二氧化碳 → 3-Butenal, 2-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-

HRID 596271笔记

反应方程式

HRID 596271 反应方程式
[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]

参与物

12

反应物 6

HCID 280二氧化碳HCID 977OxygenHCID 7751氯乙酸乙酯HCID 14798氢氧化钠HCID 5282108alpha-紫罗酮HCID 10942334甲醇钠

产物 1

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

试剂、催化剂与溶剂 5

HCID 7108吩噻嗪催化剂HCID 176醋酸溶剂HCID 962聚[6-[4-(4-氰基苯基)苯氧基]己基甲基丙烯酸酯]溶剂HCID 1049吡啶溶剂HCID 3283乙醚溶剂

反应条件

温度
5 °C

实验过程

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.

后处理

  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

来源与证据

ORD记录
ord-40bf745ef8f34eda91a55581b976ea15
来源数据集
uspto-grants-1977_03
专利号
US04010213

反应笔记

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