{"id":{"repo_id":"greece","oai_identifier":"oai:10442/1347"},"canonical_url":"https://search.dev.ndltd.org/etd/greece/oai:10442/1347","repository":{"repo_id":"greece","name":"Greek National Archive of PhD Theses","base_url":"https://phdtheses.ekt.gr/eadd_oai/request"},"display":{"title":"ΜΕΛΕΤΗ ΑΝΤΙΔΡΑΣΕΩΝ 1,3-ΔΙΠΟΛΙΚΗΣ ΚΥΚΛΟΠΡΟΣΘΗΚΗΣ ΣΕ ΕΤΕΡΟΚΥΚΛΙΚΑ ΣΥΣΤΗΜΑΤΑ","abstract":"THE MAIN PURPOSE OF THIS WORK IS TO STUDY THE 1,3-DIPOLAR CYCLOADDITION REACTIONS TO SUBSTITUTED EXOMETHYLENE-OXAZOLONES AND THIAZOLONES AND TO EXAMINE THESE REACTIONS AS A POSSIBLE SOURCE OF HETEROCYCLIC A-AMINOACID DERIVATIVES. (Z)- AND (E)-2- PHENYL-4-ARYLIDENE-5(4H)-OXAZOLONES REACT WITH NITRILIMINES AND (Z)-2-PHENYL-4-ARYLIDENE-5(4H)-THIAZOLONES WITH STABLE NITRILE OXIDES AND NITRILIMINES TO AFFORD SPIRO CYCLOADDUCTS, BY ADDITION OF THE DIPOLE ON THE EXOCYCLIC DOUBLE BOND. THE REACTIONS ARE STEREOSPECIFIC AND REGIOSELECTIVE, GIVING IN ALL CASES ONLY ONE REGIOISOMER, IN WHICH THE ANIONIC CENTER OF THE DIPOLE IS JOINED WITH THE TERTIARY CARBON ATOM OF OXAZOLONE-OR THIAZOLONE-RING. THE STRUCTURE OF THESE NEW COMPOUNDS WAS CONFIRMED BY SPECTROSCOPIC DATA AND BY CHEMICAL METHODS.THE OBSERVED REGIOCHEMISTRY IS ALSO RATIONALIZED BY FRONTIER MOLECULAR ORBITALCONSIDERATIONS OF THE REACTING SYSTEMS, USING EHMO-CALCULATIONS FOR THE MAGNITUDES OF OXAZOLONE ATOMIC ORBITAL COEFFICIENTS. ATTEMPTS TO CARRY OUT CYCLOADDITIONS REACTIONS OF THESE SYSTEMS WITH THE UNSTABLE BENZONITRILE OXIDE, NITRONES AND AZIDES WERE UNSUCCESSFUL. CYCLOADDITION REACTIONS WERE ALSO CARRIED OUT ON THE 2-PHENYL-4-ETHOXYMETHYLENE-5(4H)-OXAZOLONE. THE REGIOSELECTIVITY OF THESE REACTIONS IS DIFFERENT BECAUSE OF THE STRONG DIRECTIVE EFFECT OF THE ETHOXY MOIETY AND IN THE CYCLOADDITIONS THE ANIONIC CENTER OF THE DIPOLE IS JOINED WITH THE CARBON ATOM CARRYING THE ETHOXY-GROUP. THE CLEAVAGE OF THE ABOVE PREPARED SPIRO CYCLOADDUCTS WITH NUCLEOPHILES LEADS TO ISOXAZOLINE OR PYRAZOLINE A-AMINOACID DERIVATIVES. ESPECIALLY, CLEAVAGE REACTION WITH GLYCINE ETHYLESTER RESULTED DIPEPTIDES