Triethylamine → HCID 69215973, compound

HRID 272709Notes

Reaction equation

HRID 272709 reaction equation
[Cl:1][C:2]1[CH:11]=[CH:10][C:5]([C:6](OC)=[O:7])=[C:4]([NH:12][C:13]2[CH:18]=[C:17]([O:19][CH2:20][O:21][CH2:22][CH2:23][Si:24]([CH3:27])([CH3:26])[CH3:25])[C:16]([O:28][CH3:29])=[CH:15][C:14]=2[N+:30]([O-])=O)[CH:3]=1.O[Li].O.C(N(CC)CC)C.O.O.Cl[Sn]Cl.CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F>CN(C=O)C.O.C1COCC1.CO>[Cl:1][C:2]1[CH:11]=[CH:10][C:5]2[C:6](=[O:7])[NH:30][C:14]3[CH:15]=[C:16]([O:28][CH3:29])[C:17]([O:19][CH2:20][O:21][CH2:22][CH2:23][Si:24]([CH3:25])([CH3:27])[CH3:26])=[CH:18][C:13]=3[NH:12][C:4]=2[CH:3]=1

Participants

10

Reactant 5

HCID 8471Triethylamine2×HCID 61436Stannous chloride dihydrateHCID 168937Lithium hydroxide, monohydrateHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 69218416HCID 69218416, compound

Product 1

HCID 69215973HCID 69215973, compoundYield 89%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
65 °C

Procedure

A mixture of Example 476F (11.4 g, 23.6 mmol), LiOH.H2O (2.97 g, 70.8 mmol), methanol (200 mL), THF (100 mL) and water (10 mL) was heated at 65° C. for 4.25 hours. When hydrolysis was complete, triethylamine (65.8 mL, 472 mmol) was added, followed by SnCl2.2H2O (26.6 g, 118 mmol). The mixture was heated at 65° C. overnight, then cooled to room temperature when hydrogenation was complete. DMF (200 mL), triethylamine (16.5 mL, 118 mmol) and HATU (17.95 g, 47.2 mmol) were added and the mixture was stirred overnight, filtered through diatomaceous earth (Celite®), concentrated under vacuum, diluted with ethyl acetate, washed with water and brine, dried (MgSO4), filtered, and concentrated under vacuum. Hexane was added to a solution of the concentrate in diethyl ether to invoke formation of a solid which was filtered, rinsed with hexane, and dried under vacuum to give 8.8 g (89%) of the desired product. MS (ESI) m/e 421 (M+H)+; 1H NMR (300 MHz, DMSO-d6) □ 9.69 (s, 1H), 7.81 (s, 1H), 7.65 (d, J=8.5 Hz, 1H), 7.04 (d, J=2.0 Hz, 1H), 6.91 (dd, J=2.0, 8.5 Hz, 1H), 6.76 (s, 1H), 6.65 (s, 1H), 5.11 (s, 2H), 3.67 (s, 3H), 3.65-3.72 (m, 2H), 0.86-0.94 (m, 2H), -0.03 (s, 9H).

Workup

  1. customWhen hydrolysis
  2. temperaturecooled to room temperature when hydrogenation
  3. filtrationfiltered through diatomaceous earth (Celite®)
  4. concentrationconcentrated under vacuum
  5. additiondiluted with ethyl acetate
  6. washwashed with water and brine
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated under vacuum
  10. additionHexane was added to a solution of the
  11. concentrationconcentrate in diethyl ether
  12. filtrationwas filtered
  13. washrinsed with hexane
  14. customdried under vacuum

Sources & evidence

ORD record
ord-b13bb97bd255478bbf6cd323b86e3ea0
Source dataset
uspto-grants-2008_11
Patent number
US07456169B2

Reaction notes

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