Ethanol → HCID 66901782, compound

HRID 1188744Notes

Reaction equation

HRID 1188744 reaction equation
[N+:1]([C:4]1[CH:59]=[CH:58][C:7]([O:8][C:9]2[CH:14]=[CH:13][C:12]([N:15]([C:42]3[CH:47]=[CH:46][C:45]([O:48][C:49]4[CH:54]=[CH:53][C:52]([N+:55]([O-])=O)=[CH:51][CH:50]=4)=[CH:44][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:11][CH:10]=2)=[CH:6][CH:5]=1)([O-])=O.CC(N(C)C)=O.C(O)C.O.NN>[Pd].O>[NH2:1][C:4]1[CH:59]=[CH:58][C:7]([O:8][C:9]2[CH:14]=[CH:13][C:12]([N:15]([C:42]3[CH:47]=[CH:46][C:45]([O:48][C:49]4[CH:50]=[CH:51][C:52]([NH2:55])=[CH:53][CH:54]=4)=[CH:44][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:11][CH:10]=2)=[CH:6][CH:5]=1

Participants

7

Reactant 4

HCID 702Ethanol2×HCID 24654Hydrazine hydrate (1:1)HCID 31374DimethylacetamideHCID 86761549HCID 86761549, compound

Product 1

HCID 66901782HCID 66901782, compoundYield 54%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 962WaterSolvent

Conditions

Temperature
70 °C

Procedure

To a mixture of N,N-di[4-(4-nitrophenoxy)phenyl)]-7-(benzothiazol-2-yl)-9,9-diethyl-fluoren-2-amine (Example 11; 5.25 g, 6.6 mmol), DMAC (75 mL), ethanol (50 mL), and 10% palladium on charcoal catalyst (0.51 g) heated to 70° C., a mixture of hydrazine hydrate (4.9 mL), and ethanol (7 mL) was added in portions over 15 minutes. After two hours at 75° C., the mixture was cooled and poured into water. The separated solids were collected, and transferred to a column of silica gel. Elution with 3:1 toluene-ethyl-acetate mixture gave the product, 2.61 g (54% yield), m.p. 192-194° C. Recrystallization from a mixture of ethyl acetate and hexanes did not raise the m.p. Mass spec: m/z 736 (M+). Anal. Calcd. for C48H40N4O2S: C, 78.23%; H, 5.47%; N, 7.60%; S, 4.35%. Found: C, 78.23%; H, 5.56%; N, 7.55%; S, 4.41%. 1H NMR (CDCl3) δ ppm: 0.37 (t, 6H, 7.32 Hz), 1.88-1.97 (m, 2H), 2.03-2.11 (m, 2H), 3.57 (s, 4H), 6.64-6.73 (m, 4H), 6.85-6.92 (m, 8H), 6.94-6.98 (m, 1H), 7.00-7.10 (m, 5H), 7.36 (t, 1H, 8.16 Hz), 7.48 (t, 1H, 7.12 Hz), 7.55 (d, 1H, 8.28 Hz), 7.65 (m, 1H, 7.92 Hz), 7.89 (m, 1H, 7.6 Hz), 7.99 (dd, 1H, 1.6 and 7.92 Hz), 8.02-8.10 (m, 2H). 13C NMR (CDCl3) δ ppm: 8.58, 32.59, 56.29 (3 sp3C), 116.19, 116.64, 118.16, 119.09, 120.79, 120.84, 121.26, 121.37, 121.49, 122.86, 124.87, 125.81, 126.21, 127.22, 131.13, 134.12, 134.88, 142.36, 142.55, 144.64, 148.67, 148.86, 150.51, 152.06, 154.23, 154.53, and 168.90 (27 sp2C).

Workup

  1. additionwas added in portions over 15 minutes
  2. temperaturethe mixture was cooled
  3. customThe separated solids were collected
  4. washElution with 3:1 toluene-ethyl-acetate mixture
  5. customgave the product, 2.61 g (54% yield), m.p. 192-194° C
  6. customRecrystallization
  7. additionfrom a mixture of ethyl acetate and hexanes
  8. temperaturedid not raise the m.p. Mass spec

Sources & evidence

ORD record
ord-6008c8e811fd4df3abdc78b5f14b1057
Source dataset
uspto-grants-2014_03
Patent number
US08674057B1

Reaction notes

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