2-Aminothiophenol → HCID 66901787, compound

HRID 1188743Notes

Reaction equation

HRID 1188743 reaction equation
C[O:2][C:3]1[CH:8]=[CH:7][C:6]([N:9]([C:36]2[CH:41]=[CH:40][C:39]([O:42]C)=[CH:38][CH:37]=2)[C:10]2[CH:22]=[CH:21][C:20]3[C:19]4[C:14](=[CH:15][C:16]([C:23]5[S:24][C:25]6[CH:31]=[CH:30][CH:29]=[CH:28][C:26]=6[N:27]=5)=[CH:17][CH:18]=4)[C:13]([CH2:34][CH3:35])([CH2:32][CH3:33])[C:12]=3[CH:11]=2)=[CH:5][CH:4]=1.NC1C=CC=CC=1S.C(=O)([O-])[O-].[K+].[K+].CN1CCCC1=O>C1(C)C=CC=CC=1.C(O)(=O)C.O.O.C(O)(=O)C>[OH:2][C:3]1[CH:8]=[CH:7][C:6]([N:9]([C:36]2[CH:37]=[CH:38][C:39]([OH:42])=[CH:40][CH:41]=2)[C:10]2[CH:22]=[CH:21][C:20]3[C:19]4[C:14](=[CH:15][C:16]([C:23]5[S:24][C:25]6[CH:31]=[CH:30][CH:29]=[CH:28][C:26]=6[N:27]=5)=[CH:17][CH:18]=4)[C:13]([CH2:32][CH3:33])([CH2:34][CH3:35])[C:12]=3[CH:11]=2)=[CH:5][CH:4]=1

Participants

9

Reactant 4

HCID 87132-AminothiophenolHCID 11430Potassium CarbonateHCID 13387N-methyl-2-pyrrolidoneHCID 66901835HCID 66901835, compound

Product 1

HCID 66901787HCID 66901787, compoundYield 97%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 1140TolueneSolventHCID 21899381Acetic acid--water (1/1)Solvent

Conditions

Temperature
195 °C

Procedure

A mixture of N,N-di(4-methoxyphenyl)-7-(benzothiazol-2-yl)-9,9-diethyl-fluoren-2-amine, (Example 9; 11.0 g, 18.9 mmol), 2-aminothiophenol (9.0 mL, 10.53 g, 84.0 mmol), potassium carbonate (0.58 g, 4.2 mmol) and 1-methylpyrrolidine-2-one (NMP, 50 mL) was heated to 195° C., and held at this temperature for 6 hours. After cooling, the mixture was poured into a mixture of acetic acid (100 mL) and water (750 mL). The separated solids were collected and reslurried in a mixture of ethanol (100 mL) and toluene (50 mL), and the insoluble solids, 7.44 g, m.p. 294-297° C. were collected. Additional 2.71 g, with the same melting point was obtained by concentration of the filtrate, and slurrying the crude product in toluene. Total product recovered was 10.15 g (97% yield). A sample for analysis was prepared by heating 1 g of the sample with 2:1 acetic-acid-water mixture (75 mL), 0.98 g, m.p. 294.2-294.5° C. Mass spec: m/z 554 (M+). Anal. Calcd for C36H30N2O2S: C, 77.95%; H, 5.45%; N, 5.05%; S, 5.78%. Found; C, 77.95%; H, 5.53%; N, 5.18%; S, 5.90%. 1H NMR (DMSO-d6) δ ppm: 0.30 (t, 6H, 7.3 Hz), 1.80-1.84 (m, 2H), 1.99-2.04 (m, 2H), 6.70-6.81 (m, 6H), 6.94-6.97 (m, 4H), 7.42-7.46 (m, 1H), 7.52-7.56 (m, 1H), 7.65 (d, 1H, 8.4 Hz), 7.78 (d, 1H, 7.92 Hz), 7.97-8.13 (m, 4H), 9.38 (s, 2H). 13C NMR (DMSO-d6) δ ppm: 8.96, 32.23, 56.01 (3 sp3C), 113.42, 116.71, 118.47, 119.66, 121.28, 121.77, 122.68, 123.02, 125.69, 127.06, 127.42, 127.59, 130.52, 131.90, 134.77, 139.22, 145.09, 150.09, 150.34, 151.87, 154.15, 154.50, and 169.38 (23 sp2C).

Workup

  1. temperatureAfter cooling
  2. customThe separated solids were collected
  3. additionreslurried in a mixture of ethanol (100 mL) and toluene (50 mL)
  4. customthe insoluble solids, 7.44 g, m.p. 294-297° C. were collected
  5. customAdditional 2.71 g, with the same melting point was obtained by concentration of the filtrate
  6. customTotal product recovered
  7. customA sample for analysis was prepared

Sources & evidence

ORD record
ord-28b2f045a94e4c2a8f3c6c8d15ca083f
Source dataset
uspto-grants-2014_03
Patent number
US08674057B1

Reaction notes

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