JPS63270632A - Novel dichlorotrifluoromethyltoluene and production thereof - Google Patents
Novel dichlorotrifluoromethyltoluene and production thereofInfo
- Publication number
- JPS63270632A JPS63270632A JP10657087A JP10657087A JPS63270632A JP S63270632 A JPS63270632 A JP S63270632A JP 10657087 A JP10657087 A JP 10657087A JP 10657087 A JP10657087 A JP 10657087A JP S63270632 A JPS63270632 A JP S63270632A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- dichloro
- dctct
- dichlorotrifluoromethyltoluene
- 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.)
- Pending
Links
- VCGJIIDFWDVVQE-UHFFFAOYSA-N (1,1-dichloro-2,2,2-trifluoroethyl)benzene Chemical compound FC(F)(F)C(Cl)(Cl)C1=CC=CC=C1 VCGJIIDFWDVVQE-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- OARYHYOOIUIKFZ-UHFFFAOYSA-N 1,2-dichloro-4-methyl-5-(trifluoromethyl)benzene Chemical compound CC1=CC(Cl)=C(Cl)C=C1C(F)(F)F OARYHYOOIUIKFZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 13
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 13
- AXVLZOYLQOEKAO-UHFFFAOYSA-N 1,1,2,2,2-pentachloroethylbenzene Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)C1=CC=CC=C1 AXVLZOYLQOEKAO-UHFFFAOYSA-N 0.000 claims description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract description 36
- 239000007795 chemical reaction product Substances 0.000 abstract description 13
- -1 aluminum halide Chemical class 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- 239000003905 agrochemical Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- DZCAUMADOBDJJH-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanamine Chemical class FC(F)(F)C(N)C1=CC=CC=C1 DZCAUMADOBDJJH-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- JZWZPWDFZGTMIF-UHFFFAOYSA-N 1,2-dichloro-4-methyl-5-(trichloromethyl)benzene Chemical compound CC1=CC(Cl)=C(Cl)C=C1C(Cl)(Cl)Cl JZWZPWDFZGTMIF-UHFFFAOYSA-N 0.000 abstract 1
- AAZWIUBEVIULFT-UHFFFAOYSA-N 1-tert-butyl-2,3-dichlorobenzene Chemical compound CC(C)(C)C1=CC=CC(Cl)=C1Cl AAZWIUBEVIULFT-UHFFFAOYSA-N 0.000 abstract 1
- NSMXZYCKOJMQON-UHFFFAOYSA-N 2,3-dichloro-1-methyl-4-(trifluoromethyl)benzene Chemical compound CC1=CC=C(C(F)(F)F)C(Cl)=C1Cl NSMXZYCKOJMQON-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 24
- 239000002904 solvent Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000011259 mixed solution Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 238000001819 mass spectrum Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000003682 fluorination reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000012925 reference material Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- GWLKCPXYBLCEKC-UHFFFAOYSA-N 1,2-dichloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1Cl GWLKCPXYBLCEKC-UHFFFAOYSA-N 0.000 description 1
- ZGJVWKAKZJDBPS-UHFFFAOYSA-N 1,3-dichloro-2-methyl-4-(trichloromethyl)benzene Chemical compound CC1=C(Cl)C=CC(C(Cl)(Cl)Cl)=C1Cl ZGJVWKAKZJDBPS-UHFFFAOYSA-N 0.000 description 1
- AXAGWOKIYKENDZ-UHFFFAOYSA-N 1,3-dichloro-2-methyl-4-(trifluoromethyl)benzene Chemical compound CC1=C(Cl)C=CC(C(F)(F)F)=C1Cl AXAGWOKIYKENDZ-UHFFFAOYSA-N 0.000 description 1
