e has 4- papers published in prestigious !outrnals, conferences both in our countrD
and above, more than '- participations to the sDmposia hold in 6omania and abroad.
3.$atents
1.+rocedure for preparation of diethDlzinc +atent 6(%(4$ from 19*1
$.+rocedure for the preparation of the dichloroacetic acid chloride +atent 6*()-1 from 194-
%. +rocedure for the preparation of the dichloroacetic acid chloride +atent 6**9)% from 1941
' +rocedure for the preparation of the dichloroacetic acid chloride +atent 6*4-9( from 1941
(. +rocedure for preparation of 1-phenDl-'-ethDloctan-1,%-dione. +atent 69-')1 from 194)
). +rocedure for the purification of sodium glucoheptonate +atent 61-1('4 from 199-
*. CatalDtical procedure for the preparation of (-al?Dl-salicDlaldehDdes +atent 61-$')% from
199-.
#. .i'nificantl8 pulished papers:
/. A.C. Raz%$, 4. 5er)hei-er, 6. 0adea a"d A.-M . &la)z, Solol!tic "ehaiour of Strained S!stems.
#he "enzo$b%bic!clo$3.1.&%hex-'-en-4-!l cation, 7e)rahedr" 8e))er$, 1()5, 22-23, /322-/812.
2. S.A. O$adchii, 4.9. Ma-a):%; ,
4.&. Sh%+i", A.C. Raz%$, <. 0ar)ha a"d =$. Ar*a: *!cloprop!lal+!l *ations of a Spiro$',4%heptane
S!stem, Russ. Chem. Bull., 1((4, 43, 2134-2138.
3. &. 9,)i-e, P. &. 8acri!, K. Na;a)a"i a"d A. C. Raz%$ Push-Pull ,zulene-"ased *hromophores -ith
.onlinear /ptical Properties Tetrahedron Lett., 1((0, 39, 6853-56.
4. A. C. Raz%$ S!ntheses of Pol!c!clic *ompounds b! /xidatie *oupling of ,zulene-1-azo-arenes
J. Chem. Soc., Perkin Trans., 1, '&&&, 28/-288.
5. A. C. Raz%$, C. Ni)% /xidatie benz!lic substitution of azulene-1-azo142-meth!lbenzene3s, J.
Chem. Soc., Perkin Trans., /, '&&&, 282-224.
6. A. C. Raz%$, C. Ni)%, S. Car*aci, 8. 0irza", S.A. Raz%$, M. P( a"d 8. 7ar; S!nthesis and reactions
of .-1azulen-1-!lmeth!lene3ar!lamines >. Chem. Soc., Perkin Trans., 1, '&&1, /223-/233.
3. A. C. Raz%$, 8. 0irza", S. Nae, 8. Cri$)ia", 6. Chirale% a"d 4. Ci-(ea"%, ,zulene-1-azop!ridine 12-
oxides Des and P!m., '&&3, "#, 223-233.
8.. A. C. Raz%$, C. Ni)%, 4. 7ec%cea"% a"d 4. Ci-(ea"%, '-Substituted 1azulen-1-!l3ethenes $ur. J.
%r!. Chem., '&&3, 411/-41/1.
2. 8. Cri$)ia", 9. Sa$a;i, P. 8. 8acri!, 0. ?""adie%, 9. A$$el+er'h$, K. Cla:$ a"d A. C. Raz%$, 4onating
Strenght of ,zulene in 5arious ,zulen-1!l Substituted *ationic 4!es6 ,pplication in .onlinear
/ptics. Chem &ater., '&&4, 1', 3543-355/.
/1.. A. C. Raz%$, C. Ni)%, C. Pa*el, C.-A. Ci%c%le$c%, 4. Ci-(ea"%, C. S)a"ci% a"d P. P. P@er,
/xidation of 1-142-substituted phen!l3-'-14-meth!lphen!l3diazene7 benz!lic substitution versus *-
azo bond brea+ing Canad. J. Chem., '&&5, 83, 244-251.
