Citronellal → Triphenylphosphine Oxide

HRID 280067

反応式

HRID 280067 の反応式
[Na].[Cl-].C(C1C=CC(C[P+:11]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=CC=1)(C)C.[PH5].CC(=CCCC(CC=[O:43])C)C>C(O)C>[C:24]1([P:11](=[O:43])([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1

参加物

6

反応物 4

HCID 7794CitronellalHCID 5360545SodiumHCID 23321400Triphenyl{[4-(propan-2-yl)phenyl]methyl}phosphanium chlorideHCID 178527699HCID 178527699、化合物

生成物 1

HCID 13097Triphenylphosphine Oxide

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

実験手順

To a stirred solution of sodium (21 g, 0.9 at) in 1500 ml of absolute ethanol was added 388 g of p-isopropylbenzyltriphenylphosphonium chloride. The resulting phosphorane solution was cooled to 15°-20° C. (The light orange color fades when the temperature is lowered!) Freshly vacuum distilled citronellal (150 g, 1 mol.) was added dropwise while keeping the reaction mixture at reflux for 4 hours. The cooled reaction mixture was filtered to remove sodium chloride, most of the alcohol was distilled off in vacuo and 500 ml of hexane was added. The triphenylphosphineoxide was allowed to crystallize and filtered off. The solvents were removed from the mother liquors under vacuum and another 500 ml of hexane added. Cooling afforded another crop of triphenylphosphineoxide. The hexane was again evaporated and the residue distilled yielding, after a small forerun of isopulegol (a contaminant of citronellal), 200 g (82%) of the desired product. bp. 150°-145° C/0.1 mm. Ratio of E to Z is app. 40:60. nD25 =1.5172.

後処理

  1. additionwas added dropwise
  2. temperatureat reflux for 4 hours
  3. customThe cooled reaction mixture
  4. filtrationwas filtered
  5. customto remove sodium chloride
  6. distillationmost of the alcohol was distilled off in vacuo and 500 ml of hexane
  7. additionwas added
  8. customto crystallize
  9. filtrationfiltered off
  10. customThe solvents were removed from the mother liquors under vacuum
  11. additionanother 500 ml of hexane added
  12. temperatureCooling

出典と根拠

ORDレコード
ord-51fd93b75f2c4c5698c2b4981260f10e
出典データセット
uspto-grants-1986_05
特許番号
USRE032147

関連ノート

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