Дисертації з теми "[3.3.0]furofuranone"

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1

Dubbert, Robert Allen. "Iron carbonyl assisted cyclocarbonylation of 1,6-enynes to bicyclo(3.3.0)octenones." Case Western Reserve University School of Graduate Studies / OhioLINK, 1993. http://rave.ohiolink.edu/etdc/view?acc_num=case1060615827.

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2

Hewitt, Jacqueline Diane. "Enantioselective preparation of cis-bicycolo[3.3.0]octane derivatives using chiral lithium amide bases." Thesis, University of Salford, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.292871.

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3

Atalar, Taner. "Synthetic Strategy Directed Towards The Synthesis Of Bicyclo[3.3.0]octa-3,5,8-triene-2,7-dione." Master's thesis, METU, 2004. http://etd.lib.metu.edu.tr/upload/12605089/index.pdf.

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Although the chemistry of benzenoid and nonbenzenoid quinones have been the subject of extensive theoretical and experimental studies, the extent of our present understanding regarding the geometries and stabilities of quinones of pentalene is meager. After studying the existence of cyclopentadienone and its reactivity as a diene and dienophile in the literature, the study of some related species, particularly the ones with fully unsaturated pentalenic structures were started. In this thesis, the elusive compound bicyclo[3.3.0]octa-3,5,8-triene-2,7-dione was tried to synthesize by using the synthetic strategy which was developed by us. We used cycloheptatriene as the starting material. The bicyclic endoperoxiedes mixture obtained by the photooxygenation of cycloheptatriene was v treated with triethylamine to give tropone in high yield. Selective reduction of tropone afforded cyclohepta-3,5-dione which was converted by the way of photochemistry to the bicyclo[3.2.0]hept-6-en-3-one. After protection of the carbonyl group, dibromocarbene was added to the double bond to give desired bicyclic compound with pentalene skeleton. Substitution of the allylic bromide with hydroxyl group followed by PCC oxidation resulted in the formation of a diketone. All efforts to convert this diketone into fully conjugated system failed.
4

Bennett, Lisa Ruth. "Enantioselective synthetic approaches to natural products based on functionalised cis-bicyclo[3.3.0]octane synthons." Thesis, University of Salford, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.262622.

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5

Pazinatto, Mariane. "Síntese de compostos 4-azabiciclo[3.3.0]octano intermediários avançados para a preparação de alcalóides hiacintacina." reponame:Biblioteca Digital de Teses e Dissertações da UFRGS, 2012. http://hdl.handle.net/10183/37802.

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Neste trabalho desenvolveu-se uma rota curta e convergente para a obtenção de esqueletos 4-azabiciclo[3.3.0]octano, intermediários avançados que contém todos os carbonos existentes na estrutura dos alcalóides pirrolizidínicos hiacintacina. Inicialmente foram realizadas reações de Michael entre alcinos ativados e o éster etílico da prolina, em condições brandas, gerando adutos enaminocarbonílicos de forma estereosseletiva para o isômero E, com rendimentos superiores a 80%. A posterior redução destes compostos enaminocarbonílicos, por hidrogenação ou por adição de hidreto, forneceu os aminodiésteres correspondentes com rendimentos entre 75 e 85%. Para o composto (2S)-1- benzilóximetil-3-etóxi-3-oxopropilpirrolidina-2-carboxilato de etila essa redução se mostrou estereosseletiva, com uma proporção de 3:1. Estes aminodiésteres foram submetidos a condensações de Dieckmann, através de duas metodologias sintéticas distintas: com a utilização de sódio metálico em refluxo de THF, e com hidreto de potássio a temperatura ambiente, e proporcionaram a obtenção de compostos enolésteres bicíclicos, com rendimentos entre 60 e 65%. Paralelamente, reações de redução com LiAlH4 destes aminodiésteres foram realizadas e proporcionaram a obtenção dos dióis correspondentes, com rendimentos entre 75 e 80%. Um derivado a-hidroxiéster foi obtido a partir da oxidação do enoléster bicíclico promovida por CeCl3.7H2O, com rendimento de 95%. A importância desta metodologia se dá ao fato de que ela proporcionou a inserção de um grupo hidroxila na posição a-éster, substituinte este, presente nos compostos-alvo.
In this work it was developed a short and convergent route for obtention of 4- azabicyclo[3.3.0]octane skeleton, advanced intermediates that possesses all existent carbons in the structure of hiacintacine pirrolizidinic alkaloids. Initially Michael reactions between activated alkynes and proline ethyl ester were performed, in mild conditions, leading to enaminocarbonylic adducts stereoselectively for isomer E, with yields higher than 80%. Further reduction of these enaminocarbonyl compounds, by hydrogenation or hydride addition, furnished the corresponding aminodiesters with yields between 75 and 85%. For the (2S)-1-benziloximethyl-3-ethoxi-3- oxopropylpirrolidine-2-ethyl carboxylate reduction has shown to be stereoselective in a 3:1 ratio. These aminodiesters were submitted to Dieckmann condensations through two distinct methodologies: using metallic sodium in refluxing THF, and with potassium hydride at ambient temperature, affording the obtention of bicyclic enolesters, with yields between 60 and 65%. In parallel, reduction reactions with LiAlH4 of these aminodiesters were performed leading to obtention of the corresponding diols, with yields between 75 and 80%. An a-hydroxyester was obtained from oxidation of the bicyclic enolester promoted by CeCl3.7H2O, in 95% yield. The importance of this methodology is the fact that it provided the insertion of an hydroxyl group in the a-ester position, a substituent present in the target compounds.
6

