Triphenylphosphine → 1-Methylamino-2,5,9-trimethyl-11-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4,6,8,10-undecapentaene

HRID 65465

反応式

HRID 65465 の反応式
[CH3:1][C:2](=[CH:5][CH:6]=[C:7]([CH3:24])[CH:8]=[CH:9][CH:10]=[C:11]([CH3:23])[CH:12]=[CH:13][C:14]1[C:19]([CH3:21])([CH3:20])[CH2:18][CH2:17][CH2:16][C:15]=1[CH3:22])[CH2:3]O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Br[N:45]1C(=O)CC[C:46]1=O>C1COCC1>[CH3:46][NH:45][CH2:3][C:2]([CH3:1])=[CH:5][CH:6]=[C:7]([CH3:24])[CH:8]=[CH:9][CH:10]=[C:11]([CH3:23])[CH:12]=[CH:13][C:14]1[C:19]([CH3:21])([CH3:20])[CH2:18][CH2:17][CH2:16][C:15]=1[CH3:22]

参加物

5

反応物 3

HCID 11776TriphenylphosphineHCID 67184N-bromobutanimideHCID 537496932,5,9-Trimethyl-11-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4,6,8,10-undecapentaene-1-ol

生成物 1

HCID 545742011-Methylamino-2,5,9-trimethyl-11-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4,6,8,10-undecapentaene

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

A solution of 2,5,9-trimethyl-11-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4,6,8,10-undecapentaene-1-ol (3.2 g, 10 mmol) and triphenylphosphine (2.88 g, 11 mmol) in 20 ml of THF is stirred in an ice bath and 1.78 g (10 mmol) of N-bromosuccinimide is added in small portions over a period of one hour. After addition, the cooling bath is removed and the temperature of the reaction mixture is allowed to rise slowly to room temperature. The mixture is concentrated in vacuo and then diluted with a mixture of ether/petroleum ether. After sitting in refrigerator for several hours, white crystals of triphenylphosphine oxide occur, which is collected by filtration. The filtrate is concentrated and dissolved in 10 ml of dry DMF. To this solution is added 2 g of triethylamine and 0.68 g of methylamine hydrochloride. The resulting mixture is stirred at room temperature for 18 hours and poured into 500 ml of ice-water. The crude product is extracted into ethylacetate and washed with water. After drying over magnesium sulfate, the solvent is removed in vacuo to give the crude product as an oil. This substance is purified on HPLC (2% ethyl acetate in hexane, silica gel column) to give 1-methylamino-2,5,9-trimethyl-11-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4,6,8,10-undecapentaene.

後処理

  1. additionAfter addition
  2. customthe cooling bath is removed
  3. customto rise slowly to room temperature
  4. concentrationThe mixture is concentrated in vacuo
  5. additiondiluted with a mixture of ether/petroleum ether
  6. waitAfter sitting in refrigerator for several hours
  7. filtrationwhich is collected by filtration
  8. concentrationThe filtrate is concentrated
  9. dissolutiondissolved in 10 ml of dry DMF
  10. additionTo this solution is added 2 g of triethylamine and 0.68 g of methylamine hydrochloride
  11. additionpoured into 500 ml of ice-water
  12. extractionThe crude product is extracted into ethylacetate
  13. washwashed with water
  14. dry with materialAfter drying over magnesium sulfate
  15. customthe solvent is removed in vacuo
  16. customto give the crude product as an oil
  17. customThis substance is purified on HPLC (2% ethyl acetate in hexane, silica gel column)

出典と根拠

ORDレコード
ord-abea137b329c455b9eb6287dd3e5184c
出典データセット
uspto-grants-1986_09
特許番号
US04614747

関連ノート

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