Chlorodiphenylphosphine → Quinoline, 8-(diphenylphosphino)-

HRID 1952001Notes

Reaction equation

HRID 1952001 reaction equation
Br[C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[N:10]=[CH:9][CH:8]=[CH:7]2.[Li]CCCC.Cl[P:18]([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>C1COCC1>[C:25]1([P:18]([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)[C:2]2[CH:3]=[CH:4][CH:5]=[C:6]3[C:11]=2[N:10]=[CH:9][CH:8]=[CH:7]3)[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1

Participants

5

Reactant 3

HCID 66180ChlorodiphenylphosphineHCID 1401098-BromoquinolineHCID 178418339Butyllithium

Product 1

HCID 628659Quinoline, 8-(diphenylphosphino)-Yield 60.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of 8-bromoquinoline (20.8 g, 100 mmol) in dry THF (200 mL) under nitrogen was added n-BuLi (62.5 mL, 1.6 M in hexanes, 100 mmol) at −78° C. and the mixture was stirred for 30 minutes. Chlorodiphenylphosphine (17.9 mL, 100 mmol) was then added and the solution was allowed to warm up to room temperature and stirred for 2 h. The solution was then cooled to −78° C. and quenched by addition of saturated aqueous NH4Cl solution (100 mL). After warming up to room temperature, the solution was filtered, the precipitated solid collected, taken up in CH2Cl2 (200 mL) and filtered over silica gel eluting with further portions of CH2Cl2 (4×200 mL). The combined filtrates were evaporated to give 1 as a light yellow solid (19 g, 60% yield). 1H NMR (400.13 MHz, CDCl3) δ 8.37 (dd, 1H, J=4.0, 1.6 Hz, C2—H), 8.17 (dd, 1H, J=8.0, 1.6 Hz, C3—H), 7.82 (d, 1H, J=8.4 Hz, C5—H), 7.44 (t, 1H, J=7.6 Hz, C6—H), 7.40 (dd, 1H, J=8.0, 4.0 Hz, C4—H), 7.3-7.2 (m, 10H, Ph-H), 7.14 (ddd, 1H, J=7.2, 3.6, 1.6 Hz, C1′—H) ppm; 13C NMR (100.61 MHz, CDCl3) δ 149.8, 149.6 (d, J=17.2 Hz), 138.4 (d, J=12.1 Hz), 137.4 (d, J=11.1 Hz), 136.2, 134.4, 134.2 (d, J=21.2 Hz), 128.8, 128.4 (d, J=19.2), 127.9, 126.57, 121.41 ppm; 31P NMR (161.97 MHz, CDCl3) δ 15.0 ppm.

Workup

  1. stirringstirred for 2 h
  2. temperatureThe solution was then cooled to −78° C.
  3. customquenched by addition of saturated aqueous NH4Cl solution (100 mL)
  4. temperatureAfter warming up to room temperature
  5. filtrationthe solution was filtered
  6. customthe precipitated solid collected
  7. filtrationfiltered over silica gel eluting with further portions of CH2Cl2 (4×200 mL)
  8. customThe combined filtrates were evaporated

Sources & evidence

ORD record
ord-eb645dac29a64bd5b7a43dd377642385
Source dataset
uspto-grants-2013_03
Patent number
US08404843B2

Reaction notes

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