Benzo-1,3-dioxole-5-acetic acid → 3-((Benzo[d][1,3]dioxol-5-yl)methyl)-6-(thiophen-2-yl)-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole

HRID 12442

反応式

HRID 12442 の反応式
[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([CH2:10][C:11](O)=O)=[CH:9][C:4]=2[O:3][CH2:2]1.[NH2:14][NH:15][C:16]([NH:18][NH2:19])=[S:17].C([O-])(O)=O.[Na+].[S:25]1[CH:29]=[CH:28][CH:27]=[C:26]1[C:30](Cl)=O>CO.C(Cl)Cl.[Cl-]>[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([CH2:10][C:11]3[N:18]4[C:16]([S:17][C:30]([C:26]5[S:25][CH:29]=[CH:28][CH:27]=5)=[N:19]4)=[N:15][N:14]=3)=[CH:9][C:4]=2[O:3][CH2:2]1

参加物

7

反応物 4

HCID 76115Benzo-1,3-dioxole-5-acetic acidHCID 789282-Thiophenecarbonyl chlorideHCID 516892Sodium BicarbonateHCID 2724189Thiocarbohydrazide

生成物 1

HCID 167360613-((Benzo[d][1,3]dioxol-5-yl)methyl)-6-(thiophen-2-yl)-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole

試薬・触媒・溶媒 2

HCID 312Chloride溶媒HCID 21226129Dichloromethane methanol溶媒

反応条件

温度
170 °C

実験手順

As shown in FIG. 2, 2-(benzo[d][1,3]dioxol-5-yl)acetic acid (1 mmol) and thiocarbonohydrazide (1.5 mmol) were heated at 170° C. for 15 min. The mixture was cooled and taken up in 5% MeOH/CH2Cl2 and saturated NaHCO3. The organics were washed with water, saturated NaCl, dried over Na2SO4, and concentrated in vacuo. The resulting 5-((benzo[d][1,3]dioxol-5-yl)methyl)-4H-4-amino-3-mercapto-1,2,4-triazole (compound 1001) was used as is in the next reaction. Accordingly, a mixture of compound 1001 and thiopene-2-carbonyl chloride (0.176 g, 1.2 mmol) suspended in excess phoshoryl chloride (˜10 mL) was refluxed 5 hours. The excess phoshoryl chloride was removed under reduced pressure and the subsequent residue was mixed with crushed ice. The solids were filtered, washed with water, and dried in vaciio. Purification by reversed-phase HPLC produced pure 3-((benzo[d][1,3]dioxol-5-yl)methyl)-6-(thiophen-2-yl)-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole (compound 2).

後処理

  1. temperatureThe mixture was cooled
  2. washThe organics were washed with water, saturated NaCl
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated in vacuo
  5. customas is in the next reaction
  6. temperaturewas refluxed 5 hours
  7. customThe excess phoshoryl chloride was removed under reduced pressure
  8. additionthe subsequent residue was mixed with crushed ice
  9. filtrationThe solids were filtered
  10. washwashed with water
  11. customdried in vaciio
  12. customPurification by reversed-phase HPLC

出典と根拠

ORDレコード
ord-ecce3c714f654f259f67249d6ff0a797
出典データセット
uspto-grants-2010_06
特許番号
US07728017B2

関連ノート

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