81290-20-2

Basic information

• Product Name: (Trifluoromethyl)trimethylsilane
• Synonyms: RUPPERT'S REAGENT;TFMTMS;TMS-CF3;TRIMETHYL(TRIFLUOROMETHYL)SILANE;(TRIMETHYLSILYL)TRIFLUOROMETHANE;(TRIFLUOROMETHYL)TRIMETHYLSILANE;TTMS;(Trifluoromethyl)-trimethylsilan
• CAS NO: 81290-20-2
• Molecular Formula: C₄H₉F₃Si
• Molecular Weight: 142.19
• Product Categories: Fluorinated Building Blocks;Fluorinating Reagents & Building Blocks for Fluorinated Biochemical Compounds;Si (Classes of Silicon Compounds);Si-(C)4 Compounds;Silicon Compounds (for Synthesis);Synthetic Organic Chemistry;organosilicon compounds;C-C Bond Formation;Chemical Synthesis;Fluorination Reagents;Organometallic Reagents;Organosilicon;Others;Synthetic Reagents;Trifluoromethylation;Ruppert's Reagent
• Mol File: 81290-20-2.mol

Chemical Properties

• Boiling Point: 54-55 °C(lit.)
• Flash Point: 14 °F
• Appearance: Clear colorless/Liquid
• Density: 0.962 g/mL at 20 °C(lit.)
• Vapor Pressure: 10.98 psi ( 55 °C)
• Refractive Index: n20/D 1.386
• Storage Temp.: 2-8°C
• Solubility: sol THF, ether, CH2Cl2.
• Water Solubility: Soluble in alcohol, THF, ether, dichloromethane, aromatic and aliphatic hydrocarbons. Soluble in water(with white smokes).
• Sensitive: Moisture Sensitive
• Merck: 14,9683
• BRN: 4241868
• CAS DataBase Reference: (Trifluoromethyl)trimethylsilane(CAS DataBase Reference)
• NIST Chemistry Reference: (Trifluoromethyl)trimethylsilane(81290-20-2)
• EPA Substance Registry System: (Trifluoromethyl)trimethylsilane(81290-20-2)

Safety Data

• Hazard Codes: F,Xi,Xn
• Statements: 11-36/37-19-36/37/38-22-40-14
• Safety Statements: 16-33-39-26-36-29-36/37
• RIDADR: UN 1993 3/PG 2
• WGK Germany: 3
• F: 10-21
• TSCA: No
• HazardClass: 3
• PackingGroup: II
• Hazardous Substances Data: 81290-20-2(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
(Trifluoromethyl)trimethylsilane is used as a trifluoromethylation reagent for enhancing metabolic stability in pharmaceutical compounds. The introduction of a trifluoromethyl group can improve the metabolic blocking properties of a compound, leading to increased effectiveness and reduced side effects.
Used in Agrochemical Industry:
In the agrochemical industry, (Trifluoromethyl)trimethylsilane is employed as a trifluoromethylation agent to modify the properties of agrochemical compounds. This can result in improved lipophilicity and binding selectivity, which are crucial for the development of more effective and targeted agrochemical products.
Used in Transition-Metal-Catalyzed Reactions:
(Trifluoromethyl)trimethylsilane is utilized as a reagent in transition-metal-catalyzed reactions, which are essential for the synthesis of various complex organic molecules. The use of this compound in such reactions can facilitate the introduction of a trifluoromethyl group, enhancing the properties of the final product.
Used in Miscellaneous Trifluoromethylation:
This organosilane compound is also used in miscellaneous trifluoromethylation reactions, where it serves as a source of the trifluoromethyl group. These reactions can be employed to modify a wide range of organic compounds, providing access to new molecules with improved properties.
Used in Addition to Carbonyl and Imine Groups:
(Trifluoromethyl)trimethylsilane is used in the addition to carbonyl and imine groups, allowing for the synthesis of various functionalized organic compounds. This can be particularly useful in the preparation of complex molecules with specific biological activities or other desired properties.

Preparation

(Trifluoromethyl)trimethylsilane is prepared from trimethylsilyl chloride and bromotrifluoromethane in the presence of a phosphorus(III) reagent that serves as a halogen acceptor.

