54781-19-0

Basic information

• Product Name: 2-(TRIMETHYLSILOXY)-1,3-CYCLOHEXADIENE
• Synonyms: 2-(TRIMETHYLSILYLOXY)-1,3-CYCLOHEXADIENE;2-(TRIMETHYLSILOXY)-1,3-CYCLOHEXADIENE;1,5-Cyclohexadienyl(trimethylsilyl) ether;2-(Trimethylsilyloxy)cyclohexa-1,3-diene;1-(Trimethylsilyloxy)-3,4-dihydrobenzene;(cyclohexa-1,5-dien-1-yloxy)triMethylsilane;2-(Trimethylsiloxy)-1,3-cyclohexadiene 95%
• CAS NO: 54781-19-0
• Molecular Formula: C₉H₁₆OSi
• Molecular Weight: 168.31
• Product Categories: Enol Ethers;Organic Building Blocks;Oxygen Compounds
• Mol File: 54781-19-0.mol

Chemical Properties

• Melting Point: 242-246 °C
• Boiling Point: 65 °C7 mm Hg(lit.)
• Flash Point: 117 °F
• Appearance: /
• Density: 0.899 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.862mmHg at 25°C
• Refractive Index: n20/D 1.462(lit.)
• Storage Temp.: 2-8°C
• BRN: 2079140
• CAS DataBase Reference: 2-(TRIMETHYLSILOXY)-1,3-CYCLOHEXADIENE(CAS DataBase Reference)
• NIST Chemistry Reference: 2-(TRIMETHYLSILOXY)-1,3-CYCLOHEXADIENE(54781-19-0)
• EPA Substance Registry System: 2-(TRIMETHYLSILOXY)-1,3-CYCLOHEXADIENE(54781-19-0)

Safety Data

• Statements: 10
• Safety Statements: 16
• RIDADR: UN 1993 3/PG 3
• WGK Germany: 3
• F: 10-21
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 54781-19-0(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Synthesis:
2-(TRIMETHYLSILOXY)-1,3-CYCLOHEXADIENE is used as a diene in the synthesis of isoquinuclidinone 2-aza[2.2.2]octa-3,5-dione, a compound of interest in pharmaceutical chemistry. Its reactivity allows it to participate in reactions with other compounds, such as p-toluenesulfonyl cyanide, to form the desired product.
Used in Chemical Research:
In the field of chemical research, 2-(TRIMETHYLSILOXY)-1,3-CYCLOHEXADIENE serves as a valuable intermediate for the development of new synthetic pathways and the creation of novel compounds. Its unique structure and reactivity make it a useful building block for researchers exploring new chemical space.
Used in Material Science:
2-(TRIMETHYLSILOXY)-1,3-CYCLOHEXADIENE may also find applications in material science, where its properties can be leveraged to develop new materials with specific characteristics. Its ability to undergo various chemical reactions can contribute to the creation of materials with tailored properties for specialized applications.

InChI:InChI=1/C9H16OSi/c1-11(2,3)10-9-7-5-4-6-8-9/h5,7-8H,4,6H2,1-3H3

Upstream product

• 930-68-7 cyclohexenone 
• 10416-59-8 N,O-bis-(trimethylsilyl)-acetamide 
• 75-77-4 chloro-trimethyl-silane 
• 724694-22-8 C₆H₈O 
• 108-18-9 diisopropylamine 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 

Downstream Products

• 4884-82-6 2-benzoyloxy-cyclohex-2-en-1-one 
• 1075747-47-5 tert-butyl 2-((1R,2R,4R)-2-hydroxy-5-phenylbicyclo[2.2.2]oct-5-en-2-yl)acetate 
• 1075747-46-4 (1S,2S,4S)-(2-hydroxy-5-phenyl-bicyclo[2.2.2]oct-5-en-2-yl)-acetic acid tert.-butyl ester 

Relevant articles and documents

DARSTELLUNG UND REAKTIONEN VON TRICARBONYL-(TRIMETHYLSILOXY-1,3-CYCLOHEXADIEN)-EISEN-KOMPLEXEN

Tricarbonyl(trimethylsiloxy-1,3-cyclohexadien)iron complexes, 5 and 6, react with triphenylmethyl tetrafluoroborate by elimination of both, hydride and the trimethylsilyl group, to give 9 and 10.The tricarbonyl(1,3-cyclohexadienyl)iron salt, 11, resulting

Three-Component Coupling of Acyl Fluorides, Silyl Enol Ethers, and Alkynes by P(III)/P(V) Catalysis

We report herein on the phosphine-catalyzed hydrovinylation reaction by three-component coupling of acyl fluorides, silyl enol ethers, and alkynoates. The key to the success of the reaction is the formal transmetalation between pentacoordinate P(V) species (i.e., fluorophosphorane) and a silyl enol ether, which allows for C-C bond formation between the polarity-mismatched sites. The bond formation that cannot be attained even by transition metal catalysis is accomplished by a P(III)/P(V) manifold.

A Solvent-Free Reaction for Silyl Enol Ethers Synthesis

Silyl enol ethers are extremely useful nucleophilic intermediates for chemical transformations because they are synthetically versatile substrates for a wide range of C-C bond-forming reactions. Here, we present a new, mild, and solvent-free procedure for the synthesis of silyl enol ethers that employs a catalytic amount of solid-supported base and an equimolar amount of N, O -(bistrimethylsilyl)acetamide as a silylating agent.

