Hydrogen-Bonded Di(hydroperoxy)alkane Adducts of the Type Cy<sub>3</sub>P=O·(HOO)<sub>2</sub>CHR (R = Alkyl)
Five representatives of a novel type of di(hydroperoxy)alkane adducts of phosphine oxides have been synthesized and fully characterized, including their solubility in organic solvents. The phosphine oxide Cy<sub>3</sub>PO (<b>1</b>) has been used in combination with the corre...
Saved in:
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2025-01-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/30/2/329 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1832587851321049088 |
|---|---|
| author | Rahym Ashirov Maya Todorovic Nattamai Bhuvanesh Janet Blümel |
| author_facet | Rahym Ashirov Maya Todorovic Nattamai Bhuvanesh Janet Blümel |
| author_sort | Rahym Ashirov |
| collection | DOAJ |
| description | Five representatives of a novel type of di(hydroperoxy)alkane adducts of phosphine oxides have been synthesized and fully characterized, including their solubility in organic solvents. The phosphine oxide Cy<sub>3</sub>PO (<b>1</b>) has been used in combination with the corresponding aldehydes to create the adducts Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CHCH<sub>3</sub> (<b>2</b>), Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CHCH<sub>2</sub>CH<sub>3</sub> (<b>3</b>), Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CH(CH<sub>2</sub>)<sub>2</sub>CH<sub>3</sub> (<b>4</b>), Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CH(CH<sub>2</sub>)<sub>3</sub>CH<sub>3</sub> (<b>5</b>), and Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CH(CH<sub>2</sub>)<sub>7</sub>CH<sub>3</sub> (<b>6</b>). All adducts crystallize easily and contain the peroxide and phosphine oxide hydrogen-bonded in 1:1 ratios. The single crystal X-ray structures of <b>2</b>–<b>6</b> and their unique features are discussed. The <sup>31</sup>P NMR spectra of the adducts <b>2</b>–<b>6</b> show downfield-shifted signals as compared to Cy<sub>3</sub>PO. In the IR spectra, the ν(P=O) wavenumbers of the adducts have smaller values than the neat phosphine oxide. All spectroscopic results of <b>2</b>–<b>6</b> show that the P=O bond is weakened by hydrogen-bonding to the di(hydroperoxy)alkane moieties. Adduct <b>6</b> selectively oxidizes PPh<sub>3</sub> to OPPh<sub>3</sub> within minutes, and nonanal is reformed in the process. The easy synthesis, handling, and administration of these stable, solid, and soluble peroxides with well-defined composition will have a positive impact on synthetic chemistry. |
| format | Article |
| id | doaj-art-5b5bdf712b1748bda8728edbf02b4410 |
| institution | Kabale University |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj-art-5b5bdf712b1748bda8728edbf02b44102025-01-24T13:43:38ZengMDPI AGMolecules1420-30492025-01-0130232910.3390/molecules30020329Hydrogen-Bonded Di(hydroperoxy)alkane Adducts of the Type Cy<sub>3</sub>P=O·(HOO)<sub>2</sub>CHR (R = Alkyl)Rahym Ashirov0Maya Todorovic1Nattamai Bhuvanesh2Janet Blümel3Department of Chemistry, Texas A&M University, College Station, TX 77842-3012, USADepartment of Chemistry, Texas A&M University, College Station, TX 77842-3012, USADepartment of Chemistry, Texas A&M University, College Station, TX 77842-3012, USADepartment of Chemistry, Texas A&M University, College Station, TX 77842-3012, USAFive representatives of a novel type of