1-Bromonaphthalene → HCID 58036794, compound

HRID 1515176Notes

Reaction equation

HRID 1515176 reaction equation
Br[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH:5]=[CH:4][CH:3]=1.[Li]CCCC.[C:17]1([P:23]([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C:24]2[CH:25]=[CH:26][CH:27]=[C:28]3[C:33]=2[N:32]=[CH:31][CH:30]=[CH:29]3)[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.[NH4+].[Cl-]>C1COCC1>[C:34]1([P:23]([C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[C:24]2[CH:25]=[CH:26][CH:27]=[C:28]3[C:33]=2[NH:32][CH:31]([C:2]2[C:11]4[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=4)[CH:5]=[CH:4][CH:3]=2)[CH:30]=[CH:29]3)[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=1

Participants

6

Reactant 4

HCID 70011-BromonaphthaleneHCID 25517Ammonium ChlorideHCID 628659Quinoline, 8-(diphenylphosphino)-HCID 178418339Butyllithium

Product 1

HCID 58036794HCID 58036794, compoundYield 98.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 1-bromonaphthalene (8.57 mL, 60 mmol) in dry THF (100 mL) under nitrogen was added n-BuLi (37.5 mL, 1.6 M in hexanes, 60 mmol) at −78° C. and the solution was stirred for 30 minutes at −78° C. before adding 8-diphenylphoshinoquinoline (1) (9.4 g, 30 mmol). After stirring at 0° C. for 10 minutes the solution was again cooled down to −78° C., saturated aqueous NH4Cl solution (10 mL) was added and the mixture was warmed to room temperature. Products were then extracted with EtOAc, washed with water and saturated aqueous NaCl, dried (MgSO4) and evaporated to give the 11 as a tan solid (13.0 g, 98%). 1H NMR (400.13 MHz, CDCl3) δ 8.0-7.9 (m, 1H, C5′—H), 7.8-7.7 (m, 1H, C8′—H), 7.66 (d, 1H, J=8.0 Hz, C2′—H), 7.5-7.3 (m, 2H, C6′/7′—H), 7.36 (d, 1H, J=6.4 Hz, C4′—H), 7.3-7.1 (m, 11H, C3′—H/Ph-H), 6.86 (dd, 1H, J=7.2, 1.2 Hz, C5—H), 6.64 (ddd, 1H, J=8.0, 6.4, 1.6 Hz, C7—H), 6.48 (t, 1H, J=7.6 Hz, C6—H), 6.35 (dd, 1H, J=9.6, 1.6 Hz, C4—H), 6.16 (t, 1H, J=1.6 Hz, C2—H), 5.70 (ddd, 1H, J=10.0, 3.6, 1.6 Hz, C3—H), 5.02 (bd, 1H, J=7.6 Hz, N—H) ppm; 13C NMR (100.61 MHz, CDCl3) δ 146.6, 146.5, 139.8, 129.5, 128.7, 128.6, 128.5, 128.4, 128.3 (m), 127.7, 135.1 (d, J=8.1 Hz), 134.9 (d, J=7.1 Hz), 134.5 (d, J=5.1 Hz), 133.9, 133.5 (d, J=13.1 Hz), 133.3 (d, J=12.1 Hz), 126.2, 125.6, 125.3, 125.2, 124.8, 124.4, 122.5, 118.8, 117.1, 116.3, 54.0 ppm; 31P NMR (161.97 MHz, CDCl3) δ −23.1 ppm.

Workup

  1. stirringAfter stirring at 0° C. for 10 minutes the solution
  2. additionwas added
  3. temperaturethe mixture was warmed to room temperature
  4. extractionProducts were then extracted with EtOAc
  5. washwashed with water and saturated aqueous NaCl
  6. dry with materialdried (MgSO4)
  7. customevaporated

Sources & evidence

ORD record
ord-f265302acc1348f9a54e7120d6585aa6
Source dataset
uspto-grants-2012_07
Patent number
US08222415B2

Reaction notes

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