JP2906650B2 - Novel method for producing fluorobenzoic acid ester compound - Google Patents
Novel method for producing fluorobenzoic acid ester compoundInfo
- Publication number
- JP2906650B2 JP2906650B2 JP2315769A JP31576990A JP2906650B2 JP 2906650 B2 JP2906650 B2 JP 2906650B2 JP 2315769 A JP2315769 A JP 2315769A JP 31576990 A JP31576990 A JP 31576990A JP 2906650 B2 JP2906650 B2 JP 2906650B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は医薬等の中間体として有用なフルオロ安息香
酸エステル化合物を、工業的に安全かつ簡便に得る新規
な製造方法に関する。The present invention relates to a novel process for industrially and safely obtaining a fluorobenzoic acid ester compound useful as an intermediate such as a medicine.
［従来の技術］ 従来より、ベンゼン環にアルコキシカルボニル基を導
入する方法として、下式（IV）で表わされる方法が知ら
れている。まず四塩化炭素とルイス酸を用いてトリクロ
ロメチル基を導入してベンゾトリクロリド化合物とす
る。しかし、この際に後処理として、過剰に使用したル
イス酸をクエンチするために大量の水を必要とする問題
がある。また、ベンゾトリクロリド化合物は沸点の高い
ものが多く、再結晶等の精製が煩雑である問題もある。[Prior Art] Conventionally, a method represented by the following formula (IV) has been known as a method for introducing an alkoxycarbonyl group into a benzene ring. First, a benzotrichloride compound is obtained by introducing a trichloromethyl group using carbon tetrachloride and a Lewis acid. However, at this time, there is a problem that a large amount of water is required as a post-treatment in order to quench the Lewis acid used excessively. In addition, many benzotrichloride compounds have a high boiling point, and there is a problem that purification such as recrystallization is complicated.
次いでベンゾトリクロリド化合物のトリクロロメチル
基を触媒の存在下、水と反応させて、部分加水分解を行
い、酸クロリドとした後、アルコール類と反応させてア
ルコキシカルボニル基に変換する。（ただし、Ｘはハロ
ゲン原子、R1はアルコール類から水酸基を除いた残基を
示す。） ［発明の解決しようとする課題］ 従来の方法では、毒性が高く、沸点の高いベンゾトリ
クロリド化合物を単離、精製する必要があり、プロセス
が煩雑であった。Next, the trichloromethyl group of the benzotrichloride compound is reacted with water in the presence of a catalyst to partially hydrolyze it to form an acid chloride, which is then reacted with an alcohol to convert to an alkoxycarbonyl group. (However, X represents a halogen atom, and R 1 represents a residue obtained by removing a hydroxyl group from alcohols.) [Problems to be Solved by the Invention] In the conventional method, it is necessary to isolate and purify a benzotrichloride compound having high toxicity and a high boiling point, and the process is complicated.
［課題を解決するための手段］ 本発明では、四塩化炭素とルイス酸を用いてベンゼン
環にトリクロロメチル基を導入しルイス酸とのコンプレ
ックスとなったベンゾトリクロリド化合物とした後、こ
のベンゾトリクロリド化合物を単離することなく、ルイ
ス酸とのコンプレックスのまま次のエステル化反応を行
う。[Means for Solving the Problems] In the present invention, a benzotrichloride compound which is complexed with a Lewis acid by introducing a trichloromethyl group into a benzene ring using carbon tetrachloride and a Lewis acid is obtained. The next esterification reaction is carried out without isolating the chloride compound while keeping the complex with the Lewis acid.
また、トリクロロメチル基をエステル化反応する際に
も、従来は２ステップにてアルコキシカルボニル基に変
換していたが、本発明ではエステル化触媒の存在下、ア
ルコール類または水を含むアルコール類を添加すること
により１ステップにてアルコキシカルボニル基に変換す
る。In addition, when a trichloromethyl group is subjected to an esterification reaction, conversion to an alkoxycarbonyl group has conventionally been performed in two steps. However, in the present invention, an alcohol or an alcohol containing water is added in the presence of an esterification catalyst. By doing so, it is converted to an alkoxycarbonyl group in one step.
従って、本発明によれば、フルオロベンゼン化合物よ
り１ポットにて、かつ２ステップでフルオロ安息香酸エ
ステル化合物を得ることができる。Therefore, according to the present invention, a fluorobenzoic acid ester compound can be obtained from a fluorobenzene compound in one pot and in two steps.
