Diethyl Ether → 2,6-Bis(methoxymethoxy)biphenyl

HRID 1511227Notes

Reaction equation

HRID 1511227 reaction equation
[C:1]1(B(O)O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].I[C:19]1[C:24]([O:25][CH2:26][O:27][CH3:28])=[CH:23][CH:22]=[CH:21][C:20]=1[O:29][CH2:30][O:31][CH3:32].CCOCC>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1>[CH3:32][O:31][CH2:30][O:29][C:20]1[CH:21]=[CH:22][CH:23]=[C:24]([O:25][CH2:26][O:27][CH3:28])[C:19]=1[C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

8

Reactant 4

HCID 3283Diethyl EtherHCID 62657Potassium Phosphate, TribasicHCID 66827Phenylboronic AcidHCID 251387872-Iodo-1,3-bis(methoxymethoxy)benzene

Product 1

HCID 251401012,6-Bis(methoxymethoxy)biphenylYield 99%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylCatalystHCID 1140TolueneSolvent2×

Procedure

Anhydrous toluene (2.0 mL) was added to a flask charged with Pd2(dba)3 (56.3 mg, 0.062 mmol), dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine (50.5 mg, 0.12 mmol), phenylboronic acid (281 mg, 2.31 mmol), and potassium phosphate (979 mg, 4.61 mmol) at room temperature. After 15 minutes, a solution of 15 (500 mg, 1.54 mmol) in anhydrous toluene (1.0 mL) was added and the resulting solution was heated to reflux for 12 hours. Upon cooling to room temperature, ether was added, the solution was filtered through SiO2 and concentrated to give 16 as a colorless amorphous solid (418 mg, 99%): 1H NMR (CDCl3, 500 MHz) 7.35-7.28 (m, 2H), 7.28-7.25 (m, 2H), 7.18-7.15 (m, 2H), 6.83 (d, J=8.3 Hz, 2H), 4.96 (s, 4H), 3.24 (s, 6H); 13C NMR (CDCl3, 125 MHz) 155.3, 155.0, 134.3, 130.8, 129.5, 128.7, 128.0, 127.6, 126.8, 122.6, 109.4 (2C), 94.9 (2C), 56.0 (2C); IR (film) νmax 2955, 2928, 2901, 2359, 2341, 1587, 1466, 1439, 1400, 1244, 1153, 1099, 1080, 1041, 922, 764, 733, 700 cm−1; HRMS (ESI+) m/z: [M+Na]+ calcd for C16H18O4, 297.1103. found, 297.1052.

Workup

  1. temperaturethe resulting solution was heated
  2. temperatureto reflux for 12 hours
  3. filtrationthe solution was filtered through SiO2
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-3664bbfadeaa45ea9038f179ed66dd90
Source dataset
uspto-grants-2012_07
Patent number
US08212011B2

Reaction notes

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