Hydrofluoric Acid → (S)-4,4,6-Trifluoro-1-isopropyl-3,4-dihydronaphthalen-2(1H)-one

HRID 2038353노트

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HRID 2038353 반응식
[F:1][C:2]1([F:13])[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([F:12])[CH:10]=2)[CH2:5][CH2:4][CH2:3]1.IN1C(=O)[CH2:18][CH2:17][C:16]1=O.F.FC1C=C2C(CCCC32SCCS3)=CC=1.S([O-])([O-])(=[O:40])=S.[Na+].[Na+]>ClCCl.N1C=CC=CC=1>[F:13][C:2]1([F:1])[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([F:12])[CH:10]=2)[C@H:5]([CH:17]([CH3:18])[CH3:16])[C:4](=[O:40])[CH2:3]1

참가 물질

8

반응물 5

HCID 14917Hydrofluoric AcidHCID 24477Sodium ThiosulfateHCID 120273N-IodosuccinimideHCID 584514381,1,7-Trifluoro-1,2,3,4-tetrahydronaphthaleneHCID 866652417'-Fluoro-3',4'-dihydro-2'H-spiro[[1,3]dithiolane-2,1'-naphthalene]

생성물 1

HCID 58451445(S)-4,4,6-Trifluoro-1-isopropyl-3,4-dihydronaphthalen-2(1H)-one수율 46%

시약·촉매·용매 2

HCID 1049Pyridine용매HCID 6344Dichloromethane용매2회

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온도
-50 °C

실험 절차

1,1,7-Trifluoro-1,2,3,4-tetrahydronaphthalene (52): A solution of N-iodosuccinimide (32.3 g, 144.0 mmol) in dichloromethane (260 mL) was cooled to −78° C. in a plastic round bottom flask. A 70% solution of hydrogen fluoride in pyridine (18 mL) followed by a dichloromethane solution (20 mL) of dithiolane 61 (8.65 g, 36.0 mmol) were added dropwise. Upon completion of addition the reaction was warmed to −50° C. and stirred at this temperature for 3 h. The reaction was then poured into ice cold saturated sodium bicarbonate (200 mL) followed by a saturated solution of sodium thiosulfate (150 mL). The colored reaction became colorless and biphasic. The organic phase was separated, dried (sodium sulfate) and concentrated to give a yellow oil. The product was purified by silica gel chromatography with a gradient heptanes/ethyl acetate eluent system on an ISCO companion system to give the desired product as a yellow oil (3.11 g, 16.7 mmol, 46% yield). 1H NMR (400 MHz, CDCl3) δ: 7.34 (d, J=8 Hz, 1H), 7.07 (m, 1H), 7.05 (m, 1H), 2.80 (brs, 2H), 2.26 (m, 2H), 1.99 (m, 2H); 19F NMR (400 MHz, CDCl3) δ: −91.7 (s, 2H), −122.8 (s, 1H).

후처리

  1. additionwere added dropwise
  2. additionUpon completion of addition the reaction
  3. customThe colored reaction
  4. customThe organic phase was separated
  5. dry with materialdried (sodium sulfate)
  6. concentrationconcentrated
  7. customto give a yellow oil
  8. customThe product was purified by silica gel chromatography with a gradient heptanes/ethyl acetate eluent system on an ISCO companion system

출처 및 근거

ORD 기록
ord-e008e0025ca44f3a8949ea72d82d7808
출처 데이터셋
uspto-grants-2013_11
특허 번호
US08575361B2

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