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Triethylamine → 1-ethyl-6-nitro-N-(3-hydroxycyclohexylmethyl)-1H-pyrazolo[3,4-b]quinolin-4-amine

HRID 1586173
ノート
印刷プレビュー

反応式

HRID 1586173 の反応式
[CH2:1]([N:3]1[C:7]2=[N:8][C:9]3[C:14]([C:15](Cl)=[C:6]2[CH:5]=[N:4]1)=[CH:13][C:12]([N+:17]([O-:19])=[O:18])=[CH:11][CH:10]=3)[CH3:2].C(N(CC)CC)C.[OH:27][CH:28]1[CH2:33][CH2:32][CH2:31][CH:30]([CH2:34][NH2:35])[CH2:29]1.[NH4+].[OH-]>C1COCC1.CS(C)=O>[CH2:1]([N:3]1[C:7]2=[N:8][C:9]3[C:14]([C:15]([NH:35][CH2:34][CH:30]4[CH2:31][CH2:32][CH2:33][CH:28]([OH:27])[CH2:29]4)=[C:6]2[CH:5]=[N:4]1)=[CH:13][C:12]([N+:17]([O-:19])=[O:18])=[CH:11][CH:10]=3)[CH3:2]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 8471TriethylamineHCID 14923Ammonium HydroxideHCID 212177131-ethyl-4-chloro-6-nitro-1H-pyrazolo[3,4-b]quinolineHCID 230098443-(Aminomethyl)cyclohexan-1-ol

生成物 1

HCID 212177071-ethyl-6-nitro-N-(3-hydroxycyclohexylmethyl)-1H-pyrazolo[3,4-b]quinolin-4-amine収率 10.5%

試薬・触媒・溶媒 2

HCID 679
Dimethyl Sulfoxide
溶媒
HCID 8028Tetrahydrofuran溶媒

反応条件

温度
110 °C

実験手順

and (b) A mixture of 1-ethyl-6-nitro-4-chloro-1H-pyrazolo[3,4-b]quinoline (2.7 g, 17.8 mmol), triethylamine (3 ml, 0.02 mol), DMSO (15 ml) and 3-hydroxycyclohexylmethylamine (4.97 g, 18 mmol) is heated at 110° C. overnight. The reaction mixture is poured into ice water (200 ml)/NH4OH (10 ml) and the solid which forms is collected by filtration. The filtrate is then extracted with CH2Cl2 (2×100 ml). The solid is stirred and sonicated with CH2Cl2 (2×200 ml), and any solids which did not go into solution are collected by filtration. All of the above CH2Cl2 filtrates and extracts are combined, washed with water and evaporated. The residue is slurried with ethyl acetate (10-15 ml)/ether (20 ml) and a red colored solid is collected by filtration and washed with ether. The solid is purified by column chromatography (2×) on silica gel (note that the solid is preloaded onto 50-100 g of silica gel) eluting with 40% THF/cyclohexane and each of the diastereomers which is isolated is dissolved in hot THF, filtered and the solvent is evaporated. Each of the residues is slurried with ethanol (5 ml), filtered and dried to afford 0.69 g of 1-ethyl-6-nitro-N-(3-hydroxycyclohexylmethyl)-1H-pyrazolo[3,4-b]quinolin-4-amine (the RS,SR diastereomer which is labelled as Example 36(a)), m.p. 236°-238° C. and 2.23 g of 1-ethyl-6-nitro-N-(3-hydroxycyclohexylmethyl)-1H-pyrazolo[3,4-b]quinolin-4-amine (the RR,SS diastereomer which is labelled as Example 36(b)), m.p. 247°-248° C.

後処理

  1. filtrationthe solid which forms is collected by filtration
  2. extractionThe filtrate is then extracted with CH2Cl2 (2×100 ml)
  3. customsonicated with CH2Cl2 (2×200 ml)
  4. filtrationare collected by filtration
  5. washwashed with water
  6. customevaporated
  7. filtrationa red colored solid is collected by filtration
  8. washwashed with ether
  9. customThe solid is purified by column chromatography (2×) on silica gel (note that the solid
  10. washeluting with 40% THF/cyclohexane
  11. customeach of the diastereomers which is isolated
  12. filtrationfiltered
  13. customthe solvent is evaporated
  14. filtrationfiltered
  15. customdried

出典と根拠

ORDレコード
ord-3541c97a307f40ee9823f5a21136d912
出典データセット
uspto-grants-1999_08
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US05942520

反応ノート

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