Formaldehyde → 9-hydroxymethyl-9-fluorene carboxylic acid

HRID 1768160노트

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HRID 1768160 반응식
[CH:1]1[C:13]2[CH:12]([C:14]([OH:16])=[O:15])[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.C([Li])CCC.[CH2:22]=[O:23].O>C1COCC1>[OH:23][CH2:22][C:12]1([C:14]([OH:16])=[O:15])[C:13]2[CH:1]=[CH:2][CH:3]=[CH:4][C:5]=2[C:6]2[C:11]1=[CH:10][CH:9]=[CH:8][CH:7]=2

참가 물질

6

반응물 4

HCID 712FormaldehydeHCID 962WaterHCID 748099-CarboxyfluoreneHCID 178418339Butyllithium

생성물 1

HCID 3450269-hydroxymethyl-9-fluorene carboxylic acid수율 81.4%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

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온도
-78 °C

실험 절차

9-fluorene carboxylic acid (4.98 g, 23.7 mmol) and anhydrous THF (300 ml) were introduced into a flame-dried reaction vessel in which the atmosphere had been replaced by nitrogen, the reaction solution was cooled to −78° C., and n-butyl lithium (41.0 ml of 1.6M hexane solution, 71.0 mmol) was added. After stirring the reaction solution at −78° C. for 30 minutes, paraformaldehyde (2.30 g, 75.0 mmol) dissolved in anhydrous THF (100 ml) was added at −78° C., and stirred at room temperature for 13 hours. Distilled water was added, the solution was extracted with ether, and the pH of the aqueous layer was adjusted to 2 using 1N hydrochloric acid. It was then extracted again with chloroform, and the organic layer was dried by anhydrous magnesium sulfate. The low-boiling fraction was distilled under reduced pressure with the rotary evaporator, and 4.21 g of crude product was thus obtained. The methylene chloride-insoluble fraction of this crude product was collected, and the target compound (4.60 g, 19.3 mmol, 80.5%) was thus obtained. 1H-NMR (500 MHz, CDCl3) d: 7.78 (d, J=7.5, 2H), 7.67 (d, J=7.5, 2H), 7.46 (dd, J=7.0, 2H), 7.54 (dd, J=8.0, 2H), 4.02(s, 4H).

후처리

  1. additionwas added at −78° C.
  2. stirringstirred at room temperature for 13 hours
  3. extractionthe solution was extracted with ether
  4. extractionIt was then extracted again with chloroform
  5. dry with materialthe organic layer was dried by anhydrous magnesium sulfate
  6. distillationThe low-boiling fraction was distilled under reduced pressure with the rotary evaporator, and 4.21 g of crude product
  7. customwas thus obtained
  8. customThe methylene chloride-insoluble fraction of this crude product was collected

출처 및 근거

ORD 기록
ord-98d1e735b8ee45a59585865579519e3a
출처 데이터셋
uspto-grants-2007_06
특허 번호
US07235620B2

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