di(hydroperoxy)alkane adducts of phosphine oxides have been synthesized and fully characterized, including their solubility in organic solvents. The phosphine oxide Cy<sub>3</sub>PO (<b>1</b>) has been used in combination with the corresponding aldehydes to create the adducts Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CHCH<sub>3</sub> (<b>2</b>), Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CHCH<sub>2</sub>CH<sub>3</sub> (<b>3</b>), Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CH(CH<sub>2</sub>)<sub>2</sub>CH<sub>3</sub> (<b>4</b>), Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CH(CH<sub>2</sub>)<sub>3</sub>CH<sub>3</sub> (<b>5</b>), and Cy<sub>3</sub>PO·(HOO)<sub>2</sub>CH(CH<sub>2</sub>)<sub>7</sub>CH<sub>3</sub> (<b>6</b>). All adducts crystallize easily and contain the peroxide and phosphine oxide hydrogen-bonded in 1:1 ratios. The single crystal X-ray structures of <b>2</b>–<b>6</b> and their unique features are discussed. The <sup>31</sup>P NMR spectra of the adducts <b>2</b>–<b>6</b> show downfield-shifted signals as compared to Cy<sub>3</sub>PO. In the IR spectra, the ν(P=O) wavenumbers of the adducts have smaller values than the neat phosphine oxide. All spectroscopic results of <b>2</b>–<b>6</b> show that the P=O bond is weakened by hydrogen-bonding to the di(hydroperoxy)alkane moieties. Adduct <b>6</b> selectively oxidizes PPh<sub>3</sub> to OPPh<sub>3</sub> within minutes, and nonanal is reformed in the process. The easy synthesis, handling, and administration of these stable, solid, and soluble peroxides with well-defined composition will have a positive impact on synthetic chemistry.https://www.mdpi.com/1420-3049/30/2/329phosphine oxidesdi(hydroperoxy)alkanesX-ray structuresmultinuclear NMRIR data |
| spellingShingle | Rahym Ashirov Maya Todorovic Nattamai Bhuvanesh Janet Blümel Hydrogen-Bonded Di(hydroperoxy)alkane Adducts of the Type Cy<sub>3</sub>P=O·(HOO)<sub>2</sub>CHR (R = Alkyl) Molecules phosphine oxides di(hydroperoxy)alkanes X-ray structures multinuclear NMR IR data |
| title | Hydrogen-Bonded Di(hydroperoxy)alkane Adducts of the Type Cy<sub>3</sub>P=O·(HOO)<sub>2</sub>CHR (R = Alkyl) |
| title_full | Hydrogen-Bonded Di(hydroperoxy)alkane Adducts of the Type Cy<sub>3</sub>P=O·(HOO)<sub>2</sub>CHR (R = Alkyl) |
| title_fullStr | Hydrogen-Bonded Di(hydroperoxy)alkane Adducts of the Type Cy<sub>3</sub>P=O·(HOO)<sub>2</sub>CHR (R = Alkyl) |
| title_full_unstemmed | Hydrogen-Bonded Di(hydroperoxy)alkane Adducts of the Type Cy<sub>3</sub>P=O·(HOO)<sub>2</sub>CHR (R = Alkyl) |
| title_short | Hydrogen-Bonded Di(hydroperoxy)alkane Adducts of the Type Cy<sub>3</sub>P=O·(HOO)<sub>2</sub>CHR (R = Alkyl) |
| title_sort | hydrogen bonded di hydroperoxy alkane adducts of the type cy sub 3 sub p o· hoo sub 2 sub chr r alkyl |
| topic | phosphine oxides di(hydroperoxy)alkanes X-ray structures multinuclear NMR IR data |
| url | https://www.mdpi.com/1420-3049/30/2/329 |
| work_keys_str_mv | AT rahymashirov hydrogenbondeddihydroperoxyalkaneadductsofthetypecysub3subpohoosub2subchrralkyl AT mayatodorovic hydrogenbondeddihydroperoxyalkaneadductsofthetypecysub3subpohoosub2subchrralkyl AT nattamaibhuvanesh hydrogenbondeddihydroperoxyalkaneadductsofthetypecysub3subpohoosub2subchrralkyl AT janetblumel hydrogenbondeddihydroperoxyalkaneadductsofthetypecysub3subpohoosub2subchrralkyl |