4-Chloro-3-nitrotoluene → 4-Methyl-2-nitro-1-(1-propen-2-yl)benzene

HRID 62039

反応式

HRID 62039 の反応式
Cl[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[CH3:12][C:13]1(C)[C:17](C)(C)OB(C(C)=C)O1.C(=O)([O-])[O-].[Na+].[Na+]>O.O1CCOCC1.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>[CH3:8][C:5]1[CH:6]=[CH:7][C:2]([C:13]([CH3:17])=[CH2:12])=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1

参加物

7

反応物 3

HCID 69764-Chloro-3-nitrotolueneHCID 10340Sodium CarbonateHCID 109974264,4,5,5-Tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolane

生成物 1

HCID 897388014-Methyl-2-nitro-1-(1-propen-2-yl)benzene収率 95.4%

試薬・触媒・溶媒 3

HCID 178418476HCID 178418476、化合物触媒HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
140 °C

実験手順

1-Chloro-4-methyl-2-nitrobenzene (0.771 mL, 5.83 mmol), 4,4,5,5-tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolane (1.32 mL, 6.99 mmol), bis(triphenyl phosphine)palladium(II) chloride (0.327 g, 0.466 mmol), sodium carbonate (0.741 g, 6.99 mmol) in water (2.9 mL) and dioxane (11.4 mL) was capped in two separate 10-20 mL vials and heated on a Biotage Initiator® microwave reactor for 30 minutes at 140° C., with external IR-sensor temperature monitoring from the side of the vessel. The contents of the two vials were combined and diluted with ethyl acetate and washed with water. The aqueous layer was extracted with ethyl acetate (2×). The combined organic layers were dried over magnesium sulfate, filtered, and concentrated. Purification by flash column chromatography using 1-5% ethyl acetate/hexanes provided the title compound as a yellow oil (0.986 g, 95%): IR (thin film) 3084 (w), 2976 (m), 2919 (w), 1641 (w), 1560 (w), 1526 (vs), 1349 (s) cm−1; 1H NMR (400 MHz, CDCl3) δ 7.68-7.65 (m, 1H), 7.37-7.32 (m, 1H), 7.21 (d, J=7.9 Hz, 1H), 5.15 (p, J=1.5 Hz, 1H), 4.91 (p, J=1.0 Hz, 1H), 2.42 (s, 3H), 2.06 (t, J=1.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 148.06, 142.71, 138.30, 136.15, 133.38, 130.32, 124.29, 115.17, 23.32, 20.81.

後処理

  1. customseparate 10-20 mL vials
  2. additiondiluted with ethyl acetate
  3. washwashed with water
  4. extractionThe aqueous layer was extracted with ethyl acetate (2×)
  5. dry with materialThe combined organic layers were dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customPurification by flash column chromatography

出典と根拠

ORDレコード
ord-2131dcd688744a948c8f0f8a8e0001c8
出典データセット
uspto-grants-2016_09
特許番号
US09445594B2

関連ノート

読み込み中…