JPH04149143A - New production of fluorobenzotrichlorides - Google Patents
New production of fluorobenzotrichloridesInfo
- Publication number
- JPH04149143A JPH04149143A JP2269418A JP26941890A JPH04149143A JP H04149143 A JPH04149143 A JP H04149143A JP 2269418 A JP2269418 A JP 2269418A JP 26941890 A JP26941890 A JP 26941890A JP H04149143 A JPH04149143 A JP H04149143A
- Authority
- JP
- Japan
- Prior art keywords
- reaction inhibitor
- mol
- reaction
- formula
- yield
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002683 reaction inhibitor Substances 0.000 claims abstract description 15
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 11
- 150000008423 fluorobenzenes Chemical class 0.000 claims abstract description 6
- 239000010457 zeolite Substances 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000741 silica gel Substances 0.000 claims abstract description 3
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000000126 substance Substances 0.000 claims abstract 4
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 2
- 238000006471 dimerization reaction Methods 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 2
- 230000000447 dimerizing effect Effects 0.000 abstract 5
- 150000001875 compounds Chemical class 0.000 abstract 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000005829 trimerization reaction Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- WZWNFRQEMDEWEO-UHFFFAOYSA-N 1,5-dichloro-2-fluoro-4-(trichloromethyl)benzene Chemical compound FC1=CC(C(Cl)(Cl)Cl)=C(Cl)C=C1Cl WZWNFRQEMDEWEO-UHFFFAOYSA-N 0.000 description 4
- JYLVSNNSOWDQQX-UHFFFAOYSA-N 1-fluoro-2-(trichloromethyl)benzene Chemical compound FC1=CC=CC=C1C(Cl)(Cl)Cl JYLVSNNSOWDQQX-UHFFFAOYSA-N 0.000 description 4
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 4
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KAVHKCGLLMKDAL-UHFFFAOYSA-N 1,2-difluoro-4-(trichloromethyl)benzene Chemical compound FC1=CC=C(C(Cl)(Cl)Cl)C=C1F KAVHKCGLLMKDAL-UHFFFAOYSA-N 0.000 description 1
- LPRRFFOICNSSMK-UHFFFAOYSA-N 1,5-dichloro-2-(dichloromethyl)-4-fluorobenzene Chemical compound FC1=CC(C(Cl)Cl)=C(Cl)C=C1Cl LPRRFFOICNSSMK-UHFFFAOYSA-N 0.000 description 1
- JXWCOCIEGOAZOG-UHFFFAOYSA-N 1,5-dichloro-2-fluoro-4-methylbenzene Chemical compound CC1=CC(F)=C(Cl)C=C1Cl JXWCOCIEGOAZOG-UHFFFAOYSA-N 0.000 description 1
- IVFBAFIIRUOMIN-UHFFFAOYSA-N 1-bromo-4,5-difluoro-2-(trichloromethyl)benzene Chemical compound FC1=CC(Br)=C(C(Cl)(Cl)Cl)C=C1F IVFBAFIIRUOMIN-UHFFFAOYSA-N 0.000 description 1
- HHFUBJHILNJHHI-UHFFFAOYSA-N 1-chloro-4,5-difluoro-2-(trichloromethyl)benzene Chemical compound FC1=CC(Cl)=C(C(Cl)(Cl)Cl)C=C1F HHFUBJHILNJHHI-UHFFFAOYSA-N 0.000 description 1
- XOJYLEJZALFLLW-UHFFFAOYSA-N 1-fluoro-4-(trichloromethyl)benzene Chemical compound FC1=CC=C(C(Cl)(Cl)Cl)C=C1 XOJYLEJZALFLLW-UHFFFAOYSA-N 0.000 description 1
- BDJZCCWUSOZUQG-UHFFFAOYSA-N 2,4-dichloro-1-fluorobenzene Chemical compound FC1=CC=C(Cl)C=C1Cl BDJZCCWUSOZUQG-UHFFFAOYSA-N 0.000 description 1
- JGMXSJMCWNCBCA-UHFFFAOYSA-N 2-chloro-1-fluoro-4-(trichloromethyl)benzene Chemical compound FC1=CC=C(C(Cl)(Cl)Cl)C=C1Cl JGMXSJMCWNCBCA-UHFFFAOYSA-N 0.000 description 1
- OPQMRQYYRSTBME-UHFFFAOYSA-N 4-chloro-1,2-difluorobenzene Chemical compound FC1=CC=C(Cl)C=C1F OPQMRQYYRSTBME-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- -1 aluminum chloride-sodium chloride Chemical compound 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
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°〔有用なフルオロベンゾ
トリクロリド類の新規な、工業的番こ安全で、かつ簡便
に高収率で得る方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel industrial method for producing useful fluorobenzotrichlorides as intermediates for pharmaceuticals, etc., in a safe, simple and high-yield manner. It's about how to get it.
