Phthalic Anhydride → 5-Phthalimido-1-pentanol

HRID 564248

반응식

HRID 564248 반응식
[C:1]1(=[O:11])[O:6][C:4](=O)[C:3]2=[CH:7][CH:8]=[CH:9][CH:10]=[C:2]12.[NH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][OH:18]>C1(C)C=CC=CC=1>[OH:18][CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][N:12]1[C:1](=[O:11])[C:2]2=[CH:10][CH:9]=[CH:8][CH:7]=[C:3]2[C:4]1=[O:6]

참가 물질

4

반응물 2

HCID 6811Phthalic AnhydrideHCID 756345-Aminopentan-1-ol

생성물 1

HCID 5948445-Phthalimido-1-pentanol수율 88%

시약·촉매·용매 1

HCID 1140Toluene용매

실험 절차

Step 1. A mixture of phthalic anhydride (1.48 g, 10 mmol) and 5-amino-1-pentanol (1.03 g, 10 mmol) in toluene (20 ml) was heated under reflux overnight. The solvent was removed under vacuum, and the residue was purified by chromatography to afford N-(5-hydroxypentyl)phthalimide (2.00 g, 88%) as a colorless oil. 1H NMR (500 MHz, CDCl3) δ 1.37-1.48 (m, 2H), 1.56-1.67 (m, 2H), 1.67-1.79 (m, 2H), 3.64 (t, J=6.5 Hz, 2H), 3.70 (t, J=7.5 Hz, 2H), 7.66-7.76 (m, 2H), 7.80-7.99 (m, 2H). Step 2. Diisopropyl azodicarboxylate (0.69 ml, 3.51 mmol) was added dropwise to a mixture of OZ288 (0.50 g, 1.4 mmol), N-(5-hydroxypentyl)phthalimide (0.65 g, 2.79 mmol), triphenylphosphine (0.92 g, 3.51 mmol), and triethylamine (0.5 ml, 3.51 mmol) in THF (50 ml) at 0° C. under N2 atmosphere. The resulting mixture was stirred at rt for 24 h. After removal of the solvent, the crude product was purified by crystallization from EtOH to afford the desired phenol ether (0.35 g, 44%) as a colorless solid. mp 115-116° C.; 1H NMR (500 MHz, CDCl3) δ 1.46-2.08 (m, 28H), 2.43-2.53 (m, 1H), 3.71 (t, J=7.0 Hz, 2H), 3.92 (t, J=6.5 Hz, 2H), 6.79 (d, J=9.0 Hz, 2H), 7.09 (d, J=9.0 Hz, 2H), 7.67-7.75 (m, 2H), 7.80-7.99 (m, 2H); 13C NMR (125.7 MHz, CDCl3) δ 23.42, 26.49, 26.89, 28.33, 28.85, 31.65, 34.76, 34.81, 36.41, 36.81, 37.85, 42.05, 67.55, 108.46, 111.34, 114.34, 123.18, 127.56, 132.15, 133.86, 138.20, 157.34, 168.43. Step 3. A mixture of the above phenol ether (0.30 g, 0.53 mmol) and hydrazine monohydrate (1 ml) in chloroform (30 ml) and methanol (3 ml) was heated at 50° C. for 24 h. After the reaction mixture was cooled to rt and filtered to the remove a solid by-product, the filtrate was washed with water (2×10 ml) and brine (10 ml), dried over MgSO4, filtered, and concentrated. The residue was dissolved in CH2Cl2 (5 ml) and a solution of methanesulfonic acid (0.05 g, 0.52 mmol) in ethyl acetate (20 ml) was added. The precipitate was collected by filtration to afford trioxolane OZ498 (0.19 g, 68%) as a colorless solid. mp 155-156° C.; 1H NMR (500 MHz, DMSO-d6) δ 1.38-1.98 (m, 28H), 2.30 (brs, 3H), 2.50-2.59 (m, 1H), 2.76-2.85 (m, 2H), 3.92 (t, J=6.3 Hz, 2H), 6.83 (d, J=8.8 Hz, 2H), 7.11 (d, =8.3 Hz, 2H), 7.63 (brs, 3H); 13C NMR (125.7 MHz, DMSO-d6) δ 22.72, 25.98, 26.39, 26.90, 28.35, 31.49, 34.28, 34.44, 35.96, 36.25, 38.97, 40.86, 67.22, 108.32, 110.71, 114.44, 127.58, 138.04, 157.08. Anal. Calcd for C28H43NO7S: C, 62.54; H, 8.06; N, 2.60. Found: C, 62.55; H, 7.93; N, 2.76.

후처리

  1. temperaturewas heated
  2. temperatureunder reflux overnight
  3. customThe solvent was removed under vacuum
  4. customthe residue was purified by chromatography

출처 및 근거

ORD 기록
ord-d380433288e7407984d78a02789d77ba
출처 데이터셋
uspto-grants-2011_11
특허 번호
US08067620B2

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