(+-)-3-Quinuclidinol → Mandelic acid, alpha-(phenylethynyl)-, 3-quinuclidinyl ester

HRID 358246

反応式

HRID 358246 の反応式
[N:1]12[CH2:8][CH2:7][CH:4]([CH2:5][CH2:6]1)[CH:3]([OH:9])[CH2:2]2.[Na].[C:11]1([C:17]([C:24]#[C:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)([OH:23])[C:18](OCC)=[O:19])[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1>C1(C)C=CC=CC=1>[C:11]1([C:17]([C:24]#[C:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)([OH:23])[C:18]([O:9][CH:3]2[CH:4]3[CH2:7][CH2:8][N:1]([CH2:6][CH2:5]3)[CH2:2]2)=[O:19])[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1

参加物

5

反応物 3

HCID 15381(+-)-3-QuinuclidinolHCID 5360545SodiumHCID 12328607Ethyl alpha-Phenyl-alpha-phenylethynylglycolate

生成物 1

HCID 56512Mandelic acid, alpha-(phenylethynyl)-, 3-quinuclidinyl ester

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒2 回

実験手順

A suspension of 3-quinuclidinol (5.1 g. 0.04 mole) and Na (~0.05 g.) in 20 ml. of toluene was heated to reflux in a flask equipped with a reflux head and stirrer. After the sodium reacted completely (about 15 minutes of refluxing), ethyl α-phenyl-α-phenylethynyl-glycolate (7.0 g., 0.025 mole) dissolved in 20 ml. of toluene was added very slowly over a two hour period. Towards the end of the addition a temperature drop of 6° was noted in the head and 10 ml. of the toluene-ethanol azeotrope slowly was distilled over. The reaction mixture was refluxed for an additional hour, and an additional 10 ml. of distillate was subsequently collected over a thirty minute period. The reaction mixture was poured on ice and acidified with 6N HCl. The toluene layer was separated and washed with several portions of 6N HCl. The combined water layers were neutralized with 10% NaOH, basified with potassium carbonate and extracted with chloroform several times. The chloroform layer was dried and subsequently stripped of volatile material in vacuo to leave a tacky solid. The material was washed with hot ether to give 5.2 g. (58%) of an off-white solid, m.p. 150°-90°. Recrystallization from benzene and then isopropanol yielded analytically pure material, m.p. 205°-8°.

後処理

  1. temperatureto reflux in a flask
  2. customequipped with a reflux head and stirrer
  3. dissolutiondissolved in 20 ml
  4. additionTowards the end of the addition a temperature drop of 6°
  5. distillationof the toluene-ethanol azeotrope slowly was distilled over
  6. temperatureThe reaction mixture was refluxed for an additional hour
  7. distillationof distillate was subsequently collected over a thirty minute period
  8. additionThe reaction mixture was poured on ice
  9. customThe toluene layer was separated
  10. washwashed with several portions of 6N HCl
  11. extractionextracted with chloroform several times
  12. dry with materialThe chloroform layer was dried
  13. customto leave a tacky solid
  14. washThe material was washed with hot ether
  15. customto give 5.2 g
  16. customRecrystallization from benzene
  17. customisopropanol yielded analytically pure material, m.p. 205°-8°

出典と根拠

ORDレコード
ord-ba0a198b66944545991940ef179db4bd
出典データセット
uspto-grants-1984_08
特許番号
US04465834

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