Hydrochloric Acid → 4-(Diphenylamino)phenylboronic Acid (contains varying amounts of Anhydride)

HRID 41781

Reaction equation

HRID 41781 reaction equation
[CH:1]1[CH:6]=[CH:5][C:4]([N:7]([C:14]2[CH:19]=[CH:18][C:17](Br)=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[CH:3][CH:2]=1.C([Li])CCC.[B:26](OC)([O:29]C)[O:27]C.Cl>CCCCCC.O1CCCC1>[C:4]1([N:7]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[C:14]2[CH:19]=[CH:18][C:17]([B:26]([OH:29])[OH:27])=[CH:16][CH:15]=2)[CH:5]=[CH:6][CH:1]=[CH:2][CH:3]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8470Trimethyl borateHCID 6428384-BromotriphenylamineHCID 178418339Butyllithium

Product 1

HCID 121669344-(Diphenylamino)phenylboronic Acid (contains varying amounts of Anhydride)Yield 59.9%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-80 °C

Procedure

10 g (30 mmol) of 4-bromotriphenylamine was put into a 500 mL three-neck flask. The air in the flask was replaced with nitrogen. To the mixture were added 20 mL of tetrahydrofuran (THF), and then the mixture was stirred at −80° C. Into this solution, 20 mL (32 mmol) of n-butyllithium (a 1.6 mol/L hexane solution) was dropped by a syringe. After the dropping, this solution was stirred at the same temperature for 1 hour. After the stirring, 40 mL (60 mmol) of trimethyl borate was added to the solution, and the solution was stirred for 1 hour while the temperature of the solution was being increased to room temperature. To the solution was added 200 mL (1.0 mol/L) of hydrochloric acid, and then the solution was stirred for about 15 hours. The organic layer was washed with a saturated sodium hydrogen carbonate solution and then a saturated saline solution. Then, the organic layer was dried with magnesium sulfate. This mixture was subjected to gravity filtration. The obtained filtrate was condensed to give a white solid. The obtained solid was recrystallized with chloroform/hexane to give 5.2 g of a white powdered solid, which was the object of the synthesis, at a yield of 58%. A synthesis scheme of Step 2 is shown in (c-2) given below.

Workup

  1. stirringAfter the dropping, this solution was stirred at the same temperature for 1 hour
  2. stirringthe solution was stirred for 1 hour while the temperature of the solution
  3. temperaturewas being increased to room temperature
  4. stirringthe solution was stirred for about 15 hours
  5. washThe organic layer was washed with a saturated sodium hydrogen carbonate solution
  6. dry with materialThen, the organic layer was dried with magnesium sulfate
  7. filtrationThis mixture was subjected to gravity filtration
  8. customcondensed
  9. customto give a white solid
  10. customThe obtained solid was recrystallized with chloroform/hexane

Sources & evidence

ORD record
ord-637c338567364dec916a49f0d7552336
Source dataset
uspto-grants-2013_09
Patent number
US08530672B2

Linked notes

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