Potassium Cyanide → trans-3-(beta-Cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylic acid, alpha-cyano-m-(p-chlorophenoxy)benzyl ester

HRID 905254

Reaktionsgleichung

Reaktionsgleichung von HRID 905254
S(Cl)(Cl)=O.[C:5]([C:7]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)=[CH:8][CH:9]1[CH:11]([C:12]([OH:14])=[O:13])[C:10]1([CH3:16])[CH3:15])#[N:6].[Cl:23][C:24]1[CH:38]=[CH:37][C:27]([O:28][C:29]2[CH:30]=[C:31]([CH:34]=[CH:35][CH:36]=2)[CH:32]=O)=[CH:26][CH:25]=1.C1OCCOCCOCCOCCOCCOC1.[C-:57]#[N:58].[K+]>C1(C)C=CC=CC=1.O>[C:5]([C:7]([C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)=[CH:8][C@H:9]1[C@H:11]([C:12]([O:14][CH:32]([C:57]#[N:58])[C:31]2[CH:34]=[CH:35][CH:36]=[C:29]([O:28][C:27]3[CH:37]=[CH:38][C:24]([Cl:23])=[CH:25][CH:26]=3)[CH:30]=2)=[O:13])[C:10]1([CH3:16])[CH3:15])#[N:6]

Komponenten

8

Edukt 5

HCID 9032Potassium CyanideHCID 24386Thionyl ChlorideHCID 2855718-Crown-6HCID 6160153-(4-Chlorophenoxy)benzaldehydeHCID 571159863-(beta-Cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylic acid

Produkt 1

HCID 86737699trans-3-(beta-Cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylic acid, alpha-cyano-m-(p-chlorophenoxy)benzyl ester

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittel2×HCID 1140TolueneLösungsmittel2×

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

Thionyl chloride (1.61 ml, 2.6 g; 0.022 mole), 3-(β-cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylic acid (4.82 g; 0.02 mole) and toluene are mixed and heated at 100° C. for 1 hour. The reaction mixture is cooled to 25° C. and a solution of m-(p-chlorophenoxy)benzaldehyde (4.65 g; 0.02 mole) and 18-crown-6 (0.49 g; 0.002 mole) in toluene (10 ml) is added. To this reaction mixture a solution of potassium cyanide (2.6 g; 0.04 mole) in water (6 ml) is added slowly while maintaining the temperature between 20°-25° C. The reaction mixture is then stirred for 18 hours at room temperature. The resultant black reaction mixture is poured in water and extracted with ether (3x). The combined ether extracts are washed with water, 10% hydrochloric acid, 10% sodium bicarbonate, water and saturated sodium chloride solution. The ether layer is dried over sodium sulfate and evaporated in vacuo to leave a brown gum. This gum is purified by dry column chromatography (silica gel; eluent: 1:1 methylene chloride:hexane) to afford the title product, a yellow glass (1.0 g, 8.6%).

Aufarbeitung

  1. temperatureThe reaction mixture is cooled to 25° C.
  2. temperaturewhile maintaining the temperature between 20°-25° C
  3. customThe resultant black reaction mixture
  4. extractionextracted with ether (3x)
  5. washThe combined ether extracts are washed with water, 10% hydrochloric acid, 10% sodium bicarbonate, water and saturated sodium chloride solution
  6. dry with materialThe ether layer is dried over sodium sulfate
  7. customevaporated in vacuo
  8. customto leave a brown gum
  9. customThis gum is purified
  10. dry with materialby dry column chromatography (silica gel; eluent: 1:1 methylene chloride:hexane)

Quellen und Nachweise

ORD-Eintrag
ord-2c76e182f78340718803c05c06b11515
Quelldatensatz
uspto-grants-1983_12
Patentnummer
US04423062

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