[(4-methoxybuta-1,3-dien-2-yl)oxy]trimethylsilane

• ChemBase ID: 126864
• Molecular Formular: C8H16O2Si
• Molecular Mass: 172.29694
• Monoisotopic Mass: 172.09195628
• SMILES: O(/C=C/C(=C)O[Si](C)(C)C)C
• Canonical SMILES: CO/C=C/C(=C)O[Si](C)(C)C
• InChI: InChI=1S/C8H16O2Si/c1-8(6-7-9-2)10-11(3,4)5/h6-7H,1H2,2-5H3
• InChIKey: SHALBPKEGDBVKK-UHFFFAOYSA-N

NAMES AND DATABASE IDS

Names

• IUPAC name: [(4-methoxybuta-1,3-dien-2-yl)oxy]trimethylsilane; {[(3E)-4-methoxybuta-1,3-dien-2-yl]oxy}trimethylsilane
• IUPAC Traditional name: danishefsky's diene
• Synonyms: Kitahara diene; trans-1-Methoxy-3-trimethylsilyloxy-1,3-butadiene; (E)-1-Methoxy-3-trimethylsilyloxy-1,3-butadiene; Danishefsky's diene; Danishefsky’s diene; trans-1-Methoxy-3-trimethylsiloxy-1,3-butadiene; Danishefsky's diene; 1-Methoxy-3-trimethylsiloxy-1,3-butadiene; Danishefsky 二烯; 反-1-甲氧基-3-(三甲基硅氧基)-1,3-丁二烯; 1-甲氧基-3-三甲基硅氧基-1,3-丁二烯

Database IDs

• CAS Number: 54125-02-9
• EC Number: 000-000-0
• MDL Number: MFCD00008498
• Beilstein Number: 1616761
• Merck Index: 146001
• PubChem SID: 24852745; 162221191; 24883977
• PubChem CID: 5366448
• Chemspider ID: 4518295
• Wikipedia Title: Danishefsky's_diene

CALCULATED PROPERTIES

• H Acceptors: 2
• H Donor: 0
• LogD (pH = 5.5): 1.6023
• LogD (pH = 7.4): 1.6023
• Log P: 1.6023
• Molar Refractivity: 45.0415 cm^3
• Polarizability: 19.297256 Å^3
• Polar Surface Area: 18.46 Å^2
• Rotatable Bonds: 4
• Lipinski's Rule of Five: true

PROPERTIES

Physical Property

• Boiling Point: 68 - 69°C (at 0.0189 kPa); 68-69 °C/14 mmHg(lit.); 68-69°C/14mm
• Flash Point: 138.2 °F; 45°C(113°F); 59 °C
• Density: 0.885 g/mL at 25 °C(lit.); 0.89 g cm^–3 (20 °C); 0.890
• Refractive Index: 1.4550; 1.4555; n20/D 1.454(lit.); n20/D 1.456

Safety Information

• Storage Warning: Moisture Sensitive
• UN Number: 1993; UN1993
• German water hazard class: 3
• Hazard Class: 3
• Packing Group: 3; III
• Risk Statements: -; 10
• Safety Statements: S23, S24/25
• TSCA Listed: 否
• GHS Pictograms: GHS02
• GHS Signal Word: Warning
• GHS Hazard statements: H226
• GHS Precautionary statements: P210-P241-P280-P303+P361+P353-P403+P235-P501A
• Personal Protective Equipment: Eyeshields, full-face respirator (US), Gloves, multi-purpose combination respirator cartridge (US), type ABEK (EN14387) respirator filter; Eyeshields, Gloves, half-mask respirator (US), multi-purpose combination respirator cartridge (US)
• RID/ADR: UN 1993 3/PG 3
• Storage Temperature: 2-8°C

Product Information

• Purity: ≥95.0% (GC); 94%; 95%; 98+%
• Grade: purum
• Impurities: 2-5% 4-methoxy-3-buten-2-one
• Linear Formula: (CH3)3SiOC(=CH2)CH=CHOCH3

DETAILS

Sigma Aldrich - 212830

Application
Funtionalized Diels-Alder diene1,2
Packaging
1, 5 g in ampule

Sigma Aldrich - 65368

Other Notes
Versatile electron rich diene for Diels-Alder reactions1,2,3,4

REFERENCES

• The diene also undergoes cycloaddition reactions with heterodienophiles. Thus addition to carbonyl groups gives 2,3-dihydro--pyrones: J. Am. Chem. Soc., 104, 358 (1982); Heterocycles, 32, 273 (1991). See also Tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium(III), 33541. For asymmetric Diels-Alder reaction with aldehydes, mediated by a chiral Lewis acid derived from BINOL ((R)-(+)-1,1'-Bi(2-naphthol), L08305) and Ti(O-i-Pr)₄, see: J. Org. Chem., 60, 5998 (1995):
  
• Reaction with imines in the presence of ZnCl₂ leads to 4-oxotetrahydropyridines: Tetrahedron Lett., 23, 3739 (1982). For an example in synthesis of the manzamine marine alkaloids, see: J. Org. Chem., 57, 5741 (1992); J. Am. Chem. Soc., 117, 2363 (1995). For enantioselective asymmetric Diels-Alder reaction with an imine catalyzed by a BINOL boron Lewis acid, see: Tetrahedron, 49, 1749 (1993). For aza Diels-Alder reactions with imines in water under neutral conditions, see: Chem. Commun., 574 (2003).
• For cycloaddition to Fullerene powder, 39722, see: J. Org. Chem., 60, 6353 (1995).
• For cycloaddition to phenyl vinyl sulfone, see: J. Org. Chem., 48, 4986 (1983). Details have been given for the addition to a cyclic vinyl sulfone: Org. Synth. Coll., 8, 38 (1993).
• Oxygen-functionalized diene, useful for the regiospecific introduction of cyclohexanone or cyclohexenone groupings by cycloaddition with dienophiles: J. Am. Chem. Soc., 96, 7807 (1974); 100, 6536, 7098 (1978). Review: Acc. Chem. Res., 14, 400 (1981); review of cycloaddition reactions of silyloxydienes: Synthesis, 85 (1983); example and discussion: Org. Synth. Coll., 7, 312 (1990):
  
• High purity grade.
• An improved procedure for the conversion of the initial adducts to enones involves treatment with TMS-OTf: J. Org. Chem., 55, 3693 (1990).