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Halogenating agents

A technology of fluorinating agents and compounds, applied in organic chemistry, etc., can solve problems such as difficult handling, unrecorded fluorinating reagents, and high price of fluorine sources

Inactive Publication Date: 2007-08-08
MITSUI CHEM INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

These two literatures record that the counter ion of the iminium halide salt contains a halide ion, but in fact only C1 is disclosed as the counter ion - Examples, especially the two documents do not record fluorinated reagents
[0007] In addition, DE-2627986 and Japanese Patent Application No. 52-156810 describe that in the preparation of perfluoroalkoxypropionyl fluoride, bis-dialkylamino-difluoromethane is used as a reaction catalyst, but no fluorination reagents are made. record
Moreover, this preparation is a method of reacting hexafluoropropylene oxide and tetraalkylurea, and the fluorine source is expensive and difficult to handle.
[0008] In summary, as a fluorinating agent with oxygen-containing functional groups, from the aspects of its preparation method, reaction selectivity, yield, and economical efficiency, the development of industrially usable fluorinating agents is not enough at present.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0405] Synthesis of 2,2-difluoro-1,3-dimethylimidazolidine (DFI)

[0406] Chlorine 2-chloro-1,3-dimethyl-imidazolinium 76.4g (0.452mol) and spray-dried product Potassium Fluoride 105.2g (1.810mol) and acetonitrile 320ml are packed in the 500ml four-necked reaction flask, in Under a nitrogen atmosphere, the reaction was carried out at 80° C. for 17 hours. After cooling the reaction liquid to 25° C., the inorganic salt was separated from the reaction liquid to obtain 414.2 g of an acetonitrile solution of DFI (MW.136.15). The concentration of DFI in the solution was 11.4%, and the yield was 77%.

[0407] The reaction liquid was distilled under reduced pressure to obtain 32 g of DFI (purity: 97.8%). The physical properties are as follows:

[0408] Boiling point 47.0℃ / 37mmHg, EIMS: 136(M + ), 117 (M + -F + ), IR (neat) cm -1 : 1486, 1385, 1295, 1242, 1085, 966, 711, F analysis: calculated value 27.9%, measured value 27.7%, 1 H-NMR (δ, ppm, CDCl 3 , TMS reference): 2.52 (s...

Embodiment 2

[0411] Synthesis of bis-dimethylamino-difluoromethane (hereinafter abbreviated as TMF)

[0412] Add spray-dried potassium fluoride (52.06 g, 0.896 mol) and 33.66 g of acetonitrile to the acetonitrile (107.82 g) solution of 33.32 g (0.224 mol) of tetramethyl-chloroformamidine chloride, and react at 85 ° C 52 hours. Then, the reaction mass was filtered to obtain an acetonitrile solution of TMF. The physical properties of TMF were measured using this acetonitrile solution. The physical property values ​​are as follows.

[0413] EIMS: 138(M + ), 119(M-F) + , F analysis: measured value 12.1%, calculated value 12.4%, 1 H-NMR (δ, ppm, CH 3 CN solvent, CH 3 CN benchmark, 24°C): 2.44(s, -CH 3 ), 13 C NMR (δ, ppm, CH 3 CN solvent, 24°C, DMSO-d 6 Benchmark): 36.1(s, -CH 3 ×4), 128.6(t,=CF 2 ).

Embodiment 3

[0415] Synthesis of bis-di-n-butylamino-difluoromethane (hereinafter abbreviated as TBF)

[0416] Add spray-dried potassium fluoride (50.92 g, 0.8864 mol) and 7.86 g of acetonitrile to the acetonitrile (181.45 g) solution of 74.36 g (0.2129 mol) of tetra-n-butyl chloride chloride (0.2129 mol) and 7.86 g of acetonitrile. React for 35 hours. The reaction mass was then filtered and the resulting filtrate separated into two layers. The two layers of the filtrate were combined, acetonitrile was distilled off under reduced pressure, and TBF was obtained as a distillation residue. The physical properties of this residue were measured. The physical property values ​​are as follows.

[0417] EIMS: 306(M + ), 287(M-F) + , F analysis: measured value 12.1%, calculated value 12.4%, 1 H-NMR (δ, ppm, solvent-free dilution, CH 3 CN reference, 24°C): 1.04 (tj=~8Hz, CH 2 CH 3 ), 1.41 (mj=~8Hz, CH 2 CH 2 CH 3 ), 1.59 (quint., j=~8Hz, CH 2 CH 2 CH 2 ), 2.92 (tj=~8Hz, NCH 2 CH 2 )...

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Abstract

Disclosed are a fluorinating agent represented by the general formula (1): wherein R1 to R4 are a substituted or unsubstituted, saturated or unsaturated alkyl group or a substituted or unsubstituted aryl group, and can be the same or different; R1 and R2 or R3 and R4 can bond to form a ring including a nitrogen atom or a nitrogen atom and other hetero atoms; or R1 and R3 can bond to form a ring including a nitrogen atom or a nitrogen atom and other hetero atoms, for example: a preparation process of the fluorinating agent and a process for preparing fluorine compounds by reacting various compounds with the fluorinating agent. The invention has also disclosed that the fluorinating agent is very effective for fluorinating oxygen containing functional compounds.

Description

technical field [0001] The present invention relates to a novel halogenating agent and its preparation method and use. Background technique [0002] For the halogenation of organic compounds, various methods have been known in the past. Generally used halogenating agents are hydrogen halides, halogen phosphides, halogen sulfides, halogen monomers, etc., but these substances are highly corrosive and toxic, and require special equipment and techniques for disposal. Therefore, various halogenation reagents are currently being developed and researched in terms of handling, safety, and reactivity. Especially for the preparation of fluorine compounds, since the fluorination reaction reagents are usually highly dangerous, compared with other halogenation reactions, a higher level of special equipment and technology is required, and the burden is also increased economically. [0003] Fluorine, hydrogen fluoride, sulfur tetrafluoride, etc. have been used in the fluorination reactio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C211/09C07D233/02C07D239/04
Inventor 园田宽冈田一成高桥章福村考记林秀俊永田辉幸高野安弘
Owner MITSUI CHEM INC