［従来の技術］
従来より、トリクロロメチル基はカルボキシル基の前駆
体と考えられていたが、例えばｐ−フルオロベンゼン［
Ｊ、 Ｙｕｒｍｉ氏ら、Ｙｉｙａｏ Ｇｏｎｇｙｅ。[Prior Art] Conventionally, trichloromethyl group was considered to be a precursor of carboxyl group, but for example, p-fluorobenzene [
J, Yurmi et al., Yiyao Gongye.
ＩＨ８）、３７０（Ｉ９８５）； ＣＡ、１０４．５０
５９３ｇ］や０−ジフルオロベンゼン［特開昭６３−１
８８６４３号公報コと四塩化炭素との反応ではビスフエ
ニルジクロロメタン類が高収率で得られ、含フッ素ペン
ゾトリフロリド類は殆ど得られていない。IH8), 370 (I985); CA, 104.50
593g] and 0-difluorobenzene [JP-A-63-1
In the reaction of No. 88643 with carbon tetrachloride, bisphenyldichloromethanes are obtained in high yield, and fluorine-containing penzotrifluorides are hardly obtained.
しかし、２，４−ジクロロ−５−フルオロベンゾトリク
ロリドは、２．４−ジクロロ−５−フルオロトルエンを
紫外線照射下で塩素化して得られる。［特開昭５８−７
４６３８号公報］［発明の解決しようとする課題］
本発明の目的は従来技術が有していた三量化反応の進行
または紫外線照射といった欠点を解決するものである。However, 2,4-dichloro-5-fluorobenzotrichloride is obtained by chlorinating 2,4-dichloro-5-fluorotoluene under ultraviolet irradiation. [Unexamined Japanese Patent Publication No. 58-7
Publication No. 4638] [Problems to be Solved by the Invention] The object of the present invention is to solve the drawbacks of the prior art, such as the progress of the trimerization reaction or the UV irradiation.
そこで本発明者らは、四塩化炭素を用いてベンゼン環に
トリクロロメチル基を導入する方法を見いだすべく鋭意
研究を重ねた結果、下記一般式（ＩＩＩ）で示されるフ
ルオロベンゼン類をルイス酸触媒下に四塩化炭素と特定
な反応条件下で反応せしめ、下記一般式（ＩＶ）で示さ
れるフルオロベンゾトリクロリド類を良好な収率で製造
する方法を見いだし、先に出願した。（特願平１．−２
９７６０９号明細書）
ＣＣＩ。Therefore, the present inventors have conducted intensive research to find a method for introducing a trichloromethyl group into a benzene ring using carbon tetrachloride. We discovered a method for producing fluorobenzotrichloride represented by the following general formula (IV) in good yield by reacting it with carbon tetrachloride under specific reaction conditions, and filed an application earlier. (Patent application Hei 1.-2
97609) CCI.
