Aspects of organophosphorus chemistry
Chapter 1 This chapter is concerned with some reactions of diphenylvinylphosphine oxide (1). Phosphine oxfide (1) is known to undergo nucleophilic additions analogous to the Michael reaction. Triphenylvinylphosphonium bromide also undergoes a number of nucleophilic additions, including the Schweiz...
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| Format: | Thesis |
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1976
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| _version_ | 1826315854930771968 |
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| author | Postle, S |
| author_facet | Postle, S |
| author_sort | Postle, S |
| collection | OXFORD |
| description | Chapter 1 This chapter is concerned with some reactions of diphenylvinylphosphine oxide (1). Phosphine oxfide (1) is known to undergo nucleophilic additions analogous to the Michael reaction. Triphenylvinylphosphonium bromide also undergoes a number of nucleophilic additions, including the Schweizer reaction. Thus, Triphenylvinylphosphonium bromide, upon treatment with the sodium salts of benzoin or salicylaldehyde, yields 2,3-diphenyl 2,5-dihydrofuran and 3,4-chromene, respectively. An attempt to extend the Schweizer reaction to phosphine oxide (1) was not not successful. <p> Several possible synthetic routes to epoxyvinyldiphenylphosphine oxide (2) have been explored.</p> <p></p> <p>Phosphine oxide (1) was found to be inert to several epoxidising conditions, for example, unbuffed trifluorperoxide/Triton B in methanol. Phosphine oxide (1) was converted to bis-(2-diphenylphosphinylethyl)peroxide (3) in 79% yield, by treatment with alkaline hydrogen peroxide. Peroxide (3) is usually stable. Reaction of (3) with lithium aluminium hydride gave 2-hydroxyethyl diphenylphosphine oxide (4) in 84% yield.</p> <p> Phosphine oxide (1) was converted to 1,2-bis-(diphenylphosphinyl)ethane (5) upon treatment with aqueous methanolic sodium hydroxide, in 96% yield. Phsophine oxide (5) had also previously been obtained by the reaction of triphenylvinylphosphonium bromide with sodium hydroxide. Phosphine oxide (5) was alos isolated in 19% yield from the treatment of phosphine oxide (4) with two mole equivalents of butyllithium, and subsequent treatment with bromine (Scheme 1).</p> <p></p> Scheme 1 <p>On the basis of the spectroscopic properties of phosphine oxide (1), it is considered that there is little congugation between the C=C and hte P=O groups. [please see pdf for full abstract]</p> |
| first_indexed | 2024-03-06T19:35:13Z |
| format | Thesis |
| id | oxford-uuid:1ed07a5e-e79d-494c-9468-33f7a97af44c |
| institution | University of Oxford |
| last_indexed | 2024-12-09T03:33:48Z |
| publishDate | 1976 |
| record_format | dspace |
| spelling | oxford-uuid:1ed07a5e-e79d-494c-9468-33f7a97af44c2024-12-01T17:21:27ZAspects of organophosphorus chemistryThesishttp://purl.org/coar/resource_type/c_db06uuid:1ed07a5e-e79d-494c-9468-33f7a97af44cPolonsky Theses Digitisation Project1976Postle, SChapter 1 This chapter is concerned with some reactions of diphenylvinylphosphine oxide (1). Phosphine oxfide (1) is known to undergo nucleophilic additions analogous to the Michael reaction. Triphenylvinylphosphonium bromide also undergoes a number of nucleophilic additions, including the Schweizer reaction. Thus, Triphenylvinylphosphonium bromide, upon treatment with the sodium salts of benzoin or salicylaldehyde, yields 2,3-diphenyl 2,5-dihydrofuran and 3,4-chromene, respectively. An attempt to extend the Schweizer reaction to phosphine oxide (1) was not not successful. <p> Several possible synthetic routes to epoxyvinyldiphenylphosphine oxide (2) have been explored.</p> <p></p> <p>Phosphine oxide (1) was found to be inert to several epoxidising conditions, for example, unbuffed trifluorperoxide/Triton B in methanol. Phosphine oxide (1) was converted to bis-(2-diphenylphosphinylethyl)peroxide (3) in 79% yield, by treatment with alkaline hydrogen peroxide. Peroxide (3) is usually stable. Reaction of (3) with lithium aluminium hydride gave 2-hydroxyethyl diphenylphosphine oxide (4) in 84% yield.</p> <p> Phosphine oxide (1) was converted to 1,2-bis-(diphenylphosphinyl)ethane (5) upon treatment with aqueous methanolic sodium hydroxide, in 96% yield. Phsophine oxide (5) had also previously been obtained by the reaction of triphenylvinylphosphonium bromide with sodium hydroxide. Phosphine oxide (5) was alos isolated in 19% yield from the treatment of phosphine oxide (4) with two mole equivalents of butyllithium, and subsequent treatment with bromine (Scheme 1).</p> <p></p> Scheme 1 <p>On the basis of the spectroscopic properties of phosphine oxide (1), it is considered that there is little congugation between the C=C and hte P=O groups. [please see pdf for full abstract]</p> |
| spellingShingle | Postle, S Aspects of organophosphorus chemistry |
| title | Aspects of organophosphorus chemistry |
| title_full | Aspects of organophosphorus chemistry |
| title_fullStr | Aspects of organophosphorus chemistry |
| title_full_unstemmed | Aspects of organophosphorus chemistry |
| title_short | Aspects of organophosphorus chemistry |
| title_sort | aspects of organophosphorus chemistry |
| work_keys_str_mv | AT postles aspectsoforganophosphoruschemistry |