Acetic Acid → HCID 86678049, compound

HRID 1852326Notes

Reaction equation

HRID 1852326 reaction equation
[CH2:1]([NH:3][CH2:4][CH3:5])[CH3:2].[CH2:6](O)[C:7]#[CH:8].[C:10]([CH2:12][C:13]([O:15][CH2:16][CH:17]([CH2:22][CH3:23])[CH2:18][CH2:19][CH2:20][CH3:21])=[O:14])#[N:11].C(O)(=O)C>C1(C)C=CC=CC=1.[O-2].[O-2].[Mn+4].ClCCl>[C:10](/[C:12](=[CH:6]\[CH:7]=[CH:8]\[N:3]([CH2:4][CH3:5])[CH2:1][CH3:2])/[C:13]([O:15][CH2:16][CH:17]([CH2:22][CH3:23])[CH2:18][CH2:19][CH2:20][CH3:21])=[O:14])#[N:11]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 7859Propargyl alcoholHCID 8021Diethylamine2×HCID 963592-Ethylhexyl cyanoacetate

Product 1

HCID 86678049HCID 86678049, compoundYield 23%

Reagents, catalysts & solvents 3

HCID 178418406HCID 178418406, compoundCatalystHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
90 °C

Procedure

Diethylamine (30 g, 0.41 mol) and propargyl alcohol (18.4 g, 0.328 mol) are dissolved in 250 ml of toluene. 72.6 g of manganese dioxide (activated, <5 μm; 2.5 equiv.) are added portionwise while controlling the strong exotherm (temperature <50° C.) and the mixture is left stirring at 90° C. for 5 hours. The reaction mixture is filtered. The yellow filtrate is poured into a reactor surmounted by a Dean and Stark apparatus. 2-Ethylhexyl cyanoacetate (61.5 g, 0.312 mol) and catalyst (0.1 equiv., 1.77 ml of acetic acid and 3.2 ml of N,N-diethylamine) are added with stirring and the reaction mixture is brought to reflux. It is left at reflux for 5 hours 30 minutes. After cooling, 500 ml of dichloromethane are added and washing is carried out once with a saturated sodium bicarbonate solution and then twice with water. The organic phase is dried and then purified on a silica bed. The first fractions are recovered and concentrated under vacuum. 21.9 g (yield: 23%) of the pure fractions of the derivative of Example 5 are thus obtained in the form of an orange-coloured gum which crystallizes; recrystallization from heptane gave the derivative of Example 5 in the form of a yellow powder

Workup

  1. customthe strong exotherm (temperature <50° C.)
  2. waitthe mixture is left
  3. filtrationThe reaction mixture is filtered
  4. additionThe yellow filtrate is poured into a reactor
  5. stirringwith stirring
  6. temperatureto reflux
  7. waitIt is left
  8. temperatureat reflux for 5 hours 30 minutes
  9. temperatureAfter cooling
  10. washwashing
  11. customThe organic phase is dried
  12. custompurified on a silica bed
  13. customThe first fractions are recovered
  14. concentrationconcentrated under vacuum
  15. custom21.9 g (yield: 23%) of the pure fractions of the derivative of Example 5 are thus obtained in the form of an orange-coloured gum which
  16. customcrystallizes
  17. customrecrystallization from heptane
  18. customgave the derivative of Example 5 in the form of a yellow powder

Sources & evidence

ORD record
ord-d8af484d40af4ef29646dbc9c15a9288
Source dataset
uspto-grants-2015_02
Patent number
US08961941B2

Reaction notes

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