Dichloromethane → HCID 86594211, compound

HRID 2095236Notes

Reaction equation

HRID 2095236 reaction equation
[C:1]([NH:9][C:10]1[C:11]2[N:12]=[CH:13][N:14]([C:23]=2[N:24]=[CH:25][N:26]=1)[C@@H:15]1[O:22][C@H:19]([CH2:20][OH:21])[C@@H:17]([OH:18])[CH2:16]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:27]([C:35]1[CH:36]=[CH:37][C:38]([N+:48]([O-:50])=[O:49])=[C:39]([CH:41]([CH3:47])[CH2:42][O:43][C:44](Cl)=[O:45])[CH:40]=1)(=[O:34])[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.C(Cl)Cl>N1C=CC=CC=1>[C:1]([NH:9][C:10]1[C:11]2[N:12]=[CH:13][N:14]([C:23]=2[N:24]=[CH:25][N:26]=1)[C@@H:15]1[O:22][C@H:19]([CH2:20][O:21][C:44]([O:43][CH2:42][CH:41]([C:39]2[CH:40]=[C:35]([C:27](=[O:34])[C:28]3[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=3)[CH:36]=[CH:37][C:38]=2[N+:48]([O-:50])=[O:49])[CH3:47])=[O:45])[C@@H:17]([OH:18])[CH2:16]1)(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 107558N-benzoyl-2'-deoxyadenosineHCID 85991107HCID 85991107, compound

Product 1

HCID 86594211HCID 86594211, compoundYield 57%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent2×

Conditions

Temperature
0 °C

Procedure

N6-benzoyl-2′-deoxyadenosine (23.63 g, 67 mmol) was dried by coevaporation with abs. pyridine (3×100 mL), dissolved in pyridine (400 mL) and cooled to 0° C. A solution of 2-(5-benzoyl-2-nitrophenyl)-1-propyl oxycarbonylchloride (19f) (35 mmol, prepared from 10.00 g of alcohol 40 in abs. CH2Cl2 (100 mL) was added drop wise over a period of 2.5 hours. After stirring over night at ambient temperature the reaction mixture was concentrated in vacuo, dissolved in CH2Cl2 and washed with water (2×200 mL). Excess N6-benzoyl-2′-deoxyadenosine precipitated as a crystalline solid from the aqueous phase and was recovered by filtration. The organic phase was diluted with toluene (100 mL), concentrated in vacuo and purified by silica column chromatography (315 g silica, column diameter 5.5 cm, gradient: CH2Cl2 to CH2Cl2/methanol 100:5) to provide 13.20 g (19.8 mmol, 57%) of the product 29 as a slightly yellow foam. 1H-NMR (250 MHz, DMSO-d6): δ11.02 and 11.01 (2s, 2H, NH), 8.67 (s, 1H, H—C(2)), 8.51 and 8.50 (2s, 2H, H—C(8)), 8.00-7.48 (m, 13H, arom.), 6.46 (m, 1H, H—C(1′)), 5.47 (d, 1H, HO—C(3′)), 4.46 (m, 1H, H—C(3′)), 4.28 (m, 4H, 2×CH2), 4.03 (m, 1H, H—C(4′)), 3.50 (m, β-CH), 2.86 (m, 1H, H—C(2″)), 2.40 (m, 1H, H—C(2′)), 1.28 (d, 3H, γ-CH3).

Workup

  1. concentrationwas concentrated in vacuo
  2. dissolutiondissolved in CH2Cl2
  3. washwashed with water (2×200 mL)
  4. customExcess N6-benzoyl-2′-deoxyadenosine precipitated as a crystalline solid from the aqueous phase
  5. filtrationwas recovered by filtration
  6. additionThe organic phase was diluted with toluene (100 mL)
  7. concentrationconcentrated in vacuo
  8. custompurified by silica column chromatography (315 g silica, column diameter 5.5 cm, gradient: CH2Cl2 to CH2Cl2/methanol 100:5)

Sources & evidence

ORD record
ord-1fc119b854974db19546c52056e15683
Source dataset
uspto-grants-2013_05
Patent number
US08445734B2

Reaction notes

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