Bromobenzene → 6-Methyl-alpha,alpha-diphenyl-1,4-dioxaspiro[4.5]decane-6-propanol

HRID 65618ノート

反応式

HRID 65618 の反応式
CO[C:3](=[O:17])[CH2:4][CH2:5][C:6]1([CH3:16])[CH2:15][CH2:14][CH2:13][CH2:12][C:7]21[O:11][CH2:10][CH2:9][O:8]2.[C:18]1([Mg]Br)[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.[Mg].Br[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.[Cl-].[NH4+]>CCOCC.CI.C1C=CC=CC=1>[CH3:16][C:6]1([CH2:5][CH2:4][C:3]([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[OH:17])[CH2:15][CH2:14][CH2:13][CH2:12][C:7]21[O:8][CH2:9][CH2:10][O:11]2

参加物

9

反応物 5

HCID 7961Bromobenzene2 回HCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 538162376-Methyl-1,4-dioxaspiro[4.5]decane-6-propionic acid methyl esterHCID 178418255HCID 178418255、化合物

生成物 1

HCID 227572906-Methyl-alpha,alpha-diphenyl-1,4-dioxaspiro[4.5]decane-6-propanol

試薬・触媒・溶媒 3

HCID 6328Methyl iodide触媒HCID 241Benzene溶媒HCID 3283Diethyl Ether溶媒4 回

実験手順

A solution of 6-methyl-1,4-dioxaspiro[4.5]decane-6-propionic acid methyl ester (52.5 g, 0.21 mole), described in Example 7, in anhydrous ether (500 ml) and dry benzene (100 ml) is added dropwise under nitrogen to a cooled (0°-5° C.) stirred solution of phenyl magnesium bromide in ether prepared from magnesium turnings (15.9 g, 0.65 mole), bromobenzene (75 ml, 0.72 mole) and anhydrous ether (500 ml). (Note: Only about 75 ml of ether is used to start the reaction with 15 drops methyl iodide and 2-3 ml bromobenzene). The mixture is stirred overnight at room temperature. Following the careful addition of saturated ammonium chloride solution (114 ml) with cooling, the resulting yellow ether layer is decanted and the precipitated magnesium salts are rinsed thoroughly with ether. The combined ether layers are steam distilled and methanol (100 ml) and 25% aqueous sodium hydroxide (150 ml) is added to the residue. The mixture is heated at reflux for 2 hr to saponify any unreacted ester. The methanol is evaporated and the residue is extracted with ether (4×). The ether extracts are dried (MgSO4) and concentrated to give 6-methyl-α,α-diphenyl-1,4-dioxaspiro[4.5]decane-6-propanol, mp 115°-117° C. after recrystallization from chloroformhexane, νmaxCHCl3 3620, 3500, 1092 cm-1.

後処理

  1. temperaturea cooled (0°-5° C.)
  2. temperaturewith cooling
  3. customthe resulting yellow ether layer is decanted
  4. washthe precipitated magnesium salts are rinsed thoroughly with ether
  5. distillationdistilled
  6. additionmethanol (100 ml) and 25% aqueous sodium hydroxide (150 ml) is added to the residue
  7. temperatureThe mixture is heated
  8. temperatureat reflux for 2 hr
  9. customThe methanol is evaporated
  10. extractionthe residue is extracted with ether (4×)
  11. dry with materialThe ether extracts are dried (MgSO4)
  12. concentrationconcentrated

出典と根拠

ORDレコード
ord-0a3d855835054a05a2dbac6537193ba1
出典データセット
uspto-grants-1978_12
特許番号
US04128560

反応ノート

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