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

HRID 2242780ノート

反応式

HRID 2242780 の反応式
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

参加物

9

反応物 4

HCID 807Iodine2 回HCID 115221-Bromo-4-iodobenzeneHCID 25517Ammonium ChlorideHCID 592073103-{[(6-Bromohexyl)oxy]methyl}-3-ethyloxetane

生成物 1

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

試薬・触媒・溶媒 4

HCID 23994Zinc触媒2 回HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 8028Tetrahydrofuran溶媒HCID 31374Dimethylacetamide溶媒

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-2a1630fbe7284a9a981742b333d01e9e
出典データセット
uspto-grants-2010_03
特許番号
US07674397B2

反応ノート

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