88738-78-7

Basic information

• Product Name: BIS(2,2,2-TRIFLUOROETHYL) (METHOXYCARBONYLMETHYL)PHOSPHONATE
• Synonyms: BIS(2,2,2-TRIFLUOROETHYL) (METHOXYCARBONYLMETHYL)PHOSPHONATE;BIS(2,2,2-TRIFLUOROETHYL)PHOSPHONOACETIC ACID METHYL ESTER;METHYL [BIS(2,2,2-TRIFLUOROETHOXY)PHOSPHINYL]ACETATE;METHYL BIS(2,2,2-TRIFLUOROETHYL)PHOSPHONOACETATE;METHYL O,O'-BIS(2,2,2-TRIFLUOROETHYL)PHOSPHONOACETATE;METHYL P,P-BIS(2,2,2-TRIFLUOROETHYL)PHOSPHONOACETATE;Bis(2,2,2-trifluoroethyl)(methoxycarbonylmethyl)phosphonate 95%;Bis(2,2,2-trifluoroethyl)(methoxycarbonylmethyl)phosphonate95%
• CAS NO: 88738-78-7
• Molecular Formula: C₇H₉F₆O₅P
• Molecular Weight: 318.11
• Product Categories: Small molecule;Horner-Emmons Reaction;Synthetic Organic Chemistry;Wittig & Horner-Emmons Reaction
• Mol File: 88738-78-7.mol

Chemical Properties

• Boiling Point: 246.6 °C at 760 mmHg
• Flash Point: >230 °F
• Appearance: Clear orange to dark orange-brown/Liquid
• Density: 1.504 g/mL at 25 °C(lit.)
• Vapor Pressure: 4.23E-09mmHg at 25°C
• Refractive Index: n20/D 1.370(lit.)
• Storage Temp.: Inert atmosphere,Room Temperature
• BRN: 3594044
• CAS DataBase Reference: BIS(2,2,2-TRIFLUOROETHYL) (METHOXYCARBONYLMETHYL)PHOSPHONATE(CAS DataBase Reference)
• NIST Chemistry Reference: BIS(2,2,2-TRIFLUOROETHYL) (METHOXYCARBONYLMETHYL)PHOSPHONATE(88738-78-7)
• EPA Substance Registry System: BIS(2,2,2-TRIFLUOROETHYL) (METHOXYCARBONYLMETHYL)PHOSPHONATE(88738-78-7)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• F: 10
• Hazardous Substances Data: 88738-78-7(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
BIS(2,2,2-TRIFLUOROETHYL) (METHOXYCARBONYLMETHYL)PHOSPHONATE is used as a synthetic intermediate for the preparation of various pharmaceutical compounds, such as trans-hydrindanes and (R)-(+)-umbelactone. Its unique structure allows for the formation of complex molecules with potential therapeutic applications.
Used in Chemical Synthesis:
BIS(2,2,2-TRIFLUOROETHYL) (METHOXYCARBONYLMETHYL)PHOSPHONATE is used as a reagent in the synthesis of cis-olefinic ester derivatives through Still-Gennari olefination of aldehyde derivatives. This reaction involves the use of 18-crown ether and potassium bis(trimethylsilyl)amide (KHMDS) to facilitate the formation of the desired product.
Used in Fragrance Industry:
BIS(2,2,2-TRIFLUOROETHYL) (METHOXYCARBONYLMETHYL)PHOSPHONATE is used as a key intermediate in the synthesis of (+)-(6S,2′S)-epicryptocaryalactone, a compound with potential applications in the fragrance industry. Its unique structure and properties make it a valuable component in creating novel and complex fragrance molecules.

Synthesis

The synthesis method of Bis(2,2,2-trifluoroethyl) (Methoxycarbonylmethyl) phosphonate is as follows: To a stirred solution of dried 18-crown-6 (4.53 g, 17.14 mmol), THF (20 mL), and Bis(2,2,2-trifluoroethyl) Phosphite (0.70 mL, 1.29 mmol), was added KHMDS (9.0 mL, 4.50 mmol, 0.5M in toluene) by syringe in a dropwise manner at -78 ℃. After 15 min, methyl chloroacetate (0.30 mL, 3.41 mmol) was added and the reaction mixture was allowed to stir for 4 hr at room temperature. The reaction mixture was diluted with EtOAc (20 mL) and then quenched with sat. ammonium chloride (50 mL). The aqueous layer was extracted with EtOAc (3 x 30 mL). The combined organic extracts were dried under anhydrous magnesium sulfate. Following filtration, the solvents were removed in vacuo. The crude product was then purified by flash column chromatography (33% EtOAc in hexanes, Rf = 0.22 in 33% EtOAc in hexanes) yielding Bis(2,2,2-trifluoroethyl) (Methoxycarbonylmethyl)phosphonate (766 mg, 2.41 mmol, 70.3%) as a yellow syrup.