//. <.-M. A"'%rea"%, A. C. Raz%$, 8. 0irza", &. 0%ica, M. Cre)% a"d C. <"ache 8lectrochemical
chlorination of azulene deriaties. 9nsight into the mechanism of anodic oxidatie chlorination
$lectrochimica (cta, '&&:, 52, 324.
,. -emer of the 0omanian /hemistr8 .ociet8
%. 5he list of the scientific communications that are relevant for the pro4ect
1. >,e ubstitution -eactions at .enz0lic Positions at (zulen-1-azo-(%4-met,0lbenzene)
compoun#s. 0echniGue &niversitD Darmstadt-7acultD of rganic ChemistrD, Darmstadt, 1CCD-
Conference
$. )ompoun#s Fit, ,emol0tic an# ,eterol0tic #ouble bon#s substitute# Fit, azulene an#
arenas. 0nt,esis& properties an# utilizations. CALI5AN230I-Caciulata !000-Conference
%.6lectroc,emical an# ),emical "xi#ation of Derivatives of (zulenes. N. D. 0otir, A. C.
6azus, C. Nitu, C. Lete, and 3. Lupu. 0he 194
th
5eeting of 0he 2lectrochemistrD 3ocietD
8Datt 6egencD +hoeni/. ct., !000, &3A-communication
' 6lectroc,emical .e,aviour of ome Derivatives of (zulene. N. D. 0otir, A. C. 6azus, C.
Lete, 3. Lupu, >unsen ColloGuium, 3eptember, !00!-Dresden-poster
(. )omparative tu#0 of ),emical an# 6lectroc,emical "xi#ation of ome (zulene
Derivatives. C. Lete, 1. +alleschi, C. Nitu, 5. >adea and A. C. 6azus 0he 4
th
International
3Dmposium on Cinetics in AnalDtical ChemistrD, 6ome, ItalD, !00%.
%. E&perience accumulated in national and international pro'rams
a)ubstitution reactions on azulenic s0stems. <alogenation, pro!ect manager, 5C0, ctober
-December 199). April - November 1994
b)"xi#ation reactions of some azulenic compoun#s& pro!ect manager, 5C0, ctober 199*-
november 1994
c)>,e stu#0 of some materials starting from unsaturate# ,omo an# ,eteroatomic s0stems
F,ic, contain azulen0l groups, pro!ect manager, AN30I, march 1999- November $---
#)>,e stu#0 of t,e s0nt,esis an# of t,e be,avior of some azulenic pro#ucts F,ic, contain
#ouble bon#s in t,e molecule, pro!ect manager, AN30I, November 1999-october $--1
e)Derivatives of 1&14-biazulena& s0nt,esis& properties& applicative importance of t,e fiel#,
pro!ect manager, 52C, ctober $--1- December $--$
f))ontributions to t,e establis,ing of t,e structure an# of t,e reactivit0 of some
azulenic compoun#s Fit, nonlinear lig,t transmission properties, pro!ect manager,
CNC3I3, AulD -December $--$
g)ubstitute# 1-v0n0lazulenes = a neF class of s0ntons useful for t,e generation of some
complex molecules an# of some materials Fit, nonlinear lig,t transmission properties
(1/") an# superior electroc,emical properties& pro!ect manager, 11'---, 52C, November
$--%-november $--(
,)>,e s0nt,esis an# t,e stu#0 of some azulen-1-azo-,eteroc0clic materials Fit, ,ig,
,0perpolarizabilit0, pro!ect manager, CNC3I3, Aune $--'-november $--'
i)<eteroaromatic compoun#s stabilize# b0 substitution Fit, azulene moieties. 0nt,esis&
stu#0 of t,eir p,0sico-c,emical an# electroc,emical properties& use# in t,e tec,ni9ue of
nonlinear lig,t transmission (1/"), pro!ect manager, 4-----, 52C, ctober $--(-present
G)Inovative electroc,emical sensors for clinic an# enviromental anal0sis& manager pro!ect,
$-----, 52C, August $--)-present
Participant !: Dr. 6ng. +ictorita >ecuceanu-doctor in chemistrD
1. Beneral experience:
- H%l: /222 B Ha"%ar: 2111 Stagiar researc assistant - Centre of rganic ChemistrD F C. D.
