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Title: The synthesis of heterocyclic compounds from Indan-1, 3-diones
Author: Roxburgh, C. J.
ISNI:       0000 0001 3538 8867
Awarding Body: Portsmouth Polytechnic
Current Institution: University of Portsmouth
Date of Award: 1988
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ABSTRACT 2-Phenyl-indan-1,3-dione reacts via a Michael addition with 2-vinylpyridine to yield 2-phenyl-2-(2-(2-pyridyl) ethyl) indan- 1,3-dione, which on catalytic hydrogenation of the pyridine ring yields, via a ring cyclization/expansion reaction, rel(12S,14aR) 12- phenyl-1~3,4,12,13,14,l4a-octahydropyrido[l,2-£] [2]benzazonin- 6,ll-dione. A lithium aluminium hydride reduction of rel(12S,14aR) 12- phenyl-l,2,3,4,12,l3,14,14a-octahydropyrido[l,2-£] [2]benzazonin- 6,ll-dione yielded rel(llS,12S,l4aR) ll-hydroxy l2-phenyl-substituted derivative as the only isomer~ Various derivatives of this system including the 12-phenyl-ll-keto compound were synthesised and the stereochemistry of these established in each case. Treatment of rel(11S,12S,14aR)12-phenyl-l,2,3,4,6,11,12,13,14,14a-decahydropyridoTl, 2~b] [2]benzazonin-l1-ol with tosylchloride yielded the spiro quaternary nitrogen compound rel(4aR,7S,7aR,13S) 1,2,3,4,4a,S, 6,7,7a,12-decahydro-7-phenylisoindolo[l~2-~]quinoliZin-13-ium tosylate via transannular displacement of the I1-tosyl group. Treatment of this with lithium aluminium hydride uncovered a novel ring expansion to rel(SS,6R,10R,13S)5,6,7,8,9,10,11,12,13,14- decahydro-13-phenyl-S,6~10~nitrilobenzocyclododecene. Treatment of rel(11~,12~,14aR) 12-phenyl-l,2,3,4,6,11,12,13,- 14,14a-decahydropyrido[l,2-b) [2)benzazonin-l1-ol with phosphorus oxychloride in pyridine yielded two compounds, rel(4aR,7S,7aR,13S) 1,2,3,4,4a,S,6,7,7a,12-decahydro-7-phenylisoindolo[1,2-d]quinolizin- 13-ium phosphate via a transannular reaction and rel(11K,12R,14aR)- 12-phenyl-l,2,3,4,6,11,12,13,14,l4a-decahydropyrido[1, 2-Q) [2]benzazonin- ll-ol with a change in piperidine/benzazonine ring fusion stereochemistry. 2-Phenyl-2-(2-(1,2,3,4-tetrahydroquinolin-2-yl)ethyl)indanl, 3-dione did not undergo the ring closure/expansion sequence and attempts to prepare 2-phenyl-2-(2-(S-ethyl-2-piperidyl)ethyl)indanl, 3-dione and 2-methyl-2-(2-(2-piperidyl) ethyl) indan-l,3-dione to investigate a similar reaction were thwarted by non-selective reduction. Hydrazinolysis of 2-phenyl-2-(3-~-phthalimido)indan-l,3-dione gave 1,2,3,4-tetrahydro-l0b-hydroxy-l-phenylpyrido[2,1-~)isoindol- 6(4li)-one as the major product. A lithium aluminium hydride reduction of this gave rel(lR,lObR) I-phenylbenzo[a]isoindole. 2-p-Methoxyphenyl-2-(2-(2-piperidyl)ethyl)indan-l,3-dione did not undergo the ring cyclization/expansion reaction to a ninemembered ring but 2-p-chlorophenyl-2-(2-(2-piperidyl)ethyl)indan- 1,3-dione gave rel(12~,14aR)12-p-chlorophenyl-l,2,3,4,l2,l3,14,14aoctahydropyrido[ 1,2-Q) [2]benzazonine-6,11-dione. Lithium aluminium hydride reduction of this gave rel(ll~,12~,14aB) and rel(llR,l2~,- 14aR) 12-p-chlorophenyl-l,2,3,4,6,ll,l2,13,l4,l4a-decahydropyrido[ l,2-QJ (2)benzazonin-ll-ol in equal amounts. A variety of analogues of the above systems were prepared to test the generality of the ring closure/expansion sequence. None of these gave the required products showing the necessity of the basic 2-phenyl-indan-l,3-dione unit for successful reaction
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Organic chemistry