CONTAINING HETEROCYCLIC RING. IN A COMPARISON WITH THE ABOVE STUDIED DIPOLAROPHILES, CYCLOADDITIONS OF METHYL-(Z)- AND (E)-A- BENZAMIDO- CINNAMATES WITH NITRILOXIDES AND NITRILIMINES WERE ALSO EXAMINED. THESE REACTIONS SHOW THESAME REGIOSELECTIVELY AND GIVE THE SAME PRODUCTS OBTAINED FROM THE METHANOLYSIS OF THE (Z)- AND (E)-SPIRO CYCLOADDUCTS RESPECTIVELY, CONFIRMING THAT NUCLEOPHILIC CLEAVAGE OF OXAZOLONE-RING IS STEREOSPECIFIC.","abstract_html":"THE MAIN PURPOSE OF THIS WORK IS TO STUDY THE 1,3-DIPOLAR CYCLOADDITION REACTIONS TO SUBSTITUTED EXOMETHYLENE-OXAZOLONES AND THIAZOLONES AND TO EXAMINE THESE REACTIONS AS A POSSIBLE SOURCE OF HETEROCYCLIC A-AMINOACID DERIVATIVES. (Z)- AND (E)-2- PHENYL-4-ARYLIDENE-5(4H)-OXAZOLONES REACT WITH NITRILIMINES AND (Z)-2-PHENYL-4-ARYLIDENE-5(4H)-THIAZOLONES WITH STABLE NITRILE OXIDES AND NITRILIMINES TO AFFORD SPIRO CYCLOADDUCTS, BY ADDITION OF THE DIPOLE ON THE EXOCYCLIC DOUBLE BOND. THE REACTIONS ARE STEREOSPECIFIC AND REGIOSELECTIVE, GIVING IN ALL CASES ONLY ONE REGIOISOMER, IN WHICH THE ANIONIC CENTER OF THE DIPOLE IS JOINED WITH THE TERTIARY CARBON ATOM OF OXAZOLONE-OR THIAZOLONE-RING. THE STRUCTURE OF THESE NEW COMPOUNDS WAS CONFIRMED BY SPECTROSCOPIC DATA AND BY CHEMICAL METHODS.THE OBSERVED REGIOCHEMISTRY IS ALSO RATIONALIZED BY FRONTIER MOLECULAR ORBITALCONSIDERATIONS OF THE REACTING SYSTEMS, USING EHMO-CALCULATIONS FOR THE MAGNITUDES OF OXAZOLONE ATOMIC ORBITAL COEFFICIENTS. ATTEMPTS TO CARRY OUT CYCLOADDITIONS REACTIONS OF THESE SYSTEMS WITH THE UNSTABLE BENZONITRILE OXIDE, NITRONES AND AZIDES WERE UNSUCCESSFUL. CYCLOADDITION REACTIONS WERE ALSO CARRIED OUT ON THE 2-PHENYL-4-ETHOXYMETHYLENE-5(4H)-OXAZOLONE. THE REGIOSELECTIVITY OF THESE REACTIONS IS DIFFERENT BECAUSE OF THE STRONG DIRECTIVE EFFECT OF THE ETHOXY MOIETY AND IN THE CYCLOADDITIONS THE ANIONIC CENTER OF THE DIPOLE IS JOINED WITH THE CARBON ATOM CARRYING THE ETHOXY-GROUP. THE CLEAVAGE OF THE ABOVE PREPARED SPIRO CYCLOADDUCTS WITH NUCLEOPHILES LEADS TO ISOXAZOLINE OR PYRAZOLINE A-AMINOACID