Cesium carbonate → HCID 118317161, compound

HRID 1497341Notes

Reaction equation

HRID 1497341 reaction equation
[C:1]([N:8]1[CH2:13][CH2:12][NH:11][CH2:10][CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].C([O-])([O-])=O.[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Br[C:67]1[CH:68]=[CH:69][C:70]([N+:78]([O-:80])=[O:79])=[C:71]([CH:77]=1)[CH2:72][NH:73][C:74](=[O:76])[CH3:75]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(C)C=CC=CC=1>[C:74]([NH:73][CH2:72][C:71]1[CH:77]=[C:67]([N:11]2[CH2:10][CH2:9][N:8]([C:1]([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2])[CH2:13][CH2:12]2)[CH:68]=[CH:69][C:70]=1[N+:78]([O-:80])=[O:79])(=[O:76])[CH3:75]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 143452tert-Butyl piperazine-1-carboxylateHCID 634876Binap, (A+-)-HCID 118307491HCID 118307491, compound

Product 1

HCID 118317161HCID 118317161, compoundYield 72%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

To an oven-dried flask, 1-boc-piperazine (3.19 g, 17.1 mmol), Cs2CO3 (5.82 g, 17.86 mmol), Pd2(dba)3 (1.44 g, 1.57 mmol), rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.89 g, 1.43 mmol), toluene (8 mL) and compound 14 (3.89 g, 14.26 mmol) were added. While stirring the reaction mixture at room temperature, the air in the flask was removed and replaced by N2. This process was repeated three times. The reaction temperature was brought to 110° C. and stirred for 8 h. Ethyl acetate (40 mL) was added to the mixture at room temperature, washed with H2O (15 mL), brine (10 mL), dried over Na2SO4 and evaporated. The brown oily material was chromatographed on a silica column, eluting with hexanes:ethyl acetate (3:7) and then changing to (1:1) to obtain the title compound 15 as light yellow solid (3.88 g, 72%). IR (KBr) νmax. cm−1: 3441 (NH), 3060 (Ar—H), 2963 (Alph-H), 1696 (C═O), 1607, 1577 (C═C), 1484, 1421 (NO2), 1243 (C—N), 1168 (C—O). 1H NMR (500 MHz, CDCl3) δ=1.49 (s, 9H, (C(CH3)3), 2.17 (s, 3H, CH3), 3.42 (br. s, 4H, 2CH2), 3.61 (br. s, 4H, 2CH2), 5.54 (s, 2H, CH2), 6.76 (dd, 1H, J=2.3, 9.3 Hz, H-6), 6.88 (br. s, 1H, H-2), 8.17 (d, 1H, J=9.4 Hz, H-5). 13C NMR (125.7 MHz, CDCl3) δ=20.93 (CH3), 28.39 (C(CH3)3), 46.82 (CH2), 50.02 (CH2), 66.12 (CH2), 80.42 (C(CH3)3), 112.30 (aromatic-C), 112.48 (aromatic-C), 128.17 (aromatic-C), 135.60 (aromatic-C), 137.03 (aromatic-C), 153.02 (aromatic-C), 154.56 (CO), 170.29 (CO). Calculated (%) for C18H26N4O5 (378.19); C, 57.13; H, 6.93; N, 14.81. found (%); C, 57.07; H, 6.99; N, 14.71.

Workup

  1. customthe air in the flask was removed
  2. customwas brought to 110° C.
  3. stirringstirred for 8 h
  4. additionEthyl acetate (40 mL) was added to the mixture at room temperature
  5. washwashed with H2O (15 mL), brine (10 mL)
  6. dry with materialdried over Na2SO4
  7. customevaporated
  8. customThe brown oily material was chromatographed on a silica column
  9. washeluting with hexanes:ethyl acetate (3:7)

Sources & evidence

ORD record
ord-67ec19fa970f49d587f0d0a2e2d8796d
Source dataset
uspto-grants-2015_12
Patent number
US09199969B1

Reaction notes

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