Mannchen, Fabian [Verfasser]. "Übergangsmetall-katalysierte Vinylcyclopropan-Umlagerung und Studien zur Struktur-Wirkungsbeziehung von Bicyclo[3.3.0]octan-Derivaten / Fabian Mannchen." München : Verlag Dr. Hut, 2015. http://d-nb.info/1075409160/34.

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7

Spieler, Jan. "Synthese chiraler Liganden mit [3.3.0]- und [3.3.1]-bicyclischem Grundgerüst und ihre Anwendung in der enantioselektiven Übergangsmetall-Katalyse." [S.l. : s.n.], 2000. http://deposit.ddb.de/cgi-bin/dokserv?idn=961741309.

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8

Jacquet, Fabienne. "Obtention de l'hydroxy-4 dioxa-2,6 bicyclo (3.3.0) octanone-8 (1S,4S,5R) par voie catalytique, et selon un procédé d'électrosynthèse organique." Grenoble 2 : ANRT, 1986. http://catalogue.bnf.fr/ark:/12148/cb37598417t.

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9

Pisoni, Diego dos Santos. "Preparação e funcionalização da (5R)-4,8-dimetilbiciclo[3.3.0]octa-1(8),3-dien-2-ona: um bloco de construção para a síntese de terpenóides." reponame:Biblioteca Digital de Teses e Dissertações da UFRGS, 2006. http://hdl.handle.net/10183/24007.

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A partir do (-)-epoxilimoneno (127) desenvolveu-se a preparação enantiosseletiva da dienona (5R)-4,8-dimetilbiciclo[3.3.0]octa-1(8),3-dien-2-ona (128), que representa um bloco de construção versátil para a síntese de produtos naturais e não-naturais opticamente ativos. A etapa-chave da síntese corresponde à conversão do aldeído quiral 163 na cianoidrina bicíclica 165, através da alquilação intramolecular da cianoidrina TMS-éter 164, conforme metodologia de Stork-Takahashi. A hidrogenação estereosseletiva da dienona 128 conduziu ao produto monossaturado 20, um intermediário avançado na preparação do ent-kelsoeno. Da mesma forma, a hidrogenação catalítica das duas ligações duplas C=C de 128 produziu o intermediário 129a, que representa a síntese formal do iridóide cis,cis-dihidronepetalactona (13). Além da preparação e funcionalização da dienona 128, investigou-se a cloração alílica de olefinas terminais, através de uma nova metodologia que emprega InCl3 na presença de NaClO. Este novo método de cloração alílica foi aplicado a diferentes substratos e forneceu cloretos alílicos com bons rendimentos.
This work describes the enantioselective preparation of (5R)-4,8-dimethylbicyclo[3.3.0]oct-1(8),3-dien-2-one (128) from (-)-limonene oxide (127). This compound holds the prospect of serving as useful building block or intermediate to prepare a variety of compounds having a bicyclo[3.3.0]octane framework. The key step is the conversion of the chiral aldehyde 163 to bicyclic cyanohydrin 165, through intramolecular alkylation of cyanohydrin TMS eter 164, according to Strok-Takahashi protocol. The stereoselective hydrogenation of dienone 128 led to monosaturated product 20, which is a important intermediate on the ent-kelsoene preparation. Also, catalytic hydrogenation of the two carbon-carbon double bonds of 128, produced 129a, which is a intermediate to formal synthesis of iridoid cis,cis-dihydronepetalactone 13. Further, a new methodology to allylic chlorination of terminal olefins which employ InCl3 in the presence of NaClO was developed. This method was applied to different compounds and furnished allylic chlorides in satisfactory yields.
10

鍾慧容. "Synthesis of 2,3,7-triazabicyclp[3.3.0]oct-2-enes and 2,3,7-triazabicyclo[3.3.0]oct-3-ene derivatives." Thesis, 1997. http://ndltd.ncl.edu.tw/handle/34001478867006978412.