（ＩＴＩ） （ＴＶ）（式中、
Ｘ＋、ＸｓはＦ、ＣＩ、Ｂｒまたは工を表わす。また、
Ｘ２は水素、Ｆ、ＣＩ、ＢｒまたはＩを表わす。）
本発明は前述した反応系に三量化反応抑制剤を加えるこ
とによって三量化反応を大幅に抑制し、高収率で目的の
フルオロベンゾトリクロリド類を得ることを特徴とする
。(ITI) (TV) (wherein,
X+ and Xs represent F, CI, Br or engineering. Also,
X2 represents hydrogen, F, CI, Br or I. ) The present invention is characterized in that the trimerization reaction is significantly suppressed by adding a trimerization reaction inhibitor to the above-mentioned reaction system, and the desired fluorobenzotrichloride is obtained in high yield.
本発明の方法は以下の反応式で表わすことができる。The method of the present invention can be expressed by the following reaction formula.
Ｘ、 ｘ３（Ｉ）
（ＩＩ）（式中、Ｘ、、Ｘ２．Ｘ、、
Ｘ、は水素、Ｆ、Ｃ１、Ｂｒまたは工を表わす。また、
ＸＸ２．Ｘ、、Ｘ４のうち少なくとも１つはフッ素であ
る。）
本発明のトリクロロメチル化反応は過剰量の四塩化炭素
中、ルイス酸触媒化はおよび三量化反応抑制剤存在化下
にフルオロベンゼン類を滴下させて反応させる。X, x3(I)
(II) (wherein, X, , X2.
X represents hydrogen, F, C1, Br or engineering. Also,
XX2. At least one of X, , X4 is fluorine. ) The trichloromethylation reaction of the present invention is carried out by dropping fluorobenzenes in an excess amount of carbon tetrachloride, catalyzed by a Lewis acid, and in the presence of a trimerization reaction inhibitor.
即ち、三量化反応抑制剤を加えることによってビスフエ
ニルジクロロメタン類の生成を大幅に抑制し、目的とす
るフルオロベンゾトリクロリド類を高収率で得ることが
できる。本性によれば、従来困難であったフルオロベン
ゼン類のトリクロロメチル化が容易に行うことができる
。That is, by adding a trimerization reaction inhibitor, the production of bisphenyldichloromethanes can be significantly suppressed, and the desired fluorobenzotrichlorides can be obtained in high yield. Due to this property, trichloromethylation of fluorobenzenes, which has been difficult in the past, can be easily carried out.
四塩化炭素の使用量は原料であるフルオロベンゼン類に
対して２〜２０倍モル、好ましくは４〜１０倍モルであ
り、反応剤かつ反応溶媒として用いる。ルイス駿触媒と
しては、塩化アルミニウム、臭化アルミニウム、塩化ア
ルミニウムー塩化ナトリウム（Ｉ：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類１モルに対して、１〜３
モル、好ましくは１．５〜２．０モルでる。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 amount of carbon tetrachloride used is 2 to 20 times the mole, preferably 4 to 10 times the mole of fluorobenzenes as raw materials, and is used as a reactant and a reaction solvent. Examples of the Lewis-Shun catalyst include aluminum chloride, aluminum bromide, aluminum chloride-sodium chloride (I:1) complex, etc. Aluminum chloride is preferred industrially, and the amount used is about 1 mole of the raw material fluorobenzene. On the other hand, 1 to 3
mol, preferably 1.5 to 2.0 mol. The reaction temperature is generally 10-80°C, preferably 60-80°C,
The reaction time is usually 10 to 60 minutes.
三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、特に好ましくは、モルデナイト等のゼオ
ライトである。Examples of the trimerization reaction inhibitor include alkali metal fluorides, silica gel, alumina, zeolites, and mixtures thereof, and particularly preferred are zeolites such as mordenite.
その使用量は原料のフルオロベンゼン類に対して０．０
５倍重量から等重量、好ましくは０．１倍重量から０５
倍重量である。The amount used is 0.0 based on the raw material fluorobenzene.
Equal weight from 5 times the weight, preferably 0.1 times the weight to 0.5 times the weight
It's twice as heavy.
反応終了後、通常の後処理および蒸留によって目的とす
るフルオロベンゾトリクロリド類が容易に得られる。After the reaction is completed, the desired fluorobenzotrichloride can be easily obtained by conventional post-treatment and distillation.
