Triphenylphosphine → N,N-dimethyl-3-[(benzo[1,3]dioxolan-4-yl)-oxy]-3-(thiophen-2-yl)-propylamine

HRID 1880620Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1880620
[CH3:1][N:2]([CH3:12])[CH2:3][CH2:4][CH:5]([C:7]1[S:8][CH:9]=[CH:10][CH:11]=1)[OH:6].O[C:14]1[C:22]2[O:21][CH2:20][O:19][C:18]=2[CH:17]=[CH:16][CH:15]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[CH3:12][N:2]([CH2:3][CH2:4][CH:5]([O:6][C:14]1[C:22]2[O:21][CH2:20][O:19][C:18]=2[CH:17]=[CH:16][CH:15]=1)[C:7]1[S:8][CH:9]=[CH:10][CH:11]=1)[CH3:1]

Komponenten

6

Edukt 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 5867271,3-Benzodioxol-4-olHCID 115864093-(Dimethylamino)-1-(2-thienyl)-1-propanol

Produkt 1

HCID 44595220N,N-dimethyl-3-[(benzo[1,3]dioxolan-4-yl)-oxy]-3-(thiophen-2-yl)-propylamineAusbeute 35 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

3-Dimethylamino-1-(thiophen-2-yl)-1-propanol (1.85 g, 0.01 mol), 4-hydroxyl-benzo[1,3]dioxolane (1.38 g, 0.01 mol) and triphenylphosphine (3.93 g, 0.015 mol) were dissolved in 80 ml of anhydrous tetrahydrofuran. The mixture was slowly added dropwise with the solution of diethyl azodicarboxylate (2.61 g, 0.015 mol) in 20 ml anhydrous tetrahydrofuran, the reaction temperature was controlled to be lower than −5° C. in an ice-salt bath. After completion of the addition, the ice-salt bath was removed, and the reaction was performed at room temperature for 24 h. After the end of reaction, tetrahydrofuran was distilled out under a reduced pressure, the resultant oily liquid was dissolved in 100 ml of ethyl acetate, washed with diluted sodium hydroxide aqueous solution and saturated sodium chloride aqueous solution separately once, dried over anhydrous sodium sulfate, and separated by silica gel column chromatography to obtain 1.07 g of N,N-dimethyl-3-[(benzo[1,3]dioxolan-4-yl)-oxy]-3-(thiophen-2-yl)-propylamine as a pale yellow oily liquid, which was dissolved in 30 ml of ethyl acetate, added with oxalic acid (0.32 g, 0.035 mol) to generate a pale yellow solid. The mixture was heated to reflux, cooled to room temperature, frozen for 2 h and filtrated. The filter cake was washed with cold ethyl acetate to obtain 1.31 g of the target compound as a pale yellow powdery solid in a yield of 33.2% and a melting point of 85-88° C. MS (m/e): 306.5 (M+1+); 1H-NMR δ (ppm, DMSO-d6): 7.46-7.48 (d, 1H, 5′-H); 7.11-7.12 (d, 1H, 3′-H); 6.95-6.97 (dd, 1H, 4′-H); 6.66-6.70 (t, 1H, 6-H); 6.53-6.59 (dd, 2H, 5,7-H); 5.97-5.98 (d, 2H, 2-H); 5.71-5.75 (t, 1H, CHO); 2.27-2.30 (t, 2H, CH2N); 2.19-2.21 (m, 1H, CH2CH2N); 2.11 (s, 6H, N(CH3)2); 2.06-2.08 (m, 1H, CH2CH2N).

Aufarbeitung

  1. customto be lower than −5° C. in an ice-salt bath
  2. additionAfter completion of the addition
  3. customthe ice-salt bath was removed
  4. customAfter the end of reaction, tetrahydrofuran
  5. distillationwas distilled out under a reduced pressure
  6. dissolutionthe resultant oily liquid was dissolved in 100 ml of ethyl acetate
  7. washwashed with diluted sodium hydroxide aqueous solution and saturated sodium chloride aqueous solution separately once
  8. dry with materialdried over anhydrous sodium sulfate
  9. customseparated by silica gel column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-c5771f872b1b4263a07b5c70f1947f67
Quelldatensatz
uspto-grants-2012_11
Patentnummer
US08318772B2

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