すなわち本発明は、下記一般式（Ｉ）で表わされるフ
ルオロベンゼン化合物をルイス酸触媒の存在下に四塩化
炭素と反応せしめて反応生成物を得、つぎに該反応生成
物にエステル化触媒を添加後、アルコール類または水を
含むアルコール類を添加し反応せしめて下記一般式（II
I）で表わされるフルオロ安息香酸エステル化合物を得
ることを特徴とするフルオロ安息香酸エステル化合物の
製造方法を提供する。That is, the present invention provides a reaction product by reacting a fluorobenzene compound represented by the following general formula (I) with carbon tetrachloride in the presence of a Lewis acid catalyst, and then adding an esterification catalyst to the reaction product. Thereafter, alcohols or alcohols containing water are added and reacted to obtain the following general formula (II)
A method for producing a fluorobenzoic acid ester compound, characterized by obtaining the fluorobenzoic acid ester compound represented by the formula (I).
（式中、X1、X2、X3、X4は、それぞれ独立して、水素原
子、フッ素原子、塩素原子、臭素原子、またはヨウ素原
子を示し、少なくとも１つはフッ素原子を示す。Ｒはア
ルコール類から水酸基を除いた残基を示す。） 本発明におけるトリクロロメチル化反応は、過剰量の
四塩化炭素中、ルイス酸触媒存在下にフルオロンベンゼ
ン化合物を滴下させて反応させる方法で行うのが好まし
い。その際、二量化反応を抑制するために二量化反応抑
制剤を加えてもよい。反応生成物中には、ベンゾトリク
ロリド化合物とルイス酸のコンプレックス（II）が生成
していると考えられ、反応後に、、ベンゾトリクロリド
化合物とルイス酸のコンプレックスをクエンチすること
なく、さらにエステル化触媒を添加後、アルコール類ま
たは水を含むアルコール類を滴下、好ましくは高温下に
滴下、することによって目的とするフロオロ安息香酸エ
ステル化合物を高収率かつ１ポットで簡便に得ることが
できる。 (Wherein, X 1 , X 2 , X 3 , and X 4 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and at least one represents a fluorine atom. R Represents a residue obtained by removing a hydroxyl group from an alcohol.) The trichloromethylation reaction in the present invention is carried out by a method in which a fluoronebenzene compound is added dropwise to an excess amount of carbon tetrachloride in the presence of a Lewis acid catalyst. Is preferred. At that time, a dimerization reaction inhibitor may be added to suppress the dimerization reaction. It is considered that a complex (II) of a benzotrichloride compound and a Lewis acid is formed in the reaction product. After the reaction, the complex of the benzotrichloride compound and the Lewis acid is further esterified without quenching. After the addition of the catalyst, the desired fluorofluorobenzoic acid ester compound can be easily obtained in a high yield in one pot by dropping alcohols or alcohols containing water, preferably at a high temperature.
本発明によれば、従来プロセス上煩雑であったベンゾ
トリクロリド化合物を単離、精製する必要がない。 According to the present invention, there is no need to isolate and purify a benzotrichloride compound which has conventionally been complicated in the process.
四塩化炭素の使用量は原料であるフルオロベンゼン化
合物に対して２〜20倍モルか好ましく、特に好ましくは
４〜10倍モルであり、四塩化炭素は反応剤かつ溶媒とし
て作用する。The amount of carbon tetrachloride used is preferably 2 to 20 times, more preferably 4 to 10 times the mol of the fluorobenzene compound as the raw material, and the carbon tetrachloride acts as a reactant and a solvent.
トリクロロメチル化反応のルイス酸触媒としては、塩
化アルミニウム、臭化アルミニウム、塩化アルミニウム
−塩化ナトリウム（1:1）錯体等が挙げられ、工業的に
は塩化アルミニウムが好ましく、その使用量は原料のフ
ルオロベンゼン化合物１モルに対して、１〜３モルが好
ましく、特に好ましくは1.5〜2.0モルである。Examples of the Lewis acid catalyst for the trichloromethylation reaction include aluminum chloride, aluminum bromide, aluminum chloride-sodium chloride (1: 1) complex, and the like. The amount is preferably from 1 to 3 mol, particularly preferably from 1.5 to 2.0 mol, per 1 mol of the benzene compound.
トリクロロメチル化反応の反応温度は一般に10〜80
℃、好ましくは60〜80℃であり、反応時間は通常10〜60
分である。The reaction temperature of the trichloromethylation reaction is generally 10 to 80
C., preferably 60-80 ° C., and the reaction time is usually 10-60
Minutes.
