41 research outputs found
HETEROCYCLIZATION WITH IMINIUM SALTS AND N-YLIDES
Novel 2,3a,6a-triazaphenalene and 1-thia-2a,5a-diaza-acenaphthene ring systems were
synthesized and their ring transformation reactions affording polycycles with bridgehead
nitrogen atom were investigated. 1,3-Dipolar cycloaddition of isoquinoline N-ylides with
azomethines and olefines were studied and the regio- and stereoselectivity of the reaction were
proved by structure elucidation and quantum chemical calculations
CONTRIBUTION TO THE SYNTHESIS OF PERMETHRIN
Several routes for the industrial synthesis of 1,1-dichloro-4-methyl-1,3-pentadiene as the
key intermediate of permethrin insecticide have been developed. During the chlorination of
1,1,1-trichloro-4-methyl-pentene-3-ol new 1,3-and 1,5-rearrangements involving chlorine were
observed. Radical species in the processes were detected by ESR spectroscopy and mechanisms
of the rearrangements were rationalized
Amino-foszfonsavak Ă©s foszfinsavak sztereoszelektĂv szintĂ©zise = Stereoselective synthesis of amino phosphonic and phosphinic acids
A projekt cĂ©lja aminofoszfonátok Ă©s foszfinátok katalitikus sztereoszelektĂv szintĂ©zise volt. KĂĽlönbözĹ‘ ?????Ă©s ?-aminofoszfonát prekurzorokbĂłl kiindulva C-C kötĂ©s kialakĂtásával állĂtottunk elĹ‘ egyik enantiomerben gazdagabb ??C-atomon szubsztituált foszfonátokat. MegállapĂtottuk, hogy a Michael-addiciĂłban alkalmazhatĂł királis katalizátor tĂpusa a prekurzor foszfonát ??helyzetű CH-csoportjának savasságátĂłl fĂĽgg. A legkevĂ©sbĂ© savas vĂ©dett foszfoglicin származĂ©kbĂłl D-glukĂłz-, ill. R-BINOL alapĂş N-tartalmĂş koronaĂ©teekkel erĹ‘s bázis jelenlĂ©tĂ©ben igen magas enantiomer-, Ă©s diasztereomer felesleget sikerĂĽlt elĂ©rni akril-nitrilek Michael-addiciĂłjában. Ciano-metilfoszfonátot, mint viszonylag könnyen deprotonálhatĂł ?-aminofoszfonsav prekurzort organokatalizátorokkal kalkonok Michael-addiciĂłjában tudtuk hasznosĂtani. KatalizátorkĂ©nt cinkona-, Ă©s TADDOL-alapĂş tiokarbamid származĂ©kokat alkalmaztunk. Az ??nitro-etilfoszfonát, mint ??helyzetben kvaterner C-atomot tartalmazĂł aminofoszfonsav származĂ©k prekurzora organokatalizált Michael-addiciĂłban aril-akrilátokkal magas enantioszelektivitással eredmĂ©nyezte a megfelelĹ‘ adduktot, melyet katalitikus hidrogĂ©nezĂ©ssel aminofoszfonáttá alakĂtottunk. Katalitikus P-C kötĂ©s kialakĂtásával dialkil-foszfitokbĂłl Ă©s iminekbĹ‘l is előállĂtottunk közel enantiomertiszta ??aminofoszfonát-származĂ©kokat TADDOL-ok titán-komplexeit alkalmazva Lewis-sav katalizátorkĂ©nt. TöbblĂ©pĂ©ses szintĂ©zisben - az irodalomban eddig nem szereplĹ‘ vegyĂĽletcsalád egyik kĂ©pviselĹ‘jĂ©t - amino-ciklopropán-foszfinsavat állĂtottunk elĹ‘. Az egyik intermedierre enzimatikus kinetikus reszolválási mĂłdszert dolgoztunk ki. | The aim of the project was the catalytic stereoselective synthesis of aminophosphonates and aminophosphinates. Several ?-, and ?-aminophosphonate precursors were used in C-C-bond forming reactions resulting in nonracemic ?-substituted aminophosphonates. It was established that the character of the catalyst suitable in the Michael addition was strongly influenced by the acidity of the ?- CH-group of the precursor. The least acidic protected phosphoglycine derivative could be applied in the Michael addition of acrilonitriles by using strong base and D-glucose/R-BINOL-based crown ethers as catalysts resulting in the adducts in high enantio-, and diastereoselectivity. Cyanomethyl phosphonate as an easily deprotonable ?-aminophosphonate precursor could be utilized in an organocatalytic Michael addition of chalchones. As catalysts chincona-, and TADDOL-based thioureas were applied. Nearly the single isomer of ?-aminophosphonates having quaternary carbon atom next to the phosphorus were obtained from ?-nitro ethylphosphonate by means of aryl acrilate in an organocatalysed Michael addition followed by catalytic hydrogenation. Nearly the single isomer of ?-aminophosphonates were also synthesised from dialkyl phosphites and imines in P-C bond formation reaction using TADDOL-Ti complex as catalyst. A substituted aminocyclopropanephosphinic acid as the first member of a new family of compound was synthesised in a multistep reaction. An enzymatic kinetic resolution was succesfully applied on one of the intermediates
POLYETHYLENE GLYCOL DERIVATIVES AND THE PHASE-TRANSFER CATALYSIS
The phase-transfer catalyst efficiency of polyethylene glycols were proven and analysed.
