Toluene → HCID 59380815, compound

HRID 2354001Notes

Reaction equation

HRID 2354001 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[NH2:14].[CH:15]12[CH2:24][CH:19]3[CH2:20][CH:21]([CH2:23][CH:17]([CH2:18]3)[C:16]1=O)[CH2:22]2.[CH3:26][C:27]1[CH:28]=[CH:29][C:30](S(O)(=O)=O)=[CH:31][CH:32]=1.[H-].[H-].[H-].[H-].[Li+].[Al+3].[C:43]1(C)[CH:48]=CC=C[CH:44]=1>C1COCC1>[CH:15]12[CH2:24][CH:19]3[CH2:20][CH:21]([CH2:23][CH:17]([CH2:18]3)[CH:16]1[NH:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[NH:14][CH:26]1[CH:43]3[CH2:48][CH:31]4[CH2:30][CH:29]([CH2:28][CH:27]1[CH2:32]4)[CH2:44]3)[CH2:22]2

Participants

7

Reactant 5

HCID 1140TolueneHCID 6101p-Toluenesulfonic acidHCID 150752,2'-BiphenyldiamineHCID 64151AdamantanoneHCID 21226445Aluminium lithium hydride

Product 1

HCID 59380815HCID 59380815, compoundYield 100%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

614 mg (3.33 mmol) of 2,2′-diaminobiphenyl 9H and 1 g (6.65 mmol) 2-adamantanone were combined with 1% (per amine functionality) pTsOH in a Dean-Stark apparatus. The reagents were dissolved in approximately 200 mL toluene and refluxed for 72 hours. The solvent was stripped off, and 122 mg (3.22 mmol) LAH was added, followed by approximately 200 mL THF. The reaction flask was heated to 50° C. for 2 h, followed by a careful quenching with approximately 100 mL water and 10 mL sat. NH4Cl. The resulting slurry was filtered through a plug of celite, and the plug washed with CH2Cl2. The aqueous layer was washed once with CH2Cl2 (approx. 100 mL). The organic layers were combined, dried over MgSO4, filtered, and the solvent was removed, yielding pure 92-Ad in 100% yield. 1H NMR (CDCl3, 297K, 300 MHz): δ 1.38-1.97 (m, 28H), δ 3.54 (s, 2H), δ 4.05 (s, 2H), δ 6.71 (m, 4H), δ 7.11 (m, 2H), δ 7.22 (m, 2H). 13C NMR (CDCl3, 297K, 300 MHz): δ 27.4, δ 27.6, δ 31.3, δ 31.7, δ 31.8, δ 32.2, δ 37.4, δ 37.8, δ 37.9, δ 56.7, δ 111.1, δ 116.3, δ 124.0, δ 129.1, δ 130.9, δ 145.3. HRMS (ESI-EMM): m/z=453.3247 ([M+H]+), Δ=5 ppm.

Workup

  1. temperaturerefluxed for 72 hours
  2. customa careful quenching with approximately 100 mL water and 10 mL sat. NH4Cl
  3. filtrationThe resulting slurry was filtered through a plug of celite
  4. washthe plug washed with CH2Cl2
  5. washThe aqueous layer was washed once with CH2Cl2 (approx. 100 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. customthe solvent was removed
  9. customyielding pure 92-Ad in 100% yield

Sources & evidence

ORD record
ord-f329aa5f809c4f53a8eeda95fdc93830
Source dataset
uspto-grants-2010_07
Patent number
US07750149B2

Reaction notes

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