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Анотація:
碩士
中原大學
化學學系
85
Michael addition and Substitution reaction of 1-methoxycarbonyl-2,3,7-triaza bicyclo[3.3.0]oct-2-enes 2a to electron-deficient dipolarphiles(vinyl ketone、ester)、 alkyl halides , give 7-substituted 1- methoxycarbonyl-2,3,7-triaza bicyclo[3.3.0]oct-2-enes 5. 6. in good yields. Furthermore, 1-methoxycarbonyl-2,3,7-triaza bicyclo[3.3.0] oct-3-enes 7. 8. 9. , are prepared by isomerization of 1-methoxycarbonyl-2,3,7-triaza bicyclo[3.3.0]oct-2-enes 2. 5. 6. .
11

Slavik, Stefan. "Hochsubstituierte Azabicyclo[3.3.0]octane als Peptidmimetika." Phd thesis, 2005. http://tuprints.ulb.tu-darmstadt.de/594/1/Dissertation_Stefan_Slavik.pdf.

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Methoden zur asymmetrischen Synthese von Aza(poly)cyclen sind wertvolle Werkzeuge für das rationale Design potentieller Wirkstoffmoleküle. Im Rahmen dieser Arbeit sollte die von M. Reggelin entwickelte Sulfoximinauxiliar-basierte Methode zur asymmetrischen Synthese hochsubstituierter Aza(poly)cyclen strukturell und methodisch weiterentwickelt und auf die Synthese von potentiellen nichtpeptidischen Peptidmimetika angewandt werden. Im Hinblick auf mögliche Synthesen von Substanzbibliotheken wurde die Übertragung der aus γ-Hydroxyalkylierung und Michael-Addition bestehenden Synthesesequenz an lösliche Polymere untersucht. Hierbei konnte die Anknüpfung von Methylsulfoximin an Polyethylenglykolmonomethylether (MeOPEG) und lineares Polystyrol (NCPS) realisiert werden. Zwei enantio- und diastereomerenreine 2-Azabicyclo[3.3.0]octane wurden als Gerüste für potentielle Peptidmimetika in Mengen von je drei Gramm synthetisiert und die Synthesen der Edukte an die erforderlichen Mengen angepasst. Einer der Azabicyclen wurde zu zwei vollständig mit verschiedenen pharmakophoren Gruppen dekorierten potentiellen Neurokinin-Antagonisten umgesetzt. Eine Untersuchung des Einflusses der Temperatur während der γ-Hydroxyalkylierung auf die Stereoselektion zeigte, dass diese im untersuchten Temperaturbereich unabhängig ist. Dies steht im Einklang mit dem bislang favorisierten Mechanismus. Durch die Erhöhung der Reaktionstemperatur von –78 °C auf 0 °C ließen sich moderate bis erhebliche Verbesserungen der Ausbeute erreichen, in einem Fall wurde dadurch erst die Reaktion ermöglicht. Desweiteren wurden drei mit dieser Methode noch nicht realisierte Typen von Azacyclen dargestellt. Bei der Synthese eines Tetrahydrochinolin-Derivates beobachtete man eine bisher unbekannte, säurekatalysierte Cyclisierung zu -geschützten Azabicyclen. Die im Rahmen dieser Arbeit erlangten Ergebnisse erlauben die Synthese vorher nicht zugänglicher hochsubstituierter Azacyclen und konnten so die Methode, besonders im Hinblick auf die Synthese von Peptidmimetika, entscheidend erweitern.
12

Jong, Huey Ju, and 鍾慧珠. "Synthesis of 1,2,7-triazabicyclo[3.3.0]oct-2-enes." Thesis, 1994. http://ndltd.ncl.edu.tw/handle/61508905823394567423.

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13

Slavik, Stefan [Verfasser]. "Hochsubstituierte Azabicyclo[3.3.0]octane als Peptidmimetika / vorgelegt von Stefan Slavik." 2005. http://d-nb.info/976098032/34.

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14

Deng, Ru Cen, and 鄧如岑. "A further study on 1,2,7-triazabicyclo[3.3.0]-oct-2-enes." Thesis, 1996. http://ndltd.ncl.edu.tw/handle/05007424072524231001.

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15

Wang, Reuy-Shiuan, and 王瑞瑄. "(I) Study on photolysis of 2,3,7-triaza-bicyclo[3.3.0] oct-2- enes (II) Synthesis of 2,3,7-triaza-bicyclo[3.3.0]oct-2-ene derivatives by Michael addition." Thesis, 1995. http://ndltd.ncl.edu.tw/handle/54350091405000556421.

