101315-22-4

Basic information

• Product Name: 4-Penten-2-ynal, 5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-, (E)-
• CAS NO: 101315-22-4
• Molecular Formula: C14H18O
• Molecular Weight: 202.296
• Mol File: 101315-22-4.mol
• Article Data: 3

Chemical Properties

• CAS DataBase Reference: 4-Penten-2-ynal, 5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-, (E)-(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Penten-2-ynal, 5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-, (E)-(101315-22-4)
• EPA Substance Registry System: 4-Penten-2-ynal, 5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-, (E)-(101315-22-4)

Safety Data

• Hazardous Substances Data: 101315-22-4(Hazardous Substances Data)

Upstream product

• 101315-21-3 (E)-5-(2,6,6-trimethylcyclohex-1-enyl)pent-4-en-2-yn-1-ol 
• 79-77-6 (E)-β-ionone 
• 68-12-2 N,N-dimethyl-formamide 
• 73395-75-2 (E)-2-(but-1-en-3-ynyl)-1,3,3-trimethylcyclohex-1-ene 

Downstream Products

• 109051-58-3 9,10-Didehydro-19-norretinsaeurenitril 
• 111943-10-3 3-[(E)-2-(2,6,6-Trimethyl-cyclohex-1-enyl)-vinyl]-2H-azirine-2-carbaldehyde 
• 111917-85-2 (2E,4E)-3-Azido-5-(2,6,6-trimethyl-cyclohex-1-enyl)-penta-2,4-dienal 
• 101315-18-8 all-trans-9,10-Didehydro-19-norretinal 
• 101347-23-3 (2Z,4E,8E)-3-methyl-9-(2',6',6'-trimethylcyclohex-1-enyl)nona-2,4,8-trien-6-ynal 

Relevant articles and documents

9-Demethyl-9-haloretinals by Wadsworth-Emmons coupling - Easy preparation of pure (all-E), (9Z) and (11Z) isomers

5-(2′,6′,6′-Trimethyl-1′-cyclohexen-1′-yl) -4-penten-2-yn-1-al has been prepared in a one-pot process starting from β-ionone in almost quantitative yield. Using 1,4-nucleophilic addition reactions, the corresponding 9-Cl, 9-Br, 9-1 β-ionylideneacetaldehyde systems could be obtained in one step in quantitative yield as a mixture of (9Z) and (all-E) isomers. Even the corresponding fluoro derivative could be obtained in good yield as (9Z) and (all-E) isomers. In the case of a double bond having a halogen substituent, the IUPAC rules have the (E) nomenclature for a cis double bond and the (Z) for a trans double bond. Simple column chromatography gave the pure (9Z) and (all-E) form. Optimizing the Wadsworth-Emmons coupling gave the corresponding (all-E)- and (9Z)-retinonitriles in quantitative yield. Subsequent DIBAL-H reduction gave the corresponding retinals. For the preparation of the (UZ) isomers essential to vision, we found that Wadsworth-Emmons reactions with the diphenyl phosphonate group gave retinonitriles in quantitative yield, where the newly formed double bond is predominantly the (11Z) form (> 60%), together with the (9Z) isomer as minor component. The nitriles could be isolated in pure (9Z.11Z) and (9Z) forms by simple column chromatography. In the case of the (9Z,11Z)-9-demethyl-9-halo systems, a complication arose due to the unprecedented acid lability of these (9Z,11Z) aldehydes. By adjusting the DIBAL-H reduction workup procedure, these aldehydes are now available in pure form. We used this strategy to rationally synthesize (11Z)-retinal starting from β-cyclocitral as a first test for the generality of our new approach. β-Ionylideneacetaldehyde could be prepared in the (all-E) form in almost quantitative yield. Extending the conjugated chain of this molecule gave an almost quantitative yield of a mixture containing 80% (11Z)-retinal and 20% (all-E) as the minor component. Simple column chromatography gave pure (11Z)-retinal in 75% overall yield. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Synthesis of the acetylenic retinoids 9,10-didehydro-19-norretinal and 9,10,11,12-tetradehydro-19-norretinal

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