Azobisisobutyronitrile → HCID 59013524, compound

HRID 2246059Notes

Reaction equation

HRID 2246059 reaction equation
[C:1]1([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:6]=[CH:5][CH:4]=[C:3](B(O)O)[CH:2]=1.Br[C:17]1[CH:18]=[C:19]([CH3:23])[CH:20]=[CH:21][CH:22]=1.C([O-])([O-])=O.[K+].[K+].C1C(=O)N([Br:37])C(=O)C1.CC(N=NC(C#N)(C)C)(C#N)C>C1(C)C=CC=CC=1.O.C(Cl)(Cl)(Cl)Cl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:10]1([C:1]2[CH:2]=[C:3]([C:17]3[CH:18]=[C:19]([CH:20]=[CH:21][CH:22]=3)[CH2:23][Br:37])[CH:4]=[CH:5][CH:6]=2)[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1

Participants

9

Reactant 5

HCID 6547AzobisisobutyronitrileHCID 11430Potassium CarbonateHCID 115603-BromotolueneHCID 67184N-bromobutanimideHCID 2734315(3-Phenylphenyl)boronic acid

Product 1

HCID 59013524HCID 59013524, compound

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 5943Carbon TetrachlorideSolventHCID 22272177Toluene waterSolvent

Procedure

3-biphenyl boronic acid (2.0 g, 10 mmol), 3-bromotoluene (1.7 g, 10 mmol), K2CO3 (3.0 g, 21.7 mmol) and Pd(PPh3)4 (100 mg) were refluxed in toluene-H2O (50 mL, 5/1) overnight under N2. Upon extraction with diethyl ether, the crude product was then refluxed overnight with N-bromosuccimide (1.95 g, 11 mmol) and AIBN (100 mg) in anhydrous CCl4 (30 mL). After being washed successively with 5% HCl then 10% NaHCO3, the organic layer was dried and concentrated to give crude 3-(3-phenylphenyl)benzyl bromide as a white powder. This was then reacted following general method C, followed by general method D, affording compound 647 as a pale yellow powder (472 mg, 27% overall yield). Quantative 1H NMR indicated 94% purity. 1H NMR (400 MHz, CDCl3): δ 1.21 (m, 36H, CH3), 2.80 (tt, J=24.8 Hz, 6.8 Hz, 1 H, ArCH2CH), 3.15 (td, J=17.2 Hz, 6.8 Hz, 2H, ArCH2), 5.62-5.69 (m, 8H, POCH2), 7.23-7.85 (m, 13H, aromatic); 31P NMR (162 MHz, CDCl3): 6 20.52.

Workup

  1. extractionUpon extraction with diethyl ether
  2. washAfter being washed successively with 5% HCl
  3. dry with material10% NaHCO3, the organic layer was dried
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-972455099602498cad0617d5c5e52df4
Source dataset
uspto-grants-2010_03
Patent number
US07687482B2

Reaction notes

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