JP2021134186A - Novel strong acid and use thereof - Google Patents

Abstract

To provide a novel strong acid that has a high proton activity equal to or higher than that of previously known super strong acids and has the advantage of not generating hydrofluoric acid by hydrolysis, and to provide use thereof.SOLUTION: Provided is an acid represented by the following general formula (1) [(R1)(R2)(R3)(R4)Ga]-H+ [I] [In formula (1), R1 to R4, independently of each other, represent a phenyl group optionally substituted with a group selected from the group consisting of a perfluoroalkyl group, a perfluoroalkoxy group, a nitro group, a cyano group, an acyl group and a halogen, or a perfluoroalkyl group.].SELECTED DRAWING: None

Description

The present invention has the following general formula (1).
[(R ¹ ) (R ² ) (R ³ ) (R ⁴ ) Ga] ⁻ H ⁺ [I]
[In formula (1), R ^{1 to} R ⁴ may be independently substituted with a group selected from the group consisting of a perfluoroalkyl group, a perfluoroalkoxy group, a nitro group, a cyano group, an acyl group and a halogen. Represents a phenyl group or a perfluoroalkyl group. ]
With respect to the acid represented by.
The present invention further relates to the use of acids according to the present invention.

_{HPF 6} , HSbF ₆ , and HPF ₃ (C ₂ F ₅ ) ₃ , which are known as super strong acids, are used as catalysts in organic chemistry, but these super strong acids are easily hydrolyzed by water and hydrogen fluoride. Since acid is generated, special care must be taken in handling.

K. G. Rutherford, W. Redmond Org. Synth. Coll. Vol. 5, 133

Therefore, an object of the present invention is to provide a novel superstrong acid that does not have the drawbacks of the prior art.

The present inventors have arrived at the present invention as a result of studies for achieving the above object.
That is, the present invention has the following general formula (1).
[(R ¹ ) (R ² ) (R ³ ) (R ⁴ ) Ga] ⁻ H ⁺ (1)
[In formula (1), R ^{1 to} R ⁴ may be independently substituted with a group selected from the group consisting of a perfluoroalkyl group, a perfluoroalkoxy group, a nitro group, a cyano group, an acyl group and a halogen. Represents a phenyl group or a perfluoroalkyl group. ]
It is an acid represented by.

It has the effect of having a high proton activity equal to or higher than that of the super strong acids known so far and not generating hydrofluoric acid by hydrolysis.

In the general formula (1), R ^{1 to} R ⁴ may be independently substituted with a group selected from the group consisting of a perfluoroalkyl group, a perfluoroalkoxy group, a nitro group, a cyano group, an acyl group and a halogen. Represents a phenyl group or a perfluoroalkyl group.
Preferably R ^{1 to} R ⁴ is a perfluoroalkyl group or a phenyl group substituted with a fluorine atom, and particularly preferably R ^{1 to} R ⁴ is a pentafluorophenyl group or a bis (trifluoromethyl) phenyl group.

