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Aniline → n'-[7-Chloro-5-(2-chlorophenyl)-2,3-dihydro-1-methyl-2-oxo-1h-1,4-benzodiazepin-3-yl]-n-methyl-n-[2-methyl-4-(4-morpholinyl)phenyl]thiourea

HRID 2223069
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 2223069
[CH3:1][C:2]1[CH:7]=[C:6]([N:8]2[CH2:13][CH2:12][O:11][CH2:10][CH2:9]2)[CH:5]=[CH:4][C:3]=1[NH2:14].[CH:15](N(C(C)C)CC)(C)C.ClC(OC)=O.NC1C=CC=CC=1.[Cl:36][C:37]1[CH:38]=[CH:39][C:40]2[N:46]([CH3:47])[C:45](=[O:48])[CH:44]([N:49]=[C:50]=[S:51])[N:43]=[C:42]([C:52]3[CH:57]=[CH:56][CH:55]=[CH:54][C:53]=3[Cl:58])[C:41]=2[CH:59]=1>C(Cl)Cl>[Cl:36][C:37]1[CH:38]=[CH:39][C:40]2[N:46]([CH3:47])[C:45](=[O:48])[CH:44]([NH:49][C:50](=[S:51])[N:14]([CH3:15])[C:3]3[CH:4]=[CH:5][C:6]([N:8]4[CH2:9][CH2:10][O:11][CH2:12][CH2:13]4)=[CH:7][C:2]=3[CH3:1])[N:43]=[C:42]([C:52]3[CH:57]=[CH:56][CH:55]=[CH:54][C:53]=3[Cl:58])[C:41]=2[CH:59]=1
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Komponenten

7

Edukt 5

HCID 6115AnilineHCID 6586Methyl chloroformateHCID 81531DiisopropylethylamineHCID 219550002-Methyl-4-(morpholin-4-yl)anilineHCID 597139767-Chloro-5-(2-chlorophenyl)-1,3-dihydro-3-isothiocyanato-1-methyl-2h-1,4-benzodiazepin-2-one

Produkt 1

HCID 10312153
n'-[7-Chloro-5-(2-chlorophenyl)-2,3-dihydro-1-methyl-2-oxo-1h-1,4-benzodiazepin-3-yl]-n-methyl-n-[2-methyl-4-(4-morpholinyl)phenyl]thiourea
Ausbeute 75 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

A solution of 2-methyl4-(4-morpholinyl)benzenamine (53.3 mg, 0.277 mmol) and diisopropylethylamine (0.063 mL, 0.36 mmol) in CH2Cl2 (1 mL) was cooled to 0° C. Methyl chloroformate (0.024 mL, 0.31 mmol) was added dropwise, and then the reaction was allowed to warm to room temperature and stir overnight. The reaction was diluted with CH2Cl2 (20 mL) and washed with brine (10 mL). The organic phase was dried over Na2SO4, filtered, and concentrated in vacuo. The crude product was then suspended in a 1:2 mixture of Et2O:THF (6 mL). A solution of LiAlH4 in Et2O (0.34 mL of a 1 M solution, 0.34 mmol) was added dropwise, and then the reaction mixture was heated to reflux for 1.5 h. The reaction was cooled, diluted with additional Et2O (8 mL), and quenched with Na2SO45H2O (0.98 g, 4.2 mmol). After stirring for 15 minutes, the mixture was filtered and the reaction was concentrated in vacuo. A portion of this crude aniline (0.0580 g, 0.281 mmol) was dissolved in (CH2Cl)2 (8 mL), and 7-chloro-5-(2-chlorophenyl)-1,3-dihydro-3-isothiocyanato-1-methyl-2H-1,4-benzodiazepin-2-one (0.106 g, 0.281 mmol) was added. The resulting mixture was heated at 70° C. for 14 h. The reaction was cooled and concentrated in vacuo, and the residue was purified by silica gel column chromatography (7:1 CH2Cl2:EtOAc) to provide the title compound (0.1211 g, 74%). Due to hindered rotation about one of the bonds, rotamers were observed in the 1H-NMR spectrum. 1H-NMR (CDCl3): δ 7.77-7.68 (m, 1H), 7.51 (dd, J=2.4 Hz, J=8.8 Hz, 1H), 7.43-7.36 (m, 2H), 7.34-7.28 (m, 2H), 7.16 (t, J=8.4 Hz, 1H), 7.10-7.01 (m, 2H), 6.86-6.76 (m, 2H), 6.14 and 6.10 (2×d, J=8.0 Hz, J=7.6 Hz, 1H), 3.88-3.82 (br m, 4H), 3.60 and 3.59 (2×s, 3H), 3.41 (s, 3H), 3.19 (br s, 4H), 2.24 and 2.23 (2×s, 3H). MS (ESI) (M+H)+=582. HRMS calculated for (C29H29Cl2N5O2S+H) (M+H)+: 582.1497. Found (ESI): 582.1448.

Aufarbeitung

  1. washwashed with brine (10 mL)
  2. dry with materialThe organic phase was dried over Na2SO4
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. additionThe crude product was then suspended in a 1:2 mixture of Et2O
  6. additionA solution of LiAlH4 in Et2O (0.34 mL of a 1 M solution, 0.34 mmol) was added dropwise
  7. temperaturethe reaction mixture was heated
  8. temperatureto reflux for 1.5 h
  9. temperatureThe reaction was cooled
  10. additiondiluted with additional Et2O (8 mL)
  11. customquenched with Na2SO45H2O (0.98 g, 4.2 mmol)
  12. stirringAfter stirring for 15 minutes
  13. filtrationthe mixture was filtered
  14. concentrationthe reaction was concentrated in vacuo
  15. temperatureThe resulting mixture was heated at 70° C. for 14 h
  16. temperatureThe reaction was cooled
  17. concentrationconcentrated in vacuo
  18. customthe residue was purified by silica gel column chromatography (7:1 CH2Cl2:EtOAc)

Quellen und Nachweise

ORD-Eintrag
ord-13ff327a9c3f4d4095ec6b37a45d3ea3
Quelldatensatz
uspto-grants-2008_05
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07375101B2

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