また、三量化反応抑制剤は反応後デカンテーションによ
って、または水でクエンチ後、濾過、乾燥によって再使
用することができる。Moreover, the trimerization reaction inhibitor can be reused by decantation after the reaction, or by quenching with water, filtering, and drying.
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。Examples of the present invention will be described in more detail below.
［実施例１コ
撹拌機、還流冷却器、温度計および滴下ロートをつけた
２００ｍ１の４つロフラスコ中に、四塩化炭素９３．３
ｇ（０，６１モル）、塩化アルミニウム２０．２ｇ
（０，１５モル）およびモルデナイト（東ソー製ＨＳＺ
−６４ＯＮＡＡ） ５．０ｇヲ仕込ミ、還流下ｒ１．３
−ジクロロ−４−フルオロベンゼン１０．０ｇ（０，０
６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
に冷却後、反応混合物を氷水３００ｍ１中に注いだ。固
体を濾別後、有機層を分液し、水層を５０ｍ１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ｌＯＯ＋ｎｌの水で洗浄し、次に５％炭酸
水素ナトリウム水溶液１００ｍ１で洗浄し、さらに１０
０ｍ１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１４．５ｇ （収率８４，４％）得られた。[Example 1] In a 200 ml four-bottle flask equipped with a stirrer, reflux condenser, thermometer and addition funnel, 93.3 g of carbon tetrachloride was added.
g (0.61 mol), aluminum chloride 20.2 g
(0.15 mol) and mordenite (HSZ manufactured by Tosoh)
-64ONAA) Pour 5.0g, reflux r1.3
-dichloro-4-fluorobenzene 10.0g (0,0
6 mol) to 0.5 to slowly generate hydrochloric acid gas.
It dripped in time. The generated hydrochloric acid gas was absorbed with an aqueous sodium hydroxide solution. After the dropwise addition was completed, the reaction mixture was allowed to react for 10 minutes, and after cooling to room temperature, the reaction mixture was poured into 300 ml of ice water. After separating the solids by filtration, the organic layer was separated, and the aqueous layer was extracted three times with 50 ml of methylene chloride. The methylene chloride layer was mixed with the previous organic layer, washed with 100+nl of water, and then extracted with 50 ml of methylene chloride. Wash with 100 ml of aqueous solution of 10% sodium bicarbonate, and
Washed with 0ml of water. After distilling off the solvent, the residual liquid was vacuum distilled to obtain 14.5 g (yield: 84.4%) of 2,4-dichloro-5-fluorobenzotrichloride.
［比較例１］
三量化反応抑制剤であるモルデナイトを加えない以外は
実施例１と同様に反応および後処理を行い、２．４−ジ
クロロ−５−フルオロベンゾトリクロリドを１０．７ｇ
（収率６２．６％）得た。[Comparative Example 1] The reaction and post-treatment were carried out in the same manner as in Example 1 except that mordenite, which is a trimerization reaction inhibitor, was not added, and 10.7 g of 2,4-dichloro-5-fluorobenzotrichloride was used.
(yield: 62.6%).
［比較例２コ
実施例１の装置を用いて、１．２−ジクロロエタン５０
ｍ１、四塩化炭素１８．６ｇ （０，１２モル）およ
び塩化アルミニウム２０．２ｇ （０，１５モル）の混
合物中に、１，３−ジクロロ−４−フルオロベンゼン１
０．Ｏｇ （０，０６モル）を３０℃で３０分で摘下し
、その後、４０℃で反応させた。実施例１と同様に処理
すると、２．４−ジクロロ−５−フルオロベンゾトリク
ロリドが１．５９ｇ （収率９．３％）および蒸留残
が得られた。蒸留残をトルエンから再結晶するとビス−
（２，４−ジクロロ−５−フルオロフェニル）ジクロロ
メタンが白色結晶として１２．５ｇ （収率８０％）得
られた。[Comparative Example 2] Using the apparatus of Example 1, 1,2-dichloroethane 50
m1, 1,3-dichloro-4-fluorobenzene 1 in a mixture of 18.6 g (0.12 mol) of carbon tetrachloride and 20.2 g (0.15 mol) of aluminum chloride.
