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

HRID 2285952Notes

Reaction equation

HRID 2285952 reaction equation
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]

Participants

8

Reactant 5

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 1140TolueneSolvent2×

Conditions

Temperature
100 °C

Procedure

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 (3×). 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%).

Workup

  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 (3×)
  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)

Sources & evidence

ORD record
ord-4dd25dc4448b441d862a4467269edadd
Source dataset
uspto-grants-1982_04
Patent number
US04325969

Reaction notes

Loading…