18301-46-7

Basic information

• Product Name: 4-(Trimethylsilyl)pyridine
• Synonyms: 4-(Trimethylsilyl)pyridine;Trimethyl(4-pyridyl)silane
• CAS NO: 18301-46-7
• Molecular Formula: C₈H₁₃NSi
• Molecular Weight: 151.28102
• Mol File: 18301-46-7.mol

Chemical Properties

• Boiling Point: 195.2°Cat760mmHg
• Flash Point: 71.8°C
• Appearance: /
• Density: 0.9g/cm³
• Vapor Pressure: 0.595mmHg at 25°C
• Refractive Index: 1.474
• Storage Temp.: 2-8°C
• CAS DataBase Reference: 4-(Trimethylsilyl)pyridine(CAS DataBase Reference)
• NIST Chemistry Reference: 4-(Trimethylsilyl)pyridine(18301-46-7)
• EPA Substance Registry System: 4-(Trimethylsilyl)pyridine(18301-46-7)

Safety Data

• Hazardous Substances Data: 18301-46-7(Hazardous Substances Data)

Usage

Uses

Used in Organic Synthesis:
4-(Trimethylsilyl)pyridine is utilized as a reagent and catalyst in organic synthesis for its ability to facilitate reactions with electrophilic species. Its role as a Lewis base enables it to accelerate reaction rates and activate certain substrates, thereby streamlining the synthesis of a variety of organic compounds.
Used as a Deprotonating Agent:
In the synthesis of various organic compounds, 4-(Trimethylsilyl)pyridine serves as an effective deprotonating agent. This function is crucial for the formation of specific organic products, particularly in reactions where the removal of a proton is a key step in the synthesis process.

InChI:InChI=1/C8H13NSi/c1-10(2,3)8-4-6-9-7-5-8/h4-7H,1-3H3

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 1120-87-2 4-bromopyridin 
• 29173-25-9 1,4-bis(trimethylsilyl)-1-aza-2,5-cyclohexadiene 
• 292638-85-8 acrylic acid methyl ester 
• 107-13-1 acrylonitrile 
• 78-94-4 methyl vinyl ketone 
• 626-60-8 3-Chloropyridine 
• 110-86-1 pyridine 
• 54711-92-1 trimethylsilanide ion 
• 1450-14-2 1,1,1,2,2,2-hexamethyldisilane 
• 541-41-3 chloroformic acid ethyl ester 

Downstream Products

• 75746-59-7 7-trimethylsilyl-3-benzoyl-1,2-dicarbomethoxyindolizine 
• 75746-57-5 4-trimethylsilylpyridinium benzoylmethylid 
• 872-85-5 pyridine-4-carbaldehyde 
• 75746-55-3 N-phenacyl-4-trimethylsilylpyridinium bromide 
• 58163-76-1 4-(((trimethylsilyl)oxy)(phenyl)methyl)pyridine 

Relevant articles and documents

Characterization of covalent Ene adduct intermediates in "hydride equivalent" transfers in a dihydropyridine model for NADH reduction reactions

A study of the reactions of an NADH model, 1,4-di(trimethylsilyl)-1,4- dihydropyridine, 7, with a series of α,β-unsaturated cyano and carbonyl compounds has produced the first direct evidence for an obligatory covalent adduct between a dihydropyridine and substrate in a reduction reaction. The reactions were monitored by NMR spectroscopy. In all reactions studied, the covalent adduct was the first new species detected and its decomposition to form products could be observed. Concentrations of adducts were sufficiently high at steady-state that their structures could be determined directly from NMR spectra of the reaction mixtures; adduct structures are those expected from an Ene reaction between 7 and the substrate. This first reaction step results in transfer of the C4 hydrogen nucleus of 7 to the substrate and formation of a covalent bond between C2 of the dihydropyridine ring and the substrate α-atom. Discovery of these Ene-adduct intermediates completes the spectrum of mechanisms observed in NADH model reactions to span those with free radical intermediates, no detectable intermediates and now covalent intermediates. The geometry of the transition state for formation of the Ene adduct is compared with those of theoretical transition state models and crystal structures of enzyme-substrate/inhibitor complexes to suggest a relative orientation for the dihydropyridine ring and the substrate in an initial cyclic transition state that is flexible enough to accommodate all observed mechanistic outcomes.