- KFAKZJUYBOYVKA-UHFFFAOYSA-N 1,4-dichloro-2-methylbenzene Chemical compound CC1=CC(Cl)=CC=C1Cl KFAKZJUYBOYVKA-UHFFFAOYSA-N 0.000 description 1
- RDEYUZDOZDTPKA-UHFFFAOYSA-N 1,5-dichloro-2-methyl-4-(trichloromethyl)benzene Chemical compound CC1=CC(C(Cl)(Cl)Cl)=C(Cl)C=C1Cl RDEYUZDOZDTPKA-UHFFFAOYSA-N 0.000 description 1
- JIJFXGFHPXLJME-UHFFFAOYSA-N 1-(dichloromethyl)-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1C(Cl)Cl JIJFXGFHPXLJME-UHFFFAOYSA-N 0.000 description 1
- IRUOMPGNAULIQG-UHFFFAOYSA-N 1-[dichloro-[2-(dichloromethyl)phenyl]methyl]-2-(dichloromethyl)benzene Chemical compound ClC(Cl)C1=CC=CC=C1C(Cl)(Cl)C1=CC=CC=C1C(Cl)Cl IRUOMPGNAULIQG-UHFFFAOYSA-N 0.000 description 1
- WXXNRTSLXRLWBS-UHFFFAOYSA-N 2,3-dichloro-1-methyl-4-(trichloromethyl)benzene Chemical compound CC1=CC=C(C(Cl)(Cl)Cl)C(Cl)=C1Cl WXXNRTSLXRLWBS-UHFFFAOYSA-N 0.000 description 1
- FUNUTBJJKQIVSY-UHFFFAOYSA-N 2,4-Dichlorotoluene Chemical compound CC1=CC=C(Cl)C=C1Cl FUNUTBJJKQIVSY-UHFFFAOYSA-N 0.000 description 1
- 101150032866 CDC11 gene Proteins 0.000 description 1
- 101150041968 CDC13 gene Proteins 0.000 description 1
- 101001093748 Homo sapiens Phosphatidylinositol N-acetylglucosaminyltransferase subunit P Proteins 0.000 description 1
- 102100035188 Phosphatidylinositol N-acetylglucosaminyltransferase subunit P Human genes 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- RNRDHZGWBBEZBK-UHFFFAOYSA-N n-methyl-2-(trifluoromethyl)aniline Chemical compound CNC1=CC=CC=C1C(F)(F)F RNRDHZGWBBEZBK-UHFFFAOYSA-N 0.000 description 1
- 210000001747 pupil Anatomy 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
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は医・農薬の原料として、特に除草剤の中間原料
であるメチルアミノベンゾトリフルオリドの原料として
極めて有用な新規なジクロロトリフルオロメチルトルエ
ン（以下ＤＣＴＦＴと略す。）およびその製造法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides novel dichlorotrifluoromethyltoluene which is extremely useful as a raw material for medicines and agricultural chemicals, especially as a raw material for methylaminobenzotrifluoride, which is an intermediate raw material for herbicides. (hereinafter abbreviated as DCTFT) and its manufacturing method.
［従来の技術］
０ＣＴＰＴの製造法としては、以下のものが知られてい
る。[Prior Art] The following methods are known as methods for producing 0CTPT.
２０：３
Ｊ、 Ｆｌｕｏｒ、 Ｃｈｅｍ、、 ２８１〜２９１（
１９８１）しかしながらこれ以外のＤＣＴＰＴについて
は皆無であった。20:3 J, Fluor, Chem, 281-291 (
(1981) However, there were no other DCTPTs available.
［問題点を解決するための手段］
本発明者らは、３．４−ジクロロ−６−トリフルオロメ
チルトルエン以外のＤＣＴＰＴを得るべく鋭意検討の結
果、新規な０ＣＴＰＴを有利に製造できることを見出し
本発明に到達した。[Means for Solving the Problems] As a result of intensive studies to obtain DCTPT other than 3,4-dichloro-6-trifluoromethyltoluene, the present inventors discovered that a new 0CTPT can be advantageously produced. invention has been achieved.
すなわち本発明は新規なジクロロトリフルオロメチルト
ルエン（ただし３．４−ジクロロ−６−トリフルオロメ
チルトルエンを除く）およびその製造法であり、製造法
は、ジクロロトリクロロメチルトルエン（ただし３．４
−ジクロロ−６−トリクロロメチルトルエンを除く）を
フッ化水素と反応させることを特徴とするジクロロトリ
フルオロメチルトルエンの製造法である。That is, the present invention is a novel dichlorotrifluoromethyltoluene (excluding 3,4-dichloro-6-trifluoromethyltoluene) and a method for producing the same.
-Dichloro-6-trichloromethyltoluene) is reacted with hydrogen fluoride.