The stability of their sodium complexes increases with the length of chain while the lipophilicity
decreases.
As a result the best phase-transfer catalyst PEO-s can be found among the medium chainlength ones
Konzorcium, fő p.: Kvantum fázisok és fázisátalakulások hangolható korrelált rendszerekben = Consortional main: Quantum phases and phase transitions in tunable correlated systems
A pályázat cĂ©lja egyfelĹ‘l mezoszkĂłpikus áramkörökbeli korrelált állapotok tanulmányozása volt nem egyensĂşlyi körĂĽlmĂ©nyek között, másfelĹ‘l pedig ultrahideg atomi rendszerek illetve korrelált modellek egzotikus állapotainak feltĂ©rkĂ©pezĂ©sĂ©t tűztĂĽk ki cĂ©lul. KiemelkedĹ‘ek a rendezetlen kvantum rendszerek lokalizált illetve ĂĽveg állapotainak leĂrására vonatkozĂł eredmĂ©nyek, az SU(N) Mott szigetelĹ‘k kvantum fázisaira vontakozĂł eredmĂ©nyeink, a kölcsönhatĂł rendszerekbeli kvantum kvencs számĂtások eredmĂ©nyei, az U(1) spin folyadĂ©kokra vonatkozĂł eredmĂ©nyeink, valamint a nem egyensĂşlyi rendszerek zaj spektrumára vonatkozĂł - kĂsĂ©rletileg is igazolt eredmĂ©nyek. A kutatás eredmĂ©nyekĂ©pp többek között 11 Physical Review Letters közlemĂ©ny, 1 Physical Review X, 1 Nanoscale publikáciĂł Ă©s 39 Physical Review cikk szĂĽletett. A kutatĂłmunkába 11 diák kapcsolĂłdott be, munkájuk nyomán 7 dĂjazott TDK dolgozat, 4 BSc diplomamunka, 4 MSc diplomamunka Ă©s 3 doktori disszertáciĂł szĂĽletett. | The goal of this proposal was to study correlated states of mesoscopic circuits under non-equilibrium conditions, on the one hand, and to search for novel exotic quantum states of tunable cold atomic systems and other correlated systems, and to characterize these states, on the other hand. Of special importance are our results regarding the various quantum phases of SU(N) Mott insulators, the results concerning the description of localized and glassy states of disordered quantum systems, the characterization of U(1) spin liquid states, our studies of quantum quench in interacting many-body systems, and finally, the theoretical results regarding the non-equilibrium noise spectrum in correlated mesoscopic circuits - also confirmed experimentally. Among others, the research project resulted in 11 Physical Review Letters, one Physical Review X, one Nanoscale, and 39 Physical Review publications. Eleven students were integrated into this project, and their devoted research resulted so far in 7 (awarded) student's research project (TDK), 4 BSc theses, 4 MSc theses, and 3 PhD dissertations
Change of the kinetics of inclusion in cucurbit[7]uril upon hydrogenation and methylation of palmatine
The inclusion of protonated (-)-tetrahydropalmatine (THP+) and dehydrocorydaline (DHC+), natural alkaloids, in the cavity of cucurbit[7]uril was monitored in real time by a spectrofluorimetric method in water at various temperatures. Both guests produced 1:1 complexes in enthalpy controlled processes without any detectable intermediates. The tight entrance of CB7 imposed substantial steric hindrance for encapsulation making the entry into the host several orders of magnitude slower than diffusion. Despite the approximate to 6 kJ mol(-1) lower activation enthalpy, the rate constant of THP+ ingression into CB7 was about 44-fold smaller at 298 K than that of DHC+ as a consequence of the considerably negative activation entropy of the former binding. The egression rates of the two studied alkaloids differed to a much lesser extent because the lower energy barrier of THP+ release was almost compensated by the unfavourable activation entropy. In comparison with the kinetics of the reversible confinement of the palmatine parent compound, the presence of the methyl substituent on the aromatic heterocyclic ring in DHC+ barely modified the rate constant of entry into CB7 but caused about 10-fold increase in the dissociation rate at 298 K
Cinchona based squaramide catalysed enantioselective Michael addition of a-nitrophosphonates to aryl acrylates: enantioselective synthesis of quaternary a-aminophosphonates
Several cinchona based squaramide catalysts were applied to the asymmetric Michael addition of α-nitroethylphosphonates to acrylic acid aryl esters, resulting in high yields and enantioselectivities. The absolute configuration of one of the quaternary α-nitrophosphonate adducts was deduced from its experimental and calculated CD spectra. The adducts were reduced to their cyclic aminophosphonates by catalytic hydrogenation
Synthesis and Application of New, Optically Active Compounds as Catalysts and Ligands in Enantioselective Reactions
New methods for efficient preparation of optically active compounds developed recently are reported. Combination of selective organometallic, organocatalytic, phase transfer catalytic and catalytic hydrogenation reactions provided numerousnew optically active members of the families of atropisomeric 1-phenylpyrrole derivatives, 4-aminobutan-1-ol and 3,4-disubstituted pyrrolidine derivatives and optically active α- and β-aminophosphonic acids. The products can be used as valuable new chiral ligands or organocatalysts and can serve as building blocks of practically important biologically active compounds