InChI:InChI=1/C21H11F5O3/c22-15-16(23)18(25)20(19(26)17(15)24)29-21(27)28-9-14-12-7-3-1-5-10(12)11-6-2-4-8-13(11)14/h1-8,14H,9H2

Upstream product

• 75-89-8 2,2,2-trifluoroethanol 
• 31460-11-4 (methoxycarbonylmethyl)phosphonic dichloride 
• 67605-34-9 methyl 2-(bis((trimethylsilyl)oxy)phosphoryl)acetate 
• 40962-37-6 phosphonoacetic acid trimethyl ester 
• 420-87-1 sodium 2,2,2-trifluoroethanolate 

Downstream Products

• 122592-49-8 (R,S)-(Z)-3-(2-Tetrahydrofuryl)propenoic acid methyl ester 
• 20754-22-7 methyl (Z)-3-(4-trifluoromethylphenyl)acrylate 
• 75128-90-4 (2Z)-decenoic acid methyl ester 
• 7367-85-3 methyl (E)-dec-2-enoate 
• 112980-51-5 (R)-methyl-4,5-dibenzyloxy-2-(Z)-pentenoate 
• 112980-52-6 (R)-methyl-4,5-dibenzyloxy-2-(E)-pentenoate 
• 111854-80-9 (Z)-(S)-4-Benzyloxycarbonylamino-6-methyl-hept-2-enoic acid methyl ester 
• 132549-28-1 (E)-(S)-4-Benzyloxycarbonylamino-6-methyl-hept-2-enoic acid methyl ester 
• 111871-62-6 (Z)-(S)-4-Benzyloxycarbonylamino-5-phenyl-pent-2-enoic acid methyl ester 
• 132618-89-4 methyl (E,4S)-4-(((benzyloxy)carbonyl)amino)-5-phenylpent-2-enoate 
• 123083-94-3 (2Z,6E)-(4S,5R,8S,9R,10S,12S,13R)-5-(tert-Butyl-dimethyl-silanyloxy)-13-[3-(2,5-dimethyl-pyrrol-1-yl)-2,5-dimethoxy-phenyl]-9,10,13-trimethoxy-4,6,8,12-tetramethyl-trideca-2,6-dienoic acid methyl ester 
• 130172-78-0 (Z)-4-[(1R,2R,3R,5S)-5-(tert-Butyl-dimethyl-silanyloxy)-2-[(E)-(S)-3-cyclohexyl-3-(tetrahydro-pyran-2-yloxy)-propenyl]-3-(tetrahydro-pyran-2-yloxy)-cyclopentyl]-but-2-enoic acid methyl ester 
• 170552-02-0 (5E,13E)-(9S,11R,15S)-11,15-bis(tetrahydropyran-2-yloxy)-9-(t-butyldimethylsiloxy)-15-cyclohexyl-2,3,4,16,17,18,19,20-octanor-5,13-prostadienoic acid methyl ester 
• 112489-56-2 methyl (Z)-(S)-4-phenylmethoxy-2-pentenoate 

Relevant articles and documents

A Straightforward, Purification-Free Procedure for the Synthesis of Ando and Still-Gennari Type Phosphonates

Z-Selective Still-Gennari and Ando modifications of the typically E-selective Horner-Wadsworth-Emmons reaction are highly valuable synthetic tools in organic chemistry. These procedures are based on application of bis(2,2,2-trifluoroethyl) phosphonates or diaryl phosphonates, respectively, for the olefination of carbonyl groups. In our research, we present an improved, straightforward, purificationfree procedure for the synthesis of these reagents. The key step of our procedure is the reaction of phosphonic dichlorides with the appropriate sodium alkoxides, which results in 52-97% isolated yields of the desired products on a gram scale. The whole three-step process is performed in one pot. Most importantly, the product is obtained in over 95% purity after simple extraction, avoiding column chromatography and distillation. Moreover, we present the synthesis of a novel Still-Gennari type reagent, bis(1,1,1,3,3,3-hexafluoroisopropyl) phosphonates, which may exhibit improved Z-selectivity in Still-Gennari olefinations.

Stereoselective Synthesis of the Benzodihydropentalene Core of the Fijiolides

An efficient stereoselective synthesis of the enantiomer of the benzodihydropentalene core of fijiolides A and B has been achieved. The asymmetric conjugate addition of styrylboronic acid to an indenone produced the first stereocenter. Ring C was installe

Facile Two-Step Synthesis of Methyl Bis(2,2,2-trifluoroethyl)phosphonoacetate by Exploiting Garegg-Samuelsson Reaction Conditions

A facile two-step synthesis of methyl bis(2,2,2-trifluoroethyl)phosphonoacetate (Still-Gennari reagent) has been developed by exploiting Garegg-Samuelsson reaction conditions. Starting from trimethyl phosphonoacetate, Still-Gennari reagent was prepared in 94% yield via methyl 2-{bis[(trimethylsilyl)oxy]phosphoryl}acetate intermediate. This synthetic procedure was also used to prepare some kinds of Horner-Wadsworth-Emmons reagents and related compounds.

An expedient access to still-gennari phosphonates

An inexpensive and efficient route to the Still-Gennari phosphonates, methyl and ethyl bis(2,2,2-trifluoroethyl)phosphono acetates, has been developed. This short reaction sequence is operationally simple and makes these versatile reagents for the prepara

DIRECT SYNTHESIS OF Z-UNSATURATED ESTERS. A USEFUL MODIFICATION OF THE HORNER-EMMONS OLEFINATION.

New phosphonoester reagents and reaction conditions are described which yield Z-alpha,beta-unsaturated esters stereoselectively and in high yield from aliphatic and aromatic aldehydes.