Propyne → beta-Damascenone, (2Z)-

HRID 1448881ノート

反応式

HRID 1448881 の反応式
[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]

参加物

8

反応物 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

生成物 1

HCID 12309006beta-Damascenone, (2Z)-

試薬・触媒・溶媒 1

HCID 14801Manganese dioxide触媒

実験手順

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 folowing 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).

出典と根拠

ORDレコード
ord-3ee629c8bdfb4ce484b92e093a37b625
出典データセット
uspto-grants-1980_02
特許番号
US04187863

反応ノート

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