Benzene → HCID 123511801, compound

HRID 1757705Notes

Reaction equation

HRID 1757705 reaction equation
[CH3:1][O:2][C:3]1[CH:59]=[CH:58][C:6]([C:7]([O:22][CH2:23][C@@:24]2([CH:46]=[CH:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52]OS(C)(=O)=O)[O:28][C@@H:27]([N:29]3[CH:37]=[C:35]([CH3:36])[C:33](=[O:34])[NH:32][C:30]3=[O:31])[CH2:26][C@@H:25]2[O:38][SiH2:39][C:40]([CH3:45])([CH3:44])[CH:41]([CH3:43])[CH3:42])([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[C:8]2[CH:13]=[CH:12][C:11]([O:14][CH3:15])=[CH:10][CH:9]=2)=[CH:5][CH:4]=1.[N-:60]=[N+:61]=[N-:62].[Na+].C1C=CC=CC=1>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)(=O)C.CCCCCC>[CH3:15][O:14][C:11]1[CH:10]=[CH:9][C:8]([C:7]([O:22][CH2:23][C@@:24]2([CH:46]=[CH:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][N:60]=[N+:61]=[N-:62])[O:28][C@@H:27]([N:29]3[CH:37]=[C:35]([CH3:36])[C:33](=[O:34])[NH:32][C:30]3=[O:31])[CH2:26][C@@H:25]2[O:38][SiH2:39][C:40]([CH3:45])([CH3:44])[CH:41]([CH3:43])[CH3:42])([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[C:6]2[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:59][CH:58]=2)=[CH:13][CH:12]=1

Participants

6

Reactant 3

HCID 241BenzeneHCID 33557Sodium AzideHCID 123738137HCID 123738137, compound

Product 1

HCID 123511801HCID 123511801, compoundYield 96.5%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 21226206Ethyl acetate hexaneSolvent

Procedure

5'-O-(4,4'-dimethoxytrityl)-3'-O-[(dimethyl-1,1-dimethylethyl)silyl]-4'-(7-methanesulfonyloxy-1-hepten-1-yl)-thymidine (219 mg, 0.25 mmole), sodium azide (100 mg, 1.5 mmole) and tetrabutyl ammonium iodide (10 mg, 0.025 mmole) were placed in a dry flask under nitrogen and benzene (5 mL) was added. The mixture was heated under reflux for 14 hours, poured onto ice (15 mL) and extracted four times with dichloromethane (30 mL each). The combined organic extracts were washed with brine (20 mL), dried over magnesium sulfate and the solvent was removed under reduced pressure to provide a white solid. Chromatography on a silica gel column with ethyl acetate/hexane mixtures gave 5'-O-(4,4'-dimethoxytrityl)-3'-O-[(dimethyl-1,1-dimethylethyl)silyl]-4'-(7-azido-1-hepten-1-yl)-thymidine (5) (192 mg, 94%), m.p. 72°-74° C.

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 14 hours
  3. additionpoured onto ice (15 mL)
  4. extractionextracted four times with dichloromethane (30 mL each)
  5. washThe combined organic extracts were washed with brine (20 mL)
  6. dry with materialdried over magnesium sulfate
  7. customthe solvent was removed under reduced pressure
  8. customto provide a white solid

Sources & evidence

ORD record
ord-24ae7f1878064140af796685351f283a
Source dataset
uspto-grants-1995_08
Patent number
US05446137

Reaction notes

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