CN102153430B - Preparation method for fluoride aromatic organic compound - Google Patents
Preparation method for fluoride aromatic organic compound Download PDFInfo
- Publication number
- CN102153430B CN102153430B CN201110034557.3A CN201110034557A CN102153430B CN 102153430 B CN102153430 B CN 102153430B CN 201110034557 A CN201110034557 A CN 201110034557A CN 102153430 B CN102153430 B CN 102153430B
- Authority
- CN
- China
- Prior art keywords
- aromatic organic
- aldehyde radical
- organic compounds
- fluoride
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 *c(cc1O2)ccc1OC2(F)F Chemical compound *c(cc1O2)ccc1OC2(F)F 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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
The present invention relates to a kind of chemical synthesis route, relate to the preparation method of fluorinated aromatic organic compounds particularly; More specifically, the present invention relates to fluoro-1, the 3-benzene of use 2,2-bis-and the luxuriant method of fluoridizing the aromatic organic compounds with aldehyde radical of two Evil.
Background technology
The fluorizating agent of the known organic compound fluoridized is listed below:
1. inorganic fluoride.There is HF, KF (Thomas G.Richmond Chem.Rev.1994,94,373-431), CsF (William R.Dolbier Jr, fluorine chemistry magazine " Journal of FluorineChemistry " (2007)), SbF
3, SbF
5, XeF
2, IF, IF
5(Shoji Hara Tetrahedron (tetrahedron) 60 (2004) 11445-11451), BrF
3deng.
2. organic amine fluoride salt.Have (Laurent Saint-Jalmes fluorine chemistry magazine Journal of Fluorine Chemistry127 (2006): 85-90) such as butyl fluoride amine, triethylamine trihydrofluoride salt, pyridine hydrogen fluoride salts.
3. the fluorination reagent of sulfur-bearing fluorine bond.There is SF
4(see US Patent No. 2859245), diethylamino sulphur trifluoride (DAST), three (dimethylamino) sulphur (trimethyl silyl) difluoride (TASF) etc.
4. gaseous fluorinated dose of high reactivity.There is F
2, CF
3oF, CH
3cOOF, ClO
3f etc.
5. the fluorination reagent of nitrogenous fluorine bond.There are N-fluorinated pyridine trifluoroacetate, N-fluorobenzenesulfonimide, 1-chloromethyl-4-fluoro-1,4-phenodiazine drone two rings [2.2.2] octane two (a tetrafluoro borate), the fluoro-Isosorbide-5-Nitrae-phenodiazine of 1-hydroxyl-4-drone two rings [2.2.2] octane two (a tetrafluoro borate), N-fluorobenzenesulfonimide etc.(Guido?P.Pez?Chem.Rev.1996，96，1737-1755；Dominique?Cahard?Chem.Rev.2008，108，PR1-PR43。Stojan Stavber Tetrahedron Letters (Tet Lett) 48 (2007) 2671-2673).
6. containing the fluorination reagent of carbon-fluorine bond.There is fluoro-1,3-methylimidazole quinoline (DFI) (Hidetoshi Hayashi Chem.Commun., 2002, the 1618-1619 of 2,2-bis-; Tomoya Kitazume, Takuma Ebata fluorine chemistry magazine Journal of Fluorine Chemi stry 125 (2004): 1509-1511; Wolfgang Ebenbeck US Patent No. 20050085474A1) and α, fluoro-N, the N-diethyl of α-two-m-Methylphenethylamine (DFMBA) (Shoji Hara fluorine chemistry magazine Journal ofFluorine Chemistry 126 (2005): 721-725).