Nenitzescu, >ucharest.
Description, Hrganic sDnthesisI
- !anuarD $--- F september $--' #esearc assistant - Centre of rganic ChemistrD F C. D.
Nenitzescu, >ucharest.
Description, H0he chemistrD of azulenesI
- september $--' F present +cienti4ic researcer - Centre of rganic ChemistrD F C. D.
Nenitzescu, >ucharest.
Description, H0he chemistrD of azulenesI
!. 6xperience in t,e proGect fiel#:
Dr. 0ecuceanu has e/perience in sDnthesis of derivatives of azulenes, Qhich is starting materials
for another neQ compound. 0he pathQaD to obtain this compound is one original. 3he ta?e part
to the elaboration of a neQ QaD to obtain vinDl-azulenes compounds, method in agrees Qith
Hgreen chemistrDI, Qho Qants to protect the environment. In December $--) she sustains in
public her +h. D. H$-3ubstituted-1-"azulen-1-Dl#ethene. 0he substituents influence to sDnthesis,
mechanism of reaction and products proprietiesI, under supervision of Dr. 2ng. Ale/andru C.
6azus.
%. ignificantl0 publis,e# papers:
1. 1&1-.iazulene Derivatives. 0nt,eses an# -eactions& A.C. 6azus, L. >irzan, 3. Nae, C.
Nitu, <. 0ecuceanu, <. Cimpeanu, ,r-i$o-, !00! "ii#, 1'$-1(%.
!. )onsi#erations on t,e Iragmentations of some =substitute# (zulenes in t,e Mass
pectrometer A.C. 6azus, L. >irzan, +. 7ilip, 5. Danila, <. 0ecuceanu, L. Cristian, 5. +opescu,
#e$. Cim. !00!, "0(1!), )'1-').
$. !-ubstitute#((zulen-1-Hl)6t,enes A.C. 6azus, C. Nitu, <. 0ecuceanu, <. Cimpeanu,
1%ropean Jo%rnal o4 Organic Cemistry, !00$, (0, ')-1-')1-.
%. >,e )oupling )apacit0 "f Diazotize# 1-ubstitute# (minop0ri#ines - ( Mec,anical
Juantum (pproac, A.C. 6azus, L. >irzan, 3. Nae, <. 0ecuceanu, L. 0ar?o, #e$%e #o%maine
de Cimie, !00$, 4&(0#, 191-19).
5. Pat,Fa0s for t,e solvent-free con#ensation betFeen c,iff bases an# met,0lenic
compoun#s A.C. 6azus, C. Nitu, <. 0ecuceanu and L. >irzan, #e$%e #o%maine de Cimie,
!005, "!"9-1-#, *$9-*%).
7. >,e list of t,e scientific communications t,at are relevant for t,e proGect
1. (zulen-1-azopiri#ine. inteza alc,ilare.A. C. 6azus, L. >irzan, 3. Nae and <. 0ecuceanu,
Al @@<I-lea 3impozion National de Chimie. Calimanesti-Caciulata, $---.
$. )on#ensarea unor baze c,iff azulenice cu compusi cu metilen activ pentru obtinerea
unor vinilazulene. A.C. 6azus, 3. Nae, C. Nitu, <. 0ecuceanu, C. +avel, . ;aharia si <.
Cimpeanu,
A @@<III-a Conferinta Nationala de Chimie, )-4 octombrie $--', <alcea.

11.%.1.!.!. Houng -esearc,ers
In our Qor?ing team are included also Doung researchers, loo?ing after their promovation and
the elaboration of a high level +hD thesis,
1. 6nac,e )ristian-researcher, +h. D. student
+ublished papers,
1. 3Dnthesis and +roperties of '-"%P-3ubstituted azulen-1P-Dl#-$,)-diphenDl-pDridines. 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 +Dridines and +Dridinium 3alts.
3Dnthesis and 3tructure. 1. Azulene-substituted pDridines J. Heterocyclic Cem, $--*, 44,
$'(-$(-.
%. Ale/andru C. 6azus, Liviu >irzan, Claudia +avel, ana Lehadus, Andreea Corbu,

7ilip
Chiraleu and Cristian 2nache

Azulene-substituted +Dridines and +Dridinium 3alts.
