Free radical cyclization reaction method initiated by unactivated alkane C (sp3)-H functionalization

An unactivated and functionalized technology, applied in organic chemistry and other fields, can solve problems such as high bond dissociation energy and low polarity, and achieve a wide range of effects

Pending Publication Date: 2022-03-15
NINGBO UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, to the best of our knowledge, the conversion between unactivated alkanes and 2-arylbenzimidazoles has not been reported, which may be attributed to the unactivated C(sp 3 )-H bond with high bond dissociation energy (BDE) and low polarity

Method used

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  • Free radical cyclization reaction method initiated by unactivated alkane C (sp3)-H functionalization
  • Free radical cyclization reaction method initiated by unactivated alkane C (sp3)-H functionalization
  • Free radical cyclization reaction method initiated by unactivated alkane C (sp3)-H functionalization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-10

[0037] Embodiment 1-10 Reaction condition optimization experiment.

Embodiment 1

[0039]

[0040] In a Schlenk tube add 2-arylbenzimidazole 1a (52.4 mg, 0.2 mmol), cyclohexane 2a (0.2 mL), di-tert-butyl hydroperoxide (DTBP, 35.1 mg, 0.24 mmol), dodecane Sodium disulfate (SDS, 11.5mg, 0.04mmol) and H 2 O (1.8 mL). The reaction was then stirred at 90°C and sealed under air until complete consumption of starting material monitored by TLC or GC-MS analysis (reaction time 24 hours). After the reaction was completed, it was extracted three times with ethyl acetate. The organic layer was in Na 2 SO 4Dry on , solvent filtered and evaporated. The solution was concentrated under reduced pressure, and the mixture was purified by flash column chromatography to obtain the target product I-1 (86% yield); 1 H NMR (500MHz, CDCl 3 )δ: 8.50-8.49(m, 1H), 8.39-8.38(m, 1H), 7.84-7.83(m, 1H), 7.58-7.55(m, 1H), 7.49-7.41(m, 4H), 2.50- 2.46(m, 1H), 2.08-2.04(m, 1H), 1.66(s, 3H), 1.47-1.39(m, 3H), 1.27-1.24(m, 1H), 1.19-1.14(m, 1H), 1.00-0.88(m, 3H), 0.84-0.77(m, 3H); 1...

Embodiment 2

[0042] The oxidant uses tert-butyl peroxide (TBHP) instead of di-tert-butyl hydroperoxide (DTBP), and the rest of the conditions are the same as in Example 1, and the yield of the target product I-1 is 75%.

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Abstract

The invention relates to a method for preparing a benzimidazole isoquinolinone compound through free radical cyclization of 2-aryl benzimidazole initiated by C (sp3)-H bond functionalization of a cycloalkane or toluene compound in a water-phase metal-free system. The method comprises the following steps: adding a cycloalkane or toluene compound, a 2-aryl benzimidazole compound, an oxidant, a phase transfer agent and a solvent into a Schlenk reaction flask, and stirring and reacting at a certain temperature in an air atmosphere to obtain the benzimidazole isoquinolinone compound.

Description

technical field [0001] The application belongs to the field of organic synthesis, and specifically relates to an unactivated alkane C(sp) in a water phase metal-free system. 3 A method for preparing benzimidazoloisoquinolinones by free radical cyclization of 2-aryl benzimidazole compounds initiated by )-H functionalization. Background technique [0002] As an important part of life, water occupies an unshakable position among green solvents. Water is known to be non-toxic, low cost and readily available. The high heat capacity of water makes it an ideal medium for large-scale exothermic reactions, while the insolubility of organic compounds in water allows easy extraction and purification of products. On the other hand, metal-free conversion is easier to purify, and it eliminates the disadvantages of metal catalysts, such as high cost, poor durability, and the need for strong bases or complex auxiliary ligands, compared with these processes involving metal catalysis. Cons...

Claims

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Application Information

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IPC IPC(8): C07D487/04
CPCC07D487/04
Inventor 郑滟男魏文廷汪子颖
Owner NINGBO UNIV
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