In these fluorizating agents, inorganic fluoride and organic amine fluoride salt have low reactive behavior, therefore use and are restricted.SF
4to be boiling point the be toxic gas of-40.4 DEG C, it is difficult to control.Fluorine gas is very active, to such an extent as to its reaction restive.In addition, it is reported CF
3oF, CH
3cOOF and ClO
3f is volatile gas, should carefully control.Diethylamino sulphur trifluoride (DAST), XeF
2, trifluoroacetic acid N-fluorinated pyridine drone etc. the fluorination reagent of nitrogenous fluorine bond be easy to control, and can optionally to fluoridize; But they are expensive reagent, and this makes industrial use, and they can be with the problem of serving.Fluorination reagent containing carbon-fluorine bond be recent years newfound, can be the novel agent of carbon-fluorine bond by hydroxyl or convert aldehyde groups; But their industrial application also exists certain problem: DFMBA activity is poor, needing under 180 DEG C and microwave assisted could be difluoromethyl by convert aldehyde groups, at present cannot industrialization; Fluoro-1,3-methylimidazole quinoline (DFI) activity of 2,2-bis-is higher, but its sterling less stable, need be prepared into acetonitrile solution, can be subject to solvent restriction and consumption is large when carrying out correlated response.In addition, DFI and DFMBA exists with the form of amine salt, and when carrying out fluoridation, in its molecule, two fluorine only have one can be utilized, namely need with hydroxyl reaction an equivalent, with the fluorination reagent of aldehyde radical reaction needed two equivalents, the utilization ratio of fluorine only has 50%.
Fluoro-1, the 3-benzene of 2,2-bis-and two Evil luxuriant be a conventional chemical reagent of industrial scale operation, it is non-explosive but also easily control not only, be boiling point is 129 DEG C, flash-point is the stabilising liq of 32 DEG C.This compound uses as the intermediate of medicine or agricultural chemicals at present only, so far everybody and do not know that also two Evil are luxuriant fluoridizes the aromatics with aldehyde radical by fluoro-for 2,2-bis-1,3-benzene.
In sum, this area lacks a kind of new operational path improving the utilization ratio of fluorine.
Summary of the invention
The object of the invention is to obtain a kind of new operational path improving the utilization ratio of fluorine.
The second object of the present invention is fluoro-1, the 3-benzene of acquisition 2,2-bis-and the luxuriant purposes as fluorination reagent of two Evil.
In a first aspect of the present invention, provide a kind of preparation method of fluoride aromatic organic compound, comprise,
Aromatic organic compounds containing aldehyde radical is provided;
Fluoro-1, the 3-benzene of 2,2-bis-also two Evil is luxuriant as fluorizating agent and the described aromatic organic compounds generation fluoridation containing aldehyde radical, obtains fluoride aromatic organic compound.
In a specific embodiment of the present invention, described fluoride aromatic organic compound is the difluoromethyl aromatic organic compounds or difluoro methylene aromatic organic compounds that obtain after carrying out fluorine replacement by described fluorizating agent to described aldehyde radical.
In a specific embodiment of the present invention, there is relative to 1 mole the aromatic organic compounds of aldehyde radical, use fluoro-1, the 3-benzene of 2,2-bis-and the luxuriant amount of two Evil is 0.2-20 mole, preferred 0.3-5 mole, more preferably 0.4-2 mole.
In a specific embodiment of the present invention, the temperature of described fluoridation is carried out at-80 DEG C-300 DEG C, preferably 20 DEG C-160 DEG C.
In a preference, the organic compound that the temperature of described fluoridation is carried out at-80 DEG C-300 DEG C, preferably 20 DEG C-160 DEG C is benchmark, use the amount of catalyzer for 0.01-10 doubly (mol ratio).
In a specific embodiment of the present invention, described fluoridation is carried out under the existence of acid, lewis acid catalyst and/or water.
In a specific embodiment of the present invention, use acid as catalyzer.
In a specific embodiment of the present invention, the amount of described acid is that catalytic amount is to excessive.
In a specific embodiment of the present invention, relative to described in 1 mole containing the aromatic organic compounds of aldehyde radical, described catalyzer preferred amounts is 0.0001-100 mole, more preferably 0.01-10 mole.
In a specific embodiment of the present invention, this reaction can be carried out under condition of no solvent, also can carry out in conventional organic solvent.
A second aspect of the present invention provides fluoro-1, the 3-benzene of a kind of 2,2-bis-purposes that also two Evil are luxuriant, and it, as fluorizating agent and the described aromatic organic compounds generation fluoridation containing aldehyde radical, obtains fluoride aromatic organic compound.
Embodiment
The present inventor is through extensive and deep research, by improving preparation technology, obtain 2, fluoro-1, the 3-benzene of 2-bis-preparation technology that also two Evil are luxuriant, and be surprised to find that 2,2-bis-fluoro-1,3-Ben Bing bis-Evil is luxuriant to be had and excellent especially fluoridizes performance, therefore is particularly suitable as fluorination reagent and uses, and aromatic aldehyde compounds is converted into the aromatic cycle compound containing difluoromethyl.Complete the present invention on this basis.