0. Og (0.06 mol) was removed at 30°C for 30 minutes, and then reacted at 40°C. When treated in the same manner as in Example 1, 1.59 g (yield 9.3%) of 2,4-dichloro-5-fluorobenzotrichloride and a distillation residue were obtained. When the distillation residue is recrystallized from toluene, bis-
12.5 g (yield: 80%) of (2,4-dichloro-5-fluorophenyl)dichloromethane was obtained as white crystals.
［実施例２］
三量化反応抑制剤として酸化アルミニウム（メルク社製
活性型 中性）を５，０ｇ用いる以外は実施例〕と同
様に反応、後処理を行い、２．４−ジクロロ−５−フル
オロベンゾトリクロリドが１３．６ｇ （収率７９，５
％）得られた。[Example 2] The reaction and post-treatment were carried out in the same manner as in Example except that 5.0 g of aluminum oxide (manufactured by Merck & Co., Ltd., active type, neutral) was used as a trimerization reaction inhibitor, and 2,4-dichloro-5- 13.6g of fluorobenzotrichloride (yield 79.5
%) obtained.
［実施例３］
三量化反応抑制剤としてフッ化ナトリウムを６．５ｇ用
いる以外は実施例１と同様に反応、後処理を行い、２，
４−ジクロロ−５−フルオロベンゾトリクロリドが１３
．１ｇ （収率７６．５％）得られた。[Example 3] The reaction and post-treatment were carried out in the same manner as in Example 1, except that 6.5 g of sodium fluoride was used as a trimerization reaction inhibitor, and 2.
4-dichloro-5-fluorobenzotrichloride is 13
．． 1 g (yield 76.5%) was obtained.
【実施例４コ
１−クロロ−３，４−ジフルオロベンゼン１４．９ｇ（
０，１モル）、四塩化炭素１５３．８ｇ（Ｉモル）、塩
化アルミニウム３３．３ｇ （０，２５モル）およびそ
ルデナイト７．５ｇを用いて実施例１と同様にして反応
、後処理を行い、２−クロロ−４，５−ジフルオロベン
ゾトリクロリドが２４．０ｇ （収率９ｏ、２％）得ら
れた。[Example 4 14.9 g of 1-chloro-3,4-difluorobenzene (
The reaction and post-treatment were carried out in the same manner as in Example 1 using 153.8 g (1 mol) of carbon tetrachloride, 33.3 g (0.25 mol) of aluminum chloride, and 7.5 g of sorudenite. , 24.0 g (yield 9o, 2%) of 2-chloro-4,5-difluorobenzotrichloride was obtained.
［実施例５コ
１．３．４−）リフルオロベンゼン１３．２ｇ （０
，１モル）、四塩化炭素１５３．８ｇ （Ｉモル）、塩
化アルミニウム３３．３ｇ （０，２５モル）およびモ
ルデナイト６．６ｇを用いて実施例１と同様にして反応
、後処理を行い、２．４．５−トリフルオロベンゾトリ
クロリドが１２．８ｇ （収率５１．３％）得られた。[Example 5-1.3.4-) Lifluorobenzene 13.2g (0
, 1 mol), 153.8 g (I mol) of carbon tetrachloride, 33.3 g (0.25 mol) of aluminum chloride, and 6.6 g of mordenite were reacted and post-treated in the same manner as in Example 1. 12.8 g (yield 51.3%) of 4.5-trifluorobenzotrichloride was obtained.
［実施例６〕
フルオロベンゼンＬ６ｇ（０，１モル）、四塩化炭素１
５３．８ｇ （Ｉモル）、塩化アルミニウム３３．３ｇ
（０，２５モル）およびモルデナイト４．８ｇを用い
て実施例１と同様にして反応、後処理を行い。[Example 6] Fluorobenzene L 6g (0.1 mol), carbon tetrachloride 1
53.8g (I mole), aluminum chloride 33.3g
The reaction and post-treatment were carried out in the same manner as in Example 1 using (0.25 mol) and 4.8 g of mordenite.