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Анотація:
碩士
中原大學
化學學系
83
(I) 本實驗探討一系列 2,3,7-三氮-二環[3.3.0]辛-2-烯類化合物(2)的 光解反應,當化合物(2)第一位置之取代基為甲酯基時,可高產率地產生 1-甲氧基羰基-3-(2-甲氧基羰基乙基)-3-氮-二環[3.1.0]己烷化合物(3 a); 但若化合物(2)第一位置之取代基為晴類或是酮類時,由於氮上或氧上 具有未共用電子對,易參與反應,使得反應結果較為複雜,因此,反應產率不 高或是很低. 此結果發展出合成3-氮-二環[3.1.0]己烷化合物(3)的新方 法. 由陳淑娟之碩士論文得知將 2,3,7-三氮-二環[3.3.0]辛-2-烯類化合 物(2)作熱裂解反應時,可高產率地得到 3,4-二取代比各 (4). 將本實驗 之結果和陳淑娟之碩士論文的結果合并歸納可得一結論:即利用 2,3,7-三 氮-二環[3.3.0]辛-2-烯類化合物(2)為原料,可有選擇性地利用熱解反應 製備 3,4-二取代比各(4),或是利用光解反應製備 3-氮-二環[3.1.0]己烷 化合物(3). (II)本實驗利用 1-氰基-2,3,7-三氮-二環[3.3.0]辛-2-烯化 合物(1)和一系列的烯酸甲酯類化合物及乙烯基酮類化合物進行麥可加成 反應,此反應可高產率地製備 2,3,7-三氮-二環[3.3.0]辛-2-烯類化合 物(11).由反應時間之長短得知乙烯基酮類化合物之反應速率較烯酸甲酯 類化合物快,但若反應物為晴類化合物,醯安類化合物時,則不進行麥可加 成反應;若反應物為醛類化合物時,則會先形成聚合物而不進行麥可加成反 應;此結果顯示反應與烯類上拉電子基拉電子能力及取代基之推電子能力 有關;拉電子基拉電子能力愈強時,反應性愈好,取代基之推電子能力愈強 時,由於電子效應的影響,使得反應性愈差.
16

Wang, Rui Xuan, and 王瑞瑄. "Study on photolysis of 2,3,7-triaza-bicyclo[3.3.0]oct-2-enes." Thesis, 1995. http://ndltd.ncl.edu.tw/handle/44329490320171995053.

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17

Chen;Su-Jane and 陳淑娟. "Study on the pyrolysis of 2,3,7-triaza-bicyclo〔3.3.0〕oct-2-enes." Thesis, 1993. http://ndltd.ncl.edu.tw/handle/78361062578211527817.

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18

Kühl, Jochen Eduard Wilhelm. "Synthese und Verwendung chiraler Sulfoximinauxiliare bei der Darstellung von Azabicyclo[3.3.0]octan-Peptidmimetika." Phd thesis, 2008. https://tuprints.ulb.tu-darmstadt.de/933/1/Dissertation_Jochen_Kuehl.pdf.

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Peptide übernehmen im menschlichen Organismus lebensnotwendige physiologische Funktionen. Wesentliche Voraussetzung für diese physiologische Funktion ist die komplementäre dreidimensionale Ausrichtung der Seitenketten der Effektoren und Rezeptoren durch die jeweiligen peptischen Rückgrate. Die peptidischen Strukturen, die diese Ausrichtung herbeiführen, stellen aber außerhalb der nativen Umgebung der Peptide deren „pharmakologische Achillesferse“ dar, da sie sowohl hydrolytisch als auch enzymatisch gespalten werden können. Aufgrund dessen sind nichtpeptidische Mimetika attraktive Ziele für die pharmazeutische Forschung. Ziel dieser Arbeit war, das von M. Reggelin et. al. entwickelte Sulfoximinauxiliar-gestützte Verfahren zur asymmetrischen Synthese hochfunktionalisierter Aza(oligo)cyclen strukturell und methodisch weiter zu entwickeln und auf die Synthese nichtpeptidischer Peptidmimetika anzuwenden. Im Rahmen eines Projektes zur Darstellung von NK1-Antagonisten konnten mit der Synthese von dreifach mit pharmakologisch interessanten Gruppen funktionalisierten Azabicyclooctanen wichtige Erkenntnisse für die Weiterentwicklung des Konzeptes der topologischen Mimikry von Peptiden durch Azabicyclen gewonnen werden. Nach der Auswertung dieser Erkenntnisse gelang die Darstellung von Diazabicyclooctanen als Grundgerüste für β-Turnmimetika konform zur Theorie von J. B. Ball et. al.. Für die Syntheseprojekte wurden Sulfoximinauxiliare oft in größeren Mengen benötigt. Um den Zeitaufwand für die Darstellung dieser Verbindungen zu minimieren, wurde die bisherige Auxiliarsynthesesequenz unter Anpassung der Methoden an die Ansatzgrößen bis an die Grenze des Labormaßstabes optimiert. Einen alternativen Ansatz zur Optimierung der Auxiliarsynthese bildeten Studien zur Etablierung von Kreuzkupplungen an elektronenreichen Sulfoximinen, im Rahmen derer neue Verfahren zur Darstellung elektronenreicher diastereo- und enantiomerenreiner Halogenmethylsulfoximine entwickelt wurden. Mit der Cyclisierung der Halogenmethylsulfoximine zu [1,3λ6,4]-Oxa-thiazin-3-oxiden wurden hoch effiziente Zugänge zu den ersten Vertretern einer neuen Klasse diastereo-und enantiomerenreiner heterocyclischer Sulfoximin-haltiger S,O-Acetale gefunden, die sich gegenüber anderen S,O-Acetalen durch eine leichtere Hydrolysierbarkeit auszeichnen. Somit wurde eine funktionalisierende Desulfurierung unter Ausbildung einer Aldehydfunktion möglich. Die zahlreichen strukturellen und methodischen Fortschritte, die in dieser Arbeit realisiert wurden, erlauben die Darstellung bisher unzugänglicher hochfunktionalisierter Azabicyclen. Somit gelang es, die Methode von M. Reggelin et. al. in Bezug auf die Herstellung von Peptidmimetika entscheidend zu verbessern.
19

"SYNTHETIC STRATEGY DIRECTED TOWARDS THE SYNTHESIS OF BICYCLO[3.3.0]OCTA-3,5,8-TRIENE-2,7-DIONE." Master's thesis, METU, 2004. http://etd.lib.metu.edu.tr/upload/12605089/index.pdf.

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20

Yin, Shiu-Ping, and 尹淑萍. "Synthesis of 1-cyano-2,3,7-triaza-bicyclo[3.3.0]oct-2-ene derivatives by substitution." Thesis, 1995. http://ndltd.ncl.edu.tw/handle/16699145318827351148.

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21

Chen, Wen-Shan, and 陳文珊. "Study on Rearrangement in Thermal Decomposition of 2,3,7-triazabicyclo[3.3.0]oct-2-ene Derivatives." Thesis, 2007. http://ndltd.ncl.edu.tw/handle/93114897362219790462.

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Анотація:
碩士
中原大學
化學研究所
95
7-(3-oxo- butyl)-2,3,7-triazabicyclo[3.3.0]oct-2-ene can be prepared by Michael addition of 2,3,7-triazabicyclo[3.3.0]oct-2-ene to Methyl vinyl ketone . Similarly, 7-(3-oxo-butyl)-2,3,7-triazabicyclo[3.3.0]oct-2-ene can be prepared. The thermal decomposition of these compounds under argon gave pyrrole as a product. The starting material underwent (1) denitrogenation, (2) self-redox reaction, (3) dehydration, and (4) rearrangement to give the final product. This rearrangement was observed no matter the substituent at 1-position was acetyl, methoxycarbonyl or cyano as long as the substituent at 7-position was RC(=O)CH2CH2-. Furthermore, the rearrangement involved 1,3-migration of the nitrogen atom in 7-position, and the substituent at the 7-position in the product was a trans alkenyl substituent. A mechanism was proposed to account for the reaction product. However, experiments designed to confirm the mechanism did not give positive results. Therefore, furthermore study has to be carried out to look into the reaction mechanism of this rearrangement.
22

Hu, Hsin-Chi, and 扈欣祺. "Study on the thermal decomposition mechanism of cis-4-methyl-2,3,7-triazabicyclo[3.3.0]oct-2-ene derivatives." Thesis, 2008. http://ndltd.ncl.edu.tw/handle/15904947814641197345.

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Анотація:
碩士
中原大學
化學研究所
96
Thermolysis of trans-4-methyl-2,3,7-triazabicyclo[3.3.0]oct-2-ene derivatives was carried out in the hope of clarifying the thermal decomposition mechanism of 1-pyrazoline. In this experiment, we had found that, cis-6-methyl-3-azabicyclo[3.1.0]hexane was the major product while the trans-isomer and 3,4-dihydropyrrole, the product from 1,2-hydride shift, were the minor ones. The reaction which produced the major product began with cleavage of C-1 and N-2 bond, followed by 180。 rotation of N2 moiety and back attack from C-1 radical to C-4. If the above event had not happened, cleavage of the carbon-nitrogen bond in N-3 between C-4 occured. The resulting diradical recombine to produce the trans-isomer. The product of dihydropyrrol can be accounted for by the follwing mechanism. After cleavage of the C1-N2 bond, the N2 rotated to trans configuration with expect to hydrogen on the C-5. The hydrogen on the C-5 will migrate to the C-4 and, in the meantime, N2 leave to prodruce 3,4-dihydropyrrole. In the thermolysis of trans-4-methyl-2,3,7-triaza- -bicyclo[3.3.0]oct-2-ene derivatives, It was found that if the substituent group have higher electron-withdrawing capability and steric effect, the product ratio of dihydropyrrol will be increased.
23

