Propyne → beta-Damascenone, (2Z)-

HRID 903298Notes

Reaction equation

HRID 903298 reaction equation
[CH3:1][C:2]([CH2:9][CH2:10][CH:11]=[C:12]([CH3:14])[CH3:13])=[CH:3][CH:4]([OH:8])[CH:5]=[CH:6][CH3:7].CC(=CCCC(=CC=O)C)C.C#CC.CC1C=CCC(C)(C)C=1C(O)C#CC.CC1C=CCC(C)(C)C=1C(=O)C#CC.CC(CCC=C(C)C)=CC(=O)C=CC>O=[Mn]=O>[CH3:1][C:2]1[CH:9]=[CH:10][CH2:11][C:12]([CH3:13])([CH3:14])[C:3]=1[C:4](=[O:8])/[CH:5]=[CH:6]\[CH3:7]

Participants

8

Reactant 6

HCID 6335PropyneHCID 88433,7-Dimethylocta-2,6-DienalHCID 233380792,6,6-Trimethyl-1-[1-hydroxy-2-butynyl]-1,3-cyclohexadieneHCID 541583646,10-Dimethylundeca-2,5,9-trien-4-oneHCID 545494456,10-Dimethyl-4-hydroxy-2,5,9-undecatrieneHCID 705879512,6,6-Trimethyl-1-tetrolyl-1,3-cyclohexadiene

Product 1

HCID 12309006beta-Damascenone, (2Z)-

Reagents, catalysts & solvents 1

HCID 14801Manganese dioxideCatalyst

Procedure

Safranal, prepared according to Compt. rend. 262, 1725 (1966), was reacted with propyne to give 2,6,6-trimethyl-1[-1-hydroxy-2-butynyl]-1,3-cyclohexadiene, following the procedure outlined in Example 18, paragraph (b), for the reaction of citral with propyne. The above carbinol was oxidised with MnO2 to 2,6,6-trimethyl-1-tetrolyl-1,3-cyclohexadiene, following the procedure described in Example 18, paragraph (c), for the oxidation of the dihydro analogue. The above acetylenic ketone was then partially reduced to the title compound following the method described in Example 18, paragraph (a). Cis-2,6,6-trimethyl-1-crotonoyl-1,3-cyclohexadiene gave the following NMR data (CCl4): 1.06 (6 H, s), 1.69 (3 H, s), 2.09 (2 H, d, J=2.3 cps), 2.14 (3 H, d, J=5.5 cps), 5.81 (2 H, t+s, J=2.3 cps), 6.2 (2 H, complex band) ppm (δ).

Sources & evidence

ORD record
ord-f66eca6e31c14bd4a34efc6fe40fc400
Source dataset
uspto-grants-1980_10
Patent number
US04226892

Reaction notes

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