４−フルオロベンゾトリクロリドが１１．１ｇ （収率
５１．９％）得られた。11.1 g (yield 51.9%) of 4-fluorobenzotrichloride was obtained.
［実施例７コ
１．２−ジフルオロベンゼン］ｉ、４ｇ （０，１モル
）、四塩化炭素１５３．８ｇ（Ｉモル）、塩化アルミニ
ウム３３．３ｇ （０，２５モル）およびモルデナイト
５．７ｇを用いて実施例１と同様にして反応、後処理を
行い、４．５−ジフルオロベンゾトリクロリドが１５．
５ｇ （収率６７．０％）得られた。[Example 7] 4 g (0.1 mol) of 1,2-difluorobenzene, 153.8 g (1 mol) of carbon tetrachloride, 33.3 g (0.25 mol) of aluminum chloride and 5.7 g of mordenite. The reaction and post-treatment were carried out in the same manner as in Example 1 using 4,5-difluorobenzotrichloride as 15.
5g (yield 67.0%) was obtained.
ｒ実施例８］
１−り四ロー２−フルオロベンゼン１３．１ｇ （０，
１モル）、四塩化炭素１５３．８ｇ （Ｉモル）、塩化
アルミニウム３３．３ｇ （０，２５モル）およびモル
デナイト６．６ｇを用いて実施例１と同様にして反応、
後処理を行い、３−クロロ−４−フルオロベンゾトリク
ロリドが１．６．４ｇ （収率６６．２％）得られた。r Example 8] 1-di-4-2-fluorobenzene 13.1 g (0,
1 mol), carbon tetrachloride 153.8 g (I mol), aluminum chloride 33.3 g (0.25 mol) and mordenite 6.6 g in the same manner as in Example 1,
After post-treatment, 1.6.4 g (yield: 66.2%) of 3-chloro-4-fluorobenzotrichloride was obtained.
［実施例９コ
１−ブロモ−３，４−ジフルオロベンゼン１９．３ｇ（
０，１モル）、四塩化炭素１５３．８ｇ （Ｉモル）、
塩化アルミニウム３３．３ｇ （０，２５モル）および
モルデナイト１５．５ｇを用いて実施例１と同様にして
反応、後処理を行い、２−ブロモ−４，５−ジフルオロ
ベンゾトリクロリドが２４．３ｇ （収率７８．３％）
得られた。[Example 9 19.3 g of co-1-bromo-3,4-difluorobenzene (
0.1 mol), carbon tetrachloride 153.8 g (I mol),
Using 33.3 g (0.25 mol) of aluminum chloride and 15.5 g of mordenite, the reaction and post-treatment were carried out in the same manner as in Example 1, yielding 24.3 g (2-bromo-4,5-difluorobenzotrichloride). yield 78.3%)
Obtained.
［実施例１０］
１．２．３−トリクロロ−４−フルオロベンゼン２０．
０ｇ （０，１モル）、四塩化炭素１５３．８ｇ（Ｉ
モル）、塩化アルミニウム３３．３ｇ （０，２５モル
）およびモルデナイト１００ｇを用いて実施例１と同様
にして反応、後処理を行い、２．３．４− トリクロロ
−５−フルオロベンゾトリクロリドが２４．５ｇ （収
率７７２％）得られた。[Example 10] 1.2.3-Trichloro-4-fluorobenzene 20.
0g (0.1 mol), carbon tetrachloride 153.8g (I
The reaction and post-treatment were carried out in the same manner as in Example 1 using 33.3 g (0.25 mol) of aluminum chloride (0.25 mol) and 100 g of mordenite, and 2.3.4-trichloro-5-fluorobenzotrichloride .5 g (yield 772%) was obtained.
