1992 Fiscal Year Final Research Report Summary
Synthesis and Reaction of Selenoselenines from Phosphonium Ylides and Selenium
| Project/Area Number |
02640415
|
|---|
| Research Category |
Grant-in-Aid for General Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Research Field |
有機化学一般
|
|---|
| Research Institution | Fukuoka University |
|---|
Principal Investigator |
OKUMA Kentaro Fukuoka University, Dep.Chemistry, Research Associate, 理学部, 助手 (20131815)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
OHTA Hiroshi Fukuoka University, Dep.Chemistry, Professor, 理学部, 教授 (60078574)
|
|---|
| Project Period (FY) |
1990 – 1992
|
| Keywords | Phosphonium Ylide / Selenoaldehyde / Selenobenzophenone / Thiosulfin / Thioamide / Selenoselenine / Diazoalkane / Olefin |
|---|
| Research Abstract |
Phosphonium ylides have been widely utilized for the synthesis of olefins and also known to react with sulfur to afford thiocarbonyl compounds. Recently, we have found that the reaction of stable Witting reagents with elemental sulfur afforded the corresponding olefins via thioaldehydes intermediates. These results promped us to investigate the chemistry of selenocarbonyl and the related compounds from Wittig reagents.
The reaction of Wittig reagents with elemental selenium gave the corresponding olenfins in good yields. These reaction proceeded via selenocarbonyl intermediates.
When the reaction of Wittig reagents with elemental sulfur in the presence of amines, the corresponding thioamides were obtained. This is the first example of thioamide formation from Wittig reagents. However, when the reaction was carried out in the presence of elemental selenium, The corresponding selenoamides could not be obtained. Afere several trials, selenoamides were obtained in moderate yields by using ph
… More
osphonate carbanious instead of Wittig reagents.
Thiobenzophenones are generally prepared by the reaction of phosphonium ylides with elemental sulfur. However, there is no report on the isoration selenobenzophenones. When the careful experiment was carried out on the reaction of diarylmethylenetriphenylphosphorane with elemental selenium, the corresponding selenobenzophenones were isolated. The reactions of this new compound with many dienes and/or olefins were carried out.
The reactions of thioketones with diazoalkanes were well studied. However, there are relatively few reports on the reaction of selenoketones with diazoalkanes. The reaction of selenobenzophenones with diazomethane afforded the corresponding diarylethylenes and symmetrical olefins. The reaction with other diazoalkanes gave three different types of olefins. This reaction proceeded through selenadiazoline intermediates and retrocyclization was observed.
Thiosulfins were found to be formed by the reaction of Wittig reagents. with elemsntal sulfur in the presence of maleic anhydride. However, selenoselenines could not be detected by this method. Less
|
