Hexane → Diphenyl-(4-(4,4,5,5-tetramethyl-(1,3,2)dioxaborolan-2-yl)-phenyl)-amine

HRID 1261872

Reaction equation

HRID 1261872 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.[Li]CCCC.CCCCCC.C(O[B:36]1[O:40][C:39]([CH3:42])([CH3:41])[C:38]([CH3:44])([CH3:43])[O:37]1)(C)C>O.C1(C)C=CC=CC=1.C1COCC1>[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:36]3[O:40][C:39]([CH3:42])([CH3:41])[C:38]([CH3:44])([CH3:43])[O:37]3)=[CH:16][CH:15]=2)[CH:5]=[CH:6][CH:1]=[CH:2][CH:3]=1

Participants

8

Reactant 4

HCID 8058HexaneHCID 6428384-BromotriphenylamineHCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 178418339Butyllithium

Product 1

HCID 11639307Diphenyl-(4-(4,4,5,5-tetramethyl-(1,3,2)dioxaborolan-2-yl)-phenyl)-amineYield 45%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a flame-dried 3-neck, round-bottomed 500 mL flask equipped with mechanical stirring and an addition funnel was added 4-bromotriphenylamine (12.5 g, 39.5 mmol) and THF (250 mL) by cannula. The solution was cooled to −78° C. and 1.6 M n-BuLi in hexane (26.5 mL, 42.4 mmol) was added by addition funnel over 15 min. After stirring for 30 min, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9.8 mL, 48.2 mmol) was added dropwise, and the reaction mixture was allowed to warm to room temperature overnight. Toluene and water were added, and the organic phase was further washed with water, dried with MgSO4, and concentrated. The crude product was purified by column chromatography eluting with hexane, 2/1 hexane/CH2Cl2, and finally 1/1 hexane/CH2Cl2 to give 6.4 g (45%) white crystals. 1H NMR (400 MHz, CDCl3) δ: 7.66 (m, 2H), 7.26 (m, 4H), 7.10 (m, 4H), 7.04 (m, 4H); GC-MS (m/z): 371 (M+), >97% purity. Anal. Calcd. for C24H26BNO2: C, 77.64%; H, 7.06%; B, 2.91%; N, 3.77%. Found: C, 77.78%; H, 7.21%; B, 2.70%; N, 3.53%.

Workup

  1. customTo a flame-dried 3-neck, round-bottomed 500 mL flask equipped
  2. stirringAfter stirring for 30 min
  3. temperatureto warm to room temperature overnight
  4. washthe organic phase was further washed with water
  5. dry with materialdried with MgSO4
  6. concentrationconcentrated
  7. customThe crude product was purified by column chromatography
  8. washeluting with hexane, 2/1 hexane/CH2Cl2, and finally 1/1 hexane/CH2Cl2

Sources & evidence

ORD record
ord-a48ce86daca946aebe88677c8e339b5f
Source dataset
uspto-grants-2013_06
Patent number
US08471035B1

Linked notes

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