Kühl, Jochen Eduard Wilhelm [Verfasser]. "Synthese und Verwendung chiraler Sulfoximinauxiliare bei der Darstellung von Azabicyclo[3.3.0]octan-Peptidmimetika / vorgelegt von Jochen Eduard Wilhelm Kühl." 2008. http://d-nb.info/987346520/34.

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24

wang, sing-yi, and 王馨儀. "Preparation of 1-Cyano-3-azabicyclo[3.1.0]hexanesby Thermal Decomposition of 1-Cyano-2,3,7-triazabicyclo[3.3.0]oct-2-enes." Thesis, 2007. http://ndltd.ncl.edu.tw/handle/96965169621169645353.

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Анотація:
碩士
中原大學
化學研究所
94
Many derivatives of 3-azabicyclo[3.1.0]hexane are reported to be biological active and useful as pharmaceuticals , By Michael addition or nucleophilic substitution, a series of 1-Cyano-2,3,7-triazabicyclo[3.3.0]oct-2-enes derivatives can be prepared. Thermolysis of these 1-Cyano-2,3,7-triazabicyclo[3.3.0]oct-2-ene derivatives , give 3-azabicyclo[3.1.0]hexane and as the major product and 4,5-dihydropyrrole or 3-cyano-4-methyl pyrrole as the minor product. This method, which can successful synthesize many derivative of 3-azabicyclo[3.1.0]hexane with few steps and in good yields, is a novel and efficient protocol to prepare derivative of 3-azabicyclo[3.1.0]hexane.
25

Spieler, Jan [Verfasser]. "Synthese chiraler Liganden mit [3.3.0]- und [3.3.1]-bicyclischem Grundgerüst und ihre Anwendung in der enantioselektiven Übergangsmetall-Katalyse / von Jan Spieler." 2000. http://d-nb.info/961741309/34.

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26

Fan, Keng-Wei, and 范耿維. "Study on the Preparation of 1,3-disubstituted pyrrole from 2,3,7-triazabicyclo[3.3.0]oct-2-ene Derivatives by Retro Dipolar Cycloaddition." Thesis, 2009. http://ndltd.ncl.edu.tw/handle/34383513342867974738.

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Анотація:
碩士
中原大學
化學研究所
97
Derivatives of pyrrole often have biological activities, and are important in pharmacology. For example pyrrole moiety appears in pharmaceuticals as anti-inflammatory and analgesic agent, drug having blood sugar decreasing, gastric juics apoleti activity. In this study, 2,3,7-triaza-bicyclo[3.3.0] oct-2-ene derivaties, in the presence of cuprous chloride as the catalyst, and the sodium azide as ligands, undergo Retro Dipolar Cycloaddition reaction, to give 1,3-disubstituted pyrroles. The reaction conditions, such as temperature, reaction time, catalyst and solvent, on the reaction are discussed. In the synthesis of pyrrole, literature is by synthesizes the way preparation, does not have the way which takes off to prepare the synthesis pyrrole nearly. It is hard to find the research about Retro Dipolar Cycloaddition. Especially in this study in using cuprous chloride as catalyst to open ring reaction is not often see.
27

Lu, Li-Hui, and 盧麗慧. "Preparation of 3-Azabicyclo[3.1.0]hexanes and 3,4-Disubstituted pyrroles by Thermal Decomposition of 2,3,7-triazabicyclo[3.3.0]oct-2-enes." Thesis, 2008. http://ndltd.ncl.edu.tw/handle/84903278920459151403.

