Triethylamine → HCID 87901041, compound

HRID 1797385Notes

Reaction equation

HRID 1797385 reaction equation
[Cl:1][C:2]1(O)[N:19]=[CH:18][N:17]=[C:16]2[C:3]1=[N:4][CH2:5][N:6]2[C@@H:7]1[O:15][C@H:12]([CH2:13][OH:14])[C@@H:10]([OH:11])[C@H:8]1[OH:9].[CH2:21]([O:24][C:25](=[O:43])[CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][O:31][C:32]1[CH:37]=[CH:36][C:35]([CH:38](OC)OC)=[CH:34][CH:33]=1)[CH:22]=[CH2:23].O.C1(C)C=CC(S(O)(=O)=O)=CC=1.C(N(CC)CC)C>CN(C=O)C>[CH2:21]([O:24][C:25](=[O:43])[CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][O:31][C:32]1[CH:37]=[CH:36][C:35]([CH:38]2[O:11][CH:10]3[CH:12]([CH2:13][OH:14])[O:15][CH:7]([N:6]4[CH:5]=[N:4][C:3]5[C:16]4=[N:17][CH:18]=[N:19][C:2]=5[Cl:1])[CH:8]3[O:9]2)=[CH:34][CH:33]=1)[CH:22]=[CH2:23]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 521998p-Toluenesulfonic acid monohydrateHCID 69588153HCID 69588153, compoundHCID 69588555HCID 69588555, compound

Product 1

HCID 87901041HCID 87901041, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

A mixture of 6-chloroinosine (4, 32.5 g, 113 mmol) and the acetal linker 3 (47.5 g, 147 mmol) was dissolved in DMF (230 mL). p-Toluenesulfonic acid monohydrate (1.1 g, 5.7 mmol) was added, and the solution was placed on a Buechi R-134 rotavapor and agitated under reduced pressure (70 mbar) at 50° C. for 15 h. The solvent was removed in vacuo, the resulting residue was dissolved in EtOAc (1 L) and neutralized with triethyl amine (0.8 mL, 5.7 mmol). The solution was then washed with saturated aqueous NaCl (3×1 L), H2O (1 L), dried (MgSO4), filtered and concentrated. The resulting residue was taken up in EtOAc and triturated with hexanes, upon which the product precipitated as a white powder (5, 59.3 g, 109 mmol, 96%, mixture of two diastereomers): M.p.: 103-105° C.; 1H-NMR (400 MHz, CDCl3) δ=8.78 (s, 1H), 8.77 (s, 1H′), 8.41 (s, 1H), 8.33 (s, 1H′), 7.47 (d, J=8.6 ,2H), 7.37 (d, J=8.6, 2H′), 6.95 (d, J=8.5, 2H), 6.89 (d, J=8.5, 2H′), 6.24 (s, 1H), 6.19 (m, 1H, 1H′), 6.02 (s, 1H′), 5.91 (m, 1H, 1H′), 5.37-5.18 (m, 4H, 4H′), 4.77 (m, 1H, 1H′), 4.72 (s, 1H, 1H′), 4.58 (m, 2H, 2H′), 4.04-3.85 (m, 4H, 4H′), 2.37 (m, 2H, 2H′), 1.81 (m, 2H, 2H′), 1.71 (m, 2H, 2H′), 1.52 (m, 2H, 2H′); 13C -NMR (400 MHz, CDCl3) δ=173.4, 173.4, 160.5, 160.4, 152.0, 151.8, 150.8, 150.7, 132.8, 132.6, 132.3, 132.3, 132.1, 132.1, 128.2 (2C), 128.0 (2C), 127.5, 127.5, 118.3, 118.3, 114.8, 114.8, 114.6 (2C), 114.6 (2C), 108.0, 104.9, 93.5, 91.6, 86.4, 86.4, 84.3, 83.8, 83.3, 80.5, 67.9, 67.8, 65.1, 65.1, 63.2, 62.9, 34.2, 34.2, 28.9, 28.9, 25.7, 25.7, 24.7, 24.7; IR (film) ν=3233, 3109, 3073, 2934, 1727, 1595, 1396, 1245, 1194, 1167, 1101, 1073, 984, 832; HRMS (MALDI-FTMS) m/z 567.1627(567.1617 calculated for C26H29N4O7ClNa (M+Na)+).

Workup

  1. customThe solvent was removed in vacuo
  2. dissolutionthe resulting residue was dissolved in EtOAc (1 L)
  3. washThe solution was then washed with saturated aqueous NaCl (3×1 L), H2O (1 L)
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customtriturated with hexanes, upon which the product
  8. customprecipitated as a white powder (5, 59.3 g, 109 mmol, 96%, mixture of two diastereomers)

Sources & evidence

ORD record
ord-5a92c9e0a970409982ac042e355423e0
Source dataset
uspto-grants-2006_04
Patent number
US07034147B2

Reaction notes

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