Toluene → HCID 69581246, compound

HRID 427716Notes

Reaction equation

HRID 427716 reaction equation
[CH2:1]([O:8][C:9](=[O:13])[NH:10][CH:11]=[CH2:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(C)C=CC=CC=1.N1([CH:30]([NH:33][C:34]2[CH:39]=[CH:38][C:37]([C:40]([F:43])([F:42])[F:41])=[CH:36][CH:35]=2)[CH2:31][CH3:32])C2C=CC=CC=2N=N1.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>C(OCC)(=O)C>[CH2:1]([O:8][C:9](=[O:13])[NH:10][C@H:11]1[C:35]2[C:34](=[CH:39][CH:38]=[C:37]([C:40]([F:41])([F:42])[F:43])[CH:36]=2)[NH:33][C@@H:30]([CH2:31][CH3:32])[CH2:12]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 1140TolueneHCID 521998p-Toluenesulfonic acid monohydrateHCID 10931982benzyl N-ethenylcarbamateHCID 18357713HCID 18357713, compound

Product 1

HCID 69581246HCID 69581246, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

A one liter, four neck flask under nitrogen atmosphere was charged with N-vinyl-carbamic acid benzyl ester (27.66 g, 156 mmol, 1.0 equiv) and dry toluene (500 mL). (1-Benzotriazol-1-yl-propyl)-(4-trifluoromethyl-phenyl)-amine (50.0 g, 156 mmol, 1.0 equiv) and p-toluenesulfonic acid monohydrate (297 mg, 1.56 mmol, 0.01 equiv) were added, and the mixture heated to 70° C. After 2 h, the mixture was cooled to room temperature and transferred to a separatory funnel. Ethyl acetate (500 mL) was added. The mixture was washed 1×200 mL 1 N NaOH, 1×200 mL H2O, 1×200 mL brine, and dried (MgSO4). The mixture was filtered and the solids washed 1×50 mL ethyl acetate. The filtrate was concentrated to approximately 250 mL. 500 mL toluene were added, and the mixture concentrated to approximately 500 mL. 500 mL n-heptane were added, the slurry was stirred 1 h, filtered through a Buchner funnel, and dried. cis-(2-Ethyl-6-trifluoromethyl-1,2,3,4-tetrahydro-quinolin4-yl)-carbamic acid benzyl ester was isolated as a white powder (45.04 g, 76%): mp 155-157° C.; 1H NMR (DMSO-d6, 400 MHz) δ0.92 (t, 3H, J=7.5 Hz), 1.5 (m, 3H), 2.00 (m, 1H), 3.35 (m, 1H), 4.77 (m, 1H), 5.07 (d, 1H, J=12.5 Hz), 5.15 (d, 1H, J=12.5 Hz), 6.35 (s, 1H), 6.61 (d, 1H, J=8.5 Hz), 7.12 (s, 1H), 7.18 (dd, 1H, J=1.9, 8.5 Hz), 7.4 (m, 5H), 7.70 (d, 1H, J=9.1 Hz); 13C NMR (DMSO-d6, 100 MHz) δ157.03, 149.02, 137.79, 128.82, 128.23, 128.03, 125.9 (q, J=270 Hz), 125.06, 123.50, 121.73, 115.2 (q, J=31.7 Hz), 113.33, 65.85, 52.09, 47.83, 34.02, 28.68, 9.93; DEPT spectrum: quaternary carbons δ157.03, 149.02, 137.79, 125.9, 121.73, 115.2; CH carbons δ128.82, 128.23, 128.03, 125.06, 123.50, 113.33, 52.09, 47.83; CH2 carbons δ65.85, 34.02, 28.68; CH3 carbon δ9.93; IR (drifts) 3430 (m), 3303 (s), 2951 (m), 1686 (vs), 1542 (vs), 1088 (vs); MS (APCI+) m/z (rel. intensity) 379 (M+H+, 53), 228 (100); Anal. Calcd for C20H21N2O2F3: C, 63.48; H, 5.59; N, 7.40; Found: C, 63.69; H, 6.06, N, 7.36.

Workup

  1. temperaturethe mixture was cooled to room temperature
  2. customtransferred to a separatory funnel
  3. washThe mixture was washed 1×200 mL 1 N NaOH, 1×200 mL H2O, 1×200 mL brine
  4. dry with materialdried (MgSO4)
  5. filtrationThe mixture was filtered
  6. washthe solids washed 1×50 mL ethyl acetate
  7. concentrationThe filtrate was concentrated to approximately 250 mL
  8. addition500 mL toluene were added
  9. concentrationthe mixture concentrated to approximately 500 mL
  10. addition500 mL n-heptane were added
  11. filtrationfiltered through a Buchner funnel
  12. customdried

Sources & evidence

ORD record
ord-2d954ae9d804426bae39127561d313da
Source dataset
uspto-grants-2001_11
Patent number
US06313142B1

Reaction notes

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