Reactions of trimethylstannide and trimethylsiliconide anions with aromatic and heteroarornatic substrates

A parallel study was carried out on the reactions of Me3Sn- and Me3Si- ions towards aromatic and heteroaromatic substrates in hexamethylphosphoramide (HMPA) as solvent. It was found that Me3Si- ions are more reactive and therefore less selective than Me3Sn- ions. In HMPA, PhI and PhBr react with Me3Sn- ions through an HME pathway. PhCl also reacts by an HME reaction, but under photostimulation the SRN1 mechanism competes with the HME process, With PhF as sabstrate, Me3Sn- ions afford (4-fluorophenyl)trimethylstannane, presumably through a hypervalent tin species. Under irradiation, the SRN1 mechanism operates concurrently with the formation of the hypervalent tin species. Me3Si- ions, on the other hand, react with PhX (X = Cl, Br, I) to yield the ipso substitution product, presumably through the intermediacy of a hypervalent silicon species. PhF affords, upon reaction with Me3Si- ions, o- and p-fluorotrimethylsilylbenzenes together with the ipso substitution product PhSiMe3. A novel type of nucleophilic substitution mechanism takes place with Me3Si- ions upon reaction with aromatic and heteroaromatic substrates without classical leaving groups in HMPA. Copyright

A novel type of nucleophilic substitution reactions on nonactivated aromatic compounds and benzene itself with trimethylsiliconide anions.

[reaction: see text]. The reaction of fluorobenzene with Me3Si- anion (1) in HMPA at room temperature surprisingly affords o- and p-fluorotrimethylsilylbenzenes (substitution of aromatic H for TMS, 76% yield) 7a and 7b and also 14% of trimethylsilylbenzene (2). Benzene itself reacts at 50 degrees C to furnish 4 in 45% yield. Pyridine affords p-trimethylsilylpyridine quantitatively. Mechanistic studies are presented.

On the Mechanism of the Carbodesilylation of 4- or 5-Substituted 2-(Trimethylsilyl)pyridines

An "ylide mechanism" is proposed for the carbodesilylation of 2-(trimethylsilyl)pyridines with benzaldehyde.In contrast, 3- and 4-(trimethylsilyl)pyridines, react only in the presence of a base catalyst via pyridyl anions with electrophiles.The rates of the uncatalyzed carbodesilylation reactions of 4-substituted 2-(trimethylsilyl)pyridines 2 with benzaldehyde correlate very well with the resonance parameters of the substituents ?0R, whereas the rates of 5-substituted 2-(trimethylsilyl)pyridines 7 correlate with the inductive substituent parameters ?1 in the Taft equation.This is to our knowledge the first direct determination of the resonance parameters ?0R.Key Words: Pyridines, substituted 2-(trimethylsilyl)-, synthesis of, carbodesilylation of / Carbodesilylation / Rate constants

Reactions of 1,4-Bis(trimethylsilyl)-1,4-dihydropyridines with Carbonyl Compounds: A New Method for Regioselective Synthesis of 3-Alkylpyridines

A new method for the alkyl group introduction at the 3-position of pyridines is described: Reductive disilylation of pyridine, its 2-methyl, 3-methyl, and 4-methyl derivatives affords the corresponding 1,4-disilyl-1,4-dihydropyridines.Tn the presence of a catalytic amount of tetrabutylammonium fluoride, these dihydropyridines smoothly react with a variety of aldehydes and ketones to give 3-alkylpyridines.

Preparation and Reactions of 4-(Trimethylsilyl)indole

Indole or 1-(trimethylsilyl)indole was reacted sequentially with lithium-chlorotrimethylsilane and with 1,4-benzoquinone to produce 1,4-bis(trimethylsilyl)indole (50 percent and 55 percent, respectively).Methanolysis gave 4-(trimethylsilyl)indole which reacted with electrophiles at C-3.However, the derivative 1-acetyl-4-(trimethylsilyl)indole reacted with acetyl, 2-chloropropanoyl, or propenoyl chlorides via clean C-4 ipso substitution.Attemps to extend the reaction to a useful synthesis of derivatives of 5-oxo-1,3,4,5-tetrahydrobenzindole, a lysergic acid synthon, were prevented by low yields.

Functionalization of Pyridine via Direct Metallation

The isolation of mixtures of 2-, 3-, and 4-deuteriopyridine, 2-, 3-, and 4-trimethylsilylpyridine, or 2-, 3-, and 4-methylthiopyridine indicates successful metallation of pyridine with a 1:1 mixture of BuLi-ButOK in tetrahydrofuran-hexane at -100 deg C.