Chlorotrimethylsilane → n6-Benzoyl-8-bromo-5'-o-(4,4'-dimethoxytrityl)-2'-deoxyadenosine

HRID 1168666ノート

反応式

HRID 1168666 の反応式
[Br:1][C:2]1[N:3]([C:12]2[N:13]=[CH:14][N:15]=[C:16]([NH2:19])[C:17]=2[N:18]=1)[C@@H:4]1[O:11][C@H:8]([CH2:9][OH:10])[C@@H:6]([OH:7])[CH2:5]1.[CH3:20][O:21][C:22]1[CH:27]=[CH:26][C:25]([C:28](Cl)([C:35]2[CH:40]=[CH:39][C:38]([O:41][CH3:42])=[CH:37][CH:36]=2)[C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)=[CH:24][CH:23]=1.C[Si](C)(C)Cl.[C:49](Cl)(=[O:56])[C:50]1[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=1>N1C=CC=CC=1>[C:49]([NH:19][C:16]1[C:17]2[N:18]=[C:2]([Br:1])[N:3]([C:12]=2[N:13]=[CH:14][N:15]=1)[C@@H:4]1[O:11][C@H:8]([CH2:9][O:10][C:28]([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)([C:35]2[CH:40]=[CH:39][C:38]([O:41][CH3:42])=[CH:37][CH:36]=2)[C:25]2[CH:26]=[CH:27][C:22]([O:21][CH3:20])=[CH:23][CH:24]=2)[C@@H:6]([OH:7])[CH2:5]1)(=[O:56])[C:50]1[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=1

参加物

6

反応物 4

HCID 6397ChlorotrimethylsilaneHCID 7412Benzoyl chlorideHCID 965478-Bromo-2'-deoxyadenosineHCID 968311,1'-(Chlorophenylmethylene)bis(4-methoxybenzene)2 回

生成物 1

HCID 14656959n6-Benzoyl-8-bromo-5'-o-(4,4'-dimethoxytrityl)-2'-deoxyadenosine収率 41.6%

試薬・触媒・溶媒 1

HCID 1049Pyridine溶媒2 回

実験手順

8-Bromo-2′-Deoxyadenosine (7.7 gm. 22.17 mmol) was dried by co-evaporation with dry pyridine and the solid was suspended in 200 ml of dry pyridine followed by the addition of 4,4′-dimethoxytriphenylmethyl chloride (DMT-Cl) (9 gm, 26.6 mmol). After stirring for 4 hrs at RT, TLC on silica gel showed that a new product was formed and some starting material was unreacted. Another amount of DMT-Cl (3 gm) was added and stirred at RT for 2 hrs. When TLC showed that all starting material was converted to new product with higher Rf, the reaction mixture was cooled to 0 C and trimethylchlorosilane (12.042 gm., 14 ml, 110.85 mmol) was added dropwise while cooling and after 40 min. while stirring benzoyl chloride (15.58 gm, 12.88 ml, 110.85 mmol) was similarly added. The reaction was allowed to react at RT over 2 hrs. The reaction was quenched by slow addition of cold water (50 ml), followed by addition of concentrated ammonia (30%, 50 ml). After 30 min. the reaction mixture was evaporated to dryness. The residue was dissolved in water, and the solution was extracted with ethyl acetate three times, the organic layer washed with saturated sodium bicarbonate solution, and then brine. The organic phase was dried over sodium sulphate, evaporated to dryness. The product was purified on a silica column chromatography, to give a yellowish solid product (6.79 gm, 41.6%). The structure of this product was confirmed by H NMR and ES-MS.

後処理

  1. customwas formed
  2. stirringstirred at RT for 2 hrs
  3. additionwas added dropwise
  4. temperaturewhile cooling and after 40 min.
  5. additionwas similarly added
  6. customto react at RT over 2 hrs
  7. customThe reaction was quenched by slow addition of cold water (50 ml)
  8. additionfollowed by addition of concentrated ammonia (30%, 50 ml)
  9. customAfter 30 min. the reaction mixture was evaporated to dryness
  10. dissolutionThe residue was dissolved in water
  11. extractionthe solution was extracted with ethyl acetate three times
  12. washthe organic layer washed with saturated sodium bicarbonate solution
  13. dry with materialThe organic phase was dried over sodium sulphate
  14. customevaporated to dryness
  15. customThe product was purified on a silica column chromatography

出典と根拠

ORDレコード
ord-56efe3684a7e4cbdafe7530a70d03da1
出典データセット
uspto-grants-2003_09
特許番号
US06627400B1

反応ノート

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