DERIVATIVES. ESPECIALLY, CLEAVAGE REACTION WITH GLYCINE ETHYLESTER RESULTED DIPEPTIDES CONTAINING HETEROCYCLIC RING. IN A COMPARISON WITH THE ABOVE STUDIED DIPOLAROPHILES, CYCLOADDITIONS OF METHYL-(Z)- AND (E)-A- BENZAMIDO- CINNAMATES WITH NITRILOXIDES AND NITRILIMINES WERE ALSO EXAMINED. THESE REACTIONS SHOW THESAME REGIOSELECTIVELY AND GIVE THE SAME PRODUCTS OBTAINED FROM THE METHANOLYSIS OF THE (Z)- AND (E)-SPIRO CYCLOADDUCTS RESPECTIVELY, CONFIRMING THAT NUCLEOPHILIC CLEAVAGE OF OXAZOLONE-RING IS STEREOSPECIFIC.","abstract_has_math":false,"creators":["Θεσσαλονικέως, Ελισάβετ"],"institution":"Αριστοτέλειο Πανεπιστήμιο Θεσσαλονίκης (ΑΠΘ)","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1990,"date_issued":"1990","date_published":"1990","updated_at":"2026-07-24T02:24:52Z","subjects":["1,3-DIPOLAR CYCLOADDITION REACTIONS","2-PHENYL-4-ARYLIDENE-5(4H)-OXAZOLONES","2-PHENYL-4-ARYLIDENE-5(4H)-THIAZOLONES","2-PHENYL-4-ETHOXYMETHYLENE-5(4H)-OXAZOLONE","2-ΦΑΙΝΥΛΟ-4-ΑΙΘΟΞΥΜΕΘΥΛΕΝΟ-5(4Η)-ΟΞΑΖΟΛΟΝΗ","2-ΦΑΙΝΥΛΟ-4-ΑΡΥΛΙΔΕΝΟ-5(4Η)-ΘΕΙΑΖΟΛΟΝΕΣ","2-ΦΑΙΝΥΛΟ-4-ΑΡΥΛΙΔΕΝΟ-5(4Η)-ΟΞΑΖΟΛΟΝΕΣ","ISOXAZOLINE A-AMINOACID OR DIPEPTIDE DERIVATIVE","METHYL A-BENZAMIDO-CINNAMATE","Nitrile oxides","NITRILIMINES","PYRAZOLINE A-AMINOACID OR DIPEPTIDE DERIVATIVES","Α-ΒΕΝΖΑΜΙΔΟ-ΚΙΝΝΑΜΩΝΙΚΟΣ ΜΕΘΥΛΕΣΤΕΡΑΣ","Αντιδράσεις 1,3 διπολικής κυκλοπροσθήκης","ΙΣΟΞΑΖΟΛΙΝΙΚΑ ΠΑΡΑΓΩΓΑ Α-ΑΜΙΝΟΞΕΩΝ Η ΔΙΠΕΠΤΙΔΙΩ","ΝΙΤΡΙΛΙΜΙΝΕΣ","Νιτριλοξείδια","ΠΥΡΑΖΟΛΙΝΙΚΑ ΠΑΡΑΓΩΓΑ Α-ΑΜΙΝΟΞΕΩΝ Η ΔΙΠΕΠΤΙΔΙΩΝ","Φυσικές Επιστήμες","Natural Sciences","Χημεία","Chemical Sciences"],"languages":["gre"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["10.12681/eadd/1347"],"render_values":[{"text":"10.12681/eadd/1347","href":"https://doi.org/10.12681/eadd/1347","code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/10442/hedi/1347","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Θεσσαλονικέως, Ελισάβετ"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["1990"]},{"key":"dc:publisher","label":"Institution","values":["Αριστοτέλειο Πανεπιστήμιο Θεσσαλονίκης (ΑΠΘ)","Aristotle