13716-45-5

Basic information

• Product Name: DIETHYL TRIMETHYLSILYL PHOSPHITE
• Synonyms: PHOSPHOROUS ACID DIETHYL TRIMETHYLSILYL ESTER;DIETHYL TRIMETHYLSILYL PHOSPHITE;DIETHYL TRIMETHYLSILYL PHOSPHITE 96%;Diethyl trimethylsilyl phosphite >=95.0% (GC)
• CAS NO: 13716-45-5
• Molecular Formula: C₇H₁₉O₃PSi
• Molecular Weight: 210.28
• EINECS: 237-268-5
• Mol File: 13716-45-5.mol
• Article Data: 27

Chemical Properties

• Boiling Point: 58-59 °C10 mm Hg(lit.)
• Flash Point: 33 °C
• Appearance: /
• Density: 0.921 g/mL at 25 °C(lit.)
• Vapor Pressure: 4.565mmHg at 25°C
• Refractive Index: n20/D 1.413(lit.)
• CAS DataBase Reference: DIETHYL TRIMETHYLSILYL PHOSPHITE(CAS DataBase Reference)
• NIST Chemistry Reference: DIETHYL TRIMETHYLSILYL PHOSPHITE(13716-45-5)
• EPA Substance Registry System: DIETHYL TRIMETHYLSILYL PHOSPHITE(13716-45-5)

Safety Data

• Statements: 10
• Safety Statements: 23-24/25
• RIDADR: UN 1993 3/PG 3
• WGK Germany: 3
• F: 10-21
• HazardClass: 3.2
• PackingGroup: III
• Hazardous Substances Data: 13716-45-5(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 13716-45-5 differently. You can refer to the following data:
1. Diethyl Trimethylsilyl Phosphite acts as a reagent in the synthesis of substituted N-formylaminomethylenediphosphonates and derivatives. It also functions as a reagent in the synthesis of phosphonic analog of glutamic acid.
2. Diethyl trimethylsilyl phosphite was used in preparation of:diethyl 1-aryl-1-cyanomethanephosphonatesunsymmetrical ketonesketones from aldehydes via α-trimethylsiloxy-phosphonatesphosphonates

Purification Methods

Fractionate it under reduced pressure and has 3 1PMR: P -128ppm relative to H3PO4. [Sekine et al. J Org Chem 46 2097 1981, Chernyshev et al. J Gen Chem USSR (Engl Transl) 45 231 1975.]

InChI:InChI=1/C7H19O3PSi/c1-6-9-11(8,10-7-2)12(3,4)5/h6-7H2,1-5H3

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 762-04-9 Diethyl phosphonate 
• 2303-76-6 sodium diethyl phosphite 
• 70525-70-1 C₁₅H₃₈O₆P₂Si₂ 
• 5577-67-3 trimethyl(tert-butylamino)silane 
• 762-04-9 phosphonic acid diethyl ester 
• 55595-96-5 diethyl <1-(diethoxyphosphinyl)-1-phenylmethyl>phosphoramidate 
• 3385-94-2 hexamethyldisilathiane 
• 10416-59-8 N,O-bis-(trimethylsilyl)-acetamide 
• 6632-88-8 diethyl 1-hydroxy-1-methylethylphosphonate 
• 999-97-3 1,1,1,3,3,3-hexamethyl-disilazane 
• 996-50-9 N,N-diethyl-1,1,1-trimethylsilanamine 
• 25561-30-2 N,O-Bis(trimethylsilyl)trifluoroacetamide 
• 2857-97-8 trimethylsilyl bromide 

Downstream Products

• 36240-43-4 diethyl 1-(trimethylsiloxy)-1-cyclohexylphosphonate 
• 52057-49-5 [(4-Fluoro-phenyl)-trimethylsilanyloxy-methyl]-phosphonic acid diethyl ester 
• 52057-50-8 α-trimethylsiloxy-p-chlorobenzylphosphonic acid diethyl ester 
• 52146-94-8 diethyl α-trimethylsilyloxy-4-nitrobenzylphosphonate 
• 39644-59-2 Phosphoric acid diethyl ester 2,3,5,6-tetrachloro-4-trimethylsilanyloxy-phenyl ester 
• 31675-43-1 diethyl 1-phenyl-1-(trimethylsiloxy)methanephosphonate 
• 51128-50-8 2-[(trimethylsilyl)oxy]cyclohex-2-en-1-one 
• 1112-94-3 methyl 3-(diethoxyphosphinyl)-propanoate 
• 66731-80-4 diethyl 1-trimethylsilyloxy 3-phenyl 2-propenyl phosphonate 
• 135887-79-5 4-<(Diethoxyphosphoryl)(4-methoxyphenyl)methyl>-2-phenyl-5-(trimethylsiloxy)oxazol 
• 1776-87-0 diethyl (hydroxy(4-nitrophenyl)methyl)phosphonate 
• 131480-02-9 diethyl (4-acetamidophenyl)hydroxymethanephosphonate 
• 131480-08-5 diethyl (N-4-nitrophenylcarbamoyl)phosphonate 
• 1021-45-0 phosphoric acid diethyl ester-(1-phenyl-vinyl ester) 

