Heptane → 1-Methyl-3-piperidyl alpha-Ethynyl-alpha-phenylglycolate

HRID 358252

反応式

HRID 358252 の反応式
[CH3:1][N:2]1[CH2:7][CH2:6][CH2:5][CH:4]([OH:8])[CH2:3]1.[Na].CCCCCCC.[C:17]([C:19]([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)([OH:24])[C:20](OC)=[O:21])#[CH:18]>CO>[C:17]([C:19]([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)([OH:24])[C:20]([O:8][CH:4]1[CH2:5][CH2:6][CH2:7][N:2]([CH3:1])[CH2:3]1)=[O:21])#[CH:18]

参加物

6

反応物 4

HCID 8900HeptaneHCID 980163-Piperidinol, 1-methyl-HCID 5360545SodiumHCID 13371130Methyl alpha-ethynyl-alpha-phenylglycolate

生成物 1

HCID 133711501-Methyl-3-piperidyl alpha-Ethynyl-alpha-phenylglycolate

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

実験手順

1-Methyl-3-piperidinol (3.5 g., 0.03 mole) and a small piece of sodium (~0.05 g.) were refluxed in 150 ml. of n-heptane for about 1 hour in a flask equipped with a small distilling head. Methyl α-ethynyl-α-phenylglycolate (4.0 g., 0.02 mole) was then added intermittently over a one hour period with the temperature of the reaction mixture maintained at 90°. The reaction mixture was heated at 90°-95° for three hours during which time very little methanol was collected. The reaction mixture was subsequently refluxed for 11 hours and the azeotrope collected periodically. During this time sodium methoxide (0.075 g.) was added and 50 ml. of fresh n-heptane was added as an equal volume of distillate was collected simultaneously. These operations were carried out twice. Heating was stopped and a total of 0.3 ml. (38% of theory) of methanol was obtained. As the reaction mixture cooled, an oil settled out. The n-heptane was decanted and the residue was washed with ice water (3×10 ml.). Ether and ice were added to the oil and the mixture worked up as described in Example 12, to yield 1.9 g. (35%) of the product as a yellow oil. Crystallization was effected by dissolving the material in ether, adding 30°-60° petroleum ether to produce turbidity and refrigerating the solution for several days. The product melted at 92°-95° after recrystallization from hexane.

後処理

  1. temperaturemaintained at 90°
  2. customwas collected
  3. temperatureThe reaction mixture was subsequently refluxed for 11 hours
  4. customthe azeotrope collected periodically
  5. additionDuring this time sodium methoxide (0.075 g.) was added
  6. additionof fresh n-heptane was added as an equal volume of distillate
  7. customwas collected simultaneously
  8. temperatureHeating
  9. custom(38% of theory) of methanol was obtained
  10. temperatureAs the reaction mixture cooled
  11. customThe n-heptane was decanted
  12. washthe residue was washed with ice water (3×10 ml.)
  13. additionEther and ice were added to the oil
  14. customto yield 1.9 g
  15. customCrystallization
  16. dissolutionby dissolving the material in ether
  17. additionadding 30°-60° petroleum ether
  18. customto produce turbidity
  19. customfor several days
  20. customThe product melted at 92°-95° after recrystallization from hexane

出典と根拠

ORDレコード
ord-cb0f6994c0da4fceacfffd0808688fa6
出典データセット
uspto-grants-1984_08
特許番号
US04465834

関連ノート

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