Citronellal → Triphenylphosphine Oxide

HRID 280067

반응식

HRID 280067 반응식
[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

참가 물질

6

반응물 4

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

생성물 1

HCID 13097Triphenylphosphine Oxide

시약·촉매·용매 1

HCID 702Ethanol용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-51fd93b75f2c4c5698c2b4981260f10e
출처 데이터셋
uspto-grants-1986_05
특허 번호
USRE032147

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