Purification Methods

Purify it by distilling it from trap to trap in a vacuum of 20mm using a bath at 45o and Dry-ice/Me2CO bath for the trap. The liquid in the trap is then washed with ice cold H2O (3x), the top layer is collected, dried (Na2SO4), and the liquid is decanted and fractionated through a helices-packed column at atmospheric pressure. 1H, 1 3C, 1 9F, and 2 9Si NMR can be used for assessing the purity of fractions. [Ruppert et al. Tetrahedron Lett 25 2195 1984, Krishnamurti et al. J Org Chem 56 984 199, Beilstein 4 IV 3892.]

InChI:InChI=1/C4H9F3Si/c1-8(2,3)4(5,6)7/h1-3H3

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 75-63-8 Bromotrifluoromethane 
• 2314-97-8 iodotrifluoromethane 
• 1450-14-2 1,1,1,2,2,2-hexamethyldisilane 
• 75-16-1 methylmagnesium bromide 
• 109111-29-7 (trifluoro methyl) trichloro silane 
• 2283-11-6 hexaethylphosphoric triamide 
• 421-82-9 methyl trifluoromethanesulfonate 
• 426-58-4 (trifluoromethylsulfonyl)benzene 
• 456-56-4 phenyl trifluoromethylsulfide 
• 703-18-4 phenyl trifluoromethyl sulfoxide 
• 400-53-3 trimethylsilyl trifluoroacetate 
• 75-46-7 trifluoromethan 
• 65864-64-4 trimethyl(difluoromethyl)silane 

Downstream Products

• 118143-24-1 2,2,2-trifluoro-1,1-diphenyl-1-(trimethylsilyloxy)ethane 
• 585-36-4 3-(trifluoromethyl)cyclohexanone 
• 118143-28-5 1-(trifluoromethyl)-2-cyclohexen-1-ol 
• 2378-02-1 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-ol 
• 86340-78-5 2,2-difluoro-1-phenyl-1-trimethylsiloxyethene 
• 16500-37-1 Perfluor-2,3-dimethyl-2-butanol 
• 651-89-8 1,2,4,5-tetrafluoro-3,6-bis-trifluoromethyl-benzene 
• 383-11-9 4-(trifluoromethylsulfonyl)chlorobenzene 
• 426-58-4 (trifluoromethylsulfonyl)benzene 
• 383-10-8 1-methyl-4-(trifluoromethylsulfonyl)benzene 
• 1548-72-7 1-nitro-3-(trifluoromethylsulfonyl)benzene 
• 950510-09-5 trimethyl((1-(trifluoromethyl)cyclohexyl)oxy)silane 
• 159426-30-9 1-tert-Butyldimethylsilyloxy-1-phenyldifluoroethene 
• 135983-30-1 Trimethyl-((2S,3S,4R)-2,3,4,5-tetrakis-benzyloxy-1-trifluoromethyl-pentyloxy)-silane 

Relevant articles and documents

TETRAKIS(DIMETHYLAMINO)ETHYLENE/TRIFLUOROIODOMETHANE, A SPECIFIC NOVEL TETRAFLUOROMETHYLATING AGENT

At low temperatures tetrakis(dimethylamino)ethylene (I) and CF3I form a charge transfer complex, which can act as a nucleophilic trifluoromethylating agent in polar solvents according to eqn. (1): The applicability of eqn.(1) to various silicon and boron halides R-X was tested and the following trifluoromethyl-silicon and boron derivatives were obtained in resonable yields: Me3SiCF3 (II), Me2Si(CF3)2 (III), (F3C)3BNHEt2 (IV).

An efficient inexpensive electrochemical preparation of Ruppert's reagent

The electrochemical reduction of CF3Br in N,N-dimethylformamide (DMF) in the presence of Me3SiCl and a sacrificial aluminum anode provides Me3SiCF3 in ca 90% faradaic yields.

SYNTHESIS AND PROPERTIES OF (TRIFLUOROMETHYL)TRICHLOROSILANE, A VERSATILE PRECURSORFOR CF3Si COMPOUNDS

(Trifluoromethyl)trichlorosilane (I) has been prepared for the first time by the reaction of CF3SiH(NMe2)2 (III) with HCl in dibutyl ether and, as a solution in CH2Cl2, by nucleophilic trifluoromethylation of SiCl4 with CF3Br/P(NEt2)3.From this solution, I mey be isolated by HCl cleavage of its insoluble bis(pyridine) adduct (II).The aminosilane III was obtained from the reaction of HSi(Cl)(NMe2)2 with CF3Br/P(NEt2)3.Selective substitution of I without attack on the CF3Si moiety was achieved in high yields with SbF3 (-> CF3SiF3), Ag(OCN) (-> CF3Si(NCO)3 (IV)), MeOH (-> CF3Si(OMe)3 (V)), HNMe2 (CF3Si(NMe2)3 (VI)), LiAlH4 (-> CF3SiH3), MeMgBr (-> CF3SiMe3) and LiPh (-> CF3SiPh3 (VII)).With 2,2'-bipyridyl a 1/1complex (VIII) was formed.The novel compounds I to VIII have been characterized by their IR, NMR and mass spectra, and for I a vibrational analysis including a normal coordinate treatment has been performed.

