Trimethyl phosphite is an organophosphorus compound with the formula P(OCH3)3, often abbreviated P(OMe)3. It is a colorless liquid with a highly pungent odor. It is the simplest phosphite ester and finds used as a ligand in organometallic chemistry and as a reagent in organic synthesis. The molecule features a pyramidal phosphorus(III) center bound to three methoxy groups.
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| Preferred IUPAC name
Trimethyl phosphite[1] | |||
| Other names
Trimethoxyphosphine
Trimethoxyphosphane | |||
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3D model (JSmol)
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| ECHA InfoCard | 100.004.065 | ||
PubChem CID
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CompTox Dashboard (EPA)
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| Properties | |||
| C3H9O3P | |||
| Molar mass | 124.08 | ||
| Appearance | colorless liquid | ||
| Odor | distinctive, pungent[2] | ||
| Density | 1.052 | ||
| Melting point | −78 °C (−108 °F; 195 K) | ||
| Boiling point | 111 °C (232 °F; 384 K) | ||
| reacts[2] | |||
| Vapor pressure | 24 mmHg (25°C)[2] | ||
| Hazards | |||
| Flash point | 28 °C; 82 °F; 301 K[2] | ||
| NIOSH (US health exposure limits): | |||
PEL (Permissible)
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none[2] | ||
REL (Recommended)
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TWA 2 ppm (10 mg/m3)[2] | ||
IDLH (Immediate danger)
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N.D.[2] | ||
| Related compounds | |||
Related compounds
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Dimethyl methylphosphonate | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Synthesis
editTrimethyl phosphite is in principle obtainable by methanolysis of phosphorus trichloride, say in the presence of a proton accepting base. This method suffers from numerous side reactions however. The use of sodium methoxide is superior:[3]
- PCl3 + 3 NaOCH3 → P(OCH3)3 + 3 NaCl
Reactions
editTrimethyl phosphite is susceptible to oxidation to trimethyl phosphate:
- P(OCH3)3 + 0.5 O2 → OP(OCH3)3
It reacts with a catalytic amount of methyl iodide in the Arbuzov reaction to give dimethyl methylphosphonate:
- P(OCH3)3 → CH3P(O)(OCH3)2
As a ligand, trimethyl phosphite has a smaller cone angle and better acceptor properties relative to trimethylphosphine. A representative derivative is the colorless tetrahedral complex Ni(P(OMe)3)4 (m.p. 108 °C).[4] The tridentate ligand called the Kläui ligand is derived from trimethyl phosphite. The formation of this ligand illustrates the susceptibility of trimethyl phosphite (and metal complexes thereof) to the Arbuzov reaction.
Trimethyl phosphite is also used as a mild desulfurization reagent in organic synthesis, for example in the preparation of derivatives of tetrathiafulvalene.[5]
Toxicity
editReferences
edit- ^ Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 931. doi:10.1039/9781849733069-FP001. ISBN 978-0-85404-182-4.
- ^ a b c d e f g NIOSH Pocket Guide to Chemical Hazards. "#0640". National Institute for Occupational Safety and Health (NIOSH).
- ^ Crofts, Peter C.; Kosolapoff, Gennady M. (1953). "Preparation and Determination of Apparent Dissociation Constants of Some Alkylphosphonic and Dialkylphosphinic Acids1". Journal of the American Chemical Society. 75 (14): 3379–3383. doi:10.1021/ja01110a024.
- ^ Steven D. Ittel; Cushing, M. A. (1990). "Bis(1,5-Cyclooctadiene)Nickel(0)". Inorganic Syntheses. Vol. 28. pp. 98–104. doi:10.1002/9780470132593.ch25. ISBN 978-0-471-52619-3.
- ^ Larsen, Jan; Lenoir, Christine (1995). "2,2'-Bi-5,6-Dihydro-1,3-Dithiolo[4,5-b][1,4]dithiinylidene (BEDT-TTF)". Org. Synth. 72: 265. doi:10.15227/orgsyn.072.0265.
- ^ Svara, J.; Weferling, N.; Hofmann, T. "Phosphorus Compounds, Organic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_545.pub2. ISBN 978-3527306732.