3-Butenoic acid → 3-(4-Cyanophenyl)isoxazolin-5-ylacetic acid

HRID 1952787Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1952787
[C:1]([C:3]1[CH:11]=[CH:10][C:6]([CH:7]=[N:8][OH:9])=[CH:5][CH:4]=1)#[N:2].[CH:12]([CH2:14][C:15]([OH:17])=[O:16])=[CH2:13].Cl[O-].[Na+]>O1CCCC1>[C:1]([C:3]1[CH:11]=[CH:10][C:6]([C:7]2[CH2:13][CH:12]([CH2:14][C:15]([OH:17])=[O:16])[O:9][N:8]=2)=[CH:5][CH:4]=1)#[N:2]

Komponenten

5

Edukt 3

HCID 327433-Butenoic acidHCID 52147424-Cyanobenzaldehyde oximeHCID 23665760Sodium Hypochlorite

Produkt 1

HCID 110425463-(4-Cyanophenyl)isoxazolin-5-ylacetic acidAusbeute 44,9 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To a solution of 4-cyanobenzaldoxime (see Ex 43, Part A) (312 g, 2.13 mol) in tetrahydrofuran (3000 ml) at room temperature was added vinyl acetic acid (552 g, 6.41 mol). The yellow solution was cooled in an ice bath and sodium hypochlorite solution (5200 ml) was added in a dropwise fashion over 2h. After stirring overnight at room temperature the reaction was quenched with a 5% citric acid solution and diluted with 200 ml ether. The layers were separated and the aqueous acidified to pH 4 using citric acid. The acid layer was washed twice with 200 ml ether, the ether layers combined and extracted with saturated sodium bicarbonate solution. After acidifying the basic layer with citric acid, the product was extracted into 400 ml ether. The organic phase was washed three times with 150 ml water, once with brine, dried (MgSO4) and concentrated to give 220 g of 3-(4-cyanophenyl)isoxazolin-5-ylacetic acid as a white solid. Recrystallization from 25% water/ethanol yielded 165 g of analytically pure material. Anal. Calcd for C12H10N2O3 : C,62.61; H,4.38; N, 12.17. Found: C. 62.37; H 4.47; N, 11.71. 1H NMR(300 MHz, CDCl3): δ 7.77-7.76 (d, 2H, J=1.8 Hz); 7.72-7.71 (d, 2H, J=1.8 Hz); 5.22-5.14 (m, 1H); 3.63-3.54 (dd, 1H, J=10.6 Hz, 16.8 Hz); 3.19-3.11 (dd, 1H, J=7.3Hz, 16.8 Hz); 3.00-2.93 (dd, 1H, J=6.2 Hz, 16.5 Hz); 2.79-2.72 (dd, 1H, J=7.3 Hz, 16.5 Hz). IR(KBr pellet): 3202, 2244, 1736, 1610, 1432, 1416, 1194, 1152, 928, 840, 562 cm-1.

Aufarbeitung

  1. temperatureThe yellow solution was cooled in an ice bath
  2. customwas quenched with a 5% citric acid solution
  3. additiondiluted with 200 ml ether
  4. customThe layers were separated
  5. washThe acid layer was washed twice with 200 ml ether
  6. extractionextracted with saturated sodium bicarbonate solution
  7. extractionthe product was extracted into 400 ml ether
  8. washThe organic phase was washed three times with 150 ml water
  9. dry with materialonce with brine, dried (MgSO4)
  10. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-0e3713d40f9c446f9595240853fa5d2a
Quelldatensatz
uspto-grants-2000_09
Patentnummer
US06114328

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