二量化反応抑制剤としては、アルカリ金属フッ化物、
シリカゲル、アルミナ、ゼオライトおよびこれらの混合
物等が挙げられる。その使用量は原料のフルオロベンゼ
ン化合物に対して0.05倍重量〜等重量、好ましくは0.1
倍重量〜0.5倍重量である。As a dimerization reaction inhibitor, alkali metal fluoride,
Examples include silica gel, alumina, zeolite, and mixtures thereof. The amount used is 0.05 times by weight to the same weight, preferably 0.1 times the weight of the raw material fluorobenzene compound.
Double weight to 0.5 times weight.
次のエステル化反応はエステル化触媒の存在下、当量
のアルコール類または水を含むアルコール類と反応させ
るのが好ましい。またその際、前工程のトリクロロメチ
ル化反応で用いたルイス酸をクエンチするために、ルイ
ス酸と当量の水を同時に添加するのが好ましい。The subsequent esterification reaction is preferably carried out in the presence of an esterification catalyst with an equivalent amount of alcohol or alcohol containing water. In this case, it is preferable to simultaneously add a Lewis acid and an equivalent amount of water in order to quench the Lewis acid used in the trichloromethylation reaction in the previous step.
エステル化触媒としては、塩化第二鉄、塩化亜鉛、酸
化亜鉛、酸化チタンが等が挙げられるが、好ましくは、
塩化第二鉄である。エステル化触媒の使用量はフルオロ
ベンゼン化合物に対して0.1〜30モル％、好ましくは１
〜10モル％である。反応温度は、エステル化反応に用い
るアルコール類によって違うが、50℃〜160℃が好まし
く、特に好ましくは100℃〜130℃である。Examples of the esterification catalyst include ferric chloride, zinc chloride, zinc oxide, and titanium oxide.
Ferric chloride. The amount of the esterification catalyst used is 0.1 to 30 mol%, preferably 1 to 30 mol%, based on the fluorobenzene compound.
~ 10 mol%. The reaction temperature varies depending on the alcohol used in the esterification reaction, but is preferably from 50 ° C to 160 ° C, particularly preferably from 100 ° C to 130 ° C.
反応終了後、通常の後処理および蒸留によって目的と
するフルオロ安息香酸エステル化合物が容易に得られ
る。After completion of the reaction, the desired fluorobenzoate compound can be easily obtained by ordinary post-treatment and distillation.
［実施例］ 以下に本発明の実施例について、さらに具体的に説明
する。[Example] Hereinafter, an example of the present invention will be described more specifically.
「例１」 撹拌機、還流冷却器、温度計および滴下ロートをつけ
た200mlの４つ口フラスコ中に、四塩化炭素93.3g（0.61
モル）、塩化アルミニウム20.2g（0.15モル）を仕込
み、還流下にフルオロベンゼン化合物として1,3−ジク
ロロ−４−フルオロベンゼン10.0g（0.06モル）をゆる
やかに塩酸ガスが発生するように0.5時間で滴下した。
発生塩酸ガスは水酸化ナトリウム水溶液で吸収させた。
滴下終了後、10分間反応させ、室温にまで冷却した。Example 1 In a 200 ml four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 93.3 g (0.61 g) of carbon tetrachloride was placed.
Mol) and 20.2 g (0.15 mol) of aluminum chloride and 10.0 g (0.06 mol) of 1,3-dichloro-4-fluorobenzene as a fluorobenzene compound under reflux for 0.5 hour so that hydrochloric acid gas is slowly generated. It was dropped.
The generated hydrochloric acid gas was absorbed by an aqueous sodium hydroxide solution.
After the completion of the dropwise addition, the reaction was carried out for 10 minutes and cooled to room temperature.
次いで塩化第二鉄を0.05g加え、温度を120℃まで昇温
した後、水3.78g（0.21mol）およびアルコール類として
2,2,2−トリフルオロエタノール6.0g（0.06mol）の混合
液を１時間かけて滴下し、120〜130℃にてさらに１時間
反応させた。冷却後、水100gおよび塩化メチレン50gを
加え、不溶物を濾過し、分液後、水層を20gの塩化メチ
レンで２回抽出した。有機層を集め、乾燥後、溶媒を留
去し、さらに減圧蒸留することによって2,4−ジクロロ
−５−フルオロ安息香酸−2,2,2−トリフルオロエチル
を12.58g（収率72.0％）得た。Next, 0.05 g of ferric chloride was added, and the temperature was raised to 120 ° C., followed by 3.78 g (0.21 mol) of water and alcohols.
