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Studies of Reactions of Some Carbonyl Bridged

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Studies of Reactions of Some Carbonyl Bridged STUDIES OF REACTIONS OF SOME CARBONYL BRIDGED COMPOUNDS WITH IRON PENTACARBONYL LAI Chi-hung ( 黎 志 雄 ） A thesis submitted in partial fulfillment of the requirements for the degree of Master of Philosophy at The Chinese University of Hong Kong 1978 Thesis Committee: Dr. S. W. Tam, Chairman Dr. K. H. Wong Dr. T. Y. Luh Prof. A. J. Birch, F. R. S., External Examiner ACKNOWLEDGEMENT The author wishes to express his gratitude to his supervisor, Dr. S. W. Tam, for his invaluable instruction and continous encouragement throughout the course of this rsearch and the perparation of this thesis. He is indebted to Dr. T. Y. Luh, Dr. T. L. Chan, and Mr. T. C. Chiang for their helpful discussions during this investigation. His sincere thanks are also due to Mr. Y. H. Law and Mr. S. C. Wong for their assistance in the measurements of nuclear magnetic resonance spectra and mass spectra, respectively. LAI Chi-hung Department of Chemistry The Chinese University of Hong Kong May, 1978 11 SUMMARY The reactions of iron pentacarbonyl with a series of carbonyl bridged compounds, viz, 3a,4,,7,7a-tetrahydro-4,7-. methanoindene-l,,8-dione (6),.2, L4-dibromo-3a,,4,7, 7a-tetra- hydro-4,,7-methanoindene-l,,8-dione (32), 4,5, 6, 7-tetraphenyl- 3a, 4, 7, 7a-tetrahydro-4,,7-methanoindene-8-one (33) and octa- chloro-3a,4,.7,7a-tetrahydro-4,7-methanoindene-1,8-dione (39) have been investigated Treatment of (6) with iron penta- carbonyl afforded l-indanone. By using deuteriated compound (21), the course of reaction was shown first to undergo decarbonylation of the initial compound giving rise to 3a,7a- dihydroindenone (8) which was then catalyzed by iron penta- carbonyl,to undergo 1,3-hydrogen shift to yield l-indanone. Treatment of (32) with iron pentacarbonyl 'gave 4-bromo-l-indanone (55). The reaction was shown to undergo decarbonylation of the initial compound to give 2,, L--dibromo-3a, 7a-dihydroinden one (54),.and iron pentacarbonyl catalyzed rearrangement of double bond to give 2,4-dibromo-l,indanone (57), similar to that as described for compound (6), followed by. subsequent debromination of (57) by iron pentacarbonyl to yield (55). The reaction of (33) with iron pentacarbonyl produced two iron carbonyl complexes, viz, tetraphenylcyclopentadienone- iron tricarbonyl (60) and dicyclopentadienyldi-iron tetracarbonyl (4). These complexes were formed due to the fact that (33) underwent dissociation-to give tetraphenylcyclopentadienone (59) 3 and cyclopentadiene rather than decarbonylation to give the 3a,7a- dihydroindene derivative (34). As a result, (59) and cyclopenta- diene reacted individually with iron pentacarbonyl to yield the corresponding complexes (60) and (4). Compound (39) reacted with iron pentacarbonyl to give hexa- chloroindenone (61). However, the role that iron pentacarbonyl played in such reaction was unclear. 4 CONTENTS Acknowledgement ii Summary iii Introduction 1 Research Plan 5 Results and Discussion 16 Experimental 32 List of Spectra 51 References 80 5 INTRODUCTION Although the complex of platinum(II) with endo-dicyclo- pentadiene has been prepared by Hofmann and von Narbutt in 1908,1 and'its structure has been established as (1) by X-ray crystallography in 1961,2 the analogous complex of iron carbonyl (2) is still unknown in literature. Indeed, unconjugated dieneiron carbonyl complexes were not so commonly known as compared to,conjugated dieneiron carbonyl complexes.3 A well- known reported example4 of the former is thricarbonyl complex of 1,5-cyclooctadiene (3). The initial objective of this investigation. was to attempt the synthesis of the iron carbonyl complex (2). Fe(CO). Pt Fe ci Cl co co co (1) (2) (3) It sould be noted that (2) cannot be synthesized directly from dicyclopentadiene and iron pentacarbonyl, because the reaction would lead to dicyclopentadienyldi-iron tetracarbonyl (4) as previously reported.5 1 CO CO Fe Fe CO co (4) A synthetic approach to (2) is outlined in Scheme I where 3a,4,7,7a-tetrahydro-4,7-methanoindene-1,8-dione (6)6 was employed as the precursor with the hope that the corresponding iron carbonyl, complex (7) was formed, which was then subjected to reduction to yield the desired complex (2). Br Br HOCH2CH2OH 2Br7/dioxane NaOH/CH30H, H spontaneous Fe(co)5 70% H.,SO4 ? (5) (6) Z n/HC l Fe ? Fe Co CO CO CO CO Co (7) (2) Scheme I 2 Experimental results showed that only starting material (6) was recovered after a cyclohexane solution of (6) and excess iron pentacarbonyl had been heated under reflux in a nitrogen atmosphere for ca. 24 hours. However, the xylene or dioxane solutions of (6) and excess iron pentacarbonyl in similar reactions yielded l-indanone as the isolaable product. Fe(CO) Fe(CO) xylene Although the synthesis of the desired