University Of Thessaloniki (AUTH)"]},{"key":"dc:type","label":"Dc Type","values":["PhD Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["1,3-DIPOLAR CYCLOADDITION REACTIONS","2-PHENYL-4-ARYLIDENE-5(4H)-OXAZOLONES","2-PHENYL-4-ARYLIDENE-5(4H)-THIAZOLONES","2-PHENYL-4-ETHOXYMETHYLENE-5(4H)-OXAZOLONE","2-ΦΑΙΝΥΛΟ-4-ΑΙΘΟΞΥΜΕΘΥΛΕΝΟ-5(4Η)-ΟΞΑΖΟΛΟΝΗ","2-ΦΑΙΝΥΛΟ-4-ΑΡΥΛΙΔΕΝΟ-5(4Η)-ΘΕΙΑΖΟΛΟΝΕΣ","2-ΦΑΙΝΥΛΟ-4-ΑΡΥΛΙΔΕΝΟ-5(4Η)-ΟΞΑΖΟΛΟΝΕΣ","ISOXAZOLINE A-AMINOACID OR DIPEPTIDE DERIVATIVE","METHYL A-BENZAMIDO-CINNAMATE","Nitrile oxides","NITRILIMINES","PYRAZOLINE A-AMINOACID OR DIPEPTIDE DERIVATIVES","Α-ΒΕΝΖΑΜΙΔΟ-ΚΙΝΝΑΜΩΝΙΚΟΣ ΜΕΘΥΛΕΣΤΕΡΑΣ","Αντιδράσεις 1,3 διπολικής κυκλοπροσθήκης","ΙΣΟΞΑΖΟΛΙΝΙΚΑ ΠΑΡΑΓΩΓΑ Α-ΑΜΙΝΟΞΕΩΝ Η ΔΙΠΕΠΤΙΔΙΩ","ΝΙΤΡΙΛΙΜΙΝΕΣ","Νιτριλοξείδια","ΠΥΡΑΖΟΛΙΝΙΚΑ ΠΑΡΑΓΩΓΑ Α-ΑΜΙΝΟΞΕΩΝ Η ΔΙΠΕΠΤΙΔΙΩΝ","Φυσικές Επιστήμες","Natural Sciences","Χημεία","Chemical Sciences"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["gre"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["10.12681/eadd/1347","http://hdl.handle.net/10442/hedi/1347"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["THE MAIN PURPOSE OF THIS WORK IS TO STUDY THE 1,3-DIPOLAR CYCLOADDITION REACTIONS TO SUBSTITUTED EXOMETHYLENE-OXAZOLONES AND THIAZOLONES AND TO EXAMINE THESE REACTIONS AS A POSSIBLE SOURCE OF HETEROCYCLIC A-AMINOACID DERIVATIVES. (Z)- AND (E)-2- PHENYL-4-ARYLIDENE-5(4H)-OXAZOLONES REACT WITH NITRILIMINES AND (Z)-2-PHENYL-4-ARYLIDENE-5(4H)-THIAZOLONES WITH STABLE NITRILE OXIDES AND NITRILIMINES TO AFFORD SPIRO CYCLOADDUCTS, BY ADDITION OF THE DIPOLE ON THE EXOCYCLIC DOUBLE BOND. THE REACTIONS ARE STEREOSPECIFIC AND REGIOSELECTIVE, GIVING IN ALL CASES ONLY ONE REGIOISOMER, IN WHICH THE ANIONIC CENTER OF THE DIPOLE IS JOINED WITH THE TERTIARY CARBON ATOM OF OXAZOLONE-OR THIAZOLONE-RING. THE STRUCTURE OF THESE NEW COMPOUNDS WAS CONFIRMED BY SPECTROSCOPIC DATA AND BY CHEMICAL METHODS.THE OBSERVED REGIOCHEMISTRY IS ALSO RATIONALIZED BY FRONTIER MOLECULAR ORBITALCONSIDERATIONS OF THE REACTING SYSTEMS, USING EHMO-CALCULATIONS FOR THE