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Анотація:
博士
中原大學
化學研究所
96
A new processes with facile preparation and high production yield for preparing derivatives of 3-azabicyclo[3.1.0]hexane and 2,5-dihydropyrrole are proposed in this research. The 1-position of 2,3,7-tri-azabicyclo[3.3.0]oct-2-ene derivatives can be substituted by COOR or CN and 7-position can be substituted by Michael addition reaction or nucleophilic substitu- tion reaction with different functional groups, and a series of 2,3,7-triazabicyclo[3.3.0]oct-2- ene derivatives(1-11) will be prepared. A series of derivatives of 3-azabicyclo[3.1.0]hexane (1A-11A) and 2,5-dihydropyrrole(1B-11B) could be prepared by thermolysis of 2,3,7-triaza- bicyclo[3.3.0]oct-2-ene derivatives(1-11) as a precursor with proper solvent under argon. According to experiment results, the determination of major product is the functional group at the 1-position of 2,3,7-triazabicyclo[3.3.0]oct-2-enes(1-11). In the cases of Z = ester at 1-position, 2,5-dihydropyrrole(1B-8B)will be the major product. In the cases of Z = cyano, 3-azabicyclo[3.1.0]hexane(9A-11A) will then become the major product. The ratio between major and minor products is approximately 7:3. The results show that the 2,5-dihydropyrrole (1B-11B) will be completely converted into 3,4-disubstituted pyrrole(1C-11C) under room temperature and presence of air. Therefore, the 2,5-dihydropyrroles should be kept under low temperature and non-oxygen environment. A series of novel compounds and preparing methods for 3-azabicyclo[3.1.0]hexane derivatives were also completed via cyclopropanation of 2,5-dihydro pyrroles(1B-11B). High yield rate for preparing 3-azabicyclo[3.1.0]hexane(1A-11A) and 2,5-dihydropyrrole (1B-11B) were achieved by using different functional group substitution methods in this research. It is also a novel method for preparing the derivatives with higher yield rate and simpler steps than Achini’s approach. Key words: 3,4-disubstituted pyrrole, 2,5-dihydropyrrole, 3-azabicyclo[3.1.0]hexane, 2,3,7-triazabicyclo[3.3.0]oct-2-ene, 1,2-hydrogen shift, thermolysis.
28

Teng, Ju Chen, and 鄧如岑. "(I)A Further Study on 1,2,7-triazabicyclo[3.3.0]-oct-2-enes (II) Synthesis of BMIPPA&DMIPPA Ligands for Heart Imaging." Thesis, 1996. http://ndltd.ncl.edu.tw/handle/27130024723133998532.

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Анотація:
碩士
中原大學
化學學系
84
(I)本實驗探討一分子烷基疊氮與二分子丙烯酸甲酯作用後,得到的2- Pyrazoline與一系列的醛類反應,皆可得到高產率地形成1,2,7-三氮雙環 [3.3.0]辛-2-烯化合物.此化合物與一些天然的具藥性的雜環化合物有相 似的架構.而此雙五環的立體結構是利用1H-NMR之NOE實驗,及電腦分子模 擬程式及其他的參考文獻來判定此雙五環的第五位置取代基與第八位置取 代基是反向(trans).而此雙五環在空氣中易水解,其水解速率的比較為酮 類所形成之雙五環快於醛類形成之雙五環,且雙五環中,第八位置上取代基 越大者,越易水解成2-Pyrazoline. (II)脂肪酸是一種帶有直鏈烷基的有 機酸,在生物體中,經由beta氧化作用進行代謝作用,產生ATP作為生物體的 能源,故可用來測量心肌組織中脂代謝速率,結果用來診斷心肌梗塞之症 狀.故本實驗室以塞分為原料與帶甲基之-2-酸之醯氯及帶苯基之烷己酸來 反應,來合成3-甲基-15-苯基十五烷酸及3,3-二甲基-15-苯基十五烷酸,以 便與加速器產生的碘-123標幟為BMIPPA,DMIPPA,以作為核子醫學上心臟造 影之用.而合成此化合物各反應中,進行Friedel-Craft反應可高產率得到 預期產物,進行Wolff- Kishner反應產率不理想,可能與立體障礙有很大關 係,而最困難的脫硫部份,與Raney Ni活性,是否應另外加入氫氣及攪拌的 程度有著密切的關係.
29

Hsu, Hsing Wei, and 許行葦. "(1)The Preparation of Radiopharmaceutical for Dopamine Receptor D2 Imaging (2)A Further Study on Pyrolysis of 2,3,7-triaza- bicyclo[3.3.0] oct-2-enes." Thesis, 1996. http://ndltd.ncl.edu.tw/handle/05997922241456388933.

