Water → [11-(2-Ethylhexyl)-8-(2,4,6-trimethylbenzoyl)-11H-benzo[a]carbazole-5-yl]-[4-(2,2,3,3-tetrafluoropropoxy)-phenyl]-methane oxime

HRID 2172368Notes

Reaction equation

HRID 2172368 reaction equation
[CH2:1]([CH:3]([CH2:42][CH2:43][CH2:44][CH3:45])[CH2:4][N:5]1[C:17]2[C:12](=[CH:13][C:14]([C:22](=O)[C:23]3[CH:28]=[CH:27][C:26](F)=[CH:25][CH:24]=3)=[C:15]3[CH:21]=[CH:20][CH:19]=[CH:18][C:16]3=2)[C:11]2[C:6]1=[CH:7][CH:8]=[C:9]([C:31]([C:33]1[C:38]([CH3:39])=[CH:37][C:36]([CH3:40])=[CH:35][C:34]=1[CH3:41])=O)[CH:10]=2)[CH3:2].[F:46][C:47]([F:53])([CH:50]([F:52])[F:51])[CH2:48]O.[OH-:54].[Na+].[OH2:56].[N:57]1C=CC=CC=1>>[CH2:1]([CH:3]([CH2:42][CH2:43][CH2:44][CH3:45])[CH2:4][N:5]1[C:17]2[C:12](=[CH:13][C:14]([CH2:22][C:23]3[CH:28]=[CH:27][C:26]([O:54][CH2:48][C:47]([F:53])([F:46])[CH:50]([F:52])[F:51])=[CH:25][CH:24]=3)=[C:15]3[CH:21]=[CH:20][CH:19]=[CH:18][C:16]3=2)[C:11]2[C:6]1=[CH:7][CH:8]=[C:9]([C:31](=[N:57][OH:56])[C:33]1[C:38]([CH3:39])=[CH:37][C:36]([CH3:40])=[CH:35][C:34]=1[CH3:41])[CH:10]=2)[CH3:2]

Participants

6

Reactant 5

HCID 962WaterHCID 1049PyridineHCID 64412,2,3,3-Tetrafluoro-1-propanolHCID 14798Sodium HydroxideHCID 67130099[11-(2-Ethylhexyl)-5-(4-fluorobenzoyl)-11H-benzo[a]carbazol-8-yl]-(2,4,6-trimethylphenyl)-methanone

Product 1

HCID 86690533[11-(2-Ethylhexyl)-8-(2,4,6-trimethylbenzoyl)-11H-benzo[a]carbazole-5-yl]-[4-(2,2,3,3-tetrafluoropropoxy)-phenyl]-methane oximeYield 51%

Conditions

Temperature
70 °C

Procedure

To [11-(2-ethylhexyl)-5-(4-fluorobenzoyl)-11H-benzo[a]carbazol-8-yl]-(2,4,6-trimethylphenyl)-methanone (1.29 g, 2.16 mmol) in pyridine (3 ml) are added 2,2,3,3-tetrafluoro-1-propanol (0.43 g, 3.24 mmol) and sodium hydroxide (0.13 g, 3.32 mmol). The mixture is stirred at 70° C. for 23 hours, and then it is stirred at 120° C. for 24 hours. After the reaction mixture is cooled at room temperature, it is poured into water, and then the crude product is extracted with AcOEt, and washed with water and brine. After drying over MgSO4 and concentration, the crude product is purified by column chromatography on silica gel eluting with CH2Cl2 to obtain a white solid (0.80 g, 51%). The product is composed of an isomeric mixture, and the structure is confirmed by 1H-NMR spectrum (CDCl3) δ [ppm]: 0.79-0.99 (m), 1.24-1.52 (m), 2.05 (s), 2.13 (s), 2.35 (s), 2.37 (s), 4.31 (t), 4.73-4.77 (m), 5.90-6.16 (m), 6.83 (d), 6.87 (d), 6.92 (s), 6.94 (s), 7.50-7.73 (m), 7.88 (d), 8.00 (s), 8.11 (br), 8.19 (s), 8.41 (br), 8.55 (d), 8.62 (d); 19F-NMR spectrum (CDCl3). δ [ppm] −125.04, −124.90.

Workup

  1. stirringit is stirred at 120° C. for 24 hours
  2. temperatureAfter the reaction mixture is cooled at room temperature
  3. extractionthe crude product is extracted with AcOEt
  4. washwashed with water and brine
  5. dry with materialAfter drying over MgSO4 and concentration
  6. customthe crude product is purified by column chromatography on silica gel eluting with CH2Cl2

Sources & evidence

ORD record
ord-48914a2ea968453a939c60f0ff99de91
Source dataset
uspto-grants-2015_06
Patent number
US09051397B2

Reaction notes

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