A mixed solution of 6.0 g (0.06 mol) of 2,2,2-trifluoroethanol was added dropwise over 1 hour, and the mixture was further reacted at 120 to 130 ° C. for 1 hour. After cooling, 100 g of water and 50 g of methylene chloride were added, insolubles were filtered off, and after separation, the aqueous layer was extracted twice with 20 g of methylene chloride. The organic layer was collected, dried, and then the solvent was distilled off. The residue was further distilled under reduced pressure to give 12.58 g of 2,4-dichloro-5-fluorobenzoic acid-2,2,2-trifluoroethyl (yield: 72.0%). Obtained.
「例２」 アルコール類としてエタノールを2.76g（0.06mol）用
いる以外は例１と同様に反応、後処理を行い、2,4−ジ
クロロ−５−フルオロ安息香酸エチルを10.45g（収率7
3.4％）得た。"Example 2" The reaction and post-treatment were carried out in the same manner as in Example 1 except that 2.76 g (0.06 mol) of ethanol was used as alcohols, and 10.45 g of ethyl 2,4-dichloro-5-fluorobenzoate was obtained (yield 7).
3.4%).
「例３」 フルオロベンゼン化合物として１−クロロ−3,4−ジ
フルオロベンゼンを8.94g（0.06mol）、アルコール類と
してエタノールを2.76g（0.06mol）用いる以外は例１と
同様に反応、後処理を行い、２−クロロ−4,5−ジフル
オロ安息香酸エチルを9.29g（収率70.2％）得た。"Example 3" The reaction and post-treatment were performed in the same manner as in Example 1 except that 8.94 g (0.06 mol) of 1-chloro-3,4-difluorobenzene was used as the fluorobenzene compound and 2.76 g (0.06 mol) of ethanol was used as the alcohols. Then, 9.29 g (yield 70.2%) of ethyl 2-chloro-4,5-difluorobenzoate was obtained.
「例４」 フルオロベンゼン化合物としてフルオロベンゼンを5.
76g（0.06mol）、アルコール類としてエタノールを2.76
g（0.06mol）用いる以外は例１と同様に反応、後処理を
行い、４−フルオロ安息香酸エチルを6.90g（収率68.5
％）得た。"Example 4" Fluorobenzene as a fluorobenzene compound 5.
76g (0.06mol), 2.76 ethanol as alcohol
The reaction and post-treatment were carried out in the same manner as in Example 1 except that g (0.06 mol) was used, and 6.90 g of ethyl 4-fluorobenzoate was obtained (yield 68.5 g).
%)Obtained.
「例５」 フルオロベンゼン化合物として1,2−ジフルオロベン
ゼンを6.84g（0.06mol）、アルコール類としてエタノー
ルを2.76g（0.06mol）用いる以外は例１と同様に反応、
後処理を行い、3,4−ジフルオロ安息香酸エチルを7.98g
（収率71.6％）得た。"Example 5" Reaction was performed in the same manner as in Example 1, except that 6.84 g (0.06 mol) of 1,2-difluorobenzene was used as the fluorobenzene compound and 2.76 g (0.06 mol) of ethanol was used as the alcohol.
Perform post-treatment, 7.98 g of ethyl 3,4-difluorobenzoate
(71.6% yield).
「例６」 フルオロベンゼン化合物として１−ブロモ−3,4−ジ
フルオロベンゼンを11.57g（0.06mol）、アルコール類
としてエタノールを2.76g（0.06mol）用いる以外は例１
と同様に反応、後処理を行い、２−ブロモ−4,5−ジフ
ルオロ安息香酸エチルを11.47g（収率72.2％）得た。"Example 6" Example 1 except that 11.57 g (0.06 mol) of 1-bromo-3,4-difluorobenzene was used as a fluorobenzene compound and 2.76 g (0.06 mol) of ethanol was used as alcohols.
The reaction and post-treatment were carried out in the same manner as described above to obtain 11.47 g (yield 72.2%) of ethyl 2-bromo-4,5-difluorobenzoate.
「例７（比較例）」 撹拌機、還流冷却器、温度計および滴下ロートをつけ
た200mlの４つ口フラスコ中に、四塩化炭素93.3g（0.61
モル）、塩化アルミニウム20.2g（0.15モル）を仕込
み、還流下に1,3−ジクロロ−４−フルオロベンゼン10.