complex (7) was unsuccessful, the isolation of l-indanone from the reaction mixture was striking. Decarbonylation of (6) should give rise only to 3a,7a-dihydroindenone (8), and one cannot readily rationalize the facile rearrangement of the double bond from (8) to l-indanone. Furthermore, thermal suprafacial concerted 1,3-hydrogen shift is a "forbidden" process according to the Woodward and Hoffmann rules.7 3 An explanation for the formation of 1-indanorle from (8) may be offered in terms of the formation of the intermediate organometallic complex such as that indicated below where the presence of the iron atom allows the suprafacial 1,3- hydrogen shift to occur thermally. H H Fe Fe In order to establish the proposed mechanism, part of the work described in the following sections is devoted to mechanistic studies for the tranformation in question, and the rest is concerned with the synthesis of several analogous carbonyl bridged compounds and the studies of their reations towards iron pentacarbonyl. 4 RESEARCH PLAN Ⅰ. Mechanistic Studies: As described in the previous section the reaction of 3a,4,7,7a-tetrahydro-4,7-methanoindene-l,8-dione (6) with iron pentacarbonyl afforded l-indanone. One possible mechanism for such transformation is outlined in Scheme. The migration of the double bond catalyzed by iron pentacarbonyl is proposed to occur via the ustable (olefin)-Fe(CO)4 intermediate (9). Upon allylic hydrogen abstraction to form the -allyl-hydroiron tetracarbonyl (10), the bridgehead hydrogen (H3a) is shifted to the C2 position where another (olefin)-Fe(CO)4 (11) is formed. In a similar fashion, the bridgehead hydrogen (H7a) is moved to the C3 position resulting in the formation of the l-indanone (12). H3a H3a H3a Fe(CO)4 Fe(CO)3 Fe(CO)5 H7a H7a H7a (8) (9) (10) H7a Fe(CO)4 Fe(CO)3 H7a H3a H3a H3a -Fe(CO)4 H7a (11) (12) Scheme 5 H3a H3a H3a Fe(CO)2 Fe(co) 5 H7a OH7a OH 7a (8) (13) (14) Fe(CO)2 -Fe(CO)2 H3a H3a H OH 7a OH7a (16) (15) H(H5a) Fe(CO)2 H3a Scheme III H3a(H) H7a OH7a (18) (17) -Fe(CO)2 H(H3a) H3a(H) OH7a H(H3a) H3a(H) H7a (19) 6 Alternatively, as outlined in Scheme III, another possible mechanism involving a hydroxycyclopentadienyliron carbonyl complex (14) may also be operative. It is suggested that complex (14) is formed via the reaction of the enol (13) of, (8) with iron pentacarbonyl a similar analogy of alkoxycyclopentadienyliron carbonyl complex has been reported. Upon elimination of the metal, two possible isomeric.enols, viz, (15) and (16) may be generated. The keto form of (15) is the' 1-indanone (17), while (16) may undergo again the formation of another hydroxycyclopentadienyliron carbonyl complex (18) which subsequently leads to the formation of the 1-indanone (19). Although the two mechanisms described above give the same end product, i.e. 1-indanone, the distribution of the migrating hydrogens in the final product are not the same. Thus by using deuterium labelling, some information about the actual mode of the reaction may be obtained. Thus the deuteriated compound (21) was synthesized starting from cyclopentanone-2,2,.5, 5-d4 '(20) in accordance with the synthetic pathways as outlined in Scheme IV. Cyclopentanone-2,2,.5,5-d4 (20) was in turn prepared according to the procedure9 as describ.ed by Saunders Jr. using cyclopentanone and deuterium oxide as starting materials. Thus by treating (21) with iron pentacarbonyl and Identifying the distribution of deuterium in the final product 1-indanone, a distinction can be made between the two proposed mechanisms. Decarbonylation of (21) would initiallyield 7 D D D D Br Br NaOH HOCH2CH2OH D 2Br2 D D D D D H+ dioxane CH3OH 20 D D D D spontaneous 70% H2SO4 D D D D D D (21) Scheme IV the deuteriated compound (22). If the course of reaction follows the mechanism as outlined in Scheme II, then l-indanone-2,3,4,7-d4 (24) is expected. D D D D D D D D D D D (22) (23) (24) D Alternatively, if the mode of reaction follows the mechanism as outlined in Scheme III which involves keto-enol tautomerism and formation of hydroxycyclopentadienyliron carbonyl complexes, both deuteriated 1-indanone (27) and (28) as described below are expected. In fact, (28) is a mixture of (27) and (24). D D D H Fe(CO)2 D D D Fe(CO) 5 D OD OD D D D (22) (25) ( 26 ) -Fe(CO)2 -Fe(CO)2 D D H D D OD D D OD D D(H) D Fe(CO)2 N(D) D OD D D D (27) D D(H) H(D) OD D D D(H) D H(D) D 9(28) II. Reactions of the Ethylene Ketals of 3a, 4,7,7a-Tetrahydro- 4,7-methanoindene-1,8-dione (6) with Iron Pentacarbonyl: In view of the fact that reaction of (6) with iron pentadarbonyl failed to yield the desired complex (7) but only afforded 1-indanone, the bisethylene ketal (5) was taken to react with iron pentacarbonyl in the hope that the complex (29) is formed, The bisethylene ketal (5) has another advantage that it will not decarbonylate since there is no bridge carbonyl group in the molecule.
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