Triethylamine → 1,3-Bis(cyclohexylmethyl)-8-[4-(2,5,8,11,14,17,20,23,26,29-decaoxatriacont-1-yl)phenyl]-3,7-dihydro-1h-purine-2,6-dione

HRID 1835007ノート

反応式

HRID 1835007 の反応式
C(C1C=CC(C[CH2:9][O:10][CH2:11][CH2:12][O:13][CH2:14][CH2:15][O:16][CH2:17][CH2:18][O:19][CH2:20][CH2:21][O:22][CH2:23][CH2:24][O:25][CH2:26][CH2:27][O:28][CH2:29][CH2:30][O:31][CH2:32][CH2:33]OCCO)=CC=1)(O)=O.[C:40](Cl)(=[O:44])[C:41](Cl)=[O:42].C(N([CH2:51][CH3:52])CC)C.[CH:53]1([CH2:59][N:60]2[C:67]([NH2:68])=[C:66]([NH2:69])[C:64](=[O:65])[N:63]([CH2:70][CH:71]3[CH2:76][CH2:75][CH2:74][CH2:73][CH2:72]3)[C:61]2=[O:62])[CH2:58][CH2:57][CH2:56][CH2:55][CH2:54]1>ClCCl.CN(C)C=O>[CH:71]1([CH2:70][N:63]2[C:64](=[O:65])[C:66]3[NH:69][C:59]([C:53]4[CH:58]=[CH:57][C:51]([CH2:52][O:42][CH2:41][CH2:40][O:44][CH2:33][CH2:32][O:31][CH2:30][CH2:29][O:28][CH2:27][CH2:26][O:25][CH2:24][CH2:23][O:22][CH2:21][CH2:20][O:19][CH2:18][CH2:17][O:16][CH2:15][CH2:14][O:13][CH2:12][CH2:11][O:10][CH3:9])=[CH:55][CH:54]=4)=[N:68][C:67]=3[N:60]([CH2:59][CH:53]3[CH2:54][CH2:55][CH2:56][CH2:57][CH2:58]3)[C:61]2=[O:62])[CH2:76][CH2:75][CH2:74][CH2:73][CH2:72]1

参加物

7

反応物 4

HCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 222449751,3-Bis(cyclohexylmethyl)-5,6-diaminouracilHCID 23501906Nonaethyleneglycol(4-carboxybenzyl)methyl ether3 回

生成物 1

HCID 101475631,3-Bis(cyclohexylmethyl)-8-[4-(2,5,8,11,14,17,20,23,26,29-decaoxatriacont-1-yl)phenyl]-3,7-dihydro-1h-purine-2,6-dione

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide触媒HCID 6344Dichloromethane溶媒3 回

実験手順

To a solution of nonaethyleneglycol(4-carboxybenzyl)methyl ether (0.45 g, 0.80 mmol) from Example 97 part (a) above, in dichloromethane (15 ml) was added oxalyl chloride (Fluka, 0.14 ml, 1.6 mmol) and N,N dimethylformamide (one drop). This solution was allowed to stir for 0.5 hours and the volatiles were removed in vacuo to give a tan oil. This material was dissolved in dichloromethane (20 ml) and a solution of triethylamine (0.5 ml, 3.8 mmol) and 1,3-bis(cyclohexylmethyl)-5,6-diaminouracil from Example 21, part (a), (0.270 g, 0.80 mmol) in dichloromethane (10 ml) were added. This solution was allowed to stir at room temperature for 18 hours and the volatiles were removed in vacuo. The residue was dissolved in ethanol (25 ml) and the pH was adjusted to ˜13 by addition of 2N sodium hydroxide. The solution was allowed to stir at reflux for 0.5 hours and then cooled to room temperature. Chloroform (100 ml) was added and the solution was washed with 1N hydrochloric acid (50 ml), saturated aqueous sodium chloride (20 ml), dried over magnesium sulfate and filtered. The volatiles were removed in vacuo and the title compound was eluted from silica gel with 15% methanol-ethyl acetate as a tan waxy solid after solidification from ethyl acetate-hexanes (0.098 g, 14%). 1H-NMR (300 MHz, DMSO-d6) δ: 8.07 (d, J=8.2 Hz, 2H, phenylCH), 7.44 (d, J=8.1 Hz, 2H, phenylCH), 4.54 (s, 2H, CH2-phenyl), 3.89 (d, J=7.2 Hz, 2H, CH2N), 3.70 (d, J=7.2 Hz, 2H, CH2N ), 3.60-3.35 (m, 36H, 18CH2), 3.20 (s, 3H, CH3), 2.05-1.50 and 1.30-0.95 (m, 22H, cyclohexyl CH2's).

後処理

  1. customthe volatiles were removed in vacuo
  2. customto give a tan oil
  3. stirringto stir at room temperature for 18 hours
  4. customthe volatiles were removed in vacuo
  5. dissolutionThe residue was dissolved in ethanol (25 ml)
  6. additionthe pH was adjusted to ˜13 by addition of 2N sodium hydroxide
  7. stirringto stir
  8. temperatureat reflux for 0.5 hours
  9. additionChloroform (100 ml) was added
  10. washthe solution was washed with 1N hydrochloric acid (50 ml), saturated aqueous sodium chloride (20 ml)
  11. dry with materialdried over magnesium sulfate
  12. filtrationfiltered
  13. customThe volatiles were removed in vacuo
  14. washthe title compound was eluted from silica gel with 15% methanol-ethyl acetate as a tan waxy solid after solidification from ethyl acetate-hexanes (0.098 g, 14%)

出典と根拠

ORDレコード
ord-33393c8c7c654bc98ff6a3658be5be90
出典データセット
uspto-grants-2004_08
特許番号
US06770267B2

反応ノート

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