Nitrogen → HCID 58261495, compound

HRID 2170453Notes

Reaction equation

HRID 2170453 reaction equation
[C:1]1(B(O)O)[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1.[Cl:14][C:15]1[C:16](Br)=[C:17]([CH:23]=[CH:24][C:25]=1[C:26]([O:28][CH2:29][CH3:30])=[O:27])[C:18]([O:20][CH2:21][CH3:22])=[O:19].O.P([O-])([O-])([O-])=O.[K+].[K+].[K+].N#N>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.O1CCOCC1.C1(C)C=CC=CC=1.O>[Cl:14][C:15]1[CH:16]=[C:17]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[C:23]([C:1]2[C:10]3[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=3)[CH:4]=[CH:3][CH:2]=2)=[CH:24][C:25]=1[C:26]([O:28][CH2:29][CH3:30])=[O:27]

Participants

10

Reactant 4

HCID 947NitrogenHCID 2545321-Naphthaleneboronic acidHCID 22031701Potassium phosphate, tribasic, monohydrateHCID 67151796HCID 67151796, compound

Product 1

HCID 58261495HCID 58261495, compoundYield 65%

Reagents, catalysts & solvents 5

HCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 312751,4-DioxaneSolvent

Procedure

51 g (298 mmol) of 1-naphthylboronic acid, 100 g (298 mmol) of diethyl chlorobromoterephthalate and 144 g (626 mmol) of potassium phosphate monohydrate are initially introduced in a mixture of 600 ml of dist. water, 400 ml of toluene and 200 ml of dioxane and saturated with N2 for 30 min. 5.4 g (18 mmol) of tri(o-tolyl)phosphine and 669 mg (3 mmol) of palladium(II) acetate are subsequently added, and the mixture is heated at the boil for 3 h. After dilution with toluene, the organic phase is separated off, washed twice with water, dried over Na2SO4 and evaporated in vacuo. The oil which remains is distilled in a thin-film evaporator (p=5×10−3 mbar, T=130° C.) and isolated in the form of a yellow oil (74 g, 65%), which, according to 1H-NMR, has a purity of >95%.

Workup

  1. temperaturethe mixture is heated at the boil for 3 h
  2. customAfter dilution with toluene, the organic phase is separated off
  3. washwashed twice with water
  4. dry with materialdried over Na2SO4
  5. customevaporated in vacuo
  6. distillationThe oil which remains is distilled in a thin-film evaporator (p=5×10−3 mbar, T=130° C.)

Sources & evidence

ORD record
ord-11d263f48e514ee78b7d74e0cf9cc21c
Source dataset
uspto-grants-2015_06
Patent number
US09051233B2

Reaction notes

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