Below describe in detail to various aspects of the present invention:
In the present invention, fluoro-1, the 3-benzene of 2,2-bis-two Evil are luxuriant refers to that No. CAS for 1583-59-1, English by name 2,2-Difluoro-1,3-benzodioxole, molecular weight is 158.1, and boiling point is 129 DEG C, and density is 1.31g/cm
3stabilising liq.
Its structural formula is expressed as follows:
In the present invention, the reaction formula fluoridizing the aromatic organic compounds with aldehyde radical represents one:
In above formula, I is fluoro-1, the 3-benzene of 2,2-bis-and two Evil are luxuriant; II is aromatic aldehyde, and R1, R2, R3, R4, R5 can be identical or different, represent hydrogen atom separately, halogen atom, alkyl, aralkyl, aryl, alkoxyl group, alkoxy acyl, nitro, cyano group, amino, an alkylamino, dialkyl amido, amido, or alkylthio.
Also can be enumerated as reaction two
In above formula, I is 2,2-bis-fluoro-1,3-Ben Bing bis-Evil is luxuriant, V is the aldehyde compound with aromaticity, Ar can be the fragrant phenyl ring or the aromatic heterocycle that contain different substituents, can be containing substituent phenyl ring, naphthalene nucleus, pyridine, pyrimidine, pyrazine, indoles, fast quinoline, indenes, quinoline, isoquinoline 99.9, chromene, furans, thiophene, pyrroles etc., but be not limited to above-claimed cpd.
As for preparation method of the present invention and fluorizating agent, except use fluoro-1, the 3-benzene of 2,2-bis-and two Evil luxuriant outside, preferably use and be selected from acid, Lewis acid or water as catalyzer.It is further preferred that use acid as this catalysts.
The object lesson of described catalyzer comprises the hydrogen halide such as sulfuric acid, nitric acid, phosphoric acid, Tripyrophosphoric acid, hydrogen fluoride, hydrofluoric acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hyperbromic acid, Periodic acid, or haloid acid, hypohalous acid, halous acid, hydracid and high hydracid;
Fluosulfonic acid, chlorsulfonic acid, methylsulfonic acid, ethyl sulfonic acid, trifluoromethane sulfonic acid, difluoromethyl sulfonic acid, trichloromethyl sulfonic acid, perfluoro butyl sulfonic acid, perfluoro octyl sulfonic acid, Phenylsulfonic acid, toluenesulphonic acids, nitrobenzene-sulfonic acid etc., or the sulfonic acid of the Polymer-supported such as polystyrolsulfon acid, sulfonate resin of fluoridizing;
Monoprotic acid or the polyprotonic acids such as formic acid, acetic acid, propionic acid, Mono Chloro Acetic Acid, bromoacetic acid, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, oxyacetic acid, lactic acid, phenylformic acid, oxalic acid, succsinic acid.
SO
3, BF
3, BCl
3, B (OCH
3)
3, AlCl
3, AlBr
3, SbF
3, SbCl
3, SbCl
5, SbF
5, PF
3, PF
5, AsF
3, AsCl
3, AsF
5, TiCl
4, NbF
5, TaF
5deng Louis acid or their ether complexes;
HBF
4, HPF
6, HAsF
6, HSbF
6, HSbCl
6deng the acid that Louis acid is formed with halogenation heteroatoms, or their ether complexes;
Two or more above-mentioned mixture can also be adopted.The present invention use acid can load on several carrier.The example of carrier comprises SiO
2, methylated SiO
2, Al
2o
3, Al
2o
3-WB, MoO
3, ThO
2, ZrO
2, TiO
2, Cr
2o
3, SiO
2-TiO
2, SiO
2-ZrO
2, TiO
2-ZrO
2, Al
2o
3-B
2o
3, SiO
2-WO
3, SiO
2-NH
4f, HSO
3cl-Al
2o
3, HF-NH
4-Y, HF-Al
2o
3, NH
4f-SiO
2-Al
2o
3, AlF
3-Al
2o
3, Ru-F-Al
2o
3, F-Al
2o
3, KF-Al
2o
3, AlPO
4, AlF
3, alumina, kaolin, gac, graphite, platinum-graphite, ion exchange resin, metal sulfate, muriate, the alloy such as metal, Al-Mg, Ni-Mo such as Al, the polymkeric substance etc. such as polystyrene.
