Nitrogen → HCID 57755080, compound

HRID 547872Notes

Reaction equation

HRID 547872 reaction equation
[C:1]1([C:7]#[C:8][C:9]2[CH:14]=[CH:13][C:12](B(O)O)=[CH:11][CH:10]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:18]1([C:24]#[C:25][C:26]2[CH:31]=[CH:30][C:29](Br)=[CH:28][CH:27]=2)[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.N#N.[CH2:35]([Li])[CH2:36]CC.COB(OC)OC.[CH2:47]1[CH2:51][O:50][CH2:49][CH2:48]1>>[C:1]1([C:7]#[C:8][C:9]2[CH:14]=[CH:13][C:12]([C:35]3[CH:36]=[C:49]([OH:50])[CH:48]=[C:47]([C:29]4[CH:30]=[CH:31][C:26]([C:25]#[C:24][C:18]5[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=5)=[CH:27][CH:28]=4)[CH:51]=3)=[CH:11][CH:10]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 6

HCID 947NitrogenHCID 8028TetrahydrofuranHCID 8470Trimethyl borateHCID 2908881-bromo-4-(phenylethynyl)benzeneHCID 66774889HCID 66774889, compoundHCID 178418339Butyllithium

Product 1

HCID 57755080HCID 57755080, compound

Conditions

Temperature
-78 °C

Procedure

Synthesis of 4-(phenylethynyl)phenyl boronic acid (JACS, 2004, 126, 5798): In a flame-dried flask, 4-(phenylethynyl)-1-bromobenzene (15.0 g, 58.4 mmol) was dissolved in dry THF (225 mL). The solution was treated with 3 cycles of evacuation and refilling with N2, then chilled to −78° C. in a dry ice/acetone bath. To the stirred solution was added a solution of n-butyllithium in hexanes (1.6 M, 40 mL, 1.1 eq) by syringe over the course of 10 minutes. The resulting solution was stirred for an additional 30 minutes before trimethylborate (9.77 mL, 9.1 g, 1.5 eq) was added slowly over 15 minutes. After stirring for an additional 15 minutes, the cooling bath was removed and the solution was allowed to warm to room temperature and stir for 16 h. At this time, 2 M HCl (aqueous) (375 mL) was added, and the biphasic system was stirred vigorously for 2 hours. Ethyl acetate was added, and the organic layer was separated, dried (MgSO4), filtered and evaporated. Methylene chloride (100 mL) was added to the solid residue, which was crushed and mixed into a paste, then filtered and washed with additional portions of methylene chloride to give 8.5 g of the title compound as a white powder.

Workup

  1. additionwas added slowly over 15 minutes
  2. customthe cooling bath was removed
  3. temperatureto warm to room temperature
  4. stirringstir for 16 h
  5. additionAt this time, 2 M HCl (aqueous) (375 mL) was added
  6. stirringthe biphasic system was stirred vigorously for 2 hours
  7. additionEthyl acetate was added
  8. customthe organic layer was separated
  9. dry with materialdried (MgSO4)
  10. filtrationfiltered
  11. customevaporated
  12. additionMethylene chloride (100 mL) was added to the solid residue, which
  13. customwas crushed
  14. additionmixed into a paste
  15. filtrationfiltered
  16. washwashed with additional portions of methylene chloride

Sources & evidence

ORD record
ord-b19d54be83a84dbbad44c255b0087322
Source dataset
uspto-grants-2011_05
Patent number
US07939620B2

Reaction notes

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