Acetic Acid → 2-Phenylhexahydro-2,5-methanopentalene-3a-carboxylic acid

HRID 1015567노트

반응식

HRID 1015567 반응식
[OH-].[Na+].BrBr.Br[O-].[C:7]1([C:13]23[CH2:21][CH:17]4C[CH:19]([CH2:20]2)[C:15](C(=O)C)([CH2:16]4)[CH2:14]3)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[CH3:25][C:26]([OH:28])=[O:27]>O1CCOCC1.O>[C:7]1([C:13]23[CH2:14][CH:15]4[CH2:16][CH:17]([CH2:21]2)[C:25]([C:26]([OH:28])=[O:27])([CH2:19]4)[CH2:20]3)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

참가 물질

8

반응물 5

HCID 176Acetic AcidHCID 14798Sodium HydroxideHCID 24408BromineHCID 5460626HypobromiteHCID 593749561-(2-Phenylhexahydro-2,5-methanopentalen-3a-yl)ethanone

생성물 1

HCID 673007182-Phenylhexahydro-2,5-methanopentalene-3a-carboxylic acid수율 64%

시약·촉매·용매 2

HCID 962Water용매2회HCID 312751,4-Dioxane용매2회

실험 절차

To a stirred mixture of NaOH (2.4 g, 60.0 mmol), H2O (16 mL), and 1,4 dioxane (2 mL) at ice bath temperature was added Br2 (0.56 mL, 10.4 mmol) and stirred for 15 minutes. The resulting hypobromite solution was added dropwise to a stirred solution of 1-(1-phenyltricyclo[3.3.1.03,7]non-3-yl)ethanone obtained from preparation I (1.0 g, 4.0 mmol) in 1,4-dioxane (6 mL) at ice bath temperature. After stirring the reaction mixture at r.t. for 1 h, it was again cooled to ice bath temperature and quenched by adding AcOH (3.6 mL, 60 mmol). The reaction mixture was diluted with water and extracted with EtOAc. The combined organic layer was washed with brine, dried over Na2SO4, and the solvent was removed under reduced pressure to obtain 1-phenyltricyclo[3.3.1.03,7]nonane-3-carboxylic acid (0.62 g) in 64% yield. m/z (M+1) 243; 1H NMR (CDCl3) 300 MHz δ 7.40-7.25 (m, 4H), 7.25-7.18 (m, 1H), 2.90-2.86 (m, 1H), 2.54-2.48 (m, 1H), 2.38 (ddd, J=2.0, 2.0, 11.0 Hz, 1H), 2.20-2.05 (m, 4H), 1.98-1.78 (m, 5H), 1.70 (dd, J=2.8, 11.5 Hz, 1H).

후처리

  1. stirringAfter stirring the reaction mixture at r.t. for 1 h
  2. temperatureit was again cooled to ice bath temperature
  3. customquenched
  4. extractionextracted with EtOAc
  5. washThe combined organic layer was washed with brine
  6. dry with materialdried over Na2SO4
  7. customthe solvent was removed under reduced pressure

출처 및 근거

ORD 기록
ord-d44fc4896ca64a8898fa89e55ecfa94e
출처 데이터셋
uspto-grants-2011_07
특허 번호
US07985759B2

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