The amount optional autocatalysis amount of the above-mentioned acid used in the present invention is to excessive.Organic compound relative to 1 mole containing the aldehyde radical be fluorinated, preferred amounts is 0.0001-100 mole, more preferably 0.01-10 mole.Above-mentioned acid can also be used as reaction solvent.Now, the quantity of solvent used is selected from a small amount of to excessive.
In preparation method of the present invention, there is relative to 1 mole the organic compound of aldehyde radical, use fluoro-1, the 3-benzene of 2,2-bis-and the luxuriant amount of two Evil is 0.2-20 mole, preferred 0.3-5 mole.More preferably 0.4-2 mole, and with the organic compound carried out at-80 DEG C-300 DEG C, preferably 20 DEG C-160 DEG C for benchmark, use the amount of catalyzer for 0.01-10 doubly (mol ratio).
The use of reaction solvent not necessarily, but can use reaction solvent.The object lesson of reaction solvent comprises pentane, hexane, heptane, cyclohexane, the aliphatic solvents such as sherwood oil, methylene dichloride, ethylene dichloride, chloroform, fluoro trichloromethane, vinyl trichloride, chloro-1, the 2-bis-bromo-vinyl trichloride of 2-, 1,2-dibromo HFC-236fa, 1,2-dibromo four still ethane, 1,1-difluoro tetrachloroethane, 1,2-difluoro tetrachloroethane, seven fluoro-2,3,3-tri-chlorobutanes, 1,1,1,3 ,-tetrachloro tetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1,1,1-Refrigerant R 113, the aliphatics halide solvents such as polychlorotrifluoroethylene, methyl-formiate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, isopropyl acetate, gamma-butyrolactone, propylene carbonate, Deng esters solvent, acetonitrile, the nitrile solvents such as propionitrile, benzene, toluene, ethylbenzene, propyl benzene, dimethylbenzene, chlorobenzene, dichlorobenzene, fluorobenzene, phenylfluoroform, p-chloro benzo trifluoride-99, bromobenzene, the aromatic solvents such as oil of mirbane, ether, dipropyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, glycol dimethyl ether, the ether solvents such as diethylene glycol dimethyl ether, DMF (DMF), dimethyl sulfoxide (DMSO) (DMSO), water, Nitromethane 99Min., N, N-diethylformamide, 1-Methyl-2-Pyrrolidone, 1,3-dimethyl-2 imidazolidone, tetramethyl-urea, 1,3-dimethylpropylene urea, hexamethyl mebenil (HMPA) etc.They can use separately or with the form of two or more mixtures.
Add organic compound and fluoro-1, the 3-benzene of 2,2-bis-and two Evil order that is luxuriant, catalyzer can be arbitrary, as long as do not have permanent interval between them.
As no specific instructions, various raw material of the present invention all can be obtained by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Above-mentioned synthetic method is the synthetic route of part of compounds of the present invention, according to above-mentioned example, those skilled in the art can synthesize other compounds of the present invention by adjustment diverse ways, or those skilled in the art can synthesize compound of the present invention according to existing known technology.The compound of synthesis can be further purified further by modes such as column chromatography, high performance liquid chromatography or crystallizations.
Other aspects of the present invention, due to disclosure herein, are apparent to those skilled in the art.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, measures according to national standard usually.If there is no corresponding national standard, then according to general international standard, normal condition or carry out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all numbers are weight part, and all per-cent is weight percentage, and described polymericular weight is number-average molecular weight.
Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Embodiment 1
The preparation that also two Evil are luxuriant of fluoro-1, the 3-benzene of 2,2-bis-:
Step one:
By piperonyl cyclonene (244g, 2mol, 1.0eq), AIBN (2.00g) is dissolved in 500ml phenylfluoroform, 100ml phenylfluoroform is added in four-hole bottle, be heated to backflow, while dropping piperonyl cyclonene/AIBN/ phenylfluoroform solution, pass into chlorine, within 8 hours, led to, continue stirring 0.5 hour.Then reduce pressure reaction solution precipitation, then decompression steam chloro-1, the 3-benzene of 2,2-bis-and two Evil luxuriant, obtain 363g, yield 95%.