Relevant articles and documents

Structures of products of the reactions of halotriorganosilanes with triethyl phosphite and with sodium dialkyl phosphites

1. The reaction of bromotriethylsilane with triethyl phosphite at high temperatures (155-180°) goes with formation mainly of silyl-substituted tervalent phosphorus derivatives, which readily combine with sulfur and undergo Arbuzov reaction with ethyl bromide. 2. In the reactions of trialkylhalosilanes with sodium diethyl phosphite the products are not quinquevalent phosphorus compounds containing the Si-P bond as was supposed earlier, but the isomeric tervalent phosphorus compounds containing the Si-O-P link. 3. The thione-thiol isomerization of Si-P was effected in presence of ethyl bromide.

A new selenium-transferring reagent - Triphenylphosphine selenide

Triphenylphosphine selenide and its polymer-supported counterpart are found to be efficient selenium-transferring reagents for the conversion of H-phosphonate diesters and phosphite triesters into the corresponding phosphoroselenoate derivatives.

New Synthesis of Diethyl Trimethylsilyl Phosphite

Diethyl phosphonate rapidly reacted with hexamethyldisilazane at 20°C in the presence of 52 mol % of zinc(II) chloride to give 76% of diethyl trimethylsilyl phosphite.

Synthesis of Rovafovir Etalafenamide (Part III): Evolution of the Synthetic Process to the Phosphonamidate Fragment

Phosphonamidate 1 is a key fragment in the assembly of rovafovir etalafenamide, a novel nucleotide reverse transcriptase inhibitor under development at Gilead Sciences for the treatment of HIV infection. An early manufacturing route, relying on simulated moving bed (SMB) chromatography for the separation of phosphorus diastereomers, was executed on scale to produce multiple batches of 1. However, developing alternative synthetic conditions became desirable in consideration of the high production cost, long lead time, and high process mass intensity (PMI) associated with SMB. Several strategies to improve these factors are described herein, including epimerization and recycling of the undesired (R)-phosphorus diastereomer, design of stereoselective approaches to establish the desired (S)-configuration at phosphorus, and identification of conditions or derivatives to allow for selective crystallization. Ultimately, a second-generation route to 1 was developed and demonstrated on scale. The new route achieves the separation of phosphorus diastereomers by means of selective crystallization, does not require SMB, and offers lower PMI, cost, and lead time.

Steric Enforcement of cis-Epoxide Formation in the Radical C-O-Coupling Reaction by Which (S)-2-Hydroxypropylphosphonate Epoxidase (HppE) Produces Fosfomycin

(S)-2-Hydroxypropylphosphonate [(S)-2-HPP, 1] epoxidase (HppE) reduces H2O2 at its nonheme-iron cofactor to install the oxirane "warhead" of the antibiotic fosfomycin. The net replacement of the C1 pro-R hydrogen of 1 by its C2 oxygen, with inversion of configuration at C1, yields the cis-epoxide of the drug [(1R,2S)-epoxypropylphosphonic acid (cis-Fos, 2)]. Here we show that HppE achieves ～95% selectivity for C1 inversion and cis-epoxide formation via steric guidance of a radical-coupling mechanism. Published structures of the HppE·FeII·1 and HppE·ZnII·2 complexes reveal distinct pockets for C3 of the substrate and product and identify four hydrophobic residues - Leu120, Leu144, Phe182, and Leu193 - close to C3 in one of the complexes. Replacement of Leu193 in the substrate C3 pocket with the bulkier Phe enhances stereoselectivity (cis:trans ～99:1), whereas the Leu120Phe substitution in the product C3 pocket diminishes it (～82:18). Retention of C1 configuration and trans-epoxide formation become predominant with the bulk-reducing Phe182Ala substitution in the substrate C3 pocket (～13:87), trifluorination of C3 (～23:77), or both (～1:99). The effect of C3 trifluorination is counteracted by the more constrained substrate C3 pockets in the Leu193Phe (～56:44) and Leu144Phe/Leu193Phe (～90:10) variants. The ability of HppE to epoxidize substrate analogues bearing halogens at C3, C1, or both is inconsistent with a published hypothesis of polar cyclization via a C1 carbocation. Rather, specific enzyme-substrate contacts drive inversion of the C1 radical - as proposed in a recent computational study - to direct formation of the more potently antibacterial cis-epoxide by radicaloid C-O coupling.