3Dnthesis and 3tructure. $. Azulene-substituted pDridinium salts J. Heterocyclic Cem
$--*, 44, $(1-$)-.
$. )ristea Mi,aela-research assistant-Institute of rganic ChemistrD C. D. Nenitzescu
+ublished papers,
1.1,%-Dipolar cDcloaddition reactions of 1-"%-nitrophenacDl#-1,1--phenanthrolinium N-
Dlide Qith activated al?Dnes 7. Dumitrascu, C. Draghici, 5. 6. Caira, A. >adoiu, L. >arbu, 5.
Cristea ,r-i$oc, !005 (7), 1)(-1*%
$. 3Dnthesis and @-raD 3tructure of a neQ +DrroloR1,$-bS-pDridazine Derivative 5. 6.
Caira, 7. Dumitrascu, C. Draghici, D. Dumitrascu, 5. Cristea 5olec%les, !005, 1!, %)--%)).
% Azulene Derivatives 3oluble In +olar 3olvents. 1-"Azulen-1-Dl#-$-"0hien-$- or %-Dl#-
2thenes Ale/andru C. 6azus, Liviu >irzan, <ictorita 0ecuceanu, 5ihaela Cristea, #e$. #o%m.
Cim, in print
%. Dragu (n#reea- research assistant-Institute of rganic ChemistrD C. D. Nenitzescu
0he activities at Qhich theD Qill participate are in conformitD Qith those registrated in the plan
of the pro!ect implementation, theD Qill participate at the documentation from the chemical
literature for the pro!ect, for the preparation of the starting materials needed in the sDnthesis of
bisazoic monoazulenic, of bisazoic metha and para diazulenic, of bisazoic ortho mono and
diazulenic, of functionalized azulenic derivatives and, finallD for the preparation of
polDazoderivatives.
11.%.! "t,er resources
10.%.!.1. Iinancial resources
/bAectis@,ctiities Buman
;esources
1om x luna3
H%-a" re$%rce$ F-a)erial$
A++re*ia)i"G PC B(rHec)
crdi"a)r
< /...4 B e!ec%)a")$ /...4
financial
resources from
buget
1;/.3
S#,C8 9 '&&)@3 months
Documentation for t,e s0nt,esis of t,e
starting materialsE preliminar0 attempts
) persons T
-.() months
+C F the assignation of the
responsabilities in the frame
of the pro!ect
<B 15'C@!00!
1"1.1.#, )1%-)
'"*.1.#, %----
1%"1'.1%#, 4)9'
Completion of the documentation about the
information e/istent in the literature regarding
the investigated target
+C , 21, 2$, 2%, 2', 2( F
documentation
0he preparation of starting materials necesarD
for the ne/t steps
2$, 2%, 2', 2( F the
preparation starting materials
0he analDsis and characterization of the starting
materials
+C, 21, 2$, 2% F the
analDsis and characterization
of starting meterials
>(B6 II = !00D @ % mont,s
>,e preparation of monoazulenic bisazoic
#erivatives
) persons T
-.*( months
+C F the assignation of the
responsabilities in the frame
of the ob!ective
<B 15'C@!00!
1"1.1.#, 1%---
'"*.1.#, 1-----
1%"1'.1%#, $----
0he sDnthesis of monoazulenic bisazoic
derivatives
2$, 2', 2( F the preparation
starting materials
0he characterization of the obtained products
Correlation of the &<-<I;, 53 and N56
spectra Qith the structure of the obtained bis azo
derivatives
+C, 21, 2$, 2% F product
characterization
2lectrochemical studies +C, 21 F electrochemical
studies
>(B6 III = !00D @ ' mont,s
>,e preparation of t,e #iazulenic bisazoic
#erivatives (isomers met,a an# para)
) persons T
1.%1 months
+C F the assignation of the
responsabilities in the frame
of the ob!ective
<B 15'C@!00!
