Hydrazine hydrate (1:1) → HCID 66901830, compound

HRID 1188742Notes

Reaction equation

HRID 1188742 reaction equation
[N+:1]([C:4]1[CH:59]=[CH:58][C:7]([O:8][C:9]2[CH:10]=[C:11]([N:15]([C:42]3[CH:47]=[CH:46][CH:45]=[C:44]([O:48][C:49]4[CH:54]=[CH:53][C:52]([N+:55]([O-])=O)=[CH:51][CH:50]=4)[CH:43]=3)[C:16]3[CH:28]=[CH:27][C:26]4[C:25]5[C:20](=[CH:21][C:22]([C:29]6[S:30][C:31]7[CH:37]=[CH:36][CH:35]=[CH:34][C:32]=7[N:33]=6)=[CH:23][CH:24]=5)[C:19]([CH2:40][CH3:41])([CH2:38][CH3:39])[C:18]=4[CH:17]=3)[CH:12]=[CH:13][CH:14]=2)=[CH:6][CH:5]=1)([O-])=O.O1CCCC1.C(O)C.O.NN>[Pd].O>[NH2:1][C:4]1[CH:59]=[CH:58][C:7]([O:8][C:9]2[CH:10]=[C:11]([N:15]([C:42]3[CH:47]=[CH:46][CH:45]=[C:44]([O:48][C:49]4[CH:50]=[CH:51][C:52]([NH2:55])=[CH:53][CH:54]=4)[CH:43]=3)[C:16]3[CH:28]=[CH:27][C:26]4[C:25]5[C:20](=[CH:21][C:22]([C:29]6[S:30][C:31]7[CH:37]=[CH:36][CH:35]=[CH:34][C:32]=7[N:33]=6)=[CH:23][CH:24]=5)[C:19]([CH2:38][CH3:39])([CH2:40][CH3:41])[C:18]=4[CH:17]=3)[CH:12]=[CH:13][CH:14]=2)=[CH:6][CH:5]=1

Participants

6

Reactant 3

HCID 24654Hydrazine hydrate (1:1)HCID 21873804Tetrahydrofuran ethanolHCID 86761548HCID 86761548, compound

Product 1

HCID 66901830HCID 66901830, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of N,N-di[3-(4-nitrophenoxy)phenyl]-7-(benzothiazol-2-yl)-9,9-diethyl-fluoren-2-amine (Example 7; 13.68 g, 17.2 mmol) in 300 mL of 1/1 tetrahydrofuran/ethanol mixture under argon was added 10% palladium/carbon (500 mg). The mixture was heated to 60° C., and hydrazine hydrate (12.7 mL, ˜206 mmol) was added slowly over 40 min by addition funnel. The solution became dark, fluorescent green and, after 8 hr, was cooled to room temperature and poured into 1.5 L of distilled water. After a few hours of stirring to evaporate some THF, a fine yellow solid was filtered and purified by column chromatography eluting with ethyl acetate/toluene. The product was further slurried in 100 mL of hot EtOH, filtered at room temperature, and dried in vacuo at 70° C. overnight to give 8.4 g (65%). 1H NMR (400 MHz, CDCl3) δ ppm: 8.08 (m, 2H), 8.01 (dd, J1=8 Hz, J2=1.6 Hz, 1H), 7.91 (d, J=8 Hz, 1H), 7.70 (d, J=8 Hz, 1H), 7.48-7.55 (m, 1H), 7.35-7.42 (m, 1H), 7.05-7.18 (m, 4H), 6.52-6.59 (m, 2H), 3.5-3.6 (br. s, 4H), 1.95-2.15 (m, 4H), 0.34 (t, J=7 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ ppm: 168.97, 159.73, 154.38, 152.23, 150.91, 149.04, 148.61, 147.69, 144.56, 142.72, 135.98, 135.07, 131.71, 129.98, 127.39, 126.42, 125.11, 124.19, 123.08, 121.68, 121.59, 121.19, 121.00, 119.60, 119.54, 117.90, 116.31, 113.33, 111.70, 56.57, 32.77, 8.73; MS (m/z): 736 (M+); Anal. Calcd. for C48H40N4O2S: C, 78.23%; H, 5.47%; N, 7.60%; S, 4.35%%. Found: C, 78.01%%; H, 5.60%%; N, 7.62%%; S, 4.31%.

Workup

  1. temperaturewas cooled to room temperature
  2. customto evaporate some THF
  3. filtrationa fine yellow solid was filtered
  4. custompurified by column chromatography
  5. washeluting with ethyl acetate/toluene
  6. filtrationfiltered at room temperature
  7. customdried in vacuo at 70° C. overnight
  8. customto give 8.4 g (65%)

Sources & evidence

ORD record
ord-36fb97f4fa0d4f26afdab3bc0e63e227
Source dataset
uspto-grants-2014_03
Patent number
US08674057B1

Reaction notes

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