本発明の化合物の原料であるジクロロトリクロロメチル
トルエン（ＤＣＴＣＴ）は対応するジクロロトルエンか
ら容易に製造でき、具体的にはハロゲン化アルミニウム
の存在下四塩化炭素を反応させるものであるが、この反
応における四塩化炭素の使用量は、原料のジクロロトル
エンに対して１〜１０モルを使用し、溶媒として使用し
てもよい。 ハロゲン化アルミニウムとしては、無水塩
化アルミニウム、無水臭化アルミニウムなどが挙げられ
、その使用量は原料のジクロロトルエンに対して１〜６
モル、望ましくは１〜３モルである。ハロゲン化アルミ
ニウムはＤＣＴＣＴと錯体を形成するためハロゲン化ア
ルミニウムが不足する場合には、ジクロロビス（ジクロ
ロメチルフェニル）メタン（以下ＤＣＢＭという、）な
る副生成物が選択的に生成スル。また、ハロゲン化アル
ミニウムを過剰に使用してもＤＣＴＣＴの選択率は増加
しない。Dichlorotrichloromethyltoluene (DCTCT), which is a raw material for the compound of the present invention, can be easily produced from the corresponding dichlorotoluene, and specifically, carbon tetrachloride is reacted in the presence of aluminum halide. The amount of carbon tetrachloride to be used is 1 to 10 moles based on dichlorotoluene as a raw material, and it may be used as a solvent. Examples of aluminum halides include anhydrous aluminum chloride and anhydrous aluminum bromide, and the amount used is 1 to 6
mol, preferably 1 to 3 mol. Aluminum halide forms a complex with DCTCT, so when aluminum halide is insufficient, a byproduct called dichlorobis(dichloromethylphenyl)methane (hereinafter referred to as DCBM) is selectively produced. Furthermore, excessive use of aluminum halide does not increase the selectivity of DCTCT.
反応温度は０〜１００℃であり、望ましくは２０〜８０
℃である。また、この反応においては溶媒を用いること
が好ましく、その溶媒としては例えば塩化メチレン、テ
トラクロロエタン、フロン類などが使用できるが、１．
２−ジクロロエタンはＤＣＴＣＴの選択性を著しく向上
させることができる溶媒であり、もっとも好ましい。反
応時間は一概には規定出来ないが、２０分〜４時間であ
る。このようにして得た反応生成物に水を添加して錯体
を分解し、容易にＤＣＴＣＴを得ることができる。The reaction temperature is 0 to 100°C, preferably 20 to 80°C.
It is ℃. In addition, it is preferable to use a solvent in this reaction, and examples of the solvent that can be used include methylene chloride, tetrachloroethane, and fluorocarbons.
2-dichloroethane is a solvent that can significantly improve the selectivity of DCTCT and is the most preferred. Although the reaction time cannot be absolutely defined, it is from 20 minutes to 4 hours. DCTCT can be easily obtained by adding water to the reaction product thus obtained to decompose the complex.
本発明の新規化合物であるＤＣＴＰＴはこのようにして
得たＤＣＴＣＴをフッ化水素と反応させるものであるが
、このフッ素化反応は、ステンレス製オートクレーブ中
にＤＣＴＣＴと理論量以上のフッ化水素を入れ、０〜１
５０℃望ましくは室温〜１００℃でおこなわれる。また
、反応圧は、３〜２０ｋｇ、／ｃｄ望ましくは８〜ｌＯ
瞳／−でおこなわれる、フン化水素量としては、ＤＣＴ
ＣＴに対して３．２〜１２倍モル望ましくは ６〜９倍
モルである０反応時間は一概には規定できないが、３〜
６時間である０反応生成物は、アルカリ水溶液により洗
浄後、減圧蒸留をおこない反応溶媒および未反応の四塩
化炭素、さらには高沸点反応生成物を除くことにより、
純度の高いジクロロトリフルオロメチルトルエン（以下
ＤＣＴＰＴという、）を容易に得ることができる。DCTPT, the new compound of the present invention, is produced by reacting the DCTCT obtained in this way with hydrogen fluoride, but this fluorination reaction is carried out by placing DCTCT and more than a theoretical amount of hydrogen fluoride in a stainless steel autoclave. , 0-1
It is carried out at 50°C, preferably room temperature to 100°C. In addition, the reaction pressure is 3 to 20 kg/cd, preferably 8 to 1O
As for the amount of hydrogen fluoride carried out in the pupil/-, DCT
It is 3.2 to 12 times the mole of CT, preferably 6 to 9 times the mole. Although the reaction time cannot be unconditionally defined, it is 3 to 12 times the mole of CT.
