Trifluoroacetic acid → HCID 22598375, compound

HRID 1760332Notes

Reaction equation

HRID 1760332 reaction equation
C(=O)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH3:13].F[C:16](F)(F)[C:17](O)=O.[NH2:22][C:23]1[CH:27]=[CH:26][S:25][CH:24]=1.[OH-].[Na+]>ClCCl.O.C(OCC)C>[CH2:2]([N:22]1[C:23]2=[CH:27][CH2:26][S:25][C:24]2=[CH:23][C:24]2[S:25][CH:26]=[CH:16][C:17]1=2)[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH3:13]

Participants

8

Reactant 4

HCID 6422Trifluoroacetic acid2×HCID 14798Sodium HydroxideHCID 25311TridecanalHCID 640543Thiophen-3-amine

Product 1

HCID 22598375HCID 22598375, compoundYield 263.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of tridecanal (25.00 g, 126.04 mmol) and trifluoroacetic acid (2.00 g) in anhydrous dichloromethane (200 mL) was added dropwise to a solution of 3-aminothiophene (21.00 g, 211.78 mmol) in anhydrous dichloromethane (200 mL) at −10° C. The reaction mixture was stirred at room temperature for 1.5 h. Trifluoroacetic acid (24.15 g, 211.78 mmol) was added and the reaction mixture was then heated at reflux for 24 h. The solution was cooled and diethyl ether (300 mL) and water (100 mL) were added. The aqueous layer was basified with 0.5 N aqueous sodium hydroxide solution. The organic layer was separated. The aqueous layer was again extracted into diethyl ether (2×100 mL). The combined organic extracts were dried over sodium sulfate and concentrated in vacuo. Purification by flash chromatography (eluent: dichloromethane) afforded 4-dodecyldithieno[3,2-b:2′3′-e]pyridine (16.74 g, 22%) as a red oil: δH(CDCl3, 300 MHz) 7.76 (2H, d, 3JHH=6 Hz), 7.60 (2H, d, 3JHH=6 Hz), 3.15 (2H, t, 3JHH=7.5 Hz), 1.90 (2H, m), 1.25-1.50 (18H, m), 0.88 (3H, t, 3JHH=7.5 Hz); δC(CDCl3, 75 MHz) 155.8, 140.0, 130.3, 129.4, 125.3, 34.5, 31.9, 29.7, 29.6, 29.5, 29.4, 28.0, 22.7, 14.1.

Workup

  1. temperaturethe reaction mixture was then heated
  2. temperatureat reflux for 24 h
  3. temperatureThe solution was cooled
  4. customThe organic layer was separated
  5. extractionThe aqueous layer was again extracted into diethyl ether (2×100 mL)
  6. dry with materialThe combined organic extracts were dried over sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customPurification by flash chromatography (eluent: dichloromethane)

Sources & evidence

ORD record
ord-4c295e606a5d4a88895d0c1fd6f62317
Source dataset
uspto-grants-2005_01
Patent number
US06841677B2

Reaction notes

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