Carbon Dioxide → 3-Butenal, 2-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-

HRID 596271

반응식

HRID 596271 반응식
[CH3:1][C:2]1[CH:7](/[CH:8]=[CH:9]/[C:10]([CH3:12])=O)[C:6]([CH3:14])([CH3:13])[CH2:5][CH2:4][CH:3]=1.ClC[C:17](OCC)=[O:18].C[O-].[Na+].O=O.[OH-].[Na+].C(=O)=O>C1C2NC3C(=CC=CC=3)SC=2C=CC=1.O.C(O)(=O)C.CCOCC.N1C=CC=CC=1>[CH3:12][CH:10]([CH:9]=[CH:8][CH:7]1[C:6]([CH3:14])([CH3:13])[CH2:5][CH2:4][CH:3]=[C:2]1[CH3:1])[CH:17]=[O:18]

참가 물질

12

반응물 6

HCID 280Carbon DioxideHCID 977OxygenHCID 7751Ethyl chloroacetateHCID 14798Sodium HydroxideHCID 5282108Alpha-IononeHCID 10942334Sodium Methoxide

생성물 1

HCID 939523-Butenal, 2-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-수율 60.7%

시약·촉매·용매 5

HCID 7108Phenothiazine촉매HCID 176Acetic Acid용매HCID 962Water용매HCID 1049Pyridine용매HCID 3283Diethyl Ether용매

반응 조건

온도
5 °C

실험 절차

A mixture of 192 g of α-ionone, 165.4 g of ethyl chloroacetate, 500 mg of phenothiazine and 100 ml of pyridine is treated with 81 g of sodium methylate within 30 minutes at -10° C to -15° C with the exclusion of moisture and oxygen from the air. After the addition of 100 ml of absolute ether, the mixture is stirred for 4 hours at - 5° C and treated with 400 ml of 15% methanolic sodium hydroxide while cooling. The mixture is stirred for 1 hour at 10° C, cooled to -30° C and adjusted to a pH of about 4 by the addition of 600 ml of glacial acetic acid. After warming to room temperature, 1 liter of water is added and the mixture stirred again for 15 minutes (CO2 evolution). Extraction with hexane, washing the organic phase neutral, drying over anhydrous sodium sulphate and removal of the solvent under reduced pressure yields 190 g of a brown, liquid crude product which is subjected to fractional distillation in vacuo and produces 125 g of 2-methyl-4-(2,6,6-trimethyl-2-cyclohexenyl)-3-butenal; b.p.0.15 = 90° C; nD20 = 1.4880. Odour: woody, ionone-like, flowery.

후처리

  1. temperaturewhile cooling
  2. stirringThe mixture is stirred for 1 hour at 10° C
  3. temperaturecooled to -30° C
  4. temperatureAfter warming to room temperature
  5. extractionExtraction with hexane
  6. washwashing the organic phase neutral
  7. dry with materialdrying over anhydrous sodium sulphate and removal of the solvent under reduced pressure
  8. customyields 190 g of a brown, liquid crude product which
  9. distillationis subjected to fractional distillation in vacuo

출처 및 근거

ORD 기록
ord-40bf745ef8f34eda91a55581b976ea15
출처 데이터셋
uspto-grants-1977_03
특허 번호
US04010213

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