N-Phenyl-p-phenylenediamine → 1,2,3,4-Tetrahydroquinoline

HRID 1297161Notes

Reaction equation

HRID 1297161 reaction equation
[C:1]1([NH:7][C:8]2[CH:14]=[CH:13][C:11](N)=[CH:10][CH:9]=2)[CH:6]=[CH:5]C=CC=1.[Cl-].[In+3].[Cl-].[Cl-]>O>[NH:7]1[C:8]2[C:9](=[CH:10][CH:11]=[CH:13][CH:14]=2)[CH2:5][CH2:6][CH2:1]1

Participants

4

Reactant 2

HCID 7564N-Phenyl-p-phenylenediamineHCID 159675indium(III)chloride

Product 1

HCID 694601,2,3,4-TetrahydroquinolineYield 65%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

The mixture of 4-(N-phenylamino)-aniline (2 mmol), 2,3-dihrdrofuran (4 mmol) and indium chloride (0.2-0.4 mmol) in water was stirred at room temperature for 10 h. TLC showed the completion of the reaction. The reaction mixture was extracted with diethyl ether (3×20 ml) and drived over MgSO4. Removal of solvent and flash column chromatography on silica gel gave the 1,2,3,4-tetrahydroquinoline derivative 3-1 in 65% yield (cis/trans=86:14). IR (film): 3326, 2932, 1595, 1504, 1047 cm−1. 1HNMR and —13CNMR(DMSO-d6/TMS): cis-isomer, 7.53(s, 1H, NH), 7.08(m, 2H, Ar—H), 6.85(s, 1H, Ar—H), 6.76(m, 3H, Ar—H), 6.58(m, 2H, Ar—H), 5.09(s, 1H, NH), 4.92(d, 9b-H, J=8.0 Hz), 4.50(t, 1H, OH, J=4.8 Hz), 3.60(m, 2H), 3.30(m, 2H), 3.23(m, 1H), 2.48(m, 1H), 1.35-1.85(m, 6H). 146.77, 141.62, 133.52, 129.66, 123.36, 122.18, 121.69, 118.01, 115.69, 114.66, 75.75, 66.39, 61.52, 52.58, 42.35, 31.03, 29.42, 24.21. trans-isomer, 7.60(s, 1H, NH), 7.08(m, 2H, Ar—H), 6.91(s, 1H, Ar—H), 6.76(m, 3H, Ar—H), 6.58(m, 2H, Ar—H), 5.42(s, 1H, NH), 4.50(t, 1H, OH, J=4.8 Hz), 4.35(d, 9b-H, J=6.0 Hz), 3.75(m, 2H), 3.60(m, 2H), 3.30(m, 2H), 3.55(m, 1H), 2.24(m, 1H), 1.35-1.85(m, 5H). 146.94, 141.75, 132.65, 129.66, 123.46, 122.59, 121.00, 118.01, 115.69, 114.58, 79.81, 65.39, 61.69, 52.34, 41.41, 30.10, 29.53, 29.07. Anal. Calcd. For C20H24N2O2: C, 74.05; H, 7.46; N, 8.63. Found: C, 73.84; H, 7.81; N, 8.56.

Workup

  1. customthe completion of the reaction
  2. extractionThe reaction mixture was extracted with diethyl ether (3×20 ml)
  3. customRemoval of solvent and flash column chromatography on silica gel

Sources & evidence

ORD record
ord-e7a39bd6432044fea210e7dc8cf188db
Source dataset
uspto-grants-2007_07
Patent number
US07250423B2

Reaction notes

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