1-Bromonaphthalene → HCID 58036794, compound

HRID 1952008Notes

Reaction equation

HRID 1952008 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-932ad96103734e25b1d1e2002ac23a38
Source dataset
uspto-grants-2013_03
Patent number
US08404843B2

Reaction notes

Loading…