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Triethylamine → di(tert-butyl) 2-({[1-(chloromethyl)-5-nitro-1,2-dihydro-3H-benzo[e]indol-7-yl]sulfonyl}amino)ethyl phosphate

HRID 2238448
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 2238448
[P:1]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])([O:3][CH2:4][CH2:5][NH2:6])=[O:2].CCN(CC)CC.[Cl:24][CH2:25][CH:26]1[C:34]2[C:33]3[CH:35]=[CH:36][C:37]([S:39](Cl)(=[O:41])=[O:40])=[CH:38][C:32]=3[C:31]([N+:43]([O-:45])=[O:44])=[CH:30][C:29]=2[N:28](C(=O)C(F)(F)F)[CH2:27]1.C([O-])([O-])=O.[Cs+].[Cs+]>C1COCC1.O.CO>[P:1]([O:3][CH2:4][CH2:5][NH:6][S:39]([C:37]1[CH:36]=[CH:35][C:33]2[C:34]3[CH:26]([CH2:25][Cl:24])[CH2:27][NH:28][C:29]=3[CH:30]=[C:31]([N+:43]([O-:45])=[O:44])[C:32]=2[CH:38]=1)(=[O:41])=[O:40])([O:7][C:8]([CH3:10])([CH3:9])[CH3:11])([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:2]
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Komponenten

8

Edukt 4

HCID 8471TriethylamineHCID 10796Cesium carbonateHCID 862404572-Aminoethyl di(tert-butyl) phosphateHCID 866202591-(chloromethyl)-5-nitro-3-(trifluoroacetyl)-1,2-dihydro-3H-benzo[e]indole-7-sulfonyl chloride

Produkt 1

HCID 54762391di(tert-butyl) 2-({[1-(chloromethyl)-5-nitro-1,2-dihydro-3H-benzo[e]indol-7-yl]sulfonyl}amino)ethyl phosphate
Ausbeute 91 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 887MethanolLösungsmittelHCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

A solution of amine 226 (203 mg, 0.80 mmol) and Et3N (0.11 mL, 0.80 mmol) in THF (2 mL) was added to solution of 116 (306 mg, 0.67 mmol) in THF (8 mL) at 0° C. After 5 min the cooling bath was removed and after 10 min Cs2CO3 (0.44 g, 1.3 mmol) and MeOH (4 mL) were added. After a further 25 min the mixture was diluted with water and extracted with CH2C2 (×3). The combined extracts were dried and evaporated and the residue was purified by chromatography, eluting with EtOAc/petroleum ether (1:1 then 2:1) to give di(tert-butyl) 2-({[1-(chloromethyl)-5-nitro-1,2-dihydro-3H-benzo[e]indol-7-yl]sulfonyl}amino)ethyl phosphate (227) (351 mg, 91%) as a red-orange foam: 1H NMR [(CD3)2SO] δ 8.59 (d, J=1.6 Hz, 1H), 8.04 (d, J=8.9 Hz, 1H), 7.95 (br s, 1H, 7.79 (dd, J=8.9, 1.8 Hz, 1H, 7.77 (s, 1H), 6.74 (s, 1H), 4.28-4.20 (m, 1H), 3.95-3.86 (m, 2H), 3.83-3.72 (m, 4H), 2.99 (t, J=6.0 Hz, 2H), 1.35 (s, 18H). HMS (FAB) calcd. for C23H3335ClN3O8PS (M+) m/z 577.1415, found 577.1412.

Aufarbeitung

  1. additionwere added
  2. extractionextracted with CH2C2 (×3)
  3. customThe combined extracts were dried
  4. customevaporated
  5. customthe residue was purified by chromatography
  6. washeluting with EtOAc/petroleum ether (1:1

Quellen und Nachweise

ORD-Eintrag
ord-a7804a1ec06b464ea2a9f008cc03ca20
Quelldatensatz
uspto-grants-2010_05
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07718688B2

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