［発明の効果コ
本発明に従えば、フルオロベンゼン類から医薬中間体ど
して有用なフルオロベンゾトリクロリド類が工業的に安
全でかつ簡便に高収率で得られる。[Effects of the Invention] According to the present invention, fluorobenzotrichlorides, which are useful as pharmaceutical intermediates, can be obtained from fluorobenzenes in a high yield industrially, safely and easily.
Claims (1)
類をルイス酸触媒存在下に四塩化炭素と反応せしめる際
に、二量化反応抑制剤存在下に反応せしめることにより
、下記一般式 （II）で表わされるフルオロベンゾトリクロリド類を得
ることを特徴とするフルオロベンゾトリクロリド類の製
造方法。 ▲数式、化学式、表等があります▼（ I ） ▲数式、化学式、表等があります▼（II） （式中、Ｘ＿１、Ｘ＿２、Ｘ＿３、Ｘ＿４は水素、Ｆ、
Ｃｌ、ＢｒまたはＩを表わす。また、Ｘ＿１、Ｘ＿２、
Ｘ＿３、Ｘ＿４のうち少なくとも１つはフッ素である。 ） ２、二量化反応抑制剤が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であ
る請求項１に記載の方法。 ３、ゼオライトがモルデナイトで請求項２に記載の方法
。[Claims] 1. By reacting fluorobenzenes represented by the following general formula (I) with carbon tetrachloride in the presence of a Lewis acid catalyst and in the presence of a dimerization reaction inhibitor, the following can be obtained. A method for producing fluorobenzotrichlorides, which comprises obtaining fluorobenzotrichlorides represented by general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, X_1, X_2, X_3, X_4 are hydrogen, F,
Represents Cl, Br or I. Also, X_1, X_2,
At least one of X_3 and X_4 is fluorine. 2. The method according to claim 1, wherein the dimerization reaction inhibitor is an alkali metal fluoride, silica gel, alumina, zeolite, or a mixture thereof. 3. The method according to claim 2, wherein the zeolite is mordenite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2269418A JP2590602B2 (en) | 1990-10-09 | 1990-10-09 | New production method of fluorobenzotrichlorides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2269418A JP2590602B2 (en) | 1990-10-09 | 1990-10-09 | New production method of fluorobenzotrichlorides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04149143A true JPH04149143A (en) | 1992-05-22 |
| JP2590602B2 JP2590602B2 (en) | 1997-03-12 |
Family
ID=17472144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2269418A Expired - Fee Related JP2590602B2 (en) | 1990-10-09 | 1990-10-09 | New production method of fluorobenzotrichlorides |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2590602B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104649890A (en) * | 2015-02-15 | 2015-05-27 | 浙江永太科技股份有限公司 | Preparation method of 2,4-dichloro-5-fluorobenzoyl chloride |
| CN104725221A (en) * | 2015-03-19 | 2015-06-24 | 浙江本立化工有限公司 | Method for synthesizing 2,4-dichloro-5-fluorobenzoyl |
| CN105669435A (en) * | 2015-02-15 | 2016-06-15 | 浙江永太科技股份有限公司 | Method used for preparing 2,4-dichloro-5-fluorobenzoyl chloride |
-
1990
- 1990-10-09 JP JP2269418A patent/JP2590602B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104649890A (en) * | 2015-02-15 | 2015-05-27 | 浙江永太科技股份有限公司 | Preparation method of 2,4-dichloro-5-fluorobenzoyl chloride |
| CN105669435A (en) * | 2015-02-15 | 2016-06-15 | 浙江永太科技股份有限公司 | Method used for preparing 2,4-dichloro-5-fluorobenzoyl chloride |
| CN105669435B (en) * | 2015-02-15 | 2017-12-08 | 浙江永太科技股份有限公司 | A kind of preparation method of the fluorobenzoyl chloride of 2,4 dichloro 5 |
| CN104725221A (en) * | 2015-03-19 | 2015-06-24 | 浙江本立化工有限公司 | Method for synthesizing 2,4-dichloro-5-fluorobenzoyl |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2590602B2 (en) | 1997-03-12 |
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