Preparation method of trifluoromethyltrimethylsilane

The invention provides a preparation method of trifluoromethyltrimethylsilane. The preparation method comprises the following steps: (1) synthesizing a Grignard reagent by taking magnesium metal and trifluorohalomethane as raw materials; and (2) enabling the Grignard reagent to react with trimethyl halogenosilane, so as to prepare the trifluoromethyl trimethyl silane. The preparation method of trifluoromethyltrimethylsilane provided by the invention has the advantages of high yield, simple process, low cost and the like.

Generation and Applications of the Hydroxide Trihydrate Anion, [OH(OH2)3]?, Stabilized by a Weakly Coordinating Cation

The reaction of a strongly basic phosphazene (Schwesinger base) with water afforded the corresponding metastable hydroxide trihydrate [OH(OH2)3]? salt. This is the first hydroxide solvate that is not in contact with a cation and furthermore one of rare known water-stabilized hydroxide anions. Thermolysis in vacuum results in the decomposition of the hydroxide salt and quantitative liberation of the free phosphazene base. This approach was used to synthesize the Schwesinger base from its hydrochloride salt after anion exchange in excellent yields of over 97 %. This deprotonation method can also be used for the phosphazene-base-catalyzed preparation of the Ruppert–Prakash reagent Me3SiCF3 using fluoroform (HCF3) as the trifluoromethyl building block and sodium hydroxide as the formal deprotonation agent.

Borazine-CF3? Adducts for Rapid, Room Temperature, and Broad Scope Trifluoromethylation

A fluoroform-derived borazine CF3? transfer reagent is used to effect rapid nucleophilic reactions in the absence of additives, within minutes at 25 °C. Inorganic electrophiles spanning seven groups of the periodic table can be trifluoromethylated in high yield, including transition metals used for catalytic trifluoromethylation. Organic electrophiles included (hetero)arenes, enabling C?H and C?X trifluoromethylation reactions. Mechanistic analysis supports a dissociative mechanism for CF3? transfer, and cation modification afforded a reagent with enhanced stability.

Recyclable Trifluoromethylation Reagents from Fluoroform

We present a strategy to rationally prepare CF3- transfer reagents at ambient temperature from HCF3. We demonstrate that a highly reactive CF3- adduct can be synthesized from alkali metal hydride, HCF3, and borazine Lewis acids in quantitative yield at room temperature. These nucleophilic reagents transfer CF3- to substrates without additional chemical activation, and after CF3 transfer, the free borazine is quantitatively regenerated. These features enable syntheses of popular nucleophilic, radical, and electrophilic trifluoromethylation reagents with complete recycling of the borazine Lewis acid.

COMPLEXES FOR NUCLEOPHILIC, RADICAL, AND ELECTROPHILIC POLYFLUOROALKYLATION

Disclosed herein are borazine complexes and use of the same in perfluoroalkylation reactions.

Oxidative trifluoromethylation and fluoroolefination of unactivated olefins

Fluorine-containing organic compounds are gaining increasing importance in medicinal chemistry. Described herein is a mild and efficient method for the radical addition of olefins with TMSCF3 and TMSCF2R (R = COOEt or CF3) to deliver various α-trifluoromethylated ketones and α-fluoroolefinated ketones.

Preparation method of trifluoromethyl (trimethyl) silane

The invention discloses a preparation method of trifluoromethyl (trimethyl) silane. The preparation method comprises the following steps that (a) under the argon gas protection, metal potassium, styrene and hexamethyl disilazane take a reaction in methylbenzene until the metal potassium completely dissolves, and reaction liquid is obtained; (b) at -45 to -110 DEG C, trimethylchlorosilane is added into the reaction liquid obtained in the step (a); fluoform is introduced for reaction; after the reaction is finished, the temperature is raised to room temperature; washing and standing layering are performed; an obtained organic layer is rectified to obtain the product of the trifluoromethyl (trimethyl) silane. The preparation method has the advantages of simple process, low cost, high yield, safety and environment-friendly effect.