Step 2:
By chloro-for 2,2-bis-1, the 3-benzene also luxuriant (363g of two Evil, 1.9mol) be placed in 1000ml polytetrafluoro reaction flask, at 40 DEG C, pass into 84g hydrogen fluoride gas, led in falling back, separatory, then wash organic phase with water, add anhydrous magnesium sulfate drying, filter, rectification under vacuum, collects the product of 60-61 DEG C/50mmHg, obtains 270g, purity is 99.8%, yield 90%.
Use fluoro-1, the 3-benzene of 2,2-bis-and the luxuriant aromatic organic compounds with aldehyde radical fluoridized under following shown condition as initiator of two Evil.Result is shown in table one, table two.
Reaction method and reaction conditions as described below.
Embodiment 1 ~ 20
Fluorobenzaldehyde A (2.00g between inciting somebody to action, 16mmol, 1.0eq), 2,2-bis-fluoro-1, the 3-Ben Bing luxuriant B of bis-Evil (3.06g, 19mmol, 1.2eq) joins in 50ml tetrafluoroethylene bottle, add certain solvent of 10ml or not solubilizing agent, add catalyzer, be warming up to a certain degree, stoichiometric number hour.Stopped reaction, adds 10ml methylene dichloride, complete molten rear 10ml water washing organic phase, again by 10ml saturated sodium bicarbonate solution washing organic phase after separatory, filters, obtain organic phase after separatory.Use post look popularize law abstraction and purification product.By NMR and MS assay products, calculate reaction conversion ratio by gas chromatographic column.
React according to similar method, shown in table one specific as follows:
Table one: the reaction result of different substrate
The spectroscopic data of gained compound of the present invention is as follows, for the compound not indicating spectroscopic data, is compared, can confirm target compound by the spectroscopic data embodiment of the present invention obtained with known spectroscopic data.
The fluoro-benzal fluoride of 4-:
Bp：120℃(760mmHg)
m/z：146(M
+)，145，127，96，75。
4-nitro-benzal fluoride:
Bp：210℃(760mmHg)
1H-NMR(CDCl3)δ8.30(d，2H，J＝8.2Hz)；7.71(d，2H，J＝8.2Hz)；6.71(t，1H，J＝55.5Hz)。
19F-NMR(CDCl3)δ-113.3。
m/z：173(M
+)，127，115，107，101，77。
3-nitro-benzal fluoride:
Bp：100℃(6mmHg)
m/z：173(M
+)，154，143，127，101，77。
The chloro-benzal fluoride of 4-:
Bp：70℃(20mmHg)
The bromo-benzal fluoride of 4-
m/z：208、206(M
+)，189，187，158，156，127，107，77，50。
1H-NMR(CDCl?3)δ7.58(d，1H，J＝8.2Hz)；7.36(d，1H，J＝8.2Hz)；6.59(t，1H，J＝56.3Hz)。
19F-NMR(CDCl3)δ-110.7
13C-NMR(CDCl3)δ114.12，125.12，127.22，131.97，133.32
The fluoro-benzal fluoride of the bromo-2-of 5-
1H-NMR(CDCl3)δ7.71(m，1H)；7.56(m，1H)；7.02(t，1H，J＝9.2Hz)；6.83(t，1H，J＝54.7Hz)。
19F-NMR(CDCl3)δ-114.3，-121.2
The fluoro-benzal fluoride of the bromo-5-of 3-
m/z：226、224(M
+)，207，205，176，174，145，125，95，94，75。
The fluoro-benzal fluoride of the bromo-3-of 4-
m/z：226、224(M
+)，207，205，176，174，145，125，95，94，75。
3-bromo-5-nitro benzal fluoride
m/z：253、251(M
+)，234，232，207，205，126，125，114，75。
The fluoro-benzal fluoride of 2,3,4,5,6-five:
Bp：125℃(760mmHg)
19F-NMR(CDCl3)δ-113.6，-143.5，-149.8，-161.6。
m/z：118(M
+)，117，99，90，89，68，51。
Also two Evil are luxuriant for 2,2-bis-fluoro-5-difluoromethyl-1,3-benzene
Bp：175℃(760mmHg)
m/z：208(M
+)，189，158，141，123，114，88，75，63。
4-difluoromethyl benzoyl fluoride
m/z：174(M
+)，155，145，127，107，96，75。
4-aldehyde radical benzoyl fluoride
m/z：152(M
+)，151，123，95，75，50。
The foregoing is only preferred embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read foregoing of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (9)
1. a preparation method for fluoride aromatic organic compound, is characterized in that,
Aromatic organic compounds containing aldehyde radical is provided; The described aromatic organic compounds containing aldehyde radical as shown in the formula (II) or shown in:
II is aromatic aldehyde, R
1, R
2, R
3, R
4, R
5can be identical or different, represent hydrogen atom separately, halogen atom, alkyl, aralkyl, aryl, alkoxyl group, alkoxy acyl, nitro, amino, an alkylamino, dialkyl amido, amido, or alkylthio;
Fluoro-1, the 3-benzene of 2,2-bis-two Evil are luxuriant as fluorizating agent and the described aromatic organic compounds generation fluoridation containing aldehyde radical, described fluoridation is carried out under the existence of sour and/or water, obtains fluoride aromatic organic compound; The fluoride aromatic organic compound obtained is the difluoromethyl aromatic organic compounds obtained after carrying out fluorine replacement by described fluorizating agent to described aldehyde radical.
2. a preparation method for fluoride aromatic organic compound, is characterized in that,
Aromatic organic compounds containing aldehyde radical is provided; Shown in the described following formula V of aromatic organic compounds containing aldehyde radical:
V for having the aldehyde compound of aromaticity, and Ar is naphthalene nucleus, chromene or furans;
Fluoro-1, the 3-benzene of 2,2-bis-two Evil are luxuriant as fluorizating agent and the described aromatic organic compounds generation fluoridation containing aldehyde radical, described fluoridation is carried out under the existence of sour and/or water, obtains fluoride aromatic organic compound; The fluoride aromatic organic compound obtained is the difluoromethyl aromatic organic compounds obtained after carrying out fluorine replacement by described fluorizating agent to described aldehyde radical.
3. method as claimed in claim 1 or 2, is characterized in that having the aromatic organic compounds of aldehyde radical relative to 1 mole, and institute uses fluoro-1, the 3-benzene of 2,2-bis-amount that also two Evil are luxuriant to be 0.2-20 mole.
4. method as claimed in claim 3, is characterized in that having the aromatic organic compounds of aldehyde radical relative to 1 mole, and institute uses fluoro-1, the 3-benzene of 2,2-bis-amount that also two Evil are luxuriant to be 0.3-5 mole.
5. method as claimed in claim 4, is characterized in that having the aromatic organic compounds of aldehyde radical relative to 1 mole, and institute uses fluoro-1, the 3-benzene of 2,2-bis-amount that also two Evil are luxuriant to be 0.4-2 mole.
6. method as claimed in claim 1 or 2, it is characterized in that, the temperature of described fluoridation is at-80 DEG C-300 DEG C.
7. method as claimed in claim 6, it is characterized in that, described fluoridation is carried out at 20 DEG C-160 DEG C.
8. method as claimed in claim 1 or 2, is characterized in that, the amount of described acid is that catalytic amount is to excessive.
9. method as claimed in claim 1 or 2, it is characterized in that, described reaction is carried out in condition of no solvent or conventional organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110034557.3A CN102153430B (en) | 2011-02-01 | 2011-02-01 | Preparation method for fluoride aromatic organic compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110034557.3A CN102153430B (en) | 2011-02-01 | 2011-02-01 | Preparation method for fluoride aromatic organic compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102153430A CN102153430A (en) | 2011-08-17 |
| CN102153430B true CN102153430B (en) | 2014-12-31 |
Family
ID=44435156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110034557.3A Active CN102153430B (en) | 2011-02-01 | 2011-02-01 | Preparation method for fluoride aromatic organic compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102153430B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503750B (en) * | 2011-10-31 | 2014-03-26 | 江苏威耳化工有限公司 | Preparation method of a dichloromethyl or dichloromethylene-containing aromatic organic compound |
| ES2818736T3 (en) * | 2016-05-02 | 2021-04-13 | Dow Global Technologies Llc | Aromatic fluorination method |
| CN113045477B (en) * | 2019-12-26 | 2022-11-01 | 中蓝晨光化工研究设计院有限公司 | Preparation method of fluorine-containing primary amine intermediate |
| CN114181186A (en) * | 2021-09-23 | 2022-03-15 | 山东福尔有限公司 | Preparation method of difluoro piperonyl |
| CN116003372A (en) * | 2022-09-14 | 2023-04-25 | 多氟多新材料股份有限公司 | Preparation method of fluoroethylene carbonate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1005647A (en) * | 1963-06-07 | 1965-09-22 | Akad Wissenschaften Ddr | Process using aryloxy-phosphorus trichlorides |
