Hexane → HCID 135934897, compound

HRID 1970805Notes

Reaction equation

HRID 1970805 reaction equation
[CH2:1]([C:8]1[C:9]([NH:22][C:23](=[S:33])[CH2:24][C:25]2[CH:30]=[CH:29][C:28]([O:31]C)=[CH:27][CH:26]=2)=[N:10][CH:11]=[C:12]([C:14]2[CH:19]=[CH:18][C:17]([O:20]C)=[CH:16][CH:15]=2)[N:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.B(Br)(Br)Br.C(=O)(O)[O-].[Na+].CCCCCC>ClCCl.C(OCC)(=O)C>[CH2:1]([C:8]1[C:9]([NH:22][C:23](=[S:33])[CH2:24][C:25]2[CH:26]=[CH:27][C:28]([OH:31])=[CH:29][CH:30]=2)=[N:10][CH:11]=[C:12]([C:14]2[CH:19]=[CH:18][C:17]([OH:20])=[CH:16][CH:15]=2)[N:13]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 8058HexaneHCID 25134Boron tribromideHCID 516892Sodium BicarbonateHCID 86659538HCID 86659538, compound

Product 1

HCID 135934897HCID 135934897, compoundYield 66.6%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Under an argon atmosphere, 3-benzyl-5-(4-methoxyphenyl)-2-[(4-methoxyphenyl)thioacetylamino]pyrazine (c-44) (823 mg, 1.81 mmol) was dissolved in anhydrous dichloromethane (30 mL) and to this was added 1.0 M solution of boron tribromide in dichloromethane (6.80 mL, 6.80 mmol) at room temperature and heated to reflux for 21 h. After cooling to room temperature, to this was added saturated aqueous solution of sodium bicarbonate and concentrated under reduced pressure with a rotary evaporator to remove dichloromethane. The resulting suspension was filtrated and the residue was dried to give the crude product (591 mg) as a red solid. The crude product was dissolved in ethyl acetate and to this was added n-hexane to form a precipitate. The solid was collected by filtration and dried in vacuo to give 3-benzyl-5-(4-hydroxyphenyl)-2-[(4-hydroxyphenyl)thioacetylamino]pyrazine (coelenterathioamide) (c-45) as an orange solid (514 mg, 66.6%). Rf=0.23 (n-hexane/ethyl acetate=1/1). Mp. 101-103° C. 1H NMR (400 MHz, DMSO-d6) δ 3.90 (s, 2H), 4.00 (s, 2H), 6.71-6.77 (AABB′, 2H), 6.85-6.91 (AA′BB′, 2H), 6.97-7.03 (AA′BB′, 2H), 7.12-7.25 (m, 3H), 7.27-7.34 (m, 2H), 7.94-8.00 (AA′BB′, 2H), 8.91 (s, 1H), 9.34 (s, 1H), 9.94 (s, 1H), 12.05 (s, 1H). 13C NMR (67.8 MHz, DMSO-d6) δ 50.9, 115.1 (2C), 115.8 (2C), 126.0, 126.2, 127.0, 128.18 (2C), 128.24 (2C), 128.9 (2C), 129.9 (2C), 137.4, 138.0, 144.6, 149.9, 152.0, 156.4, 159.3, 205.3 (one carbon at benzyl position was unobservable due to over lapping with septet peak of DMSO). IR (KBr, cm−1) 515, 561, 706, 731, 837, 908, 935, 1063, 1130, 1171, 1238, 1315, 1371, 1443, 1514, 1609, 2808, 3026, 3159. HRMS (ESI+) m/z 428.1434 ((M+H)+, C25H22N3O2S+ requires 428.1427).

Workup

  1. temperatureheated
  2. temperatureto reflux for 21 h
  3. concentrationconcentrated under reduced pressure with a rotary evaporator
  4. customto remove dichloromethane
  5. filtrationThe resulting suspension was filtrated
  6. customthe residue was dried
  7. customto give the crude product (591 mg) as a red solid
  8. customto form a precipitate
  9. filtrationThe solid was collected by filtration
  10. customdried in vacuo

Sources & evidence

ORD record
ord-e5b3373d86a74b47b6723c0d2973c5ba
Source dataset
uspto-grants-2013_04
Patent number
US08431525B2

Reaction notes

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