Aniline → HCID 18420339, compound

HRID 990322Notes

Reaction equation

HRID 990322 reaction equation
N[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CO[CH:10](OC)[CH2:11][CH:12](OC)OC.C([O-])(=O)C.[Na+].[NH3+]C1C=CC=CC=1.[F:31][P-:32]([F:37])([F:36])([F:35])([F:34])[F:33].C([C:41]1[CH:46]=[CH:45][C:44]([C:47]2[CH:52]=[C:51]([CH3:53])[CH:50]=[C:49](C3C=CC=CC=3)[S+:48]=2)=[CH:43][CH:42]=1)(C)C.C(OC(=O)C)(=O)C>C(O)(=O)C.O>[F:31][P-:32]([F:37])([F:36])([F:35])([F:34])[F:33].[CH:11]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:49]1[CH:50]=[C:51]([CH3:53])[CH:52]=[C:47]([C:44]2[CH:43]=[CH:42][CH:41]=[CH:46][CH:45]=2)[S+:48]=1)([CH3:12])[CH3:10]

Participants

9

Reactant 6

HCID 6115AnilineHCID 7918Acetic AnhydrideHCID 66019TetramethoxypropaneHCID 517045Sodium AcetateHCID 371329865756-50-5HCID 18420329HCID 18420329, compound

Product 1

HCID 18420339HCID 18420339, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Procedure

C45H41F6 PS2, FW=790.90 g/mol. Aniline (2.86 g, 30.0 mmol) and 1,1,3,3-tetramethoxypropane (1.99 g, 12.1) were dissolved in acetic acid (10 mL) and heated to 80 C for 15 minutes. The solution was removed from the heat and a 60% solution of hexafluorophosphoric acid (2 mL) was slowly added. The reaction mixture was then poured into water (200 mL) and the anilinium hexafluorophosphate salt of 1,1,3,3-tetramethoxypropane, a yellow solid, was collected. Sodium acetate (0.023 g, 0.24 mmol), anilinium salt (0.044 g, 0.12 mmol), and 2-(4-Isopropylphenyl)-6-(phenyl)-4-methylthiopyrylium hexafluorophosphate (0.108 g, 0.24 mmol) are combined in a flask containing acetic anhydride (0.6 mL) and acetic acid (0.6 mL). The reaction is heated to 95 C for 8 minutes. Once the reaction is complete, the reaction mixture is poured into water and the brown precipitate is filtered off. The precipitate is dissolved in acetonitrile and crystallized out with ether. The resulting red crystals are collected in 63% yield. Melting point 165-167° C.; 1H NMR (500 MHz, CD3CN, ppm) d 7.65 (t, 2H, J=19.4 Hz), 7.34 (d, 4H, J=7.33 Hz), 7.25 (s, 10H), 7.22 (d, 4H, J=6.6 Hz), 7.09 (d, 2H, J=7.7 Hz), 6.42 (t, 1H, J=12.1 Hz), 6.23 (d, 2H, J=13.6 Hz), 2.82 (m, 2H), 1.16 (d, 12H, 7.0 Hz); UV(DCM): max 893 nm (log e 312,000±17,000 M−1 cm−1).

Workup

  1. temperatureheated to 80 C for 15 minutes
  2. customThe solution was removed from the
  3. temperatureheat
  4. additiona 60% solution of hexafluorophosphoric acid (2 mL) was slowly added
  5. additionThe reaction mixture was then poured into water (200 mL)
  6. customthe anilinium hexafluorophosphate salt of 1,1,3,3-tetramethoxypropane, a yellow solid, was collected
  7. temperatureThe reaction is heated to 95 C for 8 minutes
  8. filtrationthe brown precipitate is filtered off
  9. dissolutionThe precipitate is dissolved in acetonitrile
  10. customcrystallized out with ether
  11. customThe resulting red crystals are collected in 63% yield

Sources & evidence

ORD record
ord-1ee00b03bbbc4f4897adbbbe5e41c78d
Source dataset
uspto-grants-2002_10
Patent number
US06458967B1

Reaction notes

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