MoOPH
Structural formula | |||||||
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General | |||||||
Surname | MoOPH | ||||||
other names |
Oxodiperoxymolybdenum pyridine hexamethylphosphoramide |
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Molecular formula | C 11 H 23 MoN 3 O 6 P | ||||||
External identifiers / databases | |||||||
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properties | |||||||
Molar mass | 324.29 g mol −1 | ||||||
Physical state |
firmly |
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Melting point |
103–105 ° C (decomposition) |
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safety instructions | |||||||
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As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . |
MoOPH (or oxodiperoxymolybdenum pyridine hexamethylphosphoric acid triamide) is a molybdenum complex which Edwin Vedejs presented as a reagent for organic synthesis. The complex is used for the oxidation of carbanions .
application
MoOPH is an oxidizing agent for carbanions such as B. enolate ions . In the example shown, an enolate ion is generated with the help of lithium diisopropylamide (LDA) and hydroxylated to α-hydroxyketone ( acyloin ) by reaction with MoOPH :
Since the hexamethylphosphoric acid triamide (HMPT) used as a ligand is classified as carcinogenic , an analogue with the ligand dimethylpropyleneurea (DMPU), the so-called MoOPD (oxodiperoxymolybdenum-pyridine-dimethylpropyleneurea), was introduced.
presentation
MoOPH is produced in a three-stage reaction sequence. First, the molybdenum (VI) oxide is oxidized to diperoxide and converted with hexamethylphosphoric triamide (HMPT) to form the hydrato complex. A drying step removes the water as ligands. The complex obtained in this way is reacted with pyridine to form MoOPH, which is obtained as a yellow powder.
literature
- Bang-Chi Chen, Ping Zhou, Franklin A. Davis, Engelbert Cianek: "α-Hydroxylation of Enolates and Silyl Enol Ethers", In: Organic Reaction , Wiley 2004 doi : 10.1002 / 0471264180.or062.01 .
Individual evidence
- ↑ a b Edwin Vedejs, S. Larsen: hydroxylation of enolate with Oxodiperoxymolybdenum (pyridines) (Hexamethylphosphoric triamides), MoO 5 · Py · HMPA (MoOPH): 3-hydroxy-1,7,7-trimethylbicyclo [2.2.1] heptane -2-one In: Organic Syntheses . 64, 1986, p. 127, doi : 10.15227 / orgsyn.064.0127 ; Coll. Vol. 7, 1990, p. 277 ( PDF ).
- ↑ This substance has either not yet been classified with regard to its hazardousness or a reliable and citable source has not yet been found.
- ↑ Dietrich Spitzner, Kai Oesterreich: "Anionically Induced Domino Reactions - Synthesis of a Norpatchoulenol-Type Terpene", in: European Journal of Organic Chemistry , 2001 , 10 , 1883–1886 doi : 10.1002 / 1099-0690 (200105) 2001: 10 <1883 :: AID-EJOC1883> 3.0.CO; 2-M
- ↑ JC Anderson, SC Smith: in Synlett 1990 , 107-108.