Post-graduate theses
Current Record: 561 of 642
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| Identifier |
000035760 |
| Title |
Σύνθεση πρωτότυπων πολυαμινικών συζευγμάτων με στεμματοειδείς αιθέρες |
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Author
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Δαμιανάκος, Χαρίλαος Γεωργίου
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Thesis advisor
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Παπαϊωάννου, Διονύσιος
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| Abstract |
The aim of the present work was (i) the synthesis of conjugates of crown ethers (CEs) with polyamines and (ii) the further diacylation of one of them (145) on its two primary amino groups with retinoic acid (RA-OH) and dihydrocaffeic acid as well. In particular, in the course of the present work we prepared the following CE-conjugates with polyamines: N,N΄-di(3´-aminopropyl)-1,7-diaza-15-CE-5 (127), N,N´-di(3´-aminopropyl)-4´,4΄΄(5΄΄)-diamino-dibenzo-15-crown-5 (128), SPD-CH2-18-crown-6 (129) and N,N΄-(SPD)2-1,7-diaza-18-crown-6 (145). Our efforts to synthesize the CE-polyamine conjugates SPM-CH2-15-crown-5 (130) and N1,N8-di(methylene-18-crown-6)SPD (133) were not succesful. Our methodology followed to synthesize the conjugates 127 and 128 included attachment of 3΄-aminopropyl on the amino groups of the relevant CEs through their acylation with the succinimidyl ester of Trt-β-Ala. As regards SPD-LCE 129 and 145, the amino groups on the relevant CEs were acylated with the succinimidyl ester of the dipeptide Trt-β-Ala-GABA. All the above resulting polyamides were reduced with LiAlH4 in THF to the corresponding polyamines, which were finally detritylated on their terminal amino groups with TFA in DCM. The synthetic effort towards SPM-LCE 130 included acylation of aminomethyl-CE 156 with Trt-β-Ala-OSu, detritylation and second acylation with Trt-β-Ala-GABA-OSu. Reduction of the resulting triamide 159 with LiAlH4 failed to give pure polyamine 160 due to difficulties met with its purification with FCC. Furthermore our effort to attach hydroxymethyl-CE 163 on the terminal SPD nitrogen atoms of (ons)3SPD (162) using the Mitsunobu reaction, led to an unseparable mixture of products. Finally, the acylation of the primary amino groups of the CE-polyamine 145 with RA-OSu (155) gave the conjugate 132 impure and with satisfactory yield. Similarly, diacylation of 145 with the succinimidyl ester of O,O΄-dibenzylocaffeic acid (152) gave the impure conjugate 153 in good yield. Catalytic hydrogenation/hydrogenolysis of the latter resulted to the kukoamine A analogue 131.
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| Language |
Greek |
| Issue date |
2002-07-01 |
| Collection
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School/Department--School of Sciences and Engineering--Department of Chemistry--Post-graduate theses
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Type of Work--Post-graduate theses
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| Permanent Link |
https://elocus.lib.uoc.gr//dlib/2/0/4/metadata-dlib-2002damianakos.tkl
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| Views |
222 |
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