68269-87-4

Basic information

• Product Name: Modhephene
• Synonyms: Modhephene;(3aR,4R,6aS)-5,6-Dihydro-1,1,3,4-tetramethyl-1H,4H-3a,6a-propanopentalene;(3aS,6R,6aR)-5,6-Dihydro-1,3,3,6-tetramethyl-3H,4H-3a,6a-propanopentalene;2-Modhephene
• CAS NO: 68269-87-4
• Molecular Formula: C15H24
• Molecular Weight: 204.35106
• Mol File: 68269-87-4.mol

Chemical Properties

• Boiling Point: 267.5°C at 760 mmHg
• Flash Point: 113.8°C
• Appearance: /
• Density: 0.95g/cm³
• Vapor Pressure: 0.0134mmHg at 25°C
• Refractive Index: 1.517
• CAS DataBase Reference: Modhephene(CAS DataBase Reference)
• NIST Chemistry Reference: Modhephene(68269-87-4)
• EPA Substance Registry System: Modhephene(68269-87-4)

Safety Data

• Hazardous Substances Data: 68269-87-4(Hazardous Substances Data)

Usage

InChI:InChI=1/C15H24/c1-11-6-9-14-7-5-8-15(11,14)12(2)10-13(14,3)4/h10-11H,5-9H2,1-4H3/t11-,14?,15?/m1/s1

Upstream product

• 121402-81-1 C₁₆H₂₆O₄ 
• 121469-31-6 (3aR,6aR)-3,3-Dimethyl-3a-(4-trimethylsilanyl-but-3-ynyl)-hexahydro-pentalen-1-one 
• 121402-82-2 C₁₇H₂₈O₄ 
• 72233-31-9 3,3-dimethyl-2,3,5,6-tetrahydro-1H,4H-pentalen-1-one 
• 121402-82-2 (3aSR,6aSR)-3,3-dimethyl-3,4,5,6-tetrahydro-3a,6a-methanopentalen-1(2H)-one 1,4-di-O-methyl-D-threitol ketal 
• 121402-86-6 C₁₉H₃₂O₂Si 
• 121469-26-9 (1R,2S,5S)-8-methylene-2,6,6-trimethyltricyclo<3.3.3.0^1,5>undecan-3-one 
• 77346-98-6 (1R,2S,3R,5S)-2,3-epoxy-8-methylene-2,6,6-trimethyltricyclo<3.3.3.0^1,5>undecane 
• 77346-96-4 (1S,5S)-4,4,8-trimethyltricyclo<3.3.3.0^1,5>undec-7-en-2-one 
• 121469-22-5 (3aR,6aS)-3a-(3-butyn-1-1)-3,3-dimethyl-3,3a,4,5,6,6a-hexahydropentalen-1(2H)-one 
• 121402-84-4 (3aR,6aS)-3,3-dimethyl-3a-iodomethyl-3,3a,4,5,6,6a-hexahydropentalene-1(2H)-one 
• 77346-97-5 (1S,5S)-2-methylene-4,4,8-trimethyltricyclo<3.3.3.0^1,5>undec-7-ene 
• 121402-85-5 (3aR,6aS)-3,3-dimethyl-3a-iodomethyl-3,3a,4,5,6,6a-hexahydropentalen-1(2H)-one ethylene ketal 
• 121402-83-3 (3aS,6aS)-3,3-dimethyl-3,4,5,6-tetrahydro-3a,6a-methanopentalene-1(2H)-one 

Downstream Products

• 65372-78-3 isocomene 

Relevant articles and documents

Molecular rearrangements of (-)-modhephene and (-)-isocomene to a (-)-triquinane

The preparation and further rearrangement of (-)-modhephene (1) to a (-)-triquinane 5 has been assessed through acid catalysis. The rearrangement involved protonation, 1,2 σ-bond and methyl shifts, and deprotonation. Monitored experiments by 1H NMR spectroscopy suggested the intermediate (-)-isocomene (3), which was further evidenced when a sample of natural (-)-3 undergoes acid-catalyzed conversion to the (-)-triquinane 5. In addition, deuterated (-)-modhephene (1-d) labeled stereospecifically at the 14β geminal methyl group at C4 was synthesized, through the corresponding chiral deuterated primary alcohol, in 5 steps, starting from natural (-)-14-hydroxymodhephene (8), and rearranged under acid catalysis to elucidate the stereochemical factors that control the methyl shift at this position. The final deuterium-labeled (-)-triquinane, 5-d, obtained from [14- 2H1]-1-d was established to have deuterium in the methyl group at C5 by 13C NMR spectroscopy. This stereoselective methyl migration is in accordance with the molecular orbital demand formulated by the quantum chemical calculations performed in the present study.

HOMOCHIRAL KETALS IN ORGANIC SYNTHESIS. ENANTIOSELECTIVE PREPARATION OF (+)-MODHEPENE

An efficien, enantioselective synthesis of the title compound 1 via diastereoselective cyclopropanation is described.