Hydrochloric Acid → 4,4'-Bis(3-(hydroxymethyl)carbazol-9-yl)biphenyl

HRID 643192Notes

Reaction equation

HRID 643192 reaction equation
[BH4-].[Na+].[CH:3]([C:5]1[CH:6]=[CH:7][C:8]2[N:9]([C:18]3[CH:23]=[CH:22][C:21]([C:24]4[CH:29]=[CH:28][C:27]([N:30]5[C:42]6[CH:41]=[CH:40][C:39]([CH:43]=[O:44])=[CH:38][C:37]=6[C:36]6[C:31]5=[CH:32][CH:33]=[CH:34][CH:35]=6)=[CH:26][CH:25]=4)=[CH:20][CH:19]=3)[C:10]3[C:15]([C:16]=2[CH:17]=1)=[CH:14][CH:13]=[CH:12][CH:11]=3)=[O:4].C(O)C.ClCCl.Cl>C1COCC1.O>[OH:44][CH2:43][C:39]1[CH:40]=[CH:41][C:42]2[N:30]([C:27]3[CH:28]=[CH:29][C:24]([C:21]4[CH:20]=[CH:19][C:18]([N:9]5[C:8]6[CH:7]=[CH:6][C:5]([CH2:3][OH:4])=[CH:17][C:16]=6[C:15]6[C:10]5=[CH:11][CH:12]=[CH:13][CH:14]=6)=[CH:23][CH:22]=4)=[CH:25][CH:26]=3)[C:31]3[C:36]([C:37]=2[CH:38]=1)=[CH:35][CH:34]=[CH:33][CH:32]=3

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 4311764Sodium borohydrideHCID 21584144Dichloromethane ethanolHCID 426406674,4'-Bis(3-formylcarbazol-9-yl)biphenyl

Product 1

HCID 586256204,4'-Bis(3-(hydroxymethyl)carbazol-9-yl)biphenylYield 94%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

Sodium borohydride (2.40 g, 63.4 mmol)) was added to the 4,4′-bis(3-formylcarbazol-9-yl)biphenyl (3.42 g, 6.33 mmol) in THF (1.2 L) and the resulting suspension was stirred at room temperature for 24 h. The reaction was followed by TLC using 5% ethanol/dichloromethane as the eluent. Once the reaction was complete, the mixture was slowly poured into water (400 ml) and the mixture was left to stir at room temperature for a further 30 min. The reaction mixture was acidified to pH 1 with hydrochloric acid (5M). The product was extracted with dichloromethane (3×300 ml). The combined organic phase was washed with water (400 ml) and brine (400 ml), dried (MgSO4), filtered and the filtrate evaporated to dryness. The crude product, was purified by chromatography on silica using 50% THF/toluene as the eluent. The product was recrystallised from ethanol to give 4,4′-bis(3-(hydroxymethyl)carbazol-9-yl) biphenyl as a pale yellow solid (3.22 g, 94%) with m.p. 268° C. (dec.). Found: C, 82.51; H, 4.64; and N, 4.86. C38H28N2O2.EtOH requires C, 81.33; H, 5.80; N, 4.74%. 1H n.m.r.(300 MHz, Me2SO): δ 8.23 (2 H, d, J 7.61 Hz, aromatic H); 8.18 (2 H, s, aromatic H); 8.06 (4 H, d, J 8.19 Hz, aromatic H); 7.75 (4 H, J 8,19 Hz, aromatic H); 7.38-7.50 (8 H, m, aromatic H), 7.29 (2 H, m, aromatic H); 5.25 (2H, t, J 5.58 Hz, OH); 4.68 (4H, d, J 5.56 Hz, CH2). λmax(CH2Cl2): 216 nm (ε/Lmol−1cm−1 177 455), 240 (57 873), 271 (56 595), 294 (55 330) 329 (37 758). FTIR (solid): 3343, 1604, 1500, 1485, 1455, 1362, 1330, 1230, 803, 745 cm1.

Workup

  1. waitthe mixture was left
  2. stirringto stir at room temperature for a further 30 min
  3. extractionThe product was extracted with dichloromethane (3×300 ml)
  4. washThe combined organic phase was washed with water (400 ml) and brine (400 ml)
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. customthe filtrate evaporated to dryness
  8. customThe crude product, was purified by chromatography on silica using 50% THF/toluene as the eluent
  9. customThe product was recrystallised from ethanol

Sources & evidence

ORD record
ord-e6a62abe2d944ed6bfcf6be143d9fc9f
Source dataset
uspto-grants-2010_04
Patent number
US07700148B2

Reaction notes

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