54125-02-9

Basic information

• Product Name: 1-METHOXY-3-TRIMETHYLSILOXY-1,3-BUTADIENE
• Synonyms: TRANS-1-METHOXY-3-TRIMETHYLSILOXY-1,3-BUTADIENE;TRANS-1-METHOXY-3-(TRIMETHYLSILYLOXY)-1,3-BUTADIENE;DANISHEFSKY'S DIENE;1-METHOXY-3-TRIMETHYLSILOXY-1,3-BUTADIENE;1-METHOXY-3-(TRIMETHYLSILOXY)BUTADIENE;1-METHOXY-3-TRIMETHYLSILYLOXY-1,3-BUTADIENE;TRANS-1-METHOXY-3-TRIMETHYLSILOXY- &;1-Methoxy-3-(trimethylsiloxy)butadiene(Danishefsky`sDiene)
• CAS NO: 54125-02-9
• Molecular Formula: C₈H₁₆O₂Si
• Molecular Weight: 172.3
• EINECS: -0
• Mol File: 54125-02-9.mol
• Article Data: 14

Chemical Properties

• Boiling Point: 68-69 °C14 mm Hg(lit.)
• Flash Point: 113 °F
• Appearance: /
• Density: 0.885 g/mL at 25 °C(lit.)
• Refractive Index: n20/D 1.454(lit.)
• Storage Temp.: 2-8°C
• Water Solubility: Miscible with most organic solvents. Immiscible with water.
• Sensitive: Moisture Sensitive
• Merck: 14,6001
• BRN: 1616761
• CAS DataBase Reference: 1-METHOXY-3-TRIMETHYLSILOXY-1,3-BUTADIENE(CAS DataBase Reference)
• NIST Chemistry Reference: 1-METHOXY-3-TRIMETHYLSILOXY-1,3-BUTADIENE(54125-02-9)
• EPA Substance Registry System: 1-METHOXY-3-TRIMETHYLSILOXY-1,3-BUTADIENE(54125-02-9)

Safety Data

• Statements: 10
• Safety Statements: 23-24/25
• RIDADR: UN 1993 3/PG 3
• WGK Germany: 3
• F: 10-21
• TSCA: No
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 54125-02-9(Hazardous Substances Data)

Usage

Uses

1-Methoxy-3-trimethylsiloxy-1,3-butadiene is employed as a reagent in Mannich-Michael reaction for the synthesis of piperidinones and enaminones. As Diels-Alder diene, it is used in the synthesis of pyridones and pyranones, sulfone analogues of griseofulvin (sulfogriseofulvins) and 4H-1-aminopyrroles and 4, 5H-pyrazoles.

General Description

trans-1-methoxy-3-trimethylsiloxy-1,3-butadiene is a funtionalized Diels-Alder diene. Mukaiyama-Michael-type addition/heterocyclization of trans-1-methoxy-3-trimethylsiloxy-1,3-butadiene (Danishefsky′s diene) with 1,2-diaza-1,3-butadiene has been investigated. Asymmetric hetero-Diels-Alder cyclization of Danishefsky′s diene with benzaldehyde catalyzed by mesoporous inorganic/metalorganic hybrid materials has been reported.

Purification Methods

It may contain up to 1% of the precursor 4-methoxybut-4-ene-2-one. It is easily purified by distilling through a Vigreux column (p 11) in a vacuum and taking the middle fraction. [Danishefsky & Kitihara J Am Chem Soc 96 7807 1974, Danishefsky Acc Chem Res 14 400 1981.]

Upstream product

• 4652-27-1 4-methoxy-3-buten-2-one 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 51731-17-0 trans-4-methoxy-3-buten-2-one 
• 75-77-4 chloro-trimethyl-silane 

Downstream Products

• 91879-80-0 (1E,6E)-5-hydroxy-1-methoxy-7-phenylhepta-1,6-dien-3-one 
• 91879-81-1 (1E,6E)-1-Methoxy-7-phenyl-5-trimethylsilanyloxy-hepta-1,6-dien-3-one 
• 83095-28-7 (E)-4-Methoxy-1-[6-((E)-styryl)-4-trimethylsilanyloxy-5,6-dihydro-2H-pyran-2-yl]-but-3-en-2-one 
• 85613-04-3 2-(E-styryl)-2,3-dihydro-4H-pyran-4-one 
• 190835-53-1 (+)-(S)-2-(trans-β-styryl)-2,3-dihydro-pyran-4-one 
• 139627-54-6 (R)-2-(E)-styryl-2,3-dihydro-4H-pyran-4-one 
• 85612-99-3 [(2R,6S)-6-Methoxy-2-((E)-styryl)-3,6-dihydro-2H-pyran-4-yloxy]-trimethyl-silane 
• 51731-17-0 trans-4-methoxy-3-buten-2-one 
• 83043-44-1 2-<(Trimethylsilyl)oxy>thiophene 
• 71094-25-2 C₁₉H₁₈N₄O₆ 
• 54125-07-4 4-Acetylcyclohex-3-en-2-on 
• 62680-12-0 trans-1-Methoxy-4-phenylsebnobut-1-en-3-on 
• 54125-08-5 4-methyl-4-formylcyclohex-2-enone 
• 2581-34-2 3-methyl-4-nitrophenol 

Relevant articles and documents

Unexpected regioselectivity in the synthesis of pyranonaphthoquinone via the diels-alder reaction

The unusual regioselectivity In the Diels-Alder reactions of pyranoquinone 1 with (4,4-dlmethoxybuta-1,3-dlen-2-yloxy)trimethylsilane 2 are explored by both computations and experiments. The regioselectivity Is controlled by the electrostatic interaction of the lactone ring-oxygen and the vicinal quinone oxygen on the transition structure, which can be tuned by the terminal methyl group of the butadienes.

Enantioselective Formal [4+1] Cycloaddition of Diazoarylacetates and the Danishefsky's Diene: Stereoselective Synthesis of (-)-1,13-Herbertenediol

Rodium chiral diene complex-catalyzed enantioselective cycloaddition of aryl α-diazoarylacetates and electron-enriched Danishefsky-type dienes afforded highly functionalized and optically enriched cyclopentenones in excellent yields (up to 97% yield) and

Synthesis of a functionalized 7,6-bicyclic spiroimine ring fragment of the spirolides

The asymmetric synthesis of a functionalized 7,6-spiroimine related to the spirolides is described. Intermolecular Diels-Alder cycloaddition of a chiral trisubstituted dienophile and Danishefsky's diene enabled simultaneous installation of the C7 and C29 stereocenters. Further transformations and late-stage aza-Wittig cyclization afforded the spiroimine in good yield. During this study, an unprecedented 14-membered dialdimine was also obtained.