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

HRID 1170814ノート

反応式

HRID 1170814 の反応式
[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.CCO.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

参加物

8

反応物 4

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

生成物 1

HCID 586256204,4'-Bis(3-(hydroxymethyl)carbazol-9-yl)biphenyl

試薬・触媒・溶媒 3

HCID 702Ethanol溶媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

Sodium borohydride (2.40 g, 63.4 mmol)) was added to the 4,4′-bis(3-formyl-carbazol-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) 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, Me0SO): δ 8.23 (2 H, d, J 7.61 Hz, aromatic H); 8.18 (2H, s, aromatic H); 8.06 (4H, d, J 8, 19 Hz, aromatic H); 7.75 (4H, J 8, 19 Hz, aromatic H); 7.38-7.50 (8H, m, aromatic H), 7.29 (2H, 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−1 cm−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 cm−1.

後処理

  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
  10. customto give 4,4′-bis(3-(hydroxymethyl)carbazol-9-yl) as a pale yellow solid (3.22 g, 94%) with m.p. 268° C. (dec.)

出典と根拠

ORDレコード
ord-633ea3f586ac4b7cb7144562e1d9a1e3
出典データセット
uspto-grants-2010_11
特許番号
US07829203B2

反応ノート

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