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N-3-Bromopropylphthalimide → 1-(3-(1,3-dioxoisoindolin-2-yl)propyl)-1H-1,2,3-triazole-4-carbaldehyde

HRID 2196623
ノート
印刷プレビュー

反応式

HRID 2196623 の反応式
BrCCCN1C(=O)C2=CC=CC=C2C1=O.[N-]=[N+]=[N-].[Na+].[Al].[OH:21][CH2:22][C:23]1[N:24]=[N:25][N:26]([CH2:28][CH2:29][CH2:30][N:31]2[C:39](=[O:40])[C:38]3[C:33](=[CH:34][CH:35]=[CH:36][CH:37]=3)[C:32]2=[O:41])[CH:27]=1.N(CCCN1C(=O)C2C(=CC=CC=2)C1=O)=[N+]=[N-]>O.C(O)C#C.ClCCl.[O-2].[O-2].[Mn+4]>[O:40]=[C:39]1[C:38]2[C:33](=[CH:34][CH:35]=[CH:36][CH:37]=2)[C:32](=[O:41])[N:31]1[CH2:30][CH2:29][CH2:28][N:26]1[CH:27]=[C:23]([CH:22]=[O:21])[N:24]=[N:25]1
参加物実験手順後処理出典と根拠反応ノート

参加物

10

反応物 5

HCID 21611N-3-BromopropylphthalimideHCID 33557Sodium AzideHCID 1864562-(3-azidopropyl)-2,3-dihydro-1H-isoindole-1,3-dioneHCID 5359268AluminumHCID 591763832-(3-(4-(hydroxymethyl)-1H-1,2,3-triazol-1-yl)propyl)-isoindoline-1,3-dione2 回

生成物 1

HCID 59176630
1-(3-(1,3-dioxoisoindolin-2-yl)propyl)-1H-1,2,3-triazole-4-carbaldehyde
収率 31%

試薬・触媒・溶媒 4

HCID 178418406HCID 178418406、化合物触媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 7859Propargyl alcohol溶媒

