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

HRID 1457719ノート

反応式

HRID 1457719 の反応式
[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]

参加物

5

反応物 3

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

生成物 1

HCID 110425463-(4-Cyanophenyl)isoxazolin-5-ylacetic acid

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

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 220g 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(300MHz, CDCl3): δ 7.77-7.76 (d, 2H, J=1.8Hz); 7.72-7.71 (d, 2H, J=1.8Hz); 5.22-5.14 (m, 1H); 3.63-3.54 (dd, 1H, J=10.6Hz, 16.8Hz); 3.19-3.11 (dd, 1H, J=7.3Hz, 16.8Hz); 3.00-2.93 (dd, 1H, J=6.2Hz, 16.5Hz); 2.79-2.72 (dd, 1H, J=7.3Hz, 16.5Hz). IR(KBr pellet): 3202, 2244, 1736, 1610, 1432, 1416, 1194, 1152, 928, 840, 562 cm-1.

後処理

  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

出典と根拠

ORDレコード
ord-689bafd078de4a7cbfb4417ba0c43337
出典データセット
uspto-grants-1998_12
特許番号
US05849736

反応ノート

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