4,7-Dibromo-2,1,3-benzothiadiazole-5,6-diamine → 4,9-Dibromo-6,7-bis(3',7'-dimethyloctyl)[1,2,5]thiadiazolo[3,4-g]quinoxaline

HRID 1176161Notes

Reaction equation

HRID 1176161 reaction equation
[NH2:1][C:2]1[C:10]([NH2:11])=[C:9]([Br:12])[C:5]2=[N:6][S:7][N:8]=[C:4]2[C:3]=1[Br:13].[CH3:14][CH:15]([CH2:17][CH2:18][CH2:19][CH:20]([CH3:37])[CH2:21][CH2:22][C:23](=O)[C:24](=O)[CH2:25][CH2:26][CH:27]([CH3:34])[CH2:28][CH2:29][CH2:30][CH:31]([CH3:33])[CH3:32])[CH3:16]>C(O)(=O)C>[Br:13][C:3]1[C:4]2[C:5](=[N:6][S:7][N:8]=2)[C:9]([Br:12])=[C:10]2[C:2]=1[N:1]=[C:24]([CH2:25][CH2:26][CH:27]([CH3:34])[CH2:28][CH2:29][CH2:30][CH:31]([CH3:32])[CH3:33])[C:23]([CH2:22][CH2:21][CH:20]([CH3:37])[CH2:19][CH2:18][CH2:17][CH:15]([CH3:16])[CH3:14])=[N:11]2

Participants

4

Reactant 2

HCID 684083434,7-Dibromo-2,1,3-benzothiadiazole-5,6-diamineHCID 874415822,6,13,17-Tetramethyloctadecane-9,10-dione

Product 1

HCID 684079984,9-Dibromo-6,7-bis(3',7'-dimethyloctyl)[1,2,5]thiadiazolo[3,4-g]quinoxaline

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

5,6-Diamino-4,7-dibromobenzo[c][1,2,5]thiadiazole (0.224 g, 6.91×10−4 mol) was dissolved in acetic acid (40 ml). 2,6,13,17-Tetramethyloctadecane-9,10-dione (0.261 g, 7.71×10−4 mol) was added, and the reaction mixture was stirred for 71 h at room temperature under N2. After the solvent was evaporated, water was added, and the mixture was extracted with CHCl3. The combined organic layers were washed with water, aq. NaHCO3 and dried over Na2SO4. After the solvent was evaporated, the residue was chromatographed on silica gel with CHCl3 and further purified by size exclusion column chromatography (BioRad Bio-Beads SX-1 packed in THF, gravity flow). Yield=0.360 g (83% based on 0.224 g of 5,6-diamino-4,7-dibromobenzo[c][1,2,5]thiadiazole). 1H NMR (250 MHz, CDCl3): δ 3.01-3.22 (m, 4H, Ar—CH2), 1.11-2.09 (m, 20H, (CH3)2CHCH2 CH2CH2CH(CH3)CH2CH2Ar), 1.03 (d, 6H, J=6.5 Hz, —CH3), 0.88 (d, 12H, J=6.6 Hz, —CH3). CI MS m/z: 625.157 ((M+H)+) (calcd 625.158).

Workup

  1. customAfter the solvent was evaporated
  2. additionwater was added
  3. extractionthe mixture was extracted with CHCl3
  4. washThe combined organic layers were washed with water, aq. NaHCO3
  5. dry with materialdried over Na2SO4
  6. customAfter the solvent was evaporated
  7. customthe residue was chromatographed on silica gel with CHCl3
  8. customfurther purified by size exclusion column chromatography (BioRad Bio-Beads SX-1 packed in THF, gravity flow)

Sources & evidence

ORD record
ord-b9a8ff1b9242410ebfbc40ff48085bb5
Source dataset
uspto-grants-2010_11
Patent number
US07842758B2

Reaction notes

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