実験手順

A heavy-walled Pyrex tube was charged with a suspension of N-(3-bromopropyl)phthalimide (1.00 g, 3.72 mmol) and sodium azide (0.32 g, 4.84 mmol) in H2O (2 mL). The tube containing the resulting mixture was sealed with an aluminum crimp cap fitted with a silicon septum and then it was exposed to microwave irradiation for 30 min at a temperature of 120° C. After the irradiation, the reaction tube was cooled with high-pressure air until the temperature had fallen below 40° C. The product was extracted with ethyl acetate. The combined organic layers were dried with magnesium sulfate, filtered and concentrated in vacuo. The crude material (0.62 g, 72% yield) was used without further purification in the next step. 1H NMR (400 MHz, CDCl3) δ 7.86-7.83 (m, 2H), 7.73-7.70 (m, 2H), 3.77 (t, J=6.4 Hz, 2H), 3.36 (t, J=8.0 Hz, 2H), 1.94 (m, 2H). Step b: Preparation of 2-(3-(4-(hydroxymethyl)-1H-1,2,3-triazol-1-yl)propyl)-isoindoline-1,3-dione (21). A solution of 2-(3-azidopropyl)isoindoline-1,3-dione, 20, (0.62 g, 2.69 mmol) in propargyl alcohol (4 mL) was warmed to 90° C. and stirred for 18 h. The reaction mixture was concentrated under reduced pressure. The crude product containing both regioisomers (˜1:1 ratio) was used in the next step without further purification. ESI+ MS: m/z (rel intensity) 301.1 (100, [M+H]+). Step c: Preparation of 1-(3-(1,3-dioxoisoindolin-2-yl)propyl)-1H-1,2,3-triazole-4-carbaldehyde (22). A solution of the regioisomers 21 (0.77 g, 2.69 mmol) in dichloromethane (10 mL) was treated with manganese dioxide (0.94 g, 10.77 mmol). The resulting mixture was stirred at room temperature for 2 h. The reaction mixture was filtered through Celite and concentrated. The crude product was purified by silica gel chromatography (0-5% methanol/CH2Cl2) to afford 0.24 g (31% yield) of 22 as a single regioisomer: 1H NMR (400 MHz, CDCl3) δ 10.08 (s, 1H), 8.34 (s, 1H), 7.85-7.65 (m, 4H), 4.45 (t, J=12.0 Hz, 2H), 3.77-3.71 (m, 2H), 2.42-2.34 (m, 2H); ESI+ MS: m/z (rel intensity) 285.0 (100, [M+H]+). Step d: Preparation of 2-(3-(4-((methyl(5,6,7,8-tetrahydroquinolin-8-yl)amino)-methyl)-1H-1,2,3-triazol-1-yl)propyl)isoindoline-1,3-dione (AH). A solution of 1-(3-(1,3-dioxoisoindolin-2-yl)propyl)-1H-1,2,3-triazole-4-carbaldehyde, 22, (0.24 g, 0.84 mmol), N-methyl-N-(prop-2-ynyl)-5,6,7,8-tetrahydroquinolin-8-amine, 5, (0.17 g, 1.01 mmol), sodium triacetoxyborohydride (0.27 g, 1.26 mmol) and a catalytic amount of acetic acid (2 drops) in 1,2-dichloroethane (10 mL) was warmed to 65° C. and stirred at this temperature for 24 h. The reaction mixture was cooled to room temperature. A saturated aqueous solution of sodium bicarbonate was added. The product was extracted with dichloromethane. The combined organic layers were dried over potassium carbonate, filtered and concentrated. The crude product was purified by silica gel chromatography (0-5% methanol/CH2Cl2) to afford 0.19 g (80% yield) of the desired product, AH: 1H NMR (400 MHz, CDCl3) δ 8.45 (d, J=4.4 Hz, 1H), 7.79-7.76 (m, 2H), 7.71 (s, 1H), 7.68-7.65 (m, 2H), 7.30 (d, J=7.6 Hz, 1H), 7.00 (dd, J=4.8, 8.0 Hz, 1H), 4.32 (dt, J=3.2, 7.2 Hz, 2H), 3.91 (dd, J=6.0, 9.2 Hz, 1H), 3.77-3.66 (m, 4H), 2.82-2.70 (m, 1H), 2.70-2.60 (m, 1H), 2.29 (s, 3H), 2.29-2.23 (m, 2H), 2.12-2.02 (m, 1H), 2.02-1.92 (m, 1H), 1.92-1.80 (m, 1H), 1.70-1.56 (m, 1H); ESI+ MS: m/z (rel intensity) 431.2 (100, [M+H]+). Step e: Preparation of N-((1-(3-aminopropyl)-1H-1,2,3-triazol-4-yl)methyl)-N-methyl-5,6,7,8-tetrahydroquinolin-8-amine tetrahydrochloride (W). A solution of 2-(3-(4-((methyl(5,6,7,8-tetrahydroquinolin-8-yl)amino)-methyl)-1H-1,2,3-triazol-1-yl)propyl)isoindoline-1,3-dione, AH, (0.16 g, 0.37 mmol) in ethanol (5 mL) was treated with hydrazine (23 μL, 0.74 mmol). The resulting mixture was warmed to 80° C. and stirred for 20 h. The reaction mixture was cooled to room temperature. The white precipitate that formed was filtered and the filtrate was concentrated in vacuo. Chloroform was added. More of the precipitate crashed out and was filtered off. The solution was concentrated and dried under reduced pressure to afford 0.08 g (72% yield) of product W: 1H NMR (400 MHz, CDCl3) δ 8.47 (d, J=3.6 Hz, 1H), 7.65 (s, 1H), 7.33 (d, J=7.6 Hz, 1H), 7.02 (d, J=4.8, 8.0 Hz, 1H), 4.39 (t, J=7.2 Hz, 1H), 3.95 (dd, J=5.6, 9.2 Hz, 1H), 3.75 (q, J=13.6 Hz, 2H), 2.85-2.60 (m, 2H), 2.68 (t, J=6.8 Hz, 2H), 2.31 (s, 3H), 2.25-2.05 (m, 2H), 2.05-1.95 (m, 2H), 1.95-1.80 (m, 1H), 1.75-1.58 (m, 1H); ESI+ MS: m/z (rel intensity) 301.2 (95, [M+H]+).

後処理

  1. additionThe tube containing the resulting mixture
  2. customcap
  3. customfitted with a silicon septum
  4. customirradiation for 30 min at a temperature of 120° C
  5. customAfter the irradiation
  6. temperaturethe reaction tube was cooled with high-pressure air until the temperature
  7. customhad fallen below 40° C
  8. extractionThe product was extracted with ethyl acetate
  9. dry with materialThe combined organic layers were dried with magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customThe crude material (0.62 g, 72% yield) was used without further purification in the next step
  13. concentrationThe reaction mixture was concentrated under reduced pressure
  14. additionThe crude product containing both regioisomers (˜1:1 ratio)
  15. customwas used in the next step without further purification
  16. customStep c: Preparation of 1-(3-(1,3-dioxoisoindolin-2-yl)propyl)-1H-1,2,3-triazole-4-carbaldehyde (22)
  17. stirringThe resulting mixture was stirred at room temperature for 2 h
  18. filtrationThe reaction mixture was filtered through Celite
  19. concentrationconcentrated
  20. customThe crude product was purified by silica gel chromatography (0-5% methanol/CH2Cl2)

出典と根拠

ORDレコード
ord-3cf192b91cd44985988823d221bb0b9d
出典データセット
uspto-grants-2012_12
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08338448B2

反応ノート

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