MAGNITUDES OF OXAZOLONE ATOMIC ORBITAL COEFFICIENTS. ATTEMPTS TO CARRY OUT CYCLOADDITIONS REACTIONS OF THESE SYSTEMS WITH THE UNSTABLE BENZONITRILE OXIDE, NITRONES AND AZIDES WERE UNSUCCESSFUL. CYCLOADDITION REACTIONS WERE ALSO CARRIED OUT ON THE 2-PHENYL-4-ETHOXYMETHYLENE-5(4H)-OXAZOLONE. THE REGIOSELECTIVITY OF THESE REACTIONS IS DIFFERENT BECAUSE OF THE STRONG DIRECTIVE EFFECT OF THE ETHOXY MOIETY AND IN THE CYCLOADDITIONS THE ANIONIC CENTER OF THE DIPOLE IS JOINED WITH THE CARBON ATOM CARRYING THE ETHOXY-GROUP. THE CLEAVAGE OF THE ABOVE PREPARED SPIRO CYCLOADDUCTS WITH NUCLEOPHILES LEADS TO ISOXAZOLINE OR PYRAZOLINE A-AMINOACID DERIVATIVES. ESPECIALLY, CLEAVAGE REACTION WITH GLYCINE ETHYLESTER RESULTED DIPEPTIDES CONTAINING HETEROCYCLIC RING. IN A COMPARISON WITH THE ABOVE STUDIED DIPOLAROPHILES, CYCLOADDITIONS OF METHYL-(Z)- AND (E)-A- BENZAMIDO- CINNAMATES WITH NITRILOXIDES AND NITRILIMINES WERE ALSO EXAMINED. THESE REACTIONS SHOW THESAME REGIOSELECTIVELY AND GIVE THE SAME PRODUCTS OBTAINED FROM THE METHANOLYSIS OF THE (Z)- AND (E)-SPIRO CYCLOADDUCTS RESPECTIVELY, CONFIRMING THAT NUCLEOPHILIC CLEAVAGE OF OXAZOLONE-RING IS STEREOSPECIFIC.","ΣΚΟΠΟΣ ΤΗΣ ΕΡΓΑΣΙΑΣ ΑΥΤΗΣ ΕΙΝΑΙ Η ΜΕΛΕΤΗ ΤΩΝ ΑΝΤΙΔΡΑΣΕΩΝ 1,3- ΔΙΠΟΛΙΚΗΣ ΚΥΚΛΟΠΡΟΣΘΗΚΗΣ ΣΤΙΣ ΕΞΩΜΕΘΥΛΕΝΟ-ΟΞΑΖΟΛΟΝΕΣ ΚΑΙ ΘΕΙΑΖΟΛΟΝΕΣ ΚΑΙ Η ΣΥΝΘΕΣΗ ΜΕΣΩ ΤΩΝ ΑΝΤΙΔΡΑΣΕΩΝ ΑΥΤΩΝ ΕΤΕΡΟΚΥΚΛΙΚΩΝ ΠΑΡΑΓΩΓΩΝ ΤΩΝ Α-ΑΜΙΝΟΞΕΩΝ. ΕΙΔΙΚΟΤΕΡΑ ΚΑΤΑ ΤΗΝ ΕΠΙΔΡΑΣΗ ΝΙΤΡΙΛΙΜΙΝΩΝ ΣΤΙΣ (Ζ) ΚΑΙ (Ε)-2-ΦΑΙΝΥΛΟ- 4-ΑΡΥΛΙΔΕΝΟ- 5(4Η)-ΟΞΑΖΟΛΟΝΕΣ ΚΑΙΝΙΤΡΙΛΟΞΕΙΔΙΩΝ Η ΝΙΤΡΙΛΙΜΙΝΩΝ ΣΤΙΣ (Ζ)-2- ΦΑΙΝΥΛΟ-4-ΑΡΥΛΙΔΕΝΟ-5(4Η)-ΘΕΙΑΖΟΛΟΝΕΣ, ΣΧΗΜΑΤΙΖΟΝΤΑΙ ΣΠΕΙΡΑΝΙΚΑ ΠΡΟΙΟΝΤΑ ΠΡΟΣΘΗΚΗΣ ΣΤΟΝ ΕΞΩΚΥΚΛΙΚΟ ΔΙΠΛΟ ΔΕΣΜΟ. ΕΞΕΤΑΖΕΤΑΙ Η ΣΤΕΡΕΟ- ΚΑΙ REGIO-ΕΚΛΕΚΤΙΚΟΤΗΤΑ ΤΩΝ ΠΑΡΑΠΑΝΩ ΑΝΤΙΔΡΑΣΕΩΝ ΚΑΙ ΔΙΑΠΙΣΤΩΝΕΤΑΙ ΤΟΣΟ ΦΑΣΜΑΤΟΣΚΟΠΙΚΑ ΟΣΟ ΚΑΙ ΜΕ ΧΗΜΙΚΕΣ ΜΕΘΟΔΟΥΣ, ΟΤΙ ΤΟ REGIO-ΙΣΟΜΕΡΕΣ ΠΟΥ ΛΑΜΒΑΝΕΤΑΙ ΣΕ ΟΛΕΣ ΤΙΣ ΠΕΡΙΠΤΩΣΕΙΣ ΦΕΡΕΙ ΤΟ ΑΝΙΟΝΙΚΟ ΚΕΝΤΡΟ ΤΟΥ ΔΙΠΟΛΟΥ ΕΝΩΜΕΝΟ ΜΕ ΤΟΝ ΤΕΤΑΡΤΟΤΑΓΗ ΑΝΘΡΑΚΑ ΤΟΥ ΟΞΑΖΟΛΟΝΙΚΟΥ 'Η ΘΕΙΑΖΟΛΟΝΙΚΟΥ ΔΑΚΤΥΛΙΟΥ. Η ΠΑΡΑΤΗΡΟΥΜΕΝΗ REGIO-ΕΚΛΕΚΤΙΚΟΤΗΤΑ ΕΡΜΗΝΕΥΕΤΑΙ ΜΕ ΘΕΩΡΗΣΗ ΤΩΝ ΜΕΤΩΠΙΚΩΝ ΤΡΟΧΙΑΚΩΝ ΤΩΝ ΣΥΣΤΑΤΙΚΩΝ ΠΟΥ ΑΝΤΙΔΡΟΥΝ, ΣΥΜΦΩΝΑ ΜΕ ΕΗΜΟ ΥΠΟΛΟΓΙΣΜΟΥΣ. ΜΕΛΕΤΩΝΤΑΙ ΑΚΟΜΗ ΟΙΑΝΤΙΔΡΑΣΕΙΣ ΤΗΣ 2-ΦΑΙΝΥΛΟ-4- ΑΙΘΟΞΥΜΕΘΥΛΕΝΟ-5(4Η)-ΟΞΑΖΟΛΟΝΗΣ ΜΕ ΤΑ ΠΑΡΑΠΑΝΩ ΔΙΠΟΛΑ, ΟΙ ΟΠΟΙΕΣ ΠΑΡΟΥΣΙΑΖΟΥΝ ΔΙΑΦΟΡΕΤΙΚΗ REGIO-ΕΚΛΕΚΤΙΚΟΤΗΤΑ ΚΑΙ ΔΙΝΟΥΝ ΠΡΟΙΟΝΤΑ ΣΤΑ ΟΠΟΙΑ ΤΟ ΕΤΕΡΟΑΤΟΜΟ ΤΟΥ ΔΙΠΟΛΟΥ ΣΥΝΔΕΕΤΑΙ ΜΕ ΤΟΝ ΑΝΘΡΑΚΑ ΠΟΥ ΦΕΡΕΙ ΤΗΝ ΑΙΘΟΞΥ-ΟΜΑΔΑ. ΟΙ ΣΠΕΙΡΟ-ΙΣΟΞΑΖΟΛΙΝΕΣ ΚΑΙ ΠΥΡΑΖΟΛΙΝΕΣ ΔΙΑΝΟΙΓΟΝΤΑΙ ΜΕ ΠΥΡΗΝΟΦΙΛΑ ΑΝΤΙΔΡΑΣΤΗΡΙΑ ΜΕ ΣΧΗΜΑΤΙΣΜΟ ΕΤΕΡΟΚΥΚΛΙΚΩΝ ΠΑΡΑΓΩΓΩΝ ΤΩΝ Α-ΑΜΙΝΟΞΕΩΝ. ΕΙΔΙΚΟΤΕΡΑ,ΑΠΟ ΤΙΣ ΑΝΤΙΔΡΑΣΕΙΣ ΤΩΝ ΣΠΕΙΡΑΝΙΚΩΝ ΠΡΟΙΟΝΤΩΝ ΜΕ ΤΟΝ ΑΙΘΥΛΕΣΤΕΡΑ ΤΗΣ ΓΛΥΚΙΝΗΣ,ΑΠΟΜΟΝΩΘΗΚΑΝ ΙΣΟΞΑΖΟΛΙΝΙΚΑ ΚΑΙ ΠΥΡΑΖΟΛΙΝΙΚΑ ΔΙΠΕΠΤΙΔΙΚΑ ΠΑΡΑΓΩΓΑ. ΤΕΛΟΣ Η ΣΤΕΡΕΟΕΙΔΙΚΟΤΗΤΑ ΤΩΝ ΑΝΤΙΔΡΑΣΕΩΝ ΔΙΑΝΟΙΞΗΣ ΤΩΝ ΣΠΕΙΡΑΝΙΚΩΝ ΠΑΡΑΓΩΓΩΝ ΕΠΙΒΕΒΑΙΩΝΕΤΑΙΑΠΟ ΤΑ ΑΠΟΤΕΛΕΣΜΑΤΑ ΤΩΝ ΑΝΤΙΔΡΑΣΕΩΝ ΚΥΚΛΟΠΡΟΣΘΗΚΗΣ ΤΟΥ (Ζ) ΚΑΙ (Ε)-Α- ΒΕΝΖΑΜΙΔΟ- ΚΙΝΝΑΜΩΜΙΚΟΥ ΜΕΘΥΛΕΣΤΕΡΑ ΜΕ ΝΙΤΡΙΛΟΞΕΙΔΙΑ ΚΑΙ ΝΙΤΡΙΛΙΜΙΝΕΣ."]},{"key":"dc:title","label":"Title","values":["ΜΕΛΕΤΗ ΑΝΤΙΔΡΑΣΕΩΝ 1,3-ΔΙΠΟΛΙΚΗΣ ΚΥΚΛΟΠΡΟΣΘΗΚΗΣ ΣΕ ΕΤΕΡΟΚΥΚΛΙΚΑ ΣΥΣΤΗΜΑΤΑ","A STUDY ON THE 1,3-DIPOLAR CYCLOADDITIONS IN HETEROCYCLIC SYSTEMS"]}]}],"canonical_facts":{"dc:creator":["Θεσσαλονικέως, Ελισάβετ"],"dc:date":["1990"],"dc:description":["THE MAIN PURPOSE OF THIS WORK IS TO STUDY THE 1,3-DIPOLAR CYCLOADDITION REACTIONS TO SUBSTITUTED EXOMETHYLENE-OXAZOLONES AND THIAZOLONES AND TO EXAMINE THESE REACTIONS AS A POSSIBLE SOURCE OF HETEROCYCLIC A-AMINOACID DERIVATIVES. (Z)- AND (E)-2- PHENYL-4-ARYLIDENE-5(4H)-OXAZOLONES REACT WITH NITRILIMINES AND (Z)-2-PHENYL-4-ARYLIDENE-5(4H)-THIAZOLONES WITH STABLE NITRILE OXIDES AND NITRILIMINES TO AFFORD SPIRO CYCLOADDUCTS, BY ADDITION OF THE DIPOLE ON THE EXOCYCLIC DOUBLE BOND. THE REACTIONS ARE STEREOSPECIFIC AND REGIOSELECTIVE, GIVING IN ALL CASES ONLY ONE REGIOISOMER, IN WHICH THE ANIONIC CENTER OF THE DIPOLE IS JOINED WITH THE TERTIARY CARBON ATOM OF OXAZOLONE-OR THIAZOLONE-RING. THE STRUCTURE OF THESE NEW COMPOUNDS WAS CONFIRMED BY SPECTROSCOPIC DATA AND BY CHEMICAL METHODS.THE OBSERVED REGIOCHEMISTRY IS ALSO RATIONALIZED BY FRONTIER MOLECULAR ORBITALCONSIDERATIONS OF THE REACTING SYSTEMS, USING