1"1.1.#, 1'%-'*
1%"1'.1.#, %---
1%"1'.$.#, )---
1%"1'.%.#, %(---
1%"1'.1%#, 1$9(%
0he sDnthesis of diazulenic, metha and para
bisazoic derivatives
2$, 2%, 2', 2( F product
preparation
0he characterization of the obtained products
Correlation of the &<-<I;, 53 and N56
spectra Qith the structure of the obtained bis azo
derivatives
+C, 21, 2$, 2% F product
characterization
2lectrochemical studies +C, 21 F electrochemical
studies
>(B6 I+ = !00C @ 5 mont,s
>,e preparation of t,e #iazulenic bisazoic
#erivatives (isomer ort,o) ) persons T
-.9% months
+C +C F the assignation of
the responsabilities in the
frame of the ob!ective
<B 15'C@!00!
1"1.1.#, 41*'1
'"*.1.#, (----
1%"1'.1%#, 14$(9
0he sDnthesis of diazulenic ortho bisazoic
derivatives
2$, 2%, 2', 2( F the product
preparation
0he characterization of the obtained products
Correlation of the &<-<I;, 53 and N56
spectra Qith the structure of the obtained bis azo
derivatives
+C, 21, 2$, 2% F F
product characterization
2lectrochemical studies +C, 21 F electrochemical
studies
>(B6 + = !00C @ ' mont,s
>,e preparation of functionalize# #iazulenic
bisazoic #erivatives
) persons T
1.%1 months
+C F the assignation of the
responsabilities in the frame
of the ob!ective
<B 15'C@!00!
1"1.1.#, 1'%-'*
1%"1'.1.#, %---
1%"1'.$.#, )---
1%"1'.%.#, %(---
0he sDnthesis of the functionalized diazulenic
bisazoic derivatives
2$, 2%, 2', 2( F the product
preparation
0he characterization of the obtained products
Correlation of the &<-<I;, 53 and N56
+C, 21, 2$, 2% F F
product characterization
spectra Qith the structure of the obtained bis azo
derivatives
1%"1'.1%#, 1$9(%
2lectrochemical studies +C, 21 F electrochemical
studies
>(B6 +I = !00C @ 5 mont,s
>,e preparation of azulenic trisazoic
#erivatives
( persons T
-.9% months
+C F the assignation of the
responsabilities in the frame
of the ob!ective
<B 15'C@!00!
1"1.1.#, 1-$1*)
1%"1'.1%#, 1'4$'
0he sDnthesis of the triazulenic bisazoic
derivatives
2$, 2%, 2', 2( F the product
preparation
0he characterization of the obtained products
Correlation of the &<-<I;, 53 and N56
spectra Qith the structure of the obtained tris azo
derivatives
+C, 21, 2$, 2% F product
characterization
2lectrochemical studies +C, 21 F electrochemical
studies
>(B6 +II = !010 @ 5 mont,s
>,e valorification of t,e novelt0 aspects of t,e
results of t,e researc,
) persons T
-.9% months
+C , 21, 2$, 2%, 2', 2( F
the dissemination of the
results
<B 15'C@!00!
1"1.1.# )1%-)
1%"1'.1.#, 1(--
1%"1'.$.#, %---
1%"1'.%.#, 1*(--
1%"1'.1%#, 1))9'
0he dissemination of the results bD national or
international publishing.
11.%.!.!. >,e available infrastructure
7or the implementation of the e/periments needed for the pro!ect accomplishment the Institute
of rganic ChemistrD possesses the folloQing eGuipments and facilities for e/perimentation,
N56 3pectrometer >ru?er Advance '--,
1
8-N56, '-- 58z.
1%
C-N56, 1--.)$ 58z,
medium ageing ( U.
1as chromatograph 1C-7I33N3 <IC 9--
&<-<is 3pectrophotometer CA6E 1-- >io bought in $--(
8+LC-Agilent 1$-- 3eries Qith analDtical column LC 11$-=LC 11(-. oven for the
thermoregulation of the column, auto sampler bought in $--(
Autoclaves, stoves,
ultrasound baths,
high vacuum pumps,
stirrers, thermostats= crDostats
specific glass Qear for organic labs
devices for multiplication and document processing
netQor? of computers and peripheral eGuipment, IN026N20 connection.