Preparation method for fluoride aromatic organic compound

An organic compound, difluoromethyl aromatic technology, applied in the field of chemical synthesis routes, can solve problems such as expensive, unstable pure products, lack of fluorine, etc.

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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Diethylaminosulfur trifluoride (DAST), XeF 2 Fluorinating reagents containing nitrogen-fluorine bonds, such as N-fluoropyridinium trifluoroacetic acid, are easy to control and can be selectively fluorinated; however, they are expensive reagents, which makes their use in industry problematic
Fluorinating reagents containing carbon-fluorine bonds are newly discovered in recent years and can convert hydroxyl or aldehyde groups into carbon-fluorine bonds. Only under the promotion of ℃ and microwave can the aldehyde group be converted into difluoromethyl group, which cannot be industrialized at present; 2,2-difluoro-1,3-dimethylimidazoline (DFI) has high activity, but its pure product is not stable , needs to be prepared into acetonitrile solution, which will be limited by the solvent and used in a large amount when performing related reactions
[0011] In summary, this area lacks a new process route to improve the utilization rate of fluorine

Method used

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  • Preparation method for fluoride aromatic organic compound
  • Preparation method for fluoride aromatic organic compound
  • Preparation method for fluoride aromatic organic compound

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preparation example Construction

[0038] As for the production method and fluorinating agent of the present invention, it is preferable to use a catalyst selected from acid, Lewis acid or water in addition to 2,2-difluoro-1,3-benzodioxol. More preferably, an acid is used as a catalyst for this reaction.

[0039] Specific examples of the catalyst include sulfuric acid, nitric acid, phosphoric acid, polyphosphoric acid, hydrogen fluoride, hydrofluoric acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, perbromic acid , hydrogen halides such as periodic acid, or hydrohalic acid, hypohalous acid, halous acid, halogen acid and perhalogen acid;

[0040]Fluorosulfonic acid, chlorosulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, difluoromethanesulfonic acid, trichloromethanesulfonic acid, perfluorobutylsulfonic acid, perfluorooctanesulfonic acid , benzenesulfonic acid, toluenesulfonic acid, nitrobenzenesul...

Embodiment 1

[0055] Preparation of 2,2-difluoro-1,3-benzodioxol:

[0056] step one:

[0057] Dissolve piperonylcycline (244g, 2mol, 1.0eq) and AIBN (2.00g) in 500ml benzotrifluoride, add 100ml benzotrifluoride to a four-neck flask, heat to reflux, add piperonylcycline / AIBN / trifluorotoluene dropwise Chlorine gas was introduced into the toluene solution at the same time, and the passage was completed in 8 hours, and the stirring was continued for 0.5 hours. Then the reaction solution was desolvated under reduced pressure, and then 2,2-dichloro-1,3-benzodioxol was distilled off under reduced pressure to obtain 363 g with a yield of 95%.

[0058] Step two:

[0059] Put 2,2-dichloro-1,3-benzodioxol (363g, 1.9mol) in a 1000ml polytetrafluoroethylene reaction bottle, pass through 84g of hydrogen fluoride gas at 40°C, and pour it into water after passing through, Separate the liquid, wash the organic phase with water, add anhydrous magnesium sulfate to dry, filter, and rectify under reduced pre...

Embodiment 1～20

[0064] Add m-fluorobenzaldehyde A (2.00g, 16mmol, 1.0eq), 2,2-difluoro-1,3-benzodioxol B (3.06g, 19mmol, 1.2eq) into a 50ml polytetrafluoroethylene bottle Add 10ml of a certain solvent or no solvent, add a catalyst, raise the temperature to a certain level, and react for several hours. Stop the reaction, add 10ml of dichloromethane, wash the organic phase with 10ml of water after complete dissolution, wash the organic phase with 10ml of saturated sodium bicarbonate solution after liquid separation, and filter after liquid separation to obtain the organic phase. The product was isolated and purified using column chromatography. The product was analyzed by NMR and MS, and the reaction conversion rate was calculated by gas chromatography column.

[0065] React according to a similar method, specifically as shown in Table 1 below:

[0066] Table 1: Reaction results of different substrates

[0067]

[0068]

[0069]

[0070] The spectral data of the compounds obtained i...

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Abstract

The invention provides a preparation method for fluoride aromatic organic compound. The preparation method includes the steps of providing fluoride aromatic organic compound containing aldehyde group, and taking 2, 2-difluoro-1,3 benzodioxole as a fluorinating agent, conducting fluoridation reaction on the fluorinating agent and fluoride aromatic organic compound containing the aldehyde group so as to obtain the fluoride aromatic organic compound. The invention provides a new process route for improving the utilization rate of fluorine.

Description

technical field [0001] The present invention relates to a chemical synthesis route, in particular to a preparation method for fluorinated aromatic organic compounds; more specifically, the present invention relates to the use of 2,2-difluoro-1,3-benzodioxol to Aldehyde aromatic organic compounds method. Background technique [0002] Known fluorinating agents for fluorinating organic compounds are listed below: [0003] ① Inorganic fluoride. There are HF, KF (Thomas G. Richmond Chem. Rev. 1994, 94, 373-431), CsF (William R. Dolbier Jr, "Journal of Fluorine Chemistry" (2007)), SbF 3 , SbF 5 , XeF 2 ,IF,IF 5 (Shoji Hara Tetrahedron (tetrahedron) 60 (2004) 11445-11451), BrF 3 Wait. [0004] ②Organic amine fluoride salt. There are butylamine fluoride, triethylamine trihydrogen fluoride, pyridine hydrogen fluoride, etc. (Laurent Saint-Jalmes Journal of Fluorine Chemistry 127 (2006): 85-90). [0005] ③ Fluorinating reagents containing sulfur-fluorine bonds. have SF 4 (Se...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B39/00C07C17/00C07C25/13C07C23/10C07C201/12C07C205/11C07C253/30C07C255/50C07C63/70C07C65/30C07C51/60C07C49/653C07C45/68C07D307/38C07D317/46
Inventor 蔡国荣刘俊黄启明
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