Iodine → 3-((6-(4-Bromophenyl)hexyloxy)methyl)-3-ethyloxetane

HRID 2242780노트

반응식

HRID 2242780 반응식
II.Br[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][O:10][CH2:11][C:12]1([CH2:16][CH3:17])[CH2:15][O:14][CH2:13]1.[Br:18][C:19]1[CH:24]=[CH:23][C:22](I)=[CH:21][CH:20]=1.[NH4+].[Cl-]>CC(N(C)C)=O.[Zn].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C1COCC1>[Br:18][C:19]1[CH:24]=[CH:23][C:22]([CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][O:10][CH2:11][C:12]2([CH2:16][CH3:17])[CH2:15][O:14][CH2:13]2)=[CH:21][CH:20]=1

참가 물질

9

반응물 4

HCID 807Iodine2회HCID 115221-Bromo-4-iodobenzeneHCID 25517Ammonium ChlorideHCID 592073103-{[(6-Bromohexyl)oxy]methyl}-3-ethyloxetane

생성물 1

HCID 592073013-((6-(4-Bromophenyl)hexyloxy)methyl)-3-ethyloxetane수율 41%

시약·촉매·용매 4

HCID 23994Zinc촉매2회HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)촉매HCID 8028Tetrahydrofuran용매HCID 31374Dimethylacetamide용매

실험 절차

To a mixture of zinc powder (1.80 g, 27.5 mmol) in anhydrous DMA (20 ml) is added iodine (0.5 g, 1.97 mmol). This mixture is stirred until the red color of iodine disappeared (ca. 2 min), followed by the addition of 3-(6-bromohexyloxymethyl)-3-ethyloxetane (5.0 g, 17.9 mmol) and the resultant mixture is stirred at 85° C. for 4.5 h, then cooled to room temperature. In another flask charged with anhydrous THF (30 ml) is added 1-bromo-4-iodobenzene (7.0 g, 24.74 mmol) and Pd(dppf)Cl2 (0.5 g, 0.61 mmol). This mixture is stirred for 10 min, then the organic zinc reagent above is introduced. The reaction mixture is stirred overnight (˜16 h) at room temperature. Sat. aq. NH4Cl solution is added and the mixture is extracted with ethyl acetate (3×70 ml). The extracts are dried (Na2SO4) and evaporated under reduced pressure. The residue is purified by column chromatography on silica, eluting with petrol/ethyl acetate (10:0 to 4:1), to give a brown oil (2.6 g, 41%). 1H NMR (300 MHz, CDCl3): δ(ppm) 7.35 (d, J=8.4 Hz, 2H, Ar—H), 7.01 (d, J=8.4 Hz, 2H, Ar—H), 4.43 (d, J=5.7 Hz, 2H, OCH2), 4.34 (d, J=5.7 Hz, 2H, OCH2), 3.48 (s, 2H, OCH2), 3.41 (t, J=6.4 Hz, 2H, OCH2), 2.53 (t, J=7.9 Hz, 2H, ArCH2), 1.72 (q, J=7.6 Hz, 2H, CH2), 1.56 (m, 4H, CH2), 1.34 (m, 4H, CH2); 0.86 (t, J=7.6 Hz 3H, CH3); 13C NMR (75 MHz, CDCl3): δ (ppm) 141.6 (quat.), 131.2 (CH), 130.2 (CH), 119.3 (quat.), 78.4 (OCH2), 73.4 (OCH2), 71.4 (OCH2), 43.4 (quat.), 35.3 (CH2), 31.3 (CH2), 29.5 (CH2), 29.0 (CH2), 26.8 (CH2), 26.0 (CH2), 8.2 (CH3).

후처리

  1. custom(ca. 2 min)
  2. stirringThe reaction mixture is stirred overnight (˜16 h) at room temperature
  3. extractionthe mixture is extracted with ethyl acetate (3×70 ml)
  4. dry with materialThe extracts are dried (Na2SO4)
  5. customevaporated under reduced pressure
  6. customThe residue is purified by column chromatography on silica
  7. washeluting with petrol/ethyl acetate (10:0 to 4:1)

출처 및 근거

ORD 기록
ord-2a1630fbe7284a9a981742b333d01e9e
출처 데이터셋
uspto-grants-2010_03
특허 번호
US07674397B2

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