2-Nitrophenol → Carvone, (-)-

HRID 2308169

反応式

HRID 2308169 の反応式
[N+]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[OH:10])([O-])=O.[C:11]1(=O)[CH2:16]CCC[CH2:12]1.[CH:18]1(O)CCCCC1>C(=O)([O-])[O-].[Zn+2]>[CH3:18][C:4]1[C:5](=[O:10])[CH2:6][C@H:7]([C:11]([CH3:16])=[CH2:12])[CH2:8][CH:9]=1

参加物

5

反応物 3

HCID 69472-NitrophenolHCID 7966CyclohexanolHCID 7967Cyclohexanone2 回

生成物 1

HCID 439570Carvone, (-)-収率 63%

試薬・触媒・溶媒 1

HCID 19005Zinc Carbonate触媒

反応条件

温度
214.5 °C

実験手順

A mixture of 600 parts of R-(+)-1,2-limonene oxide, 5.7 parts of 2-nitrophenol and 12 parts of zinc carbonate was refluxed at 202-227° C. for 7 hours in a three-necked flask equipped with agitator, 3-foot distillation column, distillation head, temperature probe, and addition funnel. When the rearrangement step was completed (no 1,2-limonene oxide left in the reaction mixture), 190 parts of cyclohexanone were slowly added to the reaction mixture. The mixture was held at reflux for 2 hours at 195-200° C. and then cooled down to 120° C. The mixture of cyclohexanone and cyclohexanol was removed at 10-15 mm Hg and pot temperature below 120° C. Cyclohexanone addition step followed by reflux and removal of cyclohexanone-cyclohexanol mixture under vacuum was repeated two more times. After the oxidation step was completed, the conversion of R-(−)-carveol to R-(−)-carvone was above 95%. The catalyst was removed by filtration, and the filtrate was distilled to afford 473 parts of 80% pure R-(−)-carvone (theory yield 63% on 1,2-limonene oxide). This material was purified using conventional methods to 99.6% pure flavor grade R-(−)-carvone.

後処理

  1. customequipped with agitator, 3-foot distillation column, distillation head, temperature probe, and addition funnel
  2. additionwere slowly added to the reaction mixture
  3. temperatureat reflux for 2 hours at 195-200° C.
  4. temperaturecooled down to 120° C
  5. customwas removed at 10-15 mm Hg and pot temperature below 120° C
  6. additionCyclohexanone addition step
  7. temperatureby reflux
  8. customremoval of cyclohexanone-cyclohexanol mixture under vacuum
  9. customThe catalyst was removed by filtration
  10. distillationthe filtrate was distilled

出典と根拠

ORDレコード
ord-bd4b6f082ea24e97bf9bc05013ad3a03
出典データセット
uspto-grants-2004_12
特許番号
US06835686B2

関連ノート

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