Hydrochloric Acid → HCID 46866262, compound

HRID 1970802Notes

Reaction equation

HRID 1970802 reaction equation
[NH2:1][C:2]1[C:7]([CH2:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[N:6][C:5]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[CH:4][N:3]=1.C(N([CH2:26][CH3:27])CC)C.[CH2:28]([S:35](Cl)(=[O:37])=[O:36])[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1.Cl>ClCCl>[CH2:8]([C:7]1[C:2]([N:1]([S:35]([CH2:28][C:27]2[CH:26]=[CH:31][CH:30]=[CH:29][CH:34]=2)(=[O:37])=[O:36])[S:35]([CH2:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)(=[O:37])=[O:36])=[N:3][CH:4]=[C:5]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[N:6]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 74740Phenylmethanesulfonyl chlorideHCID 102146592-Amino-3-benzyl-5-phenylpyrazine

Product 1

HCID 46866262HCID 46866262, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Under an argon atmosphere, 2-amino-3-benzyl-5-phenylpyrazine (c-41) (852 mg, 3.26 mmol) was dissolved in anhydrous dichloromethane (25 mL), and to this was added triethylamine (1.38 mL, 9.87 mmol), and cooled to 0° C. To this was added benzylsulfonyl chloride (1.87 g, 9.80 mmol) and stirred for 23.5 h after warming to room temperature. To this was added 2 M hydrochloric acid to stop the reaction and after separating the aqueous layer and organic layer, the organic layer was washed once with water and once with saturated hydrochloric acid and then dried over anhydrous sodium sulfate. After removing anhydrous sodium sulfate by filtration, the filtrate was concentrated under reduced pressure with a rotary evaporator. The residue was purified by silica gel column chromatography (56 g, n-hexane/ethyl acetate=4/1) to give 3-benzyl-2-bis(benzylsulfonyl)amino-5-phenylpyrazine (c-42) as a reddish orange amorphous (1.27 g, 68.2%). Rf=0.70 (n-hexane/ethyl acetate=3/2). Mp. 71.5-74.5° C. UV (MeOH) λmax (log ε) 304 (4.20), 257 (4.15). UV (pH 7.4 PB) λmax (log ε) 331 (4.13), 269 (4.12). 1H NMR (400 MHz, DMSO-d6) δ 3.89 (s, 2H), 5.00 (s, 1H), 5.04 (s, 1H), 5.19 (s, 1H), 5.22 (s, 1H), 7.15 (d, J=7.0 Hz, 2H), 7.18-7.24 (m, 1H), 7.25-7.32 (m, 2H), 7.38-7.46 (m, 10H), 7.50-7.55 (m, 3H), 8.04-8.10 (m, 2H), 9.21 (s, 1H). 13C NMR (75.5 MHz, DMSO-d6/CD3OD=2/1) δ 38.3, 61.7 (1C×2), 127.0, 127.5, 127.8 (1C×2), 128.8 (2C), 129.4 (2C×2), 129.7 (2C), 129.9 (2C), 130.2 (2C), 131.3, 132.2 (2C), 135.3, 138.3, 139.6, 142.0, 153.0, 156.5. IR (KBr, cm−1) 507, 538, 557, 611, 629, 694, 723, 748, 766, 779, 876, 920, 1144, 1163, 1252, 1354, 1375, 1427, 1454, 1495, 1530, 3032. HRMS (FAB+) m/z 570.1526 (M+H, C31H28N3O4S2 requires 570.1521).

Workup

  1. temperatureafter warming to room temperature
  2. customthe reaction
  3. customafter separating the aqueous layer and organic layer
  4. washthe organic layer was washed once with water and once with saturated hydrochloric acid
  5. dry with materialdried over anhydrous sodium sulfate
  6. customAfter removing anhydrous sodium sulfate
  7. filtrationby filtration
  8. concentrationthe filtrate was concentrated under reduced pressure with a rotary evaporator
  9. customThe residue was purified by silica gel column chromatography (56 g, n-hexane/ethyl acetate=4/1)

Sources & evidence

ORD record
ord-f6ea68bcae644609b6573371b8a0b0b1
Source dataset
uspto-grants-2013_04
Patent number
US08431525B2

Reaction notes

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