Hydrogen Bromide → HCID 86751731, compound

HRID 1939876Notes

Reaction equation

HRID 1939876 reaction equation
[C:1]1([CH2:62][N:63]2[CH2:84][C:83]3[N:85]=[C:79]([CH:80]=[CH:81][CH:82]=3)[CH2:78][N:77](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:76][CH2:75][N:74](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:73][C:72]3[N:106]=[C:68]([CH:69]=[CH:70][CH:71]=3)[CH2:67][N:66](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:65][CH2:64]2)[CH:6]=[CH:5][C:4]([CH2:7][N:8]2[CH2:29][C:28]3[N:30]=[C:24]([CH:25]=[CH:26][CH:27]=3)[CH2:23][N:22](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:21][CH2:20][N:19](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:18][C:17]3[N:51]=[C:13]([CH:14]=[CH:15][CH:16]=3)[CH2:12][N:11](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:10][CH2:9]2)=[CH:3][CH:2]=1.OS(O)(=O)=O.[OH-].[Na+].[BrH:124]>CCO>[BrH:124].[BrH:124].[BrH:124].[BrH:124].[BrH:124].[BrH:124].[BrH:124].[BrH:124].[C:4]1([CH2:7][N:8]2[CH2:29][C:28]3[N:30]=[C:24]([CH:25]=[CH:26][CH:27]=3)[CH2:23][NH:22][CH2:21][CH2:20][NH:19][CH2:18][C:17]3[N:51]=[C:13]([CH:14]=[CH:15][CH:16]=3)[CH2:12][NH:11][CH2:10][CH2:9]2)[CH:5]=[CH:6][C:1]([CH2:62][N:63]2[CH2:84][C:83]3[N:85]=[C:79]([CH:80]=[CH:81][CH:82]=3)[CH2:78][NH:77][CH2:76][CH2:75][NH:74][CH2:73][C:72]3[N:106]=[C:68]([CH:69]=[CH:70][CH:71]=3)[CH2:67][NH:66][CH2:65][CH2:64]2)=[CH:2][CH:3]=1

Participants

6

Reactant 4

HCID 260Hydrogen BromideHCID 1118Sulfuric AcidHCID 14798Sodium HydroxideHCID 86751732HCID 86751732, compound

Product 1

HCID 86751731HCID 86751731, compoundYield 58%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A solution of 17,17'-[1,4-phenylenebis(methylene)]bis[3,6,14-tris(p-toluenesulphonyl)-3,6,14,17,23,24-hexaazatricyclo[17.3.1.18,12 ]tetracosa-1(23),8,10,12(24),19,21-hexaene] (280 mg, 0.166 mmol) in cone H2SO4 (2 ml) was stirred at 110° C. for 2 hours. The dark brown solution was cooled to room temperature and the pH adjusted to 14 with the addition of 10N NaOH. The aqueous phase was extracted with CHCl3 (20 ml, x 3), the combined organic phases were dried over MgSO4 and concentrated in vacuo thus affording a pale yellow oil. To a stirred solution of the oil in 10 ml of anhydrous EtOH was passed HBr(g) resulting in a white solid precipitate. After stirring for 15 minutes at room temperature the solid was filtered off, washed with ether and dried in vacuo giving 17,17'-[1,4-phenylenebis(methylene)]bis-3,6,14,17,23,24-hexaazatricyclo-[17.3.1.18,12 ]tetracosa-1(23),8,10,12(24),19,21-hexaene octahydrobromide (135 mg, 58%) as a white solid. 1H NMR (D2O) δ 3.73 (s, 8H), 3.94 (s, 8H), 4.38 (s, 8H), 4.45 (s, 8H), 6.86 (d, 2H, J=8.6 Hz), 7.19-7.24 (m, 6H), 7.47 (d, 4H, J=8.6 Hz), 7.56 (t, 2H, J=8.6 Hz), 7.87 (t, 2H, J=8.6 Hz). 13C NMR (D2O) δ 44.86, 46.77, 47.03, 53.41, 53.66, 56.18, 60.24, 124.83, 125.00, 125.06, 125.85, 132.32, 134.83, 141.99, 142.06, 152.20, 152.31, 152.41. Mass spectrum (FAB); m/e (relative intensity); 838 (M+HBr, 4), 836 (M+HBr, 4), 756 (M+1, 14), 429 (20), 307 (60), 215 (100). C44H66N12 Br8 requires C, 37.68; H, 4.74; N, 11.98; Br, 45.58; Found: C, 37.86; H, 4.94; N, 11.90; Br, 45.33.

Workup

  1. extractionThe aqueous phase was extracted with CHCl3 (20 ml, x 3)
  2. dry with materialthe combined organic phases were dried over MgSO4
  3. concentrationconcentrated in vacuo
  4. customthus affording a pale yellow oil
  5. customresulting in a white solid precipitate
  6. filtrationwas filtered off
  7. washwashed with ether
  8. customdried in vacuo

Sources & evidence

ORD record
ord-63ef8a8587d347a79f4cddb8e46dc17c
Source dataset
uspto-grants-1997_12
Patent number
US05698546

Reaction notes

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