Diethylamine → HCID 87352571, Verbindung

HRID 1012858

Reaktionsgleichung

Reaktionsgleichung von HRID 1012858
[CH3:1][O:2][C:3](=[O:55])[CH2:4][NH:5][C:6](=[O:54])[C@H:7]([NH:11][C:12](=[O:53])[C@H:13](NC(OCC1C2C=CC=CC=2C2C1=CC=CC=2)=O)[CH2:14][S:15][C:16]([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[CH:8]([CH3:10])[CH3:9].[NH:56](CC)CC.[C:61]([NH:78][C@@H:79]([C:87]([OH:89])=O)[CH2:80][C:81]1[CH:86]=[CH:85][CH:84]=[CH:83][CH:82]=1)([O:63][CH2:64][CH:65]1[C:77]2[C:72](=[CH:73][CH:74]=[CH:75][CH:76]=2)[C:71]2[C:66]1=[CH:67][CH:68]=[CH:69][CH:70]=2)=[O:62].CCN=C=NCCCN(C)C.Cl.C1C=CC2N(O)N=NC=2C=1.CCN(C(C)C)C(C)C>CC#N.C(Cl)Cl.CCCCCCC.C(Cl)Cl>[CH3:1][O:2][C:3](=[O:55])[CH2:4][NH:5][C:6](=[O:54])[C@H:7]([NH:11][C:12](=[O:53])[C@H:13]([NH:56][C:87](=[O:89])[C@H:79]([NH:78][C:61]([O:63][CH2:64][CH:65]1[C:70]2[CH:69]=[CH:68][CH:67]=[CH:66][C:71]=2[C:72]2[C:77]1=[CH:76][CH:75]=[CH:74][CH:73]=2)=[O:62])[CH2:80][C:81]1[CH:86]=[CH:85][CH:84]=[CH:83][CH:82]=1)[CH2:14][S:15][C:16]([C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[CH:8]([CH3:10])[CH3:9]

Komponenten

10

Edukt 6

HCID 8021DiethylamineHCID 757711-HydroxybenzotriazoleHCID 81531DiisopropylethylamineHCID 978332(2R)-2-((((9H-fluoren-9-yl)methoxy)carbonyl)amino)-3-phenylpropanoic acidHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 57696983HCID 57696983, Verbindung

Produkt 1

HCID 87352571HCID 87352571, VerbindungAusbeute 80 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 6344DichloromethaneLösungsmittel2×HCID 8900HeptaneLösungsmittelHCID 21877088Acetonitrile methylene chlorideLösungsmittel

Versuchsvorschrift

To a stirred solution of 3A (836 mg, 1.11 mmol) in CH3CN/CH2Cl2 (1:1, 60 mL) at RT was added Et2NH (3 mL). After stirring for 3 h at RT the reaction mixture was diluted with heptane (60 mL) and concentrated to give the crude amine as a colourless oil. To a stirred solution of Fmoc-D-phenylalanine (650 mg, 1.7 mmol) in CH2Cl2 (30 mL) was added EDAC.HCl (326 mg, 1.7 mmol), HOBt (230 mg, 1.7 mmol) and DIEA (627 μl, 3.6 mmol). After stirring at RT for 10 minutes a solution of the crude amine in CH2Cl2 (20 mL) was then added and the reaction mixture stirred for 12 h. Whereupon the reaction was washed with water (15 mL), 10% HCl (15 mL), 5% NaHCO3 (15 mL) and sat NaCl (15 mL) solutions, dried (Na2SO4), filtered, and the solvent removed to give an off white solid which was recrystallised from CH3CN to give 4B as a white solid (800 mg, 0.89 mmol, 80%): IR νmax 3264, 3053, 1742, 1701, 1636, 1532 cm−1; 1H-NMR (400 MHz, CDCl3) δ 7.75 (d, J=7.5 Hz, 2H), 7.46 (t, J=7.5 Hz, 2H), 7.41-7.31 (m, 8H), 7.30-7.07 (m, 16H), 7.01 (br s, 1H), 6.54 (br s, 2H), 5.29 (br s, 1H), 4.48-4.32 (m, 3H), 4.25-4.13 (m, 1H), 4.10 (t, J=8.5 Hz, 1H), 3.99-3.76 (m, 3H), 3.65 (s, 3H), 3.10-2.88 (m, 2H), 2.83-2.69 (m, 1H), 2.49 (dd, J=13.0, 6.3 Hz, 1H), 2.36-2.22, (m, 1H), 0.93 (t, J=7.0 Hz, 6H); 13C NMR 100 MHz 171.2 (C), 171.0 (C), 170.2 (C), 170.0 (C), 156.2 (C), 144.3 (C), 143.9 (C), 143.7 (C), 141.4 (C), 136.0 (C), 129.5 (CH), 129.3 (CH), 129.0 (CH), 128.3 (CH), 127.9 (CH), 127.4 (CH), 127.2 (CH), 127.1 (CH), 125.2 (CH), 120.1 (CH), 67.3 (CH2), 58.6 (CH), 56.2 (CH), 52.8 (CH), 52.3 (CH3), 47.2 (CH), 41.0 (CH2), 38.3 (CH2), 33.5 (CH2), 30.2 (CH), 19.4 (CH3), 17.7 (CH3); LRMS (ES+) m/z 1828 (30%, [2M+Na]+), 925 (100%, [M+Na]+).

Aufarbeitung

  1. concentrationconcentrated
  2. customto give the crude amine as a colourless oil
  3. additionwas then added
  4. stirringthe reaction mixture stirred for 12 h
  5. washWhereupon the reaction was washed with water (15 mL), 10% HCl (15 mL), 5% NaHCO3 (15 mL)
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. customthe solvent removed
  9. customto give an off white solid which
  10. customwas recrystallised from CH3CN

Quellen und Nachweise

ORD-Eintrag
ord-f283058fda2143228931e03329e0ebf8
Quelldatensatz
uspto-grants-2011_07
Patentnummer
US07977304B2

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