After washing the 0 reaction product for 6 hours with an aqueous alkali solution, the reaction product is distilled under reduced pressure to remove the reaction solvent, unreacted carbon tetrachloride, and high-boiling point reaction products.
Highly pure dichlorotrifluoromethyltoluene (hereinafter referred to as DCTPT) can be easily obtained.
本発明の新規化合物であるＤＣＴＰＴは、下記反応式に
示すように医・農薬の中間体であるアミノトリフルオロ
メチルトルエンの原料として有用な化合物である。DCTPT, which is a novel compound of the present invention, is a compound useful as a raw material for aminotrifluoromethyltoluene, which is an intermediate for medicines and agricultural chemicals, as shown in the reaction formula below.
（以下余白） 以下本発明を実施例により詳細に説明する。(Margin below) The present invention will be explained in detail below with reference to Examples.
参考例１
無水塩化アルミニウム２７．０ｇ （０，２０３モル）
と四塩化炭素１００．０ ｇの混合液中に、攪拌下２゜
３−ジクロロトルエン１６．１ｇ （０，１モル）ト四
塩化炭素５４ｇ（合計１．０モル）の混合溶液を５０〜
５２℃、２時間で滴下し、さらに２時間攪拌反応させた
。放冷後、氷水７００ １Ｉｉｌに反応液を注ぎ室温下
撹拌し塩化アルミニウムを除いた。水層を四塩化炭素で
抽出し、集めた有機層を水酸化ナトリウム水溶液で洗浄
し、無水塩化カルシウムで乾燥し、溶媒を減圧留去して
粗ＤＣＴＣＴ２４．５ｇを得た。これをガスクロマトグ
ラフィーで分析したところ２．３−ジクロロ−４−トリ
クロロメチルトルエン（ＤＣＴＣＴ■）が４２．８讐ｔ
％（収率３７．６％） 、２．３−ジクロロ−６−トリ
クロロメチルトルエン（ＤＣＴＣＴ■）が２７．１ｗｔ
％（収率２３．８％）およびジクロロビス（２，３−ジ
クロロ−４−メチルフェニル）メタンおよびジクロロビ
ス（２−メチル−３，４−ジクロロフェニル）メタン（
ＤＣＢＭ）が３０．１ｗｔ％（収率３６．６％）含有さ
れており、未反応のジクロロトルエンは検出されなかっ
た。粗ＤＣＴＣＴ２５．２ｇをｎ−ヘキサン５０ｍ１に
加えて非溶解物を除去後、口演を減圧濃縮、減圧蒸留す
ることにより、純度９９．２％のＤＣＴＣＴ■＋ＤＣＴ
ＣＴ■１０．５ｇ （０，０３７７モル、収率３７，７
％）を得た。これからガスクロマトグラフィーを用いて
純度９９．５％のＤＣＴＣＴ■（沸点１２０〜１２５℃
／ ３ｍｍＨｇ ）を０．１５ｇおよび純度９９．０％
のＤＣＴＣＴ■（沸点１０９〜１１５℃／ ３ ｍｍＨ
ｇ）を０．１２ｇに分離した。ＤＣＴＣＴ■の構造はマ
ススペクトル（Ｍ” ２７６ ）、Ｈ−ＮＭＲスペクト
ル（ＣＤＣＩ、溶媒、δ ２．８０ ３Ｈ（ＣＩ、）ｓ
、 ７：９９１Ｈ（５−Ｈ） Ｓ 、 ７．３８ １
Ｈ（６−１１）Ｓ）により確認した。Reference example 1 Anhydrous aluminum chloride 27.0g (0,203 mol)
A mixed solution of 16.1 g (0.1 mol) of 2°3-dichlorotoluene, 54 g (total 1.0 mol) of carbon tetrachloride, and 100.0 g of carbon tetrachloride was added under stirring to a mixed solution of 54 g (total 1.0 mol) of
The mixture was added dropwise at 52°C for 2 hours, and the mixture was stirred and reacted for an additional 2 hours. After cooling, the reaction solution was poured into 700 μl of ice water and stirred at room temperature to remove aluminum chloride. The aqueous layer was extracted with carbon tetrachloride, and the collected organic layer was washed with an aqueous sodium hydroxide solution, dried over anhydrous calcium chloride, and the solvent was distilled off under reduced pressure to obtain 24.5 g of crude DCTCT. When this was analyzed by gas chromatography, 2,3-dichloro-4-trichloromethyltoluene (DCTCT) was found to be 42.8 tons.
