Hydrochloric Acid → 7-(Diphenylamino)-9,9-didecylfluorene-2-carbaldehyde

HRID 1581873Notes

Reaction equation

HRID 1581873 reaction equation
Br[C:2]1[CH:14]=[C:13]2[C:5]([C:6]3[CH:7]=[CH:8][C:9]([N:35]([C:42]4[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=4)[C:36]4[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=4)=[CH:10][C:11]=3[C:12]2([CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])=[CH:4][CH:3]=1.C([Li])CCC.CN([CH:56]=[O:57])C.Cl>C1COCC1.CO>[C:36]1([N:35]([C:42]2[CH:43]=[CH:44][CH:45]=[CH:46][CH:47]=2)[C:9]2[CH:10]=[C:11]3[C:6]([C:5]4[CH:4]=[CH:3][C:2]([CH:56]=[O:57])=[CH:14][C:13]=4[C:12]3([CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])=[CH:7][CH:8]=2)[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 22723477HCID 22723477, compoundHCID 178418339Butyllithium

Product 1

HCID 227234757-(Diphenylamino)-9,9-didecylfluorene-2-carbaldehydeYield 88%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of (7-bromo-9,9-didecylfluoren-2-yl)diphenylamine (34.6 g, 0.05 mol) in THF (200 mL), cooled to less than −50° C., a solution of n-butyllithium in hexanes (1.6M, 45 mL, 0.072 mol) was added over 15 minutes. After 30 minutes, a solution of DMF (7.5 mL, 0.097 mol) in THF (40 mL) was added, and after 1 hour, the temperature was allowed to rise to 0° C. The mixture was cooled in an ice bath, and treated with dilute hydrochloric acid (7.5 mL conc. HCl mixed with 60 mL water). After dilution with toluene (200 mL), the organic phase was washed with water, aqueous sodium bicarbonate, and saturated sodium chloride solution, dried and concentrated. The residue was chromatographed over 500 g of silica gel. Elution with 20% toluene-heptane and after removal of solvent, the product, which was initially obtained as a glassy solid, on standing with methanol (150 mL), crystallized into yellow solids, 28.2 g, (88% yield), m.p. 77-78.5° C. Anal. Calcd. for C46H59NO: C, 86.06%; H, 9.26%; N, 2.18%. Found: C, 85.81%; H, 9.49%; N, 2.10%. 1H NMR (270 MHz; CDCl3, ppm): 0.61-0.65 (broad), 0.83, 0.85, 0.88 (triplet), 1.05-1.29 (complex, broad), 1.80-2.00 (complex multiplet), decyl protons, 20H; 7.02, 7.03, 7.04, 7.05, 7.06, 7.07, 7.12,, 7.15, 7.24, 7.26, 7.29, 7.59, 7.62, 7.69, 7.72, 7.80, 7.82, 7.83 (complex multiplets, aromatic protons, 16H); 10.02 (singlet, CHO proton, 1H). 13C-NMR (CDCl3, noise-decoupled, ppm): 14.11, 22.66, 23.84, 29.11, 29.29, 29.55, 29.92,31.88, 40.03, 55.15 (sp3 carbons); 118.21, 119.11, 121.70, 122.82, 123.11, 123.31, 124.38, 129.30, 130.83, 134.02, 134.51, 147.49, 147.64, 148.85, 151.30, 153.69 (sp2 carbons); 192.19 (sp2 carbon of CHO moiety).

Workup

  1. waitafter 1 hour
  2. customto rise to 0° C
  3. temperatureThe mixture was cooled in an ice bath
  4. washAfter dilution with toluene (200 mL), the organic phase was washed with water, aqueous sodium bicarbonate, and saturated sodium chloride solution
  5. customdried
  6. concentrationconcentrated
  7. customThe residue was chromatographed over 500 g of silica gel
  8. washElution with 20% toluene-heptane
  9. customafter removal of solvent
  10. customthe product, which was initially obtained as a glassy solid
  11. customcrystallized into yellow solids, 28.2 g, (88% yield), m.p. 77-78.5° C

Sources & evidence

ORD record
ord-4095ad52091f4126a387baf103a40477
Source dataset
uspto-grants-2004_05
Patent number
US06730793B1

Reaction notes

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