Trifluoroacetic acid → HCID 89309119, compound

HRID 1503621Notes

Reaction equation

HRID 1503621 reaction equation
[O:1]1[CH2:6][CH2:5][N:4](NC(N)=O)[CH2:3][CH2:2]1.[CH:11]1[CH:16]=[C:15]([C:17]2[C:27]3[CH:28]=[CH:29][C:30]([NH2:32])=[CH:31][C:26]=3[O:25][C:24]3[C:18]=2[CH:19]=[CH:20][C:21]([CH:23]=3)=[NH2+:22])[C:14]([C:33]([OH:35])=[O:34])=[CH:13][CH:12]=1.[Cl-].FC(F)(F)[C:39]([OH:41])=O.N(OCCC(C)C)=O.[N-:52]=[N+:53]=[N-].[Na+].C([O-])(O)=O.[Na+]>CC#N.C(Cl)Cl>[CH2:5]1[N:4]([C:39]([NH:22][C:21]2[CH:20]=[CH:19][C:18]3[C:17]4([O:35][C:33](=[O:34])[C:14]5[C:15]4=[CH:16][CH:11]=[CH:12][CH:13]=5)[C:27]4[CH:28]=[CH:29][C:30]([N:32]=[N+:52]=[N-:53])=[CH:31][C:26]=4[O:25][C:24]=3[CH:23]=2)=[O:41])[CH2:3][CH2:2][O:1][CH2:6]1

Participants

8

Reactant 5

HCID 6422Trifluoroacetic acidHCID 8053Isoamyl NitriteHCID 33557Sodium AzideHCID 516892Sodium BicarbonateHCID 131734319HCID 131734319, compound

Product 1

HCID 89309119HCID 89309119, compoundYield 81%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Procedure

Morpholinourea-rhodamine 110 (29.8 mg, 0.0672 mmol, 1.0 equiv) was dissolved in 7.2 mL 2:1 CH3CN:CH2Cl2 and cooled to 0° C. Trifluoroacetic acid (7.5 μL, 0.098 mmol, 1.5 equiv) was added to give a red solution, followed directly by the addition of iso-amyl nitrite (10.7 μL, 0.0796 mmol, 1.2 equiv) to give an orange solution. After stirring for 2 h at ambient temperature, sodium azide (12.4 mg, 0.191 mmol, 2.8 equiv) was added and the solution was allowed to stir for an additional 1 h. The reaction mixture was then poured into 15 mL saturated aq NaHCO3. The layers were separated and the aqueous layer was washed with an additional 2×10 mL EtOAc. The combined organic layers were dried over Na2SO4, filtered, and concentrated. The crude product was purified by silica column chromatography (4:1 Hex:EtOAc→1:1 Hex:EtOAc) to yield SF2 (25.5 mg, 81%). 1H NMR (400 MHz, CDCl3) δ 8.01 (d, 1H, J=7.2 Hz), 7.68 (t, 1H, J=7.0 Hz), 7.63 (t, 1H, J=7.4 Hz), 7.55 (d, 1H, J=2.1 Hz), 7.13 (d, 1H, J=7.4 Hz), 6.90 (m, 3H), 6.76 (d, 1H, 8.6 Hz), 6.70 (dd, 1H, J=8.5, 2.1 Hz), 6.62 (d, 1H, 8.6 Hz); 13C NMR (100 MHz, CDCl3) δ 169.64, 154.53, 153.23, 152.26, 151.45, 142.64, 141.55, 135.31, 131.21, 129.94, 129.46, 128.21, 126.18, 125.13, 123.97, 115.71, 115.43, 114.83, 112.71, 107.39, 107.30, 66.46, 44.25, 29.67; HRMS calcd for C25H20N5O5 (M+H+) 470.1459. found 470.1460.

Workup

  1. customto give a red solution
  2. customto give an orange solution
  3. stirringto stir for an additional 1 h
  4. customThe layers were separated
  5. washthe aqueous layer was washed with an additional 2×10 mL EtOAc
  6. dry with materialThe combined organic layers were dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude product was purified by silica column chromatography (4:1 Hex:EtOAc→1:1 Hex:EtOAc)

Sources & evidence

ORD record
ord-eda82848ba85471dbd3f584e746fbae6
Source dataset
uspto-grants-2015_12
Patent number
US09212189B2

Reaction notes

Loading…