Iodine → 1-Iodo-3-triphenylmethoxy-trans-1-octene

HRID 67023

反応式

HRID 67023 の反応式
[BH4-].[Na+].CC(=CC)C.B(F)(F)F.[C:12]1([C:18]([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[O:19][CH:20]([CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])[C:21]#[CH:22])[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[I:40]I>O1CCCC1.COCCOCCOC>[I:40]/[CH:22]=[CH:21]/[CH:20]([O:19][C:18]([C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1)([C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1)[C:34]1[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=1)[CH2:23][CH2:24][CH2:25][CH2:26][CH3:27]

参加物

8

反応物 5

HCID 807IodineHCID 6356Boron trifluorideHCID 105532-Methyl-2-buteneHCID 4311764Sodium borohydrideHCID 126753473-Triphenylmethoxy-1-octyne

生成物 1

HCID 201446361-Iodo-3-triphenylmethoxy-trans-1-octene

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 8150Diglyme溶媒

反応条件

温度
0 °C

実験手順

To a mixture of 0.650 g. (16.91 mole) of sodium borohydride and 3.17 g. (45.2 moles) of 2-methyl-2-butene in 40 ml. of diglyme cooled to -5° C. under an inert atmospere is added over 15 minutes 3.24 g. (22.6 moles) of boron trifluoride ethereate and the resulting mixture is stirred at 0° C. for 2 hours. To this mixture is then added over 5 minutes 8.32 g. (22.6 moles) of 3-triphenylmethoxy-1-octyne (Example 119) in 10 ml. of diglyme, the cooling bath is removed, and the mixture is stirred at ambient temperatures for 1.5 hours. The mixture is cooled to 0° C. and 6.0 g. of finely divided anhydrous trimethylamine oxide is added over 10 minutes. The cooling bath is removed and the mixture is stirred at ambient temperatures for 0.5 hour. The mixture is then poured into 200 ml. of 15% sodium hydrooxide solution, a solution of 16 g. (63 moles) of iodine in 20 ml. of tetrahydrofuran is added immediately, and the resulting mixture is stirred for 0.5 hour. The organic phase is separated and the aqueous phase is washed with ether. The combined organic phase and washings are decolorized with 5% sodium thiosulfate solution, washed with saturated brine, dried (Na2SO4), and evaporated. The residue is dry-columned chromatographed upon alumina using hexane as eluent and the title compound is isolated as an oil.

後処理

  1. additionTo a mixture of 0.650 g
  2. additionis added over 15 minutes 3.24 g
  3. additionTo this mixture is then added over 5 minutes 8.32 g
  4. customof diglyme, the cooling bath is removed
  5. additionof finely divided anhydrous trimethylamine oxide is added over 10 minutes
  6. customThe cooling bath is removed
  7. stirringthe mixture is stirred at ambient temperatures for 0.5 hour
  8. additionThe mixture is then poured into 200 ml
  9. stirringthe resulting mixture is stirred for 0.5 hour
  10. customThe organic phase is separated
  11. washthe aqueous phase is washed with ether
  12. washwashed with saturated brine
  13. dry with materialdried (Na2SO4)
  14. customevaporated
  15. customThe residue is dry-columned chromatographed upon alumina

出典と根拠

ORDレコード
ord-300a297f1360476d84b2c8d83fa09d76
出典データセット
uspto-grants-1982_08
特許番号
US04343949

関連ノート

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