The present invention also relates to the use of the acid of the present invention as a catalyst in the production of organic compounds.
The acids of the present invention are suitable as alternatives to _{HPF 6} , HSbF ₆ and HPF ₃ (C ₂ F ₅ ) _{3, especially in chemical reactions.}
The acid of the present invention is preferably used by the following methods.
-Manufacture of photosensitive polymers [CA (Chemical Abstracts) 110: 15956e]
-Production of dihydroxydiaryl compounds [CA 110: 94679t]
-Metal surface treatment [CA 110: 139975e]
-Manufacture of electrically conductive aniline polymer [CA 110: 155067r]
-Manufacture of carboxylic acids and carboxylic acid esters [CA 110: 233613g]
-Manufacture of high molecular weight diazonium compounds [CA 110: 87472n]
・ Manufacturing of epoxy resin [CA 111: 135490r]
-Manufacture of electrically conductive materials from amine-like compounds [CA 112: 46758n]
・ Manufacture of octadienol [CA 112: 98016p]
Carboaminolation or carboamidization of olefins [CA 112: 161007d]
・ Isomerization of butene [CA 112: 157653u]
-Manufacture of electrically conductive polyalkoxythiophene [CA 115: 50551u]
・ Desulfurization of oil and waste liquid [CA 116: 261878q]
-Manufacture of triglycidyl trimethylolpropane alkane-based compositions [CA 117: 92344a]
-Manufacture of polymers from styrene and carbon monoxide [CA 117: 172290v]
-Manufacture of organic salts for information storage [CA 117: 17381g]
-Manufacturing of information carriers with good light resistance [CA 115: 267063w]
-Manufacture of silicon supports for catalysts [CA 117: 74989k]
-Manufacture of pyrrole derivatives [CA 117: 70577b]
-Copolymerization of carbon monoxide and olefinically unsaturated compounds [CA 118: 7520h]
-Manufacture of electrically conductive polymers [CA 118: 137707k]
・ Manufacturing of magnetic contrast agent [CA 118: 299355x]
-Manufacturing of polymer coating [CA 119: 54608y]
-Removal of oxide layer of stainless steel [CA 119: 77272y]
-Synthesis of methyl tert-butyl ether [CA 119: 202992m]
-Production of cyclic sulfonium salt containing 5 to 7 carbons [CA 119: 249826a]
-Manufacturing of cyclosiloxane [CA 120: 108008u]
・ Refining of heavy oil and bitumen [CA 120: 195633k]
-Treatment of aluminum compounds [CA 120: 283104u]
-Manufacture of quaternary pyridinium or anilinium salt [CA 121: 9165g]
-And carbon monoxide copolymerization [CA 121: 10209f]
-Manufacture of aromatic hydroxyl compounds [CA 121: 133684q]
-Manufacture of acetate derivatives [CA 121: 157308w]
-Manufacture of resins from dialkenylbenzene and polyarylamine [CA 122: 70050c]
-Manufacture of substituted pyrolopyrimidine-4-one [CA 122: 314562q]
・ Oil recovery [CA 122: 295102w]
-Use as a non-aqueous electrolyte solution [CA 122: 118595j]
-Production of stable methyl cations [CA 124: 288639q]
-Manufacture of cyclic sulfonium salt [CA 125: 114470h]
-Manufacture of optical storage materials [CA 125: 127895a]
-Production of conjugated fluoropyridinium salt [CA 125: 119500c]
-Production of iridium / diphosphane complex [CA 126: 226760e]
・ Asymmetric hydrogenation of imine [CA 126: 225097g]
-Hydroformylation of unsaturated compounds [CA 126: 225032g]
-Polymer synthesis [CA 126: 104554v]
-Production of polymers from polycycloolefins having a silyl group [CA 127: 110414m]
-Manufacturing of ruthenium catalyst [CA 127: 83071p]
-Manufacture of ibuprofen [CA 127: 318741y]
-Production of cyclohexadienyl compound [CA 126: 212225x]
-Copolymerization of olefins [CA 126: 199931c]
-Manufacture of inorganic methylimidazolinium salt [CA 128: 167423p]
-Manufacturing of SiCO and SiC ceramic fibers [CA 128: 234151p]
-Manufacturing of thermal printing materials [CA 128: 210892e]
-Manufacturing of polymers [CA 129: 317091r]
-Production of aziridine-polyether compound [CA 131: 35901v]
-Manufacture of dicarboxylic acid diester [CA 131: 199417t]
-Hydrocarbonated aromatic hydrocarbons [CA 129: 218223d]
-Manufacture of carboxylic acids and carboxylic acid esters [CA 129: 216347y]
・ Pretreatment of lithographic printing board [CA 129: 195815g]

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the Examples. Unless otherwise specified, parts mean parts by weight and% means% by weight.

(Example 1) Synthesis of tetrakis (pentafluorophenyl) gallate acid 360 parts of super-dehydrated diethyl ether and 30 parts of pentafluorobromobenzene were placed in a 125 mL four-necked flask sufficiently dried under a nitrogen atmosphere, and these were charged with dry ice / acetone. It was cooled to −78 ° C. using a bath. 70 parts of a 2.5 mol / L n-butyllithium hexane solution was added dropwise over 10 minutes, and then the mixture was stirred at −78 ° C. for 30 minutes. To this, 68 parts of a diethyl ether solution in which 5 parts of gallium (III) chloride was dissolved was added dropwise over 10 minutes, and the mixture was stirred at −78 ° C. for 3 hours. The reaction mixture was stirred while gradually returning to room temperature, and after returning to room temperature, the mixture was further stirred for 5 hours. The precipitated solid was filtered, the reaction solution was transferred to an evaporator, and the solvent was distilled off to obtain a grayish white product. The product was washed 4 times with 50 parts of ultra-dehydrated hexane, vacuum dried overnight, methanol was added to make a 50% solution, and then passed through ^{an ion exchange resin (Amberlite @ IR120 Aldrich).} , Tetrakis (pentafluorophenyl) gallate acid was obtained. The product was ^{identified by 19} F-NMR.

(Example 2) Synthesis of tetrakis (3,5-bis (trifluoromethyl) phenyl) gallate acid 30 parts of pentafluorobromobenzene was added to 35.59 parts of 1-bromo-3,5-bis (trifluoromethyl) benzene. Tetrakiss (3,5-bis (trifluoromethyl) phenyl) gallate acid was obtained in the same manner as in Example 1 except for the modification. The product was ^{identified by 19} F-NMR.