| US5420308A (en) * | 1991-10-07 | 1995-05-30 | Bayer Aktiengesellschaft | 2,2-difluorobenzo (1,3)-dioxole-carbaldehydes and new intermediate products |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10300112A1 (en) * | 2003-01-07 | 2004-07-15 | Bayer Ag | Fluorination reagents and process for their preparation |
-
2011
- 2011-02-01 CN CN201110034557.3A patent/CN102153430B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1005647A (en) * | 1963-06-07 | 1965-09-22 | Akad Wissenschaften Ddr | Process using aryloxy-phosphorus trichlorides |
| US5420308A (en) * | 1991-10-07 | 1995-05-30 | Bayer Aktiengesellschaft | 2,2-difluorobenzo (1,3)-dioxole-carbaldehydes and new intermediate products |
Non-Patent Citations (2)
| Title |
|---|
| 1,3-苯并二氧茂及其衍生物的研究进展;周再春等;《湘潭师范学院学报》;20011231;第23卷(第4期);14-22 * |
| Nucleophilic trifluoromethylation and difluorination of substituted aromatic aldehydes with Rupperts and Deoxofluor reagents;Rajendra P. Singh et al;《Journal of Fluorine Chemistry》;20011231;第111卷;153-160 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102153430A (en) | 2011-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102153430B (en) | Preparation method for fluoride aromatic organic compound | |
| CN101663268B (en) | Process for producing arylsulfur pentafluorides | |
| KR100942901B1 (en) | The Process for Producing Fluoro Cyclic Carbonate | |
| CN103140477B (en) | Process for preparing 5-fluoro-1-alkyl-3-fluoroalkyl-1h-pyrazole-4-carbonyl chlorides and fluorides | |
| JP2014159457A (en) | Method for producing poly(pentafluorosulfanyl)aromatic compound | |
| CN104016901B (en) | Aryl halide derivatives and synthesis method thereof | |
| CN1974550B (en) | Process for the preparation of compounds having CF2O bridge | |
| JP4280030B2 (en) | Improved production of nuclear fluorinated aromatics | |
| CN109311786A (en) | The fluorinated method of aromatics | |
| CN105061124A (en) | Diarylmethane compound preparation method | |
| JP2008530221A (en) | Improved method for preparing (disubstituted propenyl) phenylalkyl substituted dihydrobenzofurans | |
| US5264639A (en) | Process for producing a 2,2-difluoropropane | |
| JP2004161769A (en) | Method for production of polyhaloalkane | |
| CN1479703A (en) | Method for producing compounds having CF2O bridge | |
| JP5853771B2 (en) | Method for producing α, α-difluoroaromatic compound | |
| CN113072420B (en) | 2-aryl substituted gem-difluoro cyclobutane compounds and preparation method thereof | |
| CN107531640B (en) | Method for producing 5-fluoro-1H-pyrazole-4-carbonyl fluoride | |
| CN104844410A (en) | Synthetic method of 1, 1-2 fluorine - 1, 3 - acetylene compounds | |
| CN105130873A (en) | 3-difluoroalkyl substituted amino oxindole derivative and synthesis method thereof | |
| CN104211565A (en) | Preparation method of anti-hepatitis c medicine intermediate | |
| EP2900634B1 (en) | Process for the preparation of optionally substituted phenyl and pyridyl pyrrolidines | |
| CN114988981B (en) | Preparation method of alpha-trifluoromethyl aryl propyne compound | |
| CN105294387A (en) | Method for preparing chlorine fluorine cyclopentene isomeride | |
| JP4524556B2 (en) | Method for producing 2-naphthol derivative | |
| EP2229355B1 (en) | Method for preparing azetidine derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200508 Address after: Room 811, strategic emerging industry incubation base, Qinchuan Park, Lanzhou New Area, Lanzhou City, Gansu Province Patentee after: Lanzhou kangpengweier Chemical Co., Ltd Address before: 224631 Jiangsu Province, Yancheng City Chemical Industry Park weft six road Patentee before: JIANGSU WEIER CHEMICAL Co.,Ltd. |