% (yield 37.6%), 27.1wt of 2.3-dichloro-6-trichloromethyltoluene (DCTCT■)
% (yield 23.8%) and dichlorobis(2,3-dichloro-4-methylphenyl)methane and dichlorobis(2-methyl-3,4-dichlorophenyl)methane (
DCBM) was contained at 30.1 wt% (yield 36.6%), and unreacted dichlorotoluene was not detected. After adding 25.2 g of crude DCTCT to 50 ml of n-hexane and removing undissolved substances, the residue was concentrated under reduced pressure and distilled under reduced pressure to obtain DCTCT+DCT with a purity of 99.2%.
CT■10.5g (0,0377 mol, yield 37.7
%) was obtained. From this, using gas chromatography, DCTCT■ with a purity of 99.5% (boiling point 120-125℃
/3mmHg) and 99.0% purity
DCTCT (boiling point 109-115℃/3 mmH
g) was separated into 0.12 g. The structure of DCTCT■ is shown in the mass spectrum (M” 276 ), H-NMR spectrum (CDCI, solvent, δ 2.80 3H (CI, )s
, 7:991H(5-H)S, 7.38 1
Confirmed by H(6-11)S).
ＤＣＴＣＴ■の構造はマススペクトル（Ｍ”２７６ ）
、Ｈ−ＮＭＲｘ ベクトル（ＣｒｌＣ１，溶媒、６２
．４７ ３８ （ＣＨ，） Ｓ、 ７．２２ １８（
４−Ｈ） Ｓ、 ？。The structure of DCTCT■ is mass spectrum (M”276)
, H-NMRx vector (CrlC1, solvent, 62
．． 47 38 (CH,) S, 7.22 18(
4-H) S, ? .
９０ １Ｈ（５−Ｈ）Ｓ ）により確認した。90 1H(5-H)S).
参考例２
無水塩化アルミニウム１０８ ｇ （０，８１２モル）
、と四塩化炭素１２５ ｇ （０，８１２モル）と、１
．２−ジクロロエタン２０５ｇの混合液中に、攪拌下、
２゜３−ジクロロトルエン６５．４ｇ （０，４０６モ
ル）と１゜２−ジクロロエタン７８．０ｇの混合溶液を
５０〜５２℃、３０分間で滴下しさらに２時間攪拌反応
させ、放冷後、氷水１０１００Ｏに反応液を注ぐ以外は
参考例１と同様の操作をおこない、粗Ｄ ＣＴ Ｃ７１
０２ｇを得た。これをガスクロマトグラフィーで分析し
たところＤＣＴＣＴ■が５１．５れ％（収率４６．８％
） 、ＤＣＴＣＴ■が３０，４ｗｔ％（収率２７．６％
）およびＤＣＢＭが１８．５ｗｔ％（収率２７．６％）
含有されており、未反応の２．３−ジクロロトルエンは
検出されなかった。Reference example 2 Anhydrous aluminum chloride 108 g (0,812 mol)
, and 125 g (0,812 mol) of carbon tetrachloride, and 1
．． In a mixed solution of 205 g of 2-dichloroethane, under stirring,
A mixed solution of 65.4 g (0,406 mol) of 2゜3-dichlorotoluene and 78.0 g of 1゜2-dichloroethane was added dropwise at 50 to 52°C over 30 minutes, stirred for another 2 hours, and left to cool, then poured into ice water. The same operation as in Reference Example 1 was performed except for pouring the reaction solution into 10100O, and the crude D CT C71
02g was obtained. When this was analyzed by gas chromatography, DCTCT■ was 51.5% (yield 46.8%).
), DCTCT■ is 30.4 wt% (yield 27.6%
) and 18.5 wt% DCBM (yield 27.6%)
However, unreacted 2,3-dichlorotoluene was not detected.
