beta-HOMOCYCLOCITRAL → 2-[4-(2,6,6-Trimethyl-1-cyclohexen-1-yl)-2-butenyl]-1, 3-dioxane

HRID 128785

반응식

HRID 128785 반응식
[CH3:1][C:2]1[CH2:7][CH2:6][CH2:5][C:4]([CH3:9])([CH3:8])[C:3]=1[CH2:10][CH:11]=O.[Br-].[O:14]1[CH2:19][CH2:18][CH2:17][O:16][CH:15]1[CH2:20][CH2:21][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[PH4+].C([Li])CCC>C1COCC1.CCCCCC.O.CN(P(N(C)C)(N(C)C)=O)C>[CH3:1][C:2]1[CH2:7][CH2:6][CH2:5][C:4]([CH3:8])([CH3:9])[C:3]=1[CH2:10][CH:11]=[CH:21][CH2:20][CH:15]1[O:16][CH2:17][CH2:18][CH2:19][O:14]1

참가 물질

9

반응물 4

HCID 61124beta-HOMOCYCLOCITRALHCID 27241682-(1,3-Dioxan-2-yl)ethyltriphenylphosphonium bromideHCID 5460504PhosphoniumHCID 178418339Butyllithium

생성물 1

HCID 540248782-[4-(2,6,6-Trimethyl-1-cyclohexen-1-yl)-2-butenyl]-1, 3-dioxane

시약·촉매·용매 4

HCID 962Water용매HCID 8028Tetrahydrofuran용매HCID 8058Hexane용매HCID 12679Hexamethylphosphoramide용매

실험 절차

Commercially available 2,6,6-trimethyl-1-cyclohexene-1-acetaldehyde is chain-extended by Wittig reaction with commercially available 2-(1,3-dioxan-2-yl)ethyl triphenylphosphonium bromide as follows: To a stirred suspension of the phosphonium salt (20.4 g) in THF (30 ml) is added HMPA (30 ml). The mixture is cooled to -70° under nitrogen and n-butyllithium (17.5 ml of 2.5M solution in hexane) is added dropwise. After 30 minutes the aldehyde (6.65 g in 10 ml THF) is added and the mixture is allowed to warm slowly to room temperature. Water and hexane are added, the organic phase is evaporated and the residue chromatographed with 40% dichloromethane in hexane to provide crude (mostly cis) 2-[4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenyl]-1, 3-dioxane as a colorless oil (5.26 g). This material is hydrogenated in ethanol over a 5% Pd/BaSO4 catalyst for 18 hr under 40 psi hydrogen. Filtration and evaporation provide crude 2-[4 -(2,6,6-trimethyl-1-cyclohexen-1-yl)butyl]-1,3-dioxane as a colorless oil. This is hydrolyzed with acid in refluxing 1:1 dioxane-water to provide 5-(2,6,6-trimethyl-1-cyclohexen-1-yl)pentanal as a colorless oil.

후처리

  1. temperatureThe mixture is cooled to -70° under nitrogen
  2. customthe organic phase is evaporated
  3. customthe residue chromatographed with 40% dichloromethane in hexane

출처 및 근거

ORD 기록
ord-11853b12d3794300bab0989917401206
출처 데이터셋
uspto-grants-1995_11
특허 번호
US05464865

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