Synthesis and performance of acyloxy-diene-fe(CO)3 complexes with variable chain lengths as enzyme-triggered carbon monoxide-releasing molecules

Novel η4-acyloxy-cyclohexadiene-Fe(CO)3 complexes (with variable length of the acyloxy chain) were synthesized as potential enzyme-triggered carbon monoxide (CO)-releasing molecules (ET-CORMs). The molecular structure of two complexes was additionally confirmed by X-ray crystallography. The enzyme-triggered CO-releasing activity of the compounds was assessed under physiological conditions (37 C, 0.1 M phosphate buffer, pH = 7.4) by headspace gas chromatography (GC) and additionally by means of a myoglobin assay (UV). The relative rate of CO release and the amount of liberated CO were found to depend on the length of the acyloxy chain and its position at the diene unit (outer or inner position). Some of the new ET-CORMs exhibited very good biological activity as assessed in different cellular assays (cytotoxicity, protective effect against hypothermia-associated cell damage, and inhibition of TNF-α-mediated VCAM-1 expression).

Iron dienylphosphate tricarbonyl complexes as water-soluble enzyme-triggered CO-releasing molecules (ET-CORMs)

A series of racemic phosphoryloxy-substituted (η4- cyclohexadiene)Fe(CO)3 complexes was synthesized by exploiting the O-phosphorylation of (dienol)Fe(CO)3 intermediates generated in situ from the corresponding triisopropylsiloxy-protected complexes. The phosphorylated products were fully characterized by spectroscopic methods, including single-crystal X-ray diffraction in four cases. Monodeprotection of two dimethyl phosphate derivatives with trimethylamine led to the tetramethylammonium salts of the (cyclohexadienyl methyl phosphate)Fe(CO) 3 complexes. These compounds are the first water-soluble enzyme-trigged CO-releasing molecules (ET-CORMs). The phosphatase-induced CO release was monitored by means of GC. The biological activity was assessed in different cellular assays. The compounds were shown to be only slightly toxic, and a moderate anti-inflammatory potential was determined in an assay based on the inhibition of inducible NO synthase (iNOS)-induced NO production.

Acyloxybutadiene tricarbonyl iron complexes as enzyme-triggered CO-releasing molecules (ET-CORMs): A structure-activity relationship study

A series of η4-acyloxycyclohexadiene-Fe(CO)3 complexes was prepared and fully characterized by spectroscopic methods including single crystal X-ray diffraction. For this purpose a new synthetic access to differently acylated 1,3- and 1,5-dienol-Fe(CO)3 complexes was developed. The enzymatically triggered CO release from these compounds was monitored (detection of CO through GC and/or by means of a myoglobin assay) and the anti-inflammatory effect of the compounds was assessed by a cellular assay based on the inhibition of NO-production by inducible NO synthase (iNOS). It was demonstrated that the properties (rate of esterase-triggered CO release, iNOS inhibition, cytotoxicity) of the complexes strongly depend on the substitution pattern of the π-ligand and the nature of the acyloxy substituent.

Iron promoted conjugate addition: Implication of the six-centered mechanism based on the isolation of the iron-enolate intermediate

Treatment of (η1-mesityl)2Fe(κ2- TMEDA) (1′) with an α,β-unsaturated carbonyl compound results in 1,4-addition of the mesityl group to give an iron enolate 3 quantitatively. The Z-configuration of the enolate suggested the

Total synthesis of (±)-garsubellin A

The first total synthesis of garsubellin A, a neurotrophic compound with potent choline acetyltransferase-inducing activity, is described. Keys for success were (1) stereoselective intermolecular aldol reaction at the C-4 position with acetaldehyde, (2) stereoelective Claisen rearrangement to introduce an allyl group to the most sterically crowded position at C-6, (3) ring-closing metathesis to construct the B-ring, and (4) Wacker-type oxidative C-ring formation. This synthetic route can be extended to an asymmetric synthesis of garsubellin A using the Koga catalytic enantioselective alkylation, which produced enantioenriched α-prenyl cyclohexenone with excellent enantioselectivity (95% ee). Copyright

Synthetic Applications in Radical/Radical Cationic Cascade Reactions

Oxidative photoinduced electron transfer (PET) reactions have been performed with various cyclic cyclopropyl(vinyl) silyl ethers bearing an olefinic or acetylenic side chain. The reactions result in bi- to tetracyclic ring systems via a fragmentation-radical/radical cationic addition reaction pathway with well defined ring juncture. The mode of cyclisation (endo/exo) can be partially controlled by addition of nucleophiles due to the suppression of radical cationic reaction pathways. Quantum chemical calculation of the cyclisation transition states underline the experimentally found selectivities. Additional mechanistic studies concerning the saturation step reveal that the final radical is saturated mostly by the solvent and traces of water in the solvent.

Structural investigations into the retro-Diels-alder reaction. Experimental and theoretical studies

The manifestations of the retro-Diels Alder reaction in the ground-state structures of a range of cyclopentadiene and cyclohexadiene cycloadducts 9-15 have been investigated by a combination of techniques. These include low-temperature X-ray crystallography, density functional calculations (B3LYP/6-31G(d,p)) on both the ground states and transition states, and the measurement of 13C-13C coupling constants. We have found that the carbon - carbon bonds (labeled bonds a and b), which break in the rDA, are longer in the cycloadducts 9-15 than in their corresponding saturated analogues 9s-15s, which cannot undergo the rDA reaction. The degree of carbon - carbon bond lengthening appears to be related to the reactivity of the cycloadduct, thus the more reactive benzoquinone cycloadducts 5b and 13 have longer carbon - carbon bonds. Those cycloadducts 14 and 15 which are predicted to undergo asynchronous reactions show differing degrees of carbon - carbon bond lengthening, reflecting the differing degrees of bond breaking at the calculated transition states for the rDA.