Benzene, 1-bromo-4-(trifluoromethyl)- → 4-Tetrahydropyranyloxy-4'-trifluormethyltolan

HRID 1020514노트

반응식

HRID 1020514 반응식
[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]#[CH:15])=[CH:10][CH:9]=1.Br[C:17]1[CH:22]=[CH:21][C:20]([C:23]([F:26])([F:25])[F:24])=[CH:19][CH:18]=1>C(NC(C)C)(C)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][C:8]1[CH:9]=[CH:10][C:11]([C:14]#[C:15][C:17]2[CH:22]=[CH:21][C:20]([C:23]([F:26])([F:25])[F:24])=[CH:19][CH:18]=2)=[CH:12][CH:13]=1

참가 물질

6

반응물 2

HCID 67872Benzene, 1-bromo-4-(trifluoromethyl)-HCID 11310191P-[Tetrahydropyran-2-yloxy]phenylacetylene

생성물 1

HCID 582885584-Tetrahydropyranyloxy-4'-trifluormethyltolan

시약·촉매·용매 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 178418476HCID 178418476, 화합물촉매HCID 7912Diisopropylamine용매

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온도
80 °C

실험 절차

A solution of 3 (12.1 g, 60 mmol) and 4-bromobenzotriflouride (14.85 g, 66 mmol) in diisopropylamine (250 ml) was heated to 30° C. under nitrogen, and the solution was degassed. Then Pd(PPh3)2Cl2 (210 mg, 0.3 mmol) and copper(I) iodide (114 mg, 0.6 mmol) were added to this clear solution. The reaction mixture was stirred for 2 hours at 80° C., and then cooled to room temperature. The salt formed during the reaction procedure was filtered off and washed well with ethyl acetate. The filtrate was evaporated to dryness and hydrolyzed with concentrated hydrochloric acid (10 ml), water (100 ml) and crushed ice (50 g), then extracted with ethyl acetate. The combined organic paste was washed with brine and dried over MgSO4. The solvent was removed in vacuo and the residue was purified by column chromatography (petroleum ether-ethyl acetate=9:1) to give a pale yellow crystals of 4. Yield 16.6 g (80%); mp 112˜113° C.; δH(CDCl3, 300 MHz): 7.59 (s, 4H, Ar—H), 7.48 (d, J=8.7, 2H, Ar—H), 7.04 (d, J=8.7, 2H, Ar—H), 5.46 (t, J=3.1, 1H, OCHO), 3.89 (m, 1H, THP), 3.62 (m, 1H, THP), 1.86˜1.62 (m, 6H, THP).

후처리

  1. customthe solution was degassed
  2. temperaturecooled to room temperature
  3. customThe salt formed during the reaction procedure
  4. filtrationwas filtered off
  5. washwashed well with ethyl acetate
  6. customThe filtrate was evaporated to dryness and hydrolyzed with concentrated hydrochloric acid (10 ml), water (100 ml)
  7. customcrushed ice (50 g)
  8. extractionextracted with ethyl acetate
  9. washThe combined organic paste was washed with brine
  10. dry with materialdried over MgSO4
  11. customThe solvent was removed in vacuo
  12. customthe residue was purified by column chromatography (petroleum ether-ethyl acetate=9:1)
  13. customto give a pale yellow crystals of 4

출처 및 근거

ORD 기록
ord-fb1cdaf54db14de0bca10ac6ab6e342e
출처 데이터셋
uspto-grants-2014_05
특허 번호
US08716355B2

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