MoOPH

Structural formula
General
Surname	MoOPH
other names	Oxodiperoxymolybdenum pyridine hexamethylphosphoramide
Molecular formula	C 11 H 23 MoN 3 O 6 P
External identifiers / databases
CAS number 23319-63-3 Wikidata Q1575618
properties
Molar mass	324.29 g mol −1
Physical state	firmly
Melting point	103–105 ° C (decomposition)
safety instructions
GHS hazard labeling no classification available
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.

${\displaystyle \mathrm {MoO_{3}{\xrightarrow[{2.HMPT}]{1.H_{2}O_{2}}}MoO_{5}(H_{2}O)[(Me_{2}N)_{3}PO]} }$ ${\displaystyle \mathrm {{\xrightarrow {0.2Torr}}MoO_{5}[(Me_{2}N)_{3}PO]} }$ ${\displaystyle \mathrm {{\xrightarrow {Pyridin}}MoO_{5}[(Me_{2}N)_{3}PO](Pyridin)} }$

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

1. ↑ ^{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 ).
2. ↑ This substance has either not yet been classified with regard to its hazardousness or a reliable and citable source has not yet been found.
3. ↑ 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
4. ↑ JC Anderson, SC Smith: in Synlett 1990 , 107-108.