EHMO-CALCULATIONS FOR THE MAGNITUDES OF OXAZOLONE ATOMIC ORBITAL COEFFICIENTS. ATTEMPTS TO CARRY OUT CYCLOADDITIONS REACTIONS OF THESE SYSTEMS WITH THE UNSTABLE BENZONITRILE OXIDE, NITRONES AND AZIDES WERE UNSUCCESSFUL. CYCLOADDITION REACTIONS WERE ALSO CARRIED OUT ON THE 2-PHENYL-4-ETHOXYMETHYLENE-5(4H)-OXAZOLONE. THE REGIOSELECTIVITY OF THESE REACTIONS IS DIFFERENT BECAUSE OF THE STRONG DIRECTIVE EFFECT OF THE ETHOXY MOIETY AND IN THE CYCLOADDITIONS THE ANIONIC CENTER OF THE DIPOLE IS JOINED WITH THE CARBON ATOM CARRYING THE ETHOXY-GROUP. THE CLEAVAGE OF THE ABOVE PREPARED SPIRO CYCLOADDUCTS WITH NUCLEOPHILES LEADS TO ISOXAZOLINE OR PYRAZOLINE A-AMINOACID DERIVATIVES. ESPECIALLY, CLEAVAGE REACTION WITH GLYCINE ETHYLESTER RESULTED DIPEPTIDES CONTAINING HETEROCYCLIC RING. IN A COMPARISON WITH THE ABOVE STUDIED DIPOLAROPHILES, CYCLOADDITIONS OF METHYL-(Z)- AND (E)-A- BENZAMIDO- CINNAMATES WITH NITRILOXIDES AND NITRILIMINES WERE ALSO EXAMINED. THESE REACTIONS SHOW THESAME REGIOSELECTIVELY AND GIVE THE SAME PRODUCTS OBTAINED FROM THE METHANOLYSIS OF THE (Z)- AND (E)-SPIRO CYCLOADDUCTS RESPECTIVELY, CONFIRMING THAT NUCLEOPHILIC CLEAVAGE OF OXAZOLONE-RING IS STEREOSPECIFIC.","ΣΚΟΠΟΣ ΤΗΣ ΕΡΓΑΣΙΑΣ ΑΥΤΗΣ ΕΙΝΑΙ Η ΜΕΛΕΤΗ ΤΩΝ ΑΝΤΙΔΡΑΣΕΩΝ 1,3- ΔΙΠΟΛΙΚΗΣ ΚΥΚΛΟΠΡΟΣΘΗΚΗΣ ΣΤΙΣ ΕΞΩΜΕΘΥΛΕΝΟ-ΟΞΑΖΟΛΟΝΕΣ ΚΑΙ ΘΕΙΑΖΟΛΟΝΕΣ ΚΑΙ Η ΣΥΝΘΕΣΗ ΜΕΣΩ ΤΩΝ ΑΝΤΙΔΡΑΣΕΩΝ ΑΥΤΩΝ ΕΤΕΡΟΚΥΚΛΙΚΩΝ ΠΑΡΑΓΩΓΩΝ ΤΩΝ Α-ΑΜΙΝΟΞΕΩΝ. ΕΙΔΙΚΟΤΕΡΑ ΚΑΤΑ ΤΗΝ ΕΠΙΔΡΑΣΗ ΝΙΤΡΙΛΙΜΙΝΩΝ ΣΤΙΣ (Ζ) ΚΑΙ (Ε)-2-ΦΑΙΝΥΛΟ- 4-ΑΡΥΛΙΔΕΝΟ- 5(4Η)-ΟΞΑΖΟΛΟΝΕΣ ΚΑΙΝΙΤΡΙΛΟΞΕΙΔΙΩΝ Η ΝΙΤΡΙΛΙΜΙΝΩΝ ΣΤΙΣ (Ζ)-2- ΦΑΙΝΥΛΟ-4-ΑΡΥΛΙΔΕΝΟ-5(4Η)-ΘΕΙΑΖΟΛΟΝΕΣ, ΣΧΗΜΑΤΙΖΟΝΤΑΙ ΣΠΕΙΡΑΝΙΚΑ ΠΡΟΙΟΝΤΑ ΠΡΟΣΘΗΚΗΣ ΣΤΟΝ ΕΞΩΚΥΚΛΙΚΟ ΔΙΠΛΟ ΔΕΣΜΟ. ΕΞΕΤΑΖΕΤΑΙ Η ΣΤΕΡΕΟ- ΚΑΙ REGIO-ΕΚΛΕΚΤΙΚΟΤΗΤΑ ΤΩΝ ΠΑΡΑΠΑΝΩ ΑΝΤΙΔΡΑΣΕΩΝ ΚΑΙ ΔΙΑΠΙΣΤΩΝΕΤΑΙ ΤΟΣΟ ΦΑΣΜΑΤΟΣΚΟΠΙΚΑ ΟΣΟ ΚΑΙ ΜΕ ΧΗΜΙΚΕΣ ΜΕΘΟΔΟΥΣ, ΟΤΙ ΤΟ REGIO-ΙΣΟΜΕΡΕΣ ΠΟΥ ΛΑΜΒΑΝΕΤΑΙ ΣΕ ΟΛΕΣ ΤΙΣ ΠΕΡΙΠΤΩΣΕΙΣ ΦΕΡΕΙ ΤΟ ΑΝΙΟΝΙΚΟ ΚΕΝΤΡΟ ΤΟΥ ΔΙΠΟΛΟΥ ΕΝΩΜΕΝΟ ΜΕ ΤΟΝ ΤΕΤΑΡΤΟΤΑΓΗ ΑΝΘΡΑΚΑ ΤΟΥ ΟΞΑΖΟΛΟΝΙΚΟΥ 'Η ΘΕΙΑΖΟΛΟΝΙΚΟΥ ΔΑΚΤΥΛΙΟΥ. Η ΠΑΡΑΤΗΡΟΥΜΕΝΗ REGIO-ΕΚΛΕΚΤΙΚΟΤΗΤΑ ΕΡΜΗΝΕΥΕΤΑΙ ΜΕ ΘΕΩΡΗΣΗ ΤΩΝ ΜΕΤΩΠΙΚΩΝ ΤΡΟΧΙΑΚΩΝ ΤΩΝ ΣΥΣΤΑΤΙΚΩΝ ΠΟΥ ΑΝΤΙΔΡΟΥΝ, ΣΥΜΦΩΝΑ ΜΕ ΕΗΜΟ ΥΠΟΛΟΓΙΣΜΟΥΣ. ΜΕΛΕΤΩΝΤΑΙ ΑΚΟΜΗ ΟΙΑΝΤΙΔΡΑΣΕΙΣ ΤΗΣ 2-ΦΑΙΝΥΛΟ-4- ΑΙΘΟΞΥΜΕΘΥΛΕΝΟ-5(4Η)-ΟΞΑΖΟΛΟΝΗΣ ΜΕ ΤΑ ΠΑΡΑΠΑΝΩ ΔΙΠΟΛΑ, ΟΙ ΟΠΟΙΕΣ ΠΑΡΟΥΣΙΑΖΟΥΝ ΔΙΑΦΟΡΕΤΙΚΗ REGIO-ΕΚΛΕΚΤΙΚΟΤΗΤΑ ΚΑΙ ΔΙΝΟΥΝ ΠΡΟΙΟΝΤΑ ΣΤΑ ΟΠΟΙΑ ΤΟ ΕΤΕΡΟΑΤΟΜΟ ΤΟΥ ΔΙΠΟΛΟΥ ΣΥΝΔΕΕΤΑΙ ΜΕ ΤΟΝ ΑΝΘΡΑΚΑ ΠΟΥ ΦΕΡΕΙ ΤΗΝ ΑΙΘΟΞΥ-ΟΜΑΔΑ. ΟΙ ΣΠΕΙΡΟ-ΙΣΟΞΑΖΟΛΙΝΕΣ ΚΑΙ ΠΥΡΑΖΟΛΙΝΕΣ ΔΙΑΝΟΙΓΟΝΤΑΙ ΜΕ ΠΥΡΗΝΟΦΙΛΑ ΑΝΤΙΔΡΑΣΤΗΡΙΑ ΜΕ ΣΧΗΜΑΤΙΣΜΟ ΕΤΕΡΟΚΥΚΛΙΚΩΝ ΠΑΡΑΓΩΓΩΝ ΤΩΝ Α-ΑΜΙΝΟΞΕΩΝ. ΕΙΔΙΚΟΤΕΡΑ,ΑΠΟ ΤΙΣ ΑΝΤΙΔΡΑΣΕΙΣ ΤΩΝ ΣΠΕΙΡΑΝΙΚΩΝ ΠΡΟΙΟΝΤΩΝ ΜΕ ΤΟΝ ΑΙΘΥΛΕΣΤΕΡΑ ΤΗΣ ΓΛΥΚΙΝΗΣ,ΑΠΟΜΟΝΩΘΗΚΑΝ ΙΣΟΞΑΖΟΛΙΝΙΚΑ ΚΑΙ ΠΥΡΑΖΟΛΙΝΙΚΑ ΔΙΠΕΠΤΙΔΙΚΑ ΠΑΡΑΓΩΓΑ. ΤΕΛΟΣ Η ΣΤΕΡΕΟΕΙΔΙΚΟΤΗΤΑ ΤΩΝ ΑΝΤΙΔΡΑΣΕΩΝ ΔΙΑΝΟΙΞΗΣ ΤΩΝ ΣΠΕΙΡΑΝΙΚΩΝ ΠΑΡΑΓΩΓΩΝ ΕΠΙΒΕΒΑΙΩΝΕΤΑΙΑΠΟ ΤΑ ΑΠΟΤΕΛΕΣΜΑΤΑ ΤΩΝ ΑΝΤΙΔΡΑΣΕΩΝ ΚΥΚΛΟΠΡΟΣΘΗΚΗΣ ΤΟΥ (Ζ) ΚΑΙ (Ε)-Α- ΒΕΝΖΑΜΙΔΟ- ΚΙΝΝΑΜΩΜΙΚΟΥ ΜΕΘΥΛΕΣΤΕΡΑ ΜΕ ΝΙΤΡΙΛΟΞΕΙΔΙΑ ΚΑΙ ΝΙΤΡΙΛΙΜΙΝΕΣ."],"dc:identifier":["10.12681/eadd/1347","http://hdl.handle.net/10442/hedi/1347"],"dc:language":["gre"],"dc:publisher":["Αριστοτέλειο Πανεπιστήμιο Θεσσαλονίκης (ΑΠΘ)","Aristotle University Of Thessaloniki (AUTH)"],"dc:subject":["1,3-DIPOLAR CYCLOADDITION REACTIONS","2-PHENYL-4-ARYLIDENE-5(4H)-OXAZOLONES","2-PHENYL-4-ARYLIDENE-5(4H)-THIAZOLONES","2-PHENYL-4-ETHOXYMETHYLENE-5(4H)-OXAZOLONE","2-ΦΑΙΝΥΛΟ-4-ΑΙΘΟΞΥΜΕΘΥΛΕΝΟ-5(4Η)-ΟΞΑΖΟΛΟΝΗ","2-ΦΑΙΝΥΛΟ-4-ΑΡΥΛΙΔΕΝΟ-5(4Η)-ΘΕΙΑΖΟΛΟΝΕΣ","2-ΦΑΙΝΥΛΟ-4-ΑΡΥΛΙΔΕΝΟ-5(4Η)-ΟΞΑΖΟΛΟΝΕΣ","ISOXAZOLINE A-AMINOACID OR DIPEPTIDE DERIVATIVE","METHYL A-BENZAMIDO-CINNAMATE","Nitrile oxides","NITRILIMINES","PYRAZOLINE A-AMINOACID OR DIPEPTIDE DERIVATIVES","Α-ΒΕΝΖΑΜΙΔΟ-ΚΙΝΝΑΜΩΝΙΚΟΣ ΜΕΘΥΛΕΣΤΕΡΑΣ","Αντιδράσεις 1,3 διπολικής κυκλοπροσθήκης","ΙΣΟΞΑΖΟΛΙΝΙΚΑ ΠΑΡΑΓΩΓΑ Α-ΑΜΙΝΟΞΕΩΝ Η ΔΙΠΕΠΤΙΔΙΩ","ΝΙΤΡΙΛΙΜΙΝΕΣ","Νιτριλοξείδια","ΠΥΡΑΖΟΛΙΝΙΚΑ ΠΑΡΑΓΩΓΑ Α-ΑΜΙΝΟΞΕΩΝ Η ΔΙΠΕΠΤΙΔΙΩΝ","Φυσικές Επιστήμες","Natural Sciences","Χημεία","Chemical Sciences"],"dc:title":["ΜΕΛΕΤΗ ΑΝΤΙΔΡΑΣΕΩΝ 1,3-ΔΙΠΟΛΙΚΗΣ ΚΥΚΛΟΠΡΟΣΘΗΚΗΣ ΣΕ ΕΤΕΡΟΚΥΚΛΙΚΑ ΣΥΣΤΗΜΑΤΑ","A STUDY ON THE 1,3-DIPOLAR CYCLOADDITIONS IN HETEROCYCLIC SYSTEMS"],"dc:type":["PhD Thesis"]},"updated_at":"2026-07-24T02:24:52Z"}