1-Adamantanecarboxylic acid → HCID 178472637, compound

HRID 1469968Notes

Reaction equation

HRID 1469968 reaction equation
Br.[CH2:2]([O:4][C:5](=[O:13])[CH2:6][N:7]1[CH:11]=[CH:10][S:9][C:8]1=[NH:12])[CH3:3].[C:14]12([C:24](O)=[O:25])[CH2:23][CH:18]3[CH2:19][CH:20]([CH2:22][CH:16]([CH2:17]3)[CH2:15]1)[CH2:21]2.F[P-](F)(F)(F)(F)F.N1(OC(N(C)C)=[N+](C)C)C2N=CC=CC=2N=N1.C(N(C(C)C)CC)(C)C>C1COCC1.C(OCC)(=O)C>[CH2:2]([O:4][C:5](=[O:13])[CH2:6][N:7]1[CH:11]=[CH:10][S:9]/[C:8]/1=[N:12]\[C:24]([C:14]12[CH2:23][CH:18]3[CH2:17][CH:16]([CH2:22][CH:20]([CH2:19]3)[CH2:21]1)[CH2:15]2)=[O:25])[CH3:3]

Participants

7

Reactant 4

HCID 132351-Adamantanecarboxylic acidHCID 81531DiisopropylethylamineHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 131728626HCID 131728626, compound

Product 1

HCID 178472637HCID 178472637, compoundYield 81%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
65 °C

Procedure

To a solution of the product from Example 77A (0.75 g, 2.8 mmol) and 1-adamantanecarboxylic acid (0.56 g, 3.1 mmol) in 14 mL of THF at 0° C. was added O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate (1.2 g, 3.1 mmol) and diisopropylethylamine (1.1 mL, 6.2 mmol). The mixture was heated to 65° C. for 2.5 hours, cooled to ambient temperature and then diluted with ethyl acetate. The mixture was washed twice with water, saturated aqueous sodium bicarbonate, and brine. The organic extract was dried over magnesium sulfate, and concentrated under reduced pressure. Purification by column chromatography (SiO2, 30-50% ethyl acetate/hexanes gradient) afforded 0.79 g (81%) of the title compound. 1H NMR (CDCl3, 300 MHz) δ ppm 1.29 (t, J=7.1 Hz, 3H), 1.69-1.76 (m, 6H), 1.93-1.94 (m, 6H), 1.99-2.04 (m, 3H), 4.25 (q, J=7.3 Hz, 2H), 4.84 (s, 2H), 6.60 (d, J=5.1 Hz, 1H), 6.93 (d, J=4.7 Hz, 1H); MS (DCI/NH3) m/z 349 (M+H)+. Anal. Calculated for C18H24N2O3S: C, 62.04; H, 6.94; N, 8.04. Found: C, 62.24; H, 7.08; N, 8.04.

Workup

  1. temperaturecooled to ambient temperature
  2. washThe mixture was washed twice with water, saturated aqueous sodium bicarbonate, and brine
  3. extractionThe organic extract
  4. dry with materialwas dried over magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customPurification by column chromatography (SiO2, 30-50% ethyl acetate/hexanes gradient)

Sources & evidence

ORD record
ord-0f5e825f0afc439789ff627c9b54b5bb
Source dataset
uspto-grants-2015_04
Patent number
US09006275B2

Reaction notes

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