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Анотація:
碩士
中原大學
化學學系
84
(I) 5-溴-N-[(1-乙基-2-砒咯啶基)甲基]-2,3-二氫苯并夫喃醯胺化合 物6,是D2 dopamine受體的拮抗劑,在核子醫學上以放射性同位素標幟, 可進行中樞神經系統受體診斷之造影,協助中樞神經系統疾病之診斷。在 本文中5-溴-N-[(1-乙基-2-砒咯啶基)甲基]-2,3-二氫苯并夫喃醯胺6, 之合成路徑是以2,3-二氫苯并夫喃為起始物,第一步驟為溴化反應,此步 驟產率甚高,可達91%,第二步驟為羧酸化反應,此步驟必須在無水無氧 狀態下操作,產率才可提高,否則會有反應不完全的副產物5-溴-2,3-二 氫苯并夫喃4出現。第三步驟為醯化反應,最後再與(S)-(-)-N-乙基-2-( 氨基甲基)砒咯啶作用,得到化合物6,其結構經核磁共振光譜及質譜證實 。從化合物1到化合物6的合成共須四個步驟,總產率為43%。 (II) 本研 究是探討2,3,7-三氮-二環[3.3.0]辛-2-烯類化合物1在不同溶劑及不同取 代基的條件下,進行熱解反應,觀察化合物1在第一位置上的各種取代基 對熱解反應的影響。在以往熱解反應中只得到3,4-二取代砒咯化合物4 和3-一氮-二環[3.1.0]己烷化合物3,此次以追蹤採樣,可觀察到有3,4- 二取代砒咯碄化合物5,此結果對熱解反應之機轉有更確定之了解。 (I) 5-Bromo-N-[(1-ethyl-2-pyrrolidiny)methyl]-2,3- dihydrobenzofuran-7-carboxamide 6 is an antagonist for D2 dopamine receptor,When the compound is labelled with radioiodine,it could be used as an image agent for brain in human,assist diagonse the disease of central nervose system。 In this paper,the synthesis of 5-Bromo-N-[(1-ethyl- -pyrrolidiny)methyl]-2,3-dihydrobenzofuran is report,The first step was Bromonation of 2,3-dihydrobenzofuran 1, wherein high yield of 5,7-dibromo-2,3-dihydrobenzofuran was obtained。In the following carboxylation reaction Oxygen and water must be excluded in order to obtain a decent yield。The acid was then converted to acyl chloride acid,reacted with (s)-(-)-2- aminomethyl-1-ethylpyrrolidine to obtain the compound 6 。 The structure was confirmed with 1H-NMR,13C-NMR and GC-Mass。 The synthesis of the compound 6 was accomplished in four steps and the total yield was 43 %。(II)In the thesis,the results of pyrolysis of 2,3,7- triaza-bicyclo[3.3.0]oct-2-enes 2,carrying various substitents in various solvent are presented。 By monitoring the the porducts of the reaction with different pyrolysis time,we comfirmed that 3-pyrroline, was the intermediate of the convertion of 2 to 3,4- disubstituted pyrrole (4) 。
30

Hsu, Teng-Yi, and 許籐譯. "(I)The influences of reaction conditions on preparations of 1-acetyl-7-(3-oxo- butyl)-2,3,7-triaza-bicyclo[3.3.0]oct-2-ene (II)Preparation of pinacol using TiCl4-Zn." Thesis, 2006. http://ndltd.ncl.edu.tw/handle/52846922544335255057.

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Анотація:
碩士
中原大學
化學研究所
94
First part This thesis addresses on the influences of reaction conditions on preparations of 1-acetyl-7-(3-oxo- butyl)-2,3,7-triaza-bicyclo[3.3.0]oct-2-ene .In previous protocol ,directly adding methyl vinyl ketone for one pot reaction ,a residual side product was produced。After a series of study ,we found that the side product that was a dihydropyran from the [4+2] cycloaddition of two molecules of methyl vinyl ketone .Thus by mixing allyl bromide and sodium azide and allowing the reaction to proceeds for 12 hours,then adding methyl vinyl ketone dropwise ,a remarkable improvement on the problem of the residual product was obtained .Then we utilize the improved conditions , replacing allyl bromide by 3-chloro-2-methyl propene ,to produce 1-methoxyl-5-methyl-7-(2-methoxylethylene)-2,3,7-triaza-bicyclo[3.3.0]oct-3-enes in one pot reaction .But these conditions were not suit methyl acrylate and acrylonitrile .Besides,This thesis also addresses on the reaction of methyl acrylate in a mixed solvents of methanol and acetone in 1:4 ratio .Although we can synthesis 1-acetyl-7-(3-oxo-butyl)-2,3,7-triaza-bicyclo[3.3.0]oct-2-ene in one pot reaction ,but we do not get a better result than previous protocol . Second part This thesis addresses on a series of study on the preparation of pinacol using TiCl4-Zn .In the past , principally utilize TiCl4-Zn to study about Wittig Reaction .Herein ,the mixture of TiCl4 and zinc powder in THF were stirred for 1 hour and then ketone was added to obtain pinacol .
31

Meyer, Imelda. "Zur sequentiellen Umwandlung von Bicyclobutylidenen in Bicyclooctene: Synthese und Umlagerung funktionalisierter Spiro[3.4]octane." Doctoral thesis, 2001. http://hdl.handle.net/11858/00-1735-0000-0006-AE8C-A.

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