Acetic Acid → 10-(4-Methylnaphth-1-yl)anthracene-9-boronic acid pinacol ester

HRID 1190234Notes

Reaction equation

HRID 1190234 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].Br[C:7]1[C:8]2[C:13]([C:14](C3C4C(=CC=CC=4)C(C)=CC=3)=[C:15]3[C:20]=1[CH:19]=[CH:18][CH:17]=[CH:16]3)=[CH:12][CH:11]=[CH:10][CH:9]=2.[B:32](OC)(OC)OC.C(O)(=O)C.[OH:43][C:44]([C:47]([OH:50])([CH3:49])[CH3:48])([CH3:46])[CH3:45].[C:51]1([CH3:57])[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=1>C(OCC)C.O>[CH3:4][C:3]1[C:56]2[C:51](=[CH:52][CH:53]=[CH:54][CH:55]=2)[C:57]([C:7]2[C:20]3[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=3)[C:14]([B:32]3[O:50][C:47]([CH3:49])([CH3:48])[C:44]([CH3:46])([CH3:45])[O:43]3)=[C:13]3[C:12]=2[CH:11]=[CH:10][CH:9]=[CH:8]3)=[CH:1][CH:2]=1

Participants

9

Reactant 6

HCID 176Acetic AcidHCID 1140TolueneHCID 6425PinacolHCID 8470Trimethyl borateHCID 597583959-Bromo-10-(4-methylnaphthalen-1-YL)anthraceneHCID 178418339Butyllithium

Product 1

HCID 5770265010-(4-Methylnaphth-1-yl)anthracene-9-boronic acid pinacol ester

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

44.0 ml (110 mmol) of n-butyllithium (2.5M in n-hexane) are added over the course of 20 min. to a vigorously stirred suspension, cooled to −78° C., of 39.7 g (100 mmol) of 9-bromo-10-(4-methylnaphth-1-yl)anthracene in 1000 ml of diethyl ether, and the mixture is subsequently stirred at −78° C. for 30 min. The suspension is allowed to warm to 20° C. over the course of 2 h, is stirred at 20° C. for a further 2 h and re-cooled to −78° C. 28.0 ml (250 mol) of trimethyl borate are added over the course of 5 min. with vigorous stirring, and the suspension is allowed to re-warm to 20° C. After 15 h at 20° C., a mixture of 15.0 ml (250 mol) of acetic acid in 200 ml of water is added, and the mixture is stirred at room temperature for a further 5 h. After the water phase has been separated off, the organic phase is evaporated to dryness under reduced pressure. 300 ml of n-hexane are added to the slurry which remains, and the mixture is stirred vigorously for 1 h. The solid formed is subsequently filtered off with suction, washed twice with 100 ml of n-hexane and sucked dry. The solid is suspended in 150 ml of toluene, 13.0 g (110 mmol) of pinacol are added, and the mixture is boiled on a water separator for 5 h. The crystals deposited after cooling of the toluene solution are filtered off with suction, recrystallised twice from DMSO and subsequently sublimed (T=350° C., p=5×10−5 mbar); yield: 30.4 g (68.4% of theory), 99.9% according to 1H-NMR.

Workup

  1. temperatureto warm to 20° C. over the course of 2 h
  2. stirringis stirred at 20° C. for a further 2 h
  3. temperaturere-cooled to −78° C
  4. temperatureto re-warm to 20° C
  5. waitAfter 15 h at 20° C.
  6. additionis added
  7. stirringthe mixture is stirred at room temperature for a further 5 h
  8. customAfter the water phase has been separated off
  9. customthe organic phase is evaporated to dryness under reduced pressure
  10. addition300 ml of n-hexane are added to the slurry which
  11. stirringthe mixture is stirred vigorously for 1 h
  12. customThe solid formed
  13. filtrationis subsequently filtered off with suction
  14. washwashed twice with 100 ml of n-hexane
  15. customsucked dry
  16. waitseparator for 5 h
  17. filtrationare filtered off with suction
  18. customrecrystallised twice from DMSO and subsequently sublimed (T=350° C., p=5×10−5 mbar)

Sources & evidence

ORD record
ord-88fdc33919fa4765898e33f2738e7dad
Source dataset
uspto-grants-2014_03
Patent number
US08674141B2

Reaction notes

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