参考例３
無水塩化アルミニウム２７．０ｇ （０，２０３モル）
と四塩化炭素１００．０ ｇの混合液中に、攪拌下２゜
４−ジクロロトルエン１６．１ｇ （０，１モル）と四
塩化炭素５４ｇ（合計１．０モル）の混合溶液を５０〜
５２℃、２時間で滴下し、さらに２時間攪拌反応させた
。放冷後、氷水７００ ｔｅｌに反応液を注ぎ室温下
撹拌し塩化アルミニウムを除いた。水層を四塩化炭素で
抽出し、集めた有機層を水酸化ナトリウム水溶液で洗浄
し、無水塩化カルシウムで乾燥し、溶媒を減圧留去して
粗ＤＣＴＣＴ２４．３ｇを得た。これをガスクロマトグ
ラフィーで分析したところ２．４−ジクロロ−５−トリ
クロロメチルトルエンが７０．２１１ｔ％（収率６１．
３％）、ＤＣＢＭが２９．８匈ｔ％（収率３５．９％）
含有されており未反応のジクロロトルエンは検出されな
かった。Reference example 3 Anhydrous aluminum chloride 27.0g (0,203 mol)
A mixed solution of 16.1 g (0.1 mol) of 2゜4-dichlorotoluene (0.1 mol) and 54 g of carbon tetrachloride (total 1.0 mol) was added to a mixed solution of 50 to 50 g of carbon tetrachloride (1.0 mol in total) under stirring.
The mixture was added dropwise at 52°C for 2 hours, and the mixture was stirred and reacted for an additional 2 hours. After cooling, the reaction solution was poured into 700 tel of ice water and stirred at room temperature to remove aluminum chloride. The aqueous layer was extracted with carbon tetrachloride, and the collected organic layer was washed with an aqueous sodium hydroxide solution, dried over anhydrous calcium chloride, and the solvent was distilled off under reduced pressure to obtain 24.3 g of crude DCTCT. When this was analyzed by gas chromatography, 2,4-dichloro-5-trichloromethyltoluene was found to be 70.211 t% (yield 61.
3%), DCBM is 29.8 t% (yield 35.9%)
Contained unreacted dichlorotoluene was not detected.
粗Ｄｃｒｃ７２４．３ｇをｎ−ヘキサン５０ｍ ｌに加
えて非溶解物を除去後、口演を減圧濃縮、減圧蒸留する
ことにより、純度９８．７％のＤＣＴＣＴ１３．８ｇ
（０，０４９６モル、収率４９．６％）を得た（融点７
９．０〜８０．２℃）、構造はマススペクトル（Ｍ”２
７３ ） 、Ｈ−ＮＭＲスペクトル（ＣＤＣＩ、溶媒、
６２．６０ Ｈ（ＣＨ，） Ｓ、 ７．７２ １８（
６−Ｈ） Ｓ、 ８゜２１ １Ｈ（３−Ｈ） ”）によ
り確認した。After adding 724.3 g of crude DCRC to 50 ml of n-hexane and removing undissolved substances, the residue was concentrated under reduced pressure and distilled under reduced pressure to obtain 13.8 g of DCTCT with a purity of 98.7%.
(0,0496 mol, yield 49.6%) (melting point 7
9.0-80.2℃), the structure is mass spectrum (M"2
73), H-NMR spectrum (CDCI, solvent,
62.60 H(CH,) S, 7.72 18(
6-H) S, 8°21 1H(3-H)'').
参考例４
無水塩化アルミニウム２７．０ｇ （０，２０３モル）
と四塩化炭素３１．５ｇ （０，２０５モル）と、１．
２−ジクロロエタン５０．５ｇの混合液中に、攪拌下、
２゜４−ジクロロトルエン１６．１ｇ （０，１モル）
と１，２−ジクロロエタン１９．１ｇの混合溶液を滴下
する以外は参考例３と同様の操作をおこない、粗ＤＣＴ
ＣＴ２４．３ｇ （純度７０．２％、収率６１．３％）
を得た。この粗ＤＣＴＣＴ中には未反応の２，４−ジク
ロロトルエンは検出されず、副生成物としてはＤＣＢＭ
のみが検出された。Reference example 4 Anhydrous aluminum chloride 27.0g (0,203 mol)
and 31.5 g (0,205 mol) of carbon tetrachloride; 1.
In a mixed solution of 50.5 g of 2-dichloroