TW201113246A - Method for preparing sulfonium salt and sulfonium salt prepared by the same - Google Patents

Abstract

There are provided a method for preparing a sulfonium salt and a sulfonium salt prepared by the method. The method for preparing a sulfonium salt includes a first step of adding a compound represented by formula (2) to a compound represented by formula (1) and subjecting the compounds to a trans-esterification reaction to produce a reaction intermediate; and a second step of adding an inorganic salt to the reaction intermediate and subjecting the compounds to a substitution reaction to produce a compound represented by the following formula (3).

Description

201113246 JSMlplf VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a cerium salt and a cerium salt produced by the method. More specifically, the present invention relates to a method for producing a cerium salt. With this method, a large amount of nickel which is mainly used for the production of an intermediate of an acid generator or the like can be synthesized in a high yield through a simplified manufacturing process. a salt; and a cerium salt produced by the method. [Prior Art] With the change of the times, in the field of finishing semiconductors or the like using photolithography, there is an increasing demand for higher resolution photoresists. A chemically amplified type photoresist composition developed in response to this demand contains an acid generator. In order to produce a resist having a higher resolution and a desired property, various types of acid generators have been invented so far. For example, Korean Patent Application No. 10-2006-0104564 (hereinafter referred to as "Patent Document 1") discloses a known agent represented by the following formula (A) as a chemically amplified anti-rice composition The acid generator in the formula: [Formula A] A+ ''〇3S-CC〇2(CH2)n—beautiful, Χ is a monocyclic or bicyclic hydrocarbon soil JX having 3 to 3G carbon materials unsubstituted, or Said ring or a plurality of positions through a filament having one carbon atom, a dilute group having 2 to 6 carbon atoms, having an alkoxy group having 2 to 6 carbon atoms or having 1 to 4 carbon atoms in 201113246 JDDIipif The perfluoroalkyl group is substituted; Q1 and Q2 each independently represent a fluorine atom or an all-I group having 1 to 6 stone anti-atoms, A represents an organic counter ion; and η is an integer of 1 to 12. . Patent Document 1 also discloses, for example, an organic compound represented by the following formula (Β) as an intermediate for producing an acid generator. Specifically, the patent document discloses a method for producing an ester compound of the formula (?) by reacting an alcohol compound represented by the following formula (C) with a carboxylic acid compound represented by the following formula (1)). [ΒΒ] Q1 ~〇3S-CC〇2(CH2)n Q2

[Formula C] H〇-<CH2)n— [Formula D]

''O3S-CCO2H 〇2 ^^' in '^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ , potassium (κ) or silver (Ag).

Here, the formula (D) is a product of a carboxylic acid form obtained by hydrolyzing a compound of the formula (1) with a strong base such as NaOH: X 201113246 [Formula l]

Wherein Ri and R2 each independently represent any one selected from the group consisting of a dentate atom, a hydroxyl group, a carboxyl group, a nitrile group, an aldehyde group, an epoxy group, an alkyl group, a cycloalkyl group, a heterocycloalkyl group, and an aromatic group. Base and heteroaryl;

Qi and Q2 each independently represent any one selected from the group consisting of a hydrogen atom, a halogen atom, and a perfluoroalkyl group; and η is an integer β of 1 to 1 然而. However, the compound of the formula (D) is via two The step reaction is obtained and the product of the f reaction step is separated by a separate purification process. Further, when the reaction intermediate generated during the purification process after the first step reaction is separated from the aqueous phase, the reaction intermediate adheres to the reaction vessel, thereby causing a problem that the yield is remarkably lowered, and this problem Industry does not want to exist. The Korean Unexamined Patent Application No. 10-2008-0099784 discloses a method for crystallizing and silk-forming an organic compound, and the document & is used to obtain a crystal using a porous film to increase the reaction in the first step. The yield is gone. However, there are limitations to using this method on an industrial scale, and because of the poor solubility of the carboxylic acid, the yield of the esterification reaction as the second step reaction is also low. "There are also too small a product particle so that the county is difficult during the purification process. The problem with the particles. SUMMARY OF THE INVENTION 8 201113246 3DMlpif The present invention is directed to this specific case, and the object of the present invention is to provide a method for producing salt-salting, which is different from the conventional two-step reaction method, which uses fewer reaction steps. The yield of the onium salt used as an intermediate of the acid generator is increased, and large-scale synthesis can be carried out without separating the product by purification in each reaction step. Another object of the present invention is to provide a phosphonium salt produced by the above-described method for producing a cerium salt. The present invention will be described in detail below, and thus the present invention can be easily implemented by those skilled in the art to which the present invention pertains. However, those skilled in the art should understand that the present invention clearly includes various modifications and The invention is not intended to be limited by the illustrative examples described herein. Unless otherwise indicated, all compounds or substituents used herein may be unsubstituted or substituted. Here, the term "substituted" means The hydrogen atom of the compound or substituent is substituted with any one selected from the group consisting of a dentate atom, a hydroxyl group, a carboxyl group, a nitrile group, a cyano group, an aldehyde group, an epoxy group, an alkyl group, a perfluoroalkane. Alkyl, hydroxyalkyl, cycloalkyl, heterocycloalkyl, alkoxy, allyl, methyl, aryl, heteroaryl, derivatives thereof, and combinations thereof. Unless otherwise indicated, "Halogen atom" means any atom selected from the group consisting of fluorine, chlorine, bromine and moth. Unless otherwise indicated, "perfhioroalkyl group" is used herein. The "alkyl group" of some or all of the hydrogen atoms via fluorodicarbon. 201113246 3551 lpif "heterocycloalkyl group" or "heteroaryl" (heter 〇) as used herein, unless otherwise indicated. "aryi gr〇Up)" means that there are i to three heteroatoms selected from the group consisting of nitrogen (N), oxygen (9), sulfur (S) and phosphorus (P) in the ring and all other atoms in the ring Is a "cyclium alkyl gr〇up" or "aryl group" of a carbon atom. Unless otherwise indicated, the "alkyl group" as used herein means having 1 to 30 carbon atoms. Linear or branched alkyl; as used herein, "allyl group" means a straight or branched allylic group having from 2 to 30 carbon atoms; "perfluoroalkyl" as used herein means A straight or branched chain perfluoroalkyl group having 1 to 3 carbon atoms; "cycloalkyl" as used herein means a cycloalkyl group having 3 to 30 carbon atoms; "heterocycloalkyl" as used herein. Means a heterocycloalkyl group having 2 to 30 carbon atoms; and "aryl" means an aryl group having 6 to 30 carbon atoms. "alkylene group" means a straight or branched alkyl group having 1 to 30 carbon atoms, and "perfluoroalkylene group" as used herein means 1 to 30 carbons. A straight-chain or branched-chain perfluoroalkylene group of atoms; as used herein, "cycloalkylene group" means a cycloalkylene group having from 3 to 30 carbon atoms; (Heterocycloalkylene group) means a heterocycloalkyl group having 2 to 30 carbon atoms; and "arylene group" as used herein means an exoaryl group having 6 to 30 carbon atoms. As used herein, unless otherwise indicated, "norbomyl group" as used herein means a monocyclic or polycyclic norbornene having a 7 to 30 carbon atom 201113246 base' and adamantylgr〇Up used herein. "Aging has an adamantyl group of 10 to 30 carbon atoms. . According to an embodiment of the present invention, there is provided a method of producing a cerium salt in which a cerium salt can be produced by a reduced reaction step and a simplified manufacturing process. Hereinafter, the method for producing the onium salt will be explained. The i ratio is different from the conventional method in which the purification process is required for each step. The salt production method is actually carried out in a step-by-step reaction without any purification process. However, for the convenience of the reader, the method will be divided into the first step and the second step. The method for producing the cerium salt comprises the steps of: adding a compound represented by the following formula (2) to a compound represented by the following formula (1) and subjecting the compound to a transesterification reaction to produce The reaction intermediate 丨 first step 'adds an inorganic salt to the reaction intermediate, and subjectes the compound to a substitution reaction to produce a compound represented by the following formula (3). [Formula 1]

[Formula 2]

HO-(R3)m-X 11 201113246 i55ilpif [Formula 3]

—Ο—[-Ral^X where in equations (1) to (3),

Ri and R2 each independently represent any one selected from the group consisting of a functional group atom, a hydroxyl group, a carboxyl group, a nitrile group, a chelating group, an epoxy group, a alkyl group, a cycloalkyl group, a heterocycloalkyl group, and an aryl group. And a heteroaryl group; & R·3 represents any one selected from the group consisting of an exothermic group, a perfluoro-extension base, a stretching ring, a heterocycloalkylene group, an exoaryl group, and a hetero-aromatic group. its.

Qi and Q2 each independently represent any one selected from the group consisting of a hydrogen atom, a dentate atom, and a total defeated base; X represents any one selected from the group consisting of hydrogen atom, cadaveric, and full gas. An alkyl group, an alkoxy group, a cycloalkyl group, a propyl group, an aryl group, and a heteroaryl group. Μ represents any one selected from the group consisting of lithium, sodium, bell, and silver; and η is an integer of 1 to 10. ; and m is an integer from 0 to 10. In the case of Qi and Q2, the halogen atom may be a fluorine atom. As the X, any alkyl '> can be used as long as it is an alkyl group having 1 to 30 carbon atoms' and the alkyl group may be a cycloalkyl group or an aryl group (more specifically, , benzyl) substituted alkyl. For X, the cycloalkyl group may be a monocyclic or polycyclic cycloalkyl group. In the case of X, at least one or more of the alkyl, alkoxy or perfluoroalkyl groups may be substituted by any one selected from the group consisting of: an ether group, an ester group, a few groups, a condensation group. Acid group, epoxy group, nitrile group, chelating group and cyano group. Specifically, 'X may be a monocyclic or polycyclic hydrocarbon group having 3 to 30 carbon atoms' which may be selected from the group consisting of adamantyl, norbornyl, cycloalkyl, heterocycloalkyl, aryl And heteroaryl. More specifically, X can be in the form of the following formula (Ι-a) to (1_h)··

The form of X represented by the formula (Ι-a) to (Ι-h) is that any one of hydrogen atoms at any position is bonded to an adjacent group, and at least one hydrogen atom constituting the hydrogen atom of the ring is formed. (Except for a hydrogen atom bonded to an adjacent group) may be substituted with any substituent selected from the group consisting of an alkyl group, an alkoxy group, and a trans-group. Specifically, in the first step reaction, the compound represented by the formula (1) and the compound represented by the formula (2) are dissolved in a solvent, and the solution is heated to reflux and scrambled to thereby generate a reaction intermediate. . The solvent may be any one selected from the group consisting of τ: vinegar, brewing, internal, alcohol, and combinations thereof, and preferably any one selected from the group consisting of: stupid, cockroach Stupid, dimethyl stupid, tooth benzene, MH husband offer its combination, but this (four) money ship here 13 201113246 3551 ipif solvent. The reflux and stirring can be carried out at a temperature of from 50 ° C to 200 ° C for 2 to 8 hours, and preferably at a temperature of from 80 ° C to 150 ° C for 3 to 6 hours. When the time and temperature of reflux and stirring are within the above ranges, the conditions are preferably used for the transesterification reaction. The reaction by-product alcohol can be removed from the reaction mixture containing the mixture of the compound of the formula (1) and the compound of the formula (2) while refluxing and stirring, or after refluxing and stirring. Removal of the by-product alcohol prevents the occurrence of a reverse reaction' and can help the reaction proceed in the desired direction, thereby increasing the reaction yield. The alcohol can be removed by any conventional method of removing the alcohol from the mixture, and generally can be moved using the low boiling point of the alcohol and preferably using the Dean-Stark apparatus. In addition to alcohol. However, the invention is not intended to be limited thereto. The reaction mixture from which the by-product alcohol has been removed may be heated again to reflux at a temperature of from 50 ° C to 200 ° C for 8 to 18 hours, and preferably at a temperature of from 80 ° C to 150 ° C. Heat to reflux for 1 to 13 hours. The reflux is preferably carried out at the above temperature and time to complete the reaction. ^ The content of the compound represented by the formula (1) and the compound represented by the formula (2) can be appropriately adjusted depending on the reaction conditions. When the compound of the formula (2) is used in a molar ratio of 1:10 with respect to the compound of the formula, the yield can be improved. After completion of the reaction by reflux, the solvent was removed and an inorganic salt was added. The mixture is subjected to a substitution reaction, thereby producing a compound represented by the formula (3). 201113246 jroupif The reaction intermediate produced in the first step is easily reacted with a nucleophilic group of an inorganic salt to thereby form a compound represented by the formula (3). The inorganic salt may be any compound as long as it can provide a nucleophilic group to the reaction intermediate, and the inorganic salt may be Group 1, Group 2, and Group 6 to Group 14 of the Periodic Table. Any of the elements of a tooth, a nitrate, a nitrite, a sulfate, a sulfite, a thiosulfate, a phosphate, a borate, an oxalate, a carbonate, a hydrogencarbonate, and an acetate. Specific examples of the inorganic salt which can be used in the present invention include lithium carbonate, sodium carbonate, potassium carbonate, silver carbonate, cesium carbonate, cesium carbonate, calcium carbonate, cesium carbonate, cesium carbonate, chromium carbonate, cesium carbonate, cobalt carbonate, Barium carbonate, nickel carbonate, cadmium carbonate, aluminum carbonate, gallium carbonate, tin carbonate, hydrogen carbonate clock, sodium hydrogencarbonate, potassium hydrogencarbonate, acetate acetate, lead acetate, sodium citrate and the like. Specifically, it is preferred to use a metal carbonate or hydrogencarbonate selected from the group consisting of lithium, sodium, potassium and silver as the inorganic salt. A hydroxide or bicarbonate of a metal selected from the group consisting of lithium, sodium, potassium, and silver is used in place of the hydroxide wire (Na〇H) or hydroxide_(K^)H) used in the related art method. When the ruthenium or the like is not taken care of, it is possible to prevent any desired hydrolysis reaction of the ruthenium oxide or hydrogen oxyhydroxide, and (4), and since the ruthenium is ruined by sodium ruthenium or hydroxide, it is not necessary to carry out the reaction in the aqueous phase. Therefore, the phenomenon that the reaction product adheres to the surface of the reaction vessel after the reaction can be avoided, whereby the yield can be increased. The content of the inorganic salt can be appropriately adjusted depending on the reaction conditions. When the inorganic salt phase is used in the molar ratio of 1:5 in the compound of the formula (1), it is preferred to substitute the compound into the inorganic salt form by 15 201113246 3551 lpif . The salt is added to the reaction intermediate produced in the first-stage reaction to prepare a ruthenium mixture, followed by a lining mixture, and the reaction is called. The agitation can be from HTC to just. It is carried out at a temperature of 2 to 9 hours, preferably 4 to 6 hours at a thief to 8 Torr. When stirring is carried out in the above temperature and time range, this is preferable from the viewpoint of increasing the yield. The reaction mixture is then washed with a washing liquid, and the liquid layer is concentrated, and then the excess solution age is added to the liquid layer. The mixture is then heated and the mixture is removed, any insoluble inorganic hydrazine is removed therefrom, and the liquid is concentrated and allowed to crystallize. Thus, the compound represented by the formula (3) produced in the reaction can be isolated. The washing liquid which can be used in the present invention may be any one selected from the group consisting of vinegar m _, tyrosine, alcohol, and combinations thereof, and specifically, any one selected from the group consisting of the following may be used. As a washing liquid: hexane, heptane, benzene, toluene, xylene, halogenated benzene, ether, diethyl ether, tetrahydrofuran, and combinations thereof. Specifically, any one selected from the group consisting of hexane, diethyl ether, heptane, acetonitrile, acetone, monomethane, and combinations thereof may be used, but the present invention is not intended to be limited thereto. After the liquid layer of the agricultural reaction mixture is used, the solvent used for excessive addition may be selected from any one of the following groups: esters, ethers, lactones, _, amines, alcohols, and combinations thereof, and specifically Any one selected from the group consisting of benzene, toluene, dinonylbenzene, halogenated benzene, diethyl ether, tetrahydrofuran, and combinations thereof may be used. Specifically, any one selected from the group consisting of ethyl acetate, diethyl ether, and combinations thereof may be used, but the present invention is not intended to be limited thereto. 201113246 JDllpif heating and stirring can be carried out when catching 80<t temperature, preferably at thief to 60t temperature, lowering 仃3 to 12 small temperature and time range _ heating mixing ^^ from the above point of view Better. The increase in product solubility is different from the conventional method and can be produced in the following ways: Further, no purification process is required in the middle of the reaction process, whereby problems occurring in the present invention, such as reaction intermediate attachment to = are reduced. Therefore, the production method of the above-mentioned one method provides the above-mentioned ones that are manufactured by using the transfer method of the method of making money, and it is easier to manufacture the above-mentioned article with the conventional technology. The compound of the formula (Α) is shown and the yield is higher. In other words, when the compound represented by the following formula (4) is reacted by the formula (7), a compound of the following formula 5 can be produced, which is an acid-producing agent used in the chemically amplified resist composition. Agent. [Formula 4] A+r A is an organic counter ion; and Z is selected from the group consisting of *, fluoride ion (F), chloride ion (C1), bromide ion (Br), 17 201113246 dish ion (I) , tetrafluoro sulphate (BF4), hexafluoroantimonate (asf6), hexafluorophosphate (PF6) and peroxylate (Cl〇4). [Formula 5]

Α+Ό Qt wherein R3 represents any one selected from the group consisting of: an extended alkyl group, a perfluoroalkylene group, a cycloalkylene group, a heterocycloalkyl group, an extended aryl group, and an extended aryl group;

Each of Qi and Q2 independently represents any one selected from the group consisting of a hydrogen atom, a functional atom, and a perfluoroalkyl group; and X represents any one selected from the group consisting of: a hydrogen atom, a hospital base, and a whole Fluoroalkyl, alkoxy, cycloalkyl, allyl, aryl and heteroaryl; A+ represents an organic relative ion; η is an integer from 1 to 10; and m is an integer from 〇 to 1〇. The process of the present invention can be produced in high yield by using a simplified reaction step and solving problems occurring in the production process of conventional methods, such as attachment of a reaction intermediate to a reaction vessel during a purification process, resulting in a decrease in yield. Salts are generally susceptible to variations and modifications of the present invention, and such changes and modifications are considered to be within the scope of the present invention. 18 201113246 ^Doapif In the following, an example of the invention will be described in detail, whereby the skilled artisan will readily practice the invention. However, the invention can be implemented without being limited to the variations and modifications of the examples described herein. EXAMPLES [Example 1] 600 g (3.12 mol) of 2,2-difluoro-2-(fluorosulfonyl)acetate (methyl 2,2-difluoro-2-(fluorosulfonyl)acetate) and 534.6 g ( 4.68 moles of cyclohexyl decyl alcohol was dissolved in 6 liters of stupid, and the mixture was heated to reflux with stirring. After 4 hours of scramble, the reaction flask was attached to the Dean-Stark apparatus and the methanol in the reaction mixture was removed. Subsequently, the Dean-Stark unit was removed and the reaction was heated to reflux for 12 hours. The solvent was removed when the reaction was completed, and 1.5 liter (4.25 mole) of a 30% aqueous solution of sodium carbonate (Na2CO3) was added to the reaction concentrate. The mixture was stirred for 5 hours. The reaction mixture was washed with diethyl ether, and the aqueous layer was concentrated, and then ethyl acetate (E A) was introduced to the concentrate. The intemal temperature was raised to about 50 ° C' and the mixture was then stirred for 6 hours. Filtration removes any insoluble inorganic salts and induces crystallization by concentrating ethyl acetate. The resulting solid in crystalline form was dried in vacuo and the solid structure was determined by ih_NMr. The solid was dried and filtered, whereby 744 g (yield: 81%) of 2-(cyclohexyl decyloxy)-1,1-difluoroethoxy ethanesulfonate (2-(cyclohexylmethoxy)-1, 1 -difluoro-2-oxoethanesulfonate) 0 19 201113246 3551 lpif W-NMR (dimethyl benzo-anthracene, internal standard · 曱四基基院): (ppm) 4.01(d, 2H), 1.66(m, 6H ), 0.81-1.27(m, 5H) [• Reaction Scheme 1]

[Example 2] 600 g (3.12 mol) of 2,2-dioxa-2-(fluorene) decyl acetate and 591 g (4.6 mol) of bicyclo [2.2.1] hept-2-yl The sterol (bicyclo[2.2,l]heptan-2-ylmethanol) was dissolved in hydrazine toluene and the solution was heated to reflux with stirring. After stirring for 4 hours, the reaction flask was attached to a Dean-Stark apparatus, and the methanol in the reaction mixture was removed and then the 'Di-Stark apparatus was removed' and the reaction was heated to reflux to maintain 丨2 hour. When the reaction was completed, the solvent was removed and an L5 liter (4.25 mole) 30% sodium carbonate (NafO3) aqueous solution was added to the reaction concentrate. The mixture was mixed for 5 hours. The reaction mixture was washed with diethyl ether, and then the aqueous layer was concentrated, and then ethyl acetate (EA) in excess of ethyl acetate. The internal temperature was raised to about thief, and then the mixture was stirred for 6 hours. Any insoluble inorganic salt was removed by filtration, and the resulting solid was crystallized in vacuo to be crystallized by concentrated ethyl acetate. The solid structure was determined by 1H-NMR. The solid was dried and filtered' thus obtained 784.8 g (yield 82.8%) 2·(bicycloP.2.1]heptan-2-yloxy)-^difluoro-2-sideoxy oxene sodium sulphate 20 201113246 (2-(bicyclo[2.2.1]heptan-2-ylmethoxy)-1,1 -difluoro-2-oxoeth anesulfonate). ^-NMRCCDsCN): (ppm) 3.82-4.91 (m, 2H), 0.65-2.31 (m, 11H) [Reaction Scheme 2]

Na+ Ό

1) -MeOH 2) Na2G03~ [Example 3] 600 g (3.12 mol) of 2,2-difluoro-2-(fluorosulfonyl)acetic acid methyl ester and 504 g (4.66 mol) of benzyl alcohol were dissolved in In 10 ml of toluene, the solution was heated to reflux with stirring. After stirring for 4 hours, the reaction flask was attached to a Dean-Stark apparatus and the sterol in the reaction mixture was removed. Subsequently, the Dean-Stark apparatus was removed and the reaction liquid was heated to reflux for 12 hours. When the reaction was complete, the solvent was removed and 1.5 liter (4.25 mole) of a 30% aqueous solution of sodium carbonate (NazCO1 2) was added to the reaction concentrate. The mixture was mixed for 5 hours. The reaction mixture was washed with diethyl ether and the aqueous layer was concentrated, then ethyl acetate (EA) Raise the internal temperature to about 5 〇, and disturb the mixture M. In addition to any insoluble no bell, concentrated acetic acid 8 is used to induce crystallization. The crystalline form of the solid was dried in vacuo and the solid structure was determined by 1H-NMR. 21 1 (^85^ 2 fluorenyl)-1,1-monofluoro-2_sodium oxyethane sulfonate 201113246 O^JIipif (2-(benzoyloxy)-1,1 -(^£111〇1* 〇-2-〇\〇6出&11£8111 [〇11&[6]. W-NMR (disulfoxide-A, internal standard: tetradecyldecane): (ppm) 7.41 (m, 5H) ), 4.82(s, 2H) [Reaction Scheme 3]

[Comparative Example] (1) Introducing 750 g of water into 3 gram of 2,2-difluoro-2-(fluorosulfonyl) acetate, and stirring the mixture, 3 〇 0 / 〇 hydrogen An aqueous solution of sodium oxide was slowly added dropwise to the mixture. The mixture was then heated to reflux with stirring for 3 hours. After cooling the reaction mixture, the reaction mixture was neutralized with concentrated hydrochloric acid, and the reaction mixture was concentrated to obtain 416 g of decyldifluoromethanesulfonate (containing inorganic salt, yield: purity: 60%). (2) Dissolve 100 grams of thiophene monofluorocarbonate (purity: 6〇%) and 76 grams of bicyclo [2.2.1] hept-2-yl sterol in 〇$ liters of diethylene , DCE), and 37 grams of p-toluenesulfoiiic add 'p-Ts0H) was added to the solution. The reaction cocktail was then heated to reflux for 5 hours. The mixture was concentrated to remove diethylene bromide, and then 5 liters of acetonitrile was added thereto. The resulting mixture was stirred. The stirred mixture was filtered and concentrated, whereby 26 g (yield: 27%) of 2-(bicyclo[2 2 </ RTI> </ RTI> </ RTI> yloxy)-1,1-difluoro-2-oxooxy ethane sulfonate was obtained. Sodium. 22 201113246 jmiplf [Reaction Process 4]

A Na?l? 2) Concentrated Hydrochloric Acid The yields of the salts prepared in Examples 1 to 3 and Comparative Examples are shown in Table 1 below. [Table 1] Example 1 Example 2 Example 3 Comparatively practical | Number of purification processes 0 0 0 1 _ Number of reaction steps 1 1 1 2 Total yield (%) 81 82.8 — 85 20.3 — Yield per step (%) - - (1) 75 (2) 27 In the case of the comparative example, it can be seen that the reaction yield of the first step indicated by (2) is remarkably lowered, so that the total yield of the comparative example is lowered to 20.3%. Conversely, in the inventive example in which no purification process is used, since the number of reaction steps is reduced to one step, the reaction process is passed to the simplification. Therefore, it can be seen that since the product is not subjected to a purification process, the reaction is made simpler and the yield is also increased. Specifically, the total reaction yield in Example 1 was as high as 81%, the total yield in Example 2 was as high as 82.8%, and the total yield in Example 3 was as high as 85%, while the total reaction yield in the comparative example was only 20.3%. . The foregoing description of the preferred embodiments of the present invention has been described in detail, but the scope of the invention is not limited thereto. A person skilled in the art can make many changes and modifications in accordance with the basic concept of the invention as defined in the following claims, and the changes and modifications are also within the scope of the invention. [The figure briefly illustrates j 11 = the (4) _ magnetic resonance spectrum produced according to the law of the present invention. 2 is a recorded salt produced according to Example 2 of the present invention. FIG. 3 is a schematic illustration of the main components of a nuclear magnetic composite manufactured according to Example 3 of the present invention.

Claims (1)

201113246 J03Iipif VII. Patent Application Range: 1. A method for producing a cerium salt, which comprises: adding a compound represented by the following formula (2) to a compound represented by the following formula (1) and transferring the compound The ester is reacted to produce a reaction intermediate; and an inorganic salt is added to the reaction intermediate, and the compound is subjected to a substitution reaction to produce a compound represented by the following formula (3): [Formula 1] [Formula 2] H〇-(R3)m-X [Formula 3] In the formulae (1) to (3), Ri and &amp; each independently represent any one selected from the group consisting of a dentate atom, a hydroxyl group, a carboxyl group, a nitrile group, an aldehyde group, and an epoxy group. An alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, and a heteroaryl group; &amp; represents any one selected from the group consisting of: an alkyl group, a full 25 201113246 fluoro extended group, a stretched wire, And the (3) each independently represents any one selected from the group consisting of a ruthenium atom, a halogen atom, and a perfluoroalkyl group; and X represents a group selected from the group consisting of Either: chlorine atom, burnt earth, perfluoroalkyl group, alkoxy group, cycloalkyl group, allyl group, aryl group and μ represent any one selected from the group consisting of: bell (^, ' steel ( And a compound of the formula In the first-reaction step, the by-product of the conversion is produced. 3. The method for producing a cerium salt according to claim 1, wherein The inorganic salt is a carbonate or hydrogencarbonate selected from the group consisting of a bell, a nano, a potassium, and a silver. The method of producing a salt as described in claim 1, wherein X is selected from the group consisting of the following: Any of: adamantyl, norbornyl, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl. / 5. - a phosphonium salt, as claimed in claims i to 4 The method for producing a cerium salt according to any one of the preceding claims.