Formaldehyde → HCID 9995192, 화합물

HRID 2427924노트

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HRID 2427924 반응식
C=O.S(=O)(=O)(O)O.[CH2:8]([N:11]1[C:19]2[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=2)[C:13]([CH2:21][C:22]([N:24]([CH3:26])[CH3:25])=[O:23])([OH:20])[C:12]1=[O:27])[CH:9]=[CH2:10].[C:28]([O-])(=[O:30])C.[Na+]>C(O)(=O)C.O>[CH2:8]([N:11]1[C:19]2[C:14](=[CH:15][C:16]([CH2:28][OH:30])=[CH:17][CH:18]=2)[C:13]([CH2:21][C:22]([N:24]([CH3:25])[CH3:26])=[O:23])([OH:20])[C:12]1=[O:27])[CH:9]=[CH2:10]

참가 물질

7

반응물 4

HCID 712FormaldehydeHCID 1118Sulfuric AcidHCID 517045Sodium AcetateHCID 99705742-(1-allyl-3-hydroxy-2-oxo-2,3-dihydro-1H-indol-3-yl)-N,N-dimethyl-acetamide

생성물 1

HCID 9995192HCID 9995192, 화합물수율 113%

시약·촉매·용매 2

HCID 176Acetic Acid용매2회HCID 962Water용매

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온도
80 °C

실험 절차

To a suspension of para-formaldehyde (36.2 g, 1.13 mol) in 150 ml of glacial acetic acid, sulfuric acid (22.2 g, 0.226 mol) is added and the mixture heated at 80° C., until a clear solution has been formed. To this, during 45 minutes a solution of 2-(1-allyl-3-hydroxy-2-oxo-2,3-dihydro-1H-indol-3-yl)-N,N-dimethyl-acetamide (example 26) (62 g, 226 mmol) in a mixture of glacial acetic acid (350 mL) and water (10 mL) is added. The red reaction mixture is stirred for another hour at 80° C., and by then all of the starting material is consumed (HPLC). Sodium acetate (46.3 g, 564 mmol) is added, and after stirring for 5 minutes an orange suspension forms. The solvent is removed on the rotavapor, and to the residue water (about 250 mL) is added. Extraction with chloroform (2×200 mL), drying the organic layer and removal of the solvent leaves the crude title product (77.7 g, quant.) as a red oil. After chromatographic purification white crystals, mp=125° C. 1H-NMR (CDCl3, 300 MHz) δ 2.71, 2.94 (AB, 2H, 2J=16.1 Hz, CH2CONMe2); 2.83, 2.84 (2 s, 3H each, N(CH3)2); 4.19, 4.25 (ABAtlyl, 2H, 2J=16.4 Hz, 3J=5.3 Hz, NCH2); 4.47 (s, 2H, CH2OH); 5.12 (dd, 1H, 2J=1.2 Hz, 3J=10.3 Hz, cis CH═CH2), 5.51 (dd, 1H, 3J=17.3 Hz, trans CH═CH2); 5.75 (ddtr, 1H, CH═CH2); 6.21 (br s, 1H, OH); 6.70 (d, 1H, 3J=7.9 Hz, H-7); 7.15 (dd, 1H, 4J=1.5 Hz, H-6); 7.37 (d, 1H, H-4). 13C-NMR (CDCl3, 75 MHz) δ 35.71, 37.84 (N(CH3)2); 38.87 (CH2CONMe2); 42.67 (NCH2); 64.80 (CH2OH); 74.46 (C-3); 109.36 (C-7); 117.73 (CH═CH2); 123.43 (C-4); 128.63 (C-6); 131.00 (C-9); 131.33 (CH═CH2); 136.35 (C-5); 141.89 (C-8); 170.53 (C-11); 176.36 (C-2).

후처리

  1. additionis added
  2. customhas been formed
  3. additionis added
  4. customThe red reaction mixture
  5. customby then all of the starting material is consumed (HPLC)
  6. stirringafter stirring for 5 minutes an orange suspension forms
  7. customThe solvent is removed on the rotavapor
  8. additionto the residue water (about 250 mL) is added
  9. extractionExtraction with chloroform (2×200 mL)
  10. customdrying
  11. customthe organic layer and removal of the solvent

출처 및 근거

ORD 기록
ord-751466690c0c4b2eb151f6e63f52eb16
출처 데이터셋
uspto-grants-2011_06
특허 번호
US07968730B2

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