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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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HRID 2238448 반응식
[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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참가 물질

8

반응물 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

생성물 1

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

시약·촉매·용매 3

HCID 887Methanol용매HCID 962Water용매HCID 8028Tetrahydrofuran용매2회

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-a7804a1ec06b464ea2a9f008cc03ca20
출처 데이터셋
uspto-grants-2010_05
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US07718688B2

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