Dichloromethane → HCID 178524009, compound

HRID 1108178Notes

Reaction equation

HRID 1108178 reaction equation
C([O:3][C:4]([C:6]1[C:17]2[S:16][C:15]([CH2:23][O:24][CH2:25][CH2:26][OH:27])([CH2:18][O:19][CH2:20][CH2:21][OH:22])[S:14][C:13]=2[C:12]([C:28]([C:67]2[C:85]3[S:86][C:87]([CH2:94][O:95][CH2:96][CH2:97][OH:98])([CH2:89][O:90][CH2:91][CH2:92][OH:93])[S:88][C:84]=3[C:83]([C:99]([O:101]CC)=[O:100])=[C:69]3[S:70][C:71]([CH2:78][O:79][CH2:80][CH2:81][OH:82])([CH2:73][O:74][CH2:75][CH2:76][OH:77])[S:72][C:68]=23)([C:30]2[C:48]3[S:49][C:50]([CH2:57][O:58][CH2:59][CH2:60][OH:61])([CH2:52][O:53][CH2:54][CH2:55][OH:56])[S:51][C:47]=3[C:46]([C:62]([O:64]CC)=[O:63])=[C:32]3[S:33][C:34]([CH2:41][O:42][CH2:43][CH2:44][OH:45])([CH2:36][O:37][CH2:38][CH2:39][OH:40])[S:35][C:31]=23)O)=[C:11]2[C:7]=1[S:8][C:9]([CH2:109][O:110][CH2:111][CH2:112][OH:113])([CH2:104][O:105][CH2:106][CH2:107][OH:108])[S:10]2)=[O:5])C.FC(F)(F)S(O)(=O)=O.ClCCl.Cl[Sn]Cl.P([O-])([O-])([O-])=O.[Na+:133].[Na+].[Na+]>C(OC(=O)C)(=O)C.N1C=CC=CC=1.C(#N)C>[C:62]([C:46]1[C:32]2[S:33][C:34]([CH2:36][O:37][CH2:38][CH2:39][OH:40])([CH2:41][O:42][CH2:43][CH2:44][OH:45])[S:35][C:31]=2[C:30]([C:28]([Na:133])([C:67]2[C:85]3[S:86][C:87]([CH2:94][O:95][CH2:96][CH2:97][OH:98])([CH2:89][O:90][CH2:91][CH2:92][OH:93])[S:88][C:84]=3[C:83]([C:99]([OH:101])=[O:100])=[C:69]3[S:70][C:71]([CH2:78][O:79][CH2:80][CH2:81][OH:82])([CH2:73][O:74][CH2:75][CH2:76][OH:77])[S:72][C:68]=23)[C:12]2[C:11]3[S:10][C:9]([CH2:109][O:110][CH2:111][CH2:112][OH:113])([CH2:104][O:105][CH2:106][CH2:107][OH:108])[S:8][C:7]=3[C:6]([C:4]([OH:3])=[O:5])=[C:17]3[S:16][C:15]([CH2:18][O:19][CH2:20][CH2:21][OH:22])([CH2:23][O:24][CH2:25][CH2:26][OH:27])[S:14][C:13]=23)=[C:48]2[C:47]=1[S:51][C:50]([CH2:57][O:58][CH2:59][CH2:60][OH:61])([CH2:52][O:53][CH2:54][CH2:55][OH:56])[S:49]2)([OH:64])=[O:63]

Participants

9

Reactant 5

HCID 6344DichloromethaneHCID 24243Trisodium PhosphateHCID 24479Stannous ChlorideHCID 62406Trifluoromethanesulfonic acidHCID 86755413HCID 86755413, compound

Product 1

HCID 178524009HCID 178524009, compound

Reagents, catalysts & solvents 3

HCID 1049PyridineSolventHCID 6342AcetonitrileSolventHCID 7918Acetic AnhydrideSolvent

Procedure

Tris(8-ethoxycarbonyl-2,2,6,6-tetra(hydroxyethoxy)methylbenzo[1,2-d:4,5-d']bis(1,3)dithiole-4-yl)methanol (see WO97/09633) (40 mg, 0.022 mmol) was dissolved in a mixture of acetic anhydride (S ml) and pyridine (10 ml) and the solution was stirred at room temperature for 2 hours. The organic solvents were removed by evaporation, the residue was dissolved in dichloromethane which was washed with water. After removal of the solvent by evaporation, the residue was dissolved in dichloromethane (8 ml) and then, a solution of trifluoromethanesulfonic acid in dichloromethane (0.58 mmol in 4 ml) was added at 0° C. After stirring for 2 minutes, a solution of SnCl2 in acetonitrile (2 mg in 2 ml) was added and the solution was stirred for another minute. The reaction mixture was poured onto an aqueous pH 7 sodium phosphate buffer, the organic phase was separated and the aqueous phase was extracted with dichloromethane (25 ml). The combined organic phases were dried (Na2SO4) and the solvent was removed by evaporation. The residue was dissolved ethanol (10 ml) and 1M aqueous solution hydroxide (3 ml) was added. After stirring for 1 hour at room temperature, the pH was adjusted to 2 using 1M aqueous HCl and then the solution was subjected to purification by preparative HPLC (RP-18, CH3CN-HCl (pH 2): 20:80). The fractions containing the pure product were combined and the acetonitrile was removed by evaporation. The residual aqueous solution was lyophilized, the residue was dissolved in water, the solution was neutralized using 1M aqueous NaOH and the solution was lyophilised again. Yield: 24 mg (62%). ESR: (1 mM in water, 100 G): singlet, linewidth 116 mG.

Workup

  1. customThe organic solvents were removed by evaporation
  2. dissolutionthe residue was dissolved in dichloromethane which
  3. washwas washed with water
  4. customAfter removal of the solvent
  5. customby evaporation
  6. dissolutionthe residue was dissolved in dichloromethane (8 ml)
  7. stirringAfter stirring for 2 minutes
  8. stirringthe solution was stirred for another minute
  9. customthe organic phase was separated
  10. extractionthe aqueous phase was extracted with dichloromethane (25 ml)
  11. dry with materialThe combined organic phases were dried (Na2SO4)
  12. customthe solvent was removed by evaporation
  13. dissolutionThe residue was dissolved ethanol (10 ml) and 1M aqueous solution hydroxide (3 ml)
  14. additionwas added
  15. stirringAfter stirring for 1 hour at room temperature
  16. customthe solution was subjected to purification by preparative HPLC (RP-18, CH3CN-HCl (pH 2): 20:80)
  17. additionThe fractions containing the pure product
  18. customthe acetonitrile was removed by evaporation
  19. dissolutionthe residue was dissolved in water

Sources & evidence

ORD record
ord-0948cfe560a5471989b495afc69bbb34
Source dataset
uspto-grants-2000_05
Patent number
US06063360

Reaction notes

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