(Example 3) Synthesis of tetrakis (3,4,5-trifluorophenyl) gallate acid 30 parts of pentafluorobromobenzene was changed to 25.63 parts of 1-bromo-3,4,5-trifluorobenzene. Tetrakiss (3,4,5-trifluorophenyl) gallate acid was obtained in the same manner as in Example 1. The product was ^{identified by 19} F-NMR.

(Example 4) Synthesis of tetrakis (4-nitrophenyl) gallate acid Tetrakis (4) was carried out in the same manner as in Example 1 except that 30 parts of pentafluorobromobenzene was changed to 24.54 parts of 1-bromo-4-nitrobenzene. -Nitrophenyl) Galate acid was obtained. The product was ^{identified by 19} F-NMR.

(Example 5) Synthesis of tetrakis (4-cyanophenyl) gallate acid Tetrakis (4-cyanophenyl) in the same manner as in Example 1 except that 30 parts of pentafluorobromobenzene was changed to 21.62 parts of 1-bromo-4-cyanobenzene. 3,5-Bis (trifluoromethyl) phenyl) gallate acid was obtained. The product was ^{identified by 19} F-NMR.

Production of photosensitive polymers, production of dihydroxydiaryl compounds, metal surface treatment, production of electroconductive aniline polymers, production of carboxylic acids and carboxylic acid esters, production of high molecular weight diazonium compounds, production of epoxy resins, production of amine-like compounds. Production of electroconductive materials, production of octadienol, carboaminolation or carboamidization of olefins, isomerization of butene, production of electroconductive polyalkoxythiophene, desulfidening of oils and effluents, composition of triglycidyl trimethylalkane bases Manufacture of compounds, polymers from styrene and carbon monoxide, organic salts for information storage, information carriers with good photoresistance, silicon supports for catalysts, pyrrole derivatives Production, copolymerization of carbon monoxide and olefinically unsaturated compounds, production of electroconductive polymers, production of magnetic contrast agents, production of polymer coatings, removal of oxide layers of stainless steel, synthesis of methyltert-butyl ether, 5- Production of cyclic sulfonium salt containing 7 carbons, production of cyclosiloxane, purification of heavy oil and bitumen, treatment of aluminum compounds, production of quaternary pyridinium or anilinium salt, copolymerization of olefins and carbon monoxide, aromatic hydroxyl Production of compounds, production of acetate derivatives, production of resins from dialkenylbenzene and polyarylamine, production of substituted pyrolopyrimidin-4-one, recovery of petroleum, use as non-aqueous electrolyte solution, stable methyl cations Production, production of cyclic sulfonium salt, production of optical storage material, production of conjugated fluoropyridinium salt, production of iridium / diphosphin complex, asymmetric hydrogenation of imine, hydroformylation of unsaturated compound, synthesis of polymer, having silyl group Production of polymers from polycycloolefins, production of ruthenium catalysts, production of ibuprofene, production of cyclohexadienyl compounds, copolymerization of olefins, production of inorganic methylimidazolinium salts, production of SiCO and SiC ceramic fibers, thermal printing materials Is preferably used for the production of polymers, the production of aziridine-polyether compounds, the production of dicarboxylic acid diesters, the hydroxylation of aromatic hydrocarbons, the production of carboxylic acids and carboxylic acid esters, and the pretreatment of lithograph printing plates.

Claims (5)

The following general formula (1)
[(R ¹ ) (R ² ) (R ³ ) (R ⁴ ) Ga] ⁻ H ⁺ [I]
[In formula (1), R ^{1 to} R ⁴ may be independently substituted with a group selected from the group consisting of a perfluoroalkyl group, a perfluoroalkoxy group, a nitro group, a cyano group, an acyl group and a halogen. Represents a phenyl group or a perfluoroalkyl group. ]
Acid represented by. The acid according to claim 1, wherein in the general formula (1), R ^{1 to} R ⁴ are phenyls substituted with a perfluoroalkyl group or a fluorine atom independently of each other. The acid according to claim 1, wherein in the general formula (1), R ^{1 to} R ⁴ are independent of each other and are a pentafluorophenyl group or a bis (trifluoromethyl) phenyl group. Use of the acid according to any one of claims 1 to 3 as a catalyst in the production of an organic compound. Use of the acid according to any one of claims 1 to _{3 as} a substitute for the _{acids HPF 6} , HSbF ₆ and HPF ₃ (C ₂ F ₅ ) 3 in a chemical reaction.