0g（0.06モル）をゆるやかに塩酸ガスが発生するように
0.5時間で滴下した。発生塩酸ガスは水酸化ナトリウム
水溶液で吸収させた。滴下終了後、10分間反応させ、室
温にまで冷却後、反応混合物を氷水300ml中に注いだ。
有機層を分液し、水層を50mlの塩化メチレンで３回抽出
後、塩化メチレン層を先の有機層と混合し、これを100m
lの水で洗浄し、次に５％炭酸水素ナトリウム水溶液100
mlで洗浄し、さらに100mlの水で洗浄した。溶媒を留去
後、残液を真空蒸留すると、2,4−ジクロロ−５−フル
オロベンゾトリクロリドが10.7g得られた。Example 7 (Comparative Example) In a 200 ml four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 93.3 g (0.61 g) of carbon tetrachloride was placed.
Mol) and 20.2 g (0.15 mol) of aluminum chloride and 1,3-dichloro-4-fluorobenzene 10.
0g (0.06mol) to generate hydrochloric acid gas slowly
It was added dropwise in 0.5 hours. The generated hydrochloric acid gas was absorbed by an aqueous sodium hydroxide solution. After the completion of the dropwise addition, the reaction was allowed to proceed for 10 minutes. After cooling to room temperature, the reaction mixture was poured into 300 ml of ice water.
The organic layer was separated, and the aqueous layer was extracted three times with 50 ml of methylene chloride.
l of water, then 100% aqueous 5% sodium bicarbonate
Washed with ml and then with 100 ml of water. After the solvent was distilled off, the residue was distilled under vacuum to obtain 10.7 g of 2,4-dichloro-5-fluorobenzotrichloride.
次いで、撹拌機、還流冷却器、温度計および滴下ロー
トをつけた200mlの４つ口フラスコ中に、得られた2,4−
ジクロロ−５−フルオロベンゾトリクロリドを10.7gお
よび塩化第二鉄を0.05g加え、温度を120℃まで昇温した
後、水0.68g（0.038mol）を30分かけて滴下し、120〜13
0℃にてさらに１時間反応させた。冷却後、塩化メチレ
ン100gを加え、不溶物を濾過し乾燥後、溶媒を留去する
ことによって2,4−ジクロロ−５−フルオロ安息香酸ク
ロリドを8.12g得た。The resulting 2,4-- was then placed in a 200 ml four-necked flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel.
After adding 10.7 g of dichloro-5-fluorobenzotrichloride and 0.05 g of ferric chloride and raising the temperature to 120 ° C., 0.68 g (0.038 mol) of water was added dropwise over 30 minutes.
The reaction was further performed at 0 ° C. for 1 hour. After cooling, 100 g of methylene chloride was added, insolubles were filtered and dried, and then the solvent was distilled off to obtain 8.12 g of 2,4-dichloro-5-fluorobenzoic acid chloride.
次いで、撹拌機、温度計および滴下ロートをつけた10
0mlの４つ口フラスコ中に、得られた2,4−ジクロロ−５
−フルオロ安息香酸クロリド8.12gおよびトリエチルア
ミン3.97g（0.039mol）を仕込み、氷冷下、2,2,2−トリ
フルオロエタノールを3.93g（0.039mol）滴下した。１
時間撹拌後、水50gおよび塩化メチレン50gを加え、分液
後、水層を20gの塩化メチレンで２回抽出した。有機層
を集め、乾燥後、溶媒を留去し、さらに減圧蒸留するこ
とによって2,4−ジクロロ−５−フロオロ安息香酸−2,
2,2−トリフルオロエチルを8.82g（収率50.5％）得た。Next, a stirrer, a thermometer and a dropping funnel were attached.
The obtained 2,4-dichloro-5 was placed in a 0 ml four-necked flask.
8.12 g of -fluorobenzoic acid chloride and 3.97 g (0.039 mol) of triethylamine were charged, and 3.93 g (0.039 mol) of 2,2,2-trifluoroethanol was added dropwise under ice cooling. 1
After stirring for 50 hours, 50 g of water and 50 g of methylene chloride were added. After liquid separation, the aqueous layer was extracted twice with 20 g of methylene chloride. The organic layer was collected, dried, evaporated, and further distilled under reduced pressure to give 2,4-dichloro-5-fluorobenzoic acid-2,2.
8.82 g (yield 50.5%) of 2,2-trifluoroethyl was obtained.
