4-Nitrobenzenesulfonyl chloride → HCID 46866264, compound

HRID 1970799Notes

Reaction equation

HRID 1970799 reaction equation
[C:1]([O:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]2[N:12]=[C:13]([CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[C:14]([NH2:17])=[N:15][CH:16]=2)=[CH:7][CH:6]=1)(=[O:3])[CH3:2].[N+:25]([C:28]1[CH:33]=[CH:32][C:31]([S:34](Cl)(=[O:36])=[O:35])=[CH:30][CH:29]=1)([O-:27])=[O:26].C(=O)(O)[O-].[Na+]>N1C=CC=CC=1.CN(C)C1C=CN=CC=1>[C:1]([O:4][C:5]1[CH:6]=[CH:7][C:8]([C:11]2[N:12]=[C:13]([CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[C:14]([N:17]([S:34]([C:31]3[CH:30]=[CH:29][C:28]([N+:25]([O-:27])=[O:26])=[CH:33][CH:32]=3)(=[O:35])=[O:36])[S:34]([C:31]3[CH:32]=[CH:33][C:28]([N+:25]([O-:27])=[O:26])=[CH:29][CH:30]=3)(=[O:36])=[O:35])=[N:15][CH:16]=2)=[CH:9][CH:10]=1)(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 74044-Nitrobenzenesulfonyl chloride2×HCID 516892Sodium BicarbonateHCID 670035525-(4-Acetoxyphenyl)-2-amino-3-benzylpyrazine

Product 1

HCID 46866264HCID 46866264, compoundYield 52.1%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolvent

Procedure

Under an argon atmosphere, 5-(4-acetoxyphenyl)-2-amino-3-benzylpyrazine (c-19) (140 mg, 438 μmol) was dissolved in pyridine (2 mL) and to this was added 4-(dimethylamino)pyridine (6.0 mg, 49 μmol). To this was added p-nitrobenzenesulfonyl chloride (293 mg, 1.32 mmol) while stirring at room temperature and stirred for 1.5 h at the same temperature. To this was further added p-nitrobenzenesulfonyl chloride (195 mg, 880 μmol) and stirred for 17 h. To this was added saturated aqueous solution of sodium bicarbonate to stop the reaction and the product was extracted twice with dichloromethane. The organic layer was washed once with water and once with saturated aqueous solution of sodium sulfate and then dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (24 g, n-hexane/ethyl acetate=4/1→3/1→7/3→ethyl acetate alone) to give 5-(4-acetoxyphenyl)-3-benzyl-2-bis(4-nitrophenylsulfonyl)aminopyrazine (c-40) as a dark brown solid (157 mg, 52.1%). Rf=0.62 (n-hexane/ethyl acetate=3/2). Mp. 227-229.5° C. (dec.). UV (MeOH, 0.3% DMSO) λmax (log ε) 309 (3.99), 258 (4.21). 1H NMR (400 MHz, DMSO-d6) δ 2.30 (s, 3H), 4.22 (s, 2H), 7.19-7.27 (m, 1H), 7.29-7.35 (m, 6H), 8.05-8.10 (AA′BB′, 4H), 8.14-8.19 (AA′BB′, 2H), 8.39-8.44 (AA′BB′, 4H), 9.13 (s, 1H). 13C NMR. (75.5 MHz, DMSO-d6) δ 20.9, 38.0, 122.8 (2C), 124.8 (2C×2), 126.6, 128.3 (2C), 128.7 (2C), 129.6 (2C), 130.7 (2C×2), 131.9, 137.3, 139.8, 140.3, 142.1 (1C×2), 151.1 (1C×2), 151.9, 152.7, 156.2, 169.0. I,R (KBr, cm−1) 548, 598, 617, 687, 737, 775, 810, 854, 880, 897, 916, 935, 1013, 1165, 1180, 1206, 1315, 1348, 1368, 1385, 1404, 1418, 1435, 1530, 1603, 1755, 3107. HRMS (FAR) m/z 690.0975 (M+H, C31H24N5O10S2 requires 690.0965).

Workup

  1. stirringstirred for 1.5 h at the same temperature
  2. stirringstirred for 17 h
  3. customthe reaction
  4. extractionthe product was extracted twice with dichloromethane
  5. washThe organic layer was washed once with water and once with saturated aqueous solution of sodium sulfate
  6. dry with materialdried over anhydrous sodium sulfate
  7. customAfter removing anhydrous sodium sulfate
  8. filtrationby filtration
  9. concentrationthe filtrate was concentrated under reduced pressure
  10. customThe residue was purified by column chromatography (24 g, n-hexane/ethyl acetate=4/1→3/1→7/3

Sources & evidence

ORD record
ord-e30b100d1a824fa5a429c6544b00ed2a
Source dataset
uspto-grants-2013_04
Patent number
US08431525B2

Reaction notes

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