［発明の効果］ 本発明に従えば、フルオロベンゼン化合物から医薬中
間体として有用なフルオロ安息香酸エステル化合物が工
業的に安全でかつ簡便に得られる。[Effect of the Invention] According to the present invention, a fluorobenzoic acid ester compound useful as a pharmaceutical intermediate can be industrially safe and easily obtained from a fluorobenzene compound.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 69/76 - 69/78 C07C 63/06 C07C 51/265 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) C07C 69/76-69/78 C07C 63/06 C07C 51/265 CA (STN) REGISTRY
Claims (5)
ンゼン化合物をルイス酸触媒の存在下に四塩化炭素と反
応せしめて反応生成物を得、つぎに該反応生成物にエス
テル化触媒を添加後、アルコール類または水を含むアル
コール類を添加し反応せしめて下記一般式（III）で表
わされるフルオロ安息香酸エステル化合物を得ることを
特徴とするフルオロ安息香酸エステル化合物の製造方
法。 （式中、X1、X2、X3、X4は、それぞれ独立して、水素原
子、フッ素原子、塩素原子、臭素原子、またはヨウ素原
子を示し、少なくとも１つはフッ素原子を示す。Ｒはア
ルコール類から水酸基を除いた残基を示す。）1. A fluorobenzene compound represented by the following general formula (I) is reacted with carbon tetrachloride in the presence of a Lewis acid catalyst to obtain a reaction product, and then an esterification catalyst is added to the reaction product. Thereafter, an alcohol or an alcohol containing water is added and reacted to obtain a fluorobenzoate compound represented by the following general formula (III), thereby producing a fluorobenzoate compound. (Wherein, X 1 , X 2 , X 3 , and X 4 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and at least one represents a fluorine atom. R Represents a residue obtained by removing a hydroxyl group from alcohols.)
ルオロベンゾトリクロリド化合物とルイス酸とのコンプ
レックスを含む反応生成物である請求項１記載の製造方
法。 2. The method according to claim 1, wherein the reaction product is a reaction product containing a complex of a fluorobenzotrichloride compound represented by the general formula (II) and a Lewis acid.
トリクロリド化合物とルイス酸とのコンプレックスと、
アルコール類または水を含むアルコール類とを、エステ
ル化触媒の存在下で反応せしめて下記一般式（III）で
表わされるフルオロ安息香酸エステル化合物を得ること
を特徴とするフルオロ安息香酸エステル化合物の製造方
法。 （式中、X1、X2、X3、X4は、それぞれ独立して、水素原
子、フッ素原子、塩素原子、臭素原子、またはヨウ素原
子を示し、少なくとも１つはフッ素原子を示す。Ｒはア
ルコール類から水酸基を除いた残基を示す。）3. A complex of a fluorobenzotrichloride compound represented by the general formula (II) and a Lewis acid,
A method for producing a fluorobenzoic acid ester compound, comprising reacting an alcohol or an alcohol containing water in the presence of an esterification catalyst to obtain a fluorobenzoic acid ester compound represented by the following general formula (III): . (Wherein, X 1 , X 2 , X 3 , and X 4 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and at least one represents a fluorine atom. R Represents a residue obtained by removing a hydroxyl group from alcohols.)
子であり、かつ、X4がフッ素原子である請求項１、２、
または３記載の製造方法。4. The method according to claim 1, wherein X 1 and X 3 are chlorine atoms, X 2 is a hydrogen atom, and X 4 is a fluorine atom.
Or the production method according to 3.
エチル基である請求項１、２、３、または４記載の製造
方法。5. The method according to claim 1, wherein R is an ethyl group or a 2,2,2-trifluoroethyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2315769A JP2906650B2 (en) | 1990-11-22 | 1990-11-22 | Novel method for producing fluorobenzoic acid ester compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2315769A JP2906650B2 (en) | 1990-11-22 | 1990-11-22 | Novel method for producing fluorobenzoic acid ester compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04187660A JPH04187660A (en) | 1992-07-06 |
| JP2906650B2 true JP2906650B2 (en) | 1999-06-21 |
Family
ID=18069327
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2315769A Expired - Fee Related JP2906650B2 (en) | 1990-11-22 | 1990-11-22 | Novel method for producing fluorobenzoic acid ester compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2906650B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115819215A (en) * | 2022-11-08 | 2023-03-21 | 广东省科学院化工研究所 | Method for synthesizing carboxylic acid derivative by Lewis acid catalysis |
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1990
- 1990-11-22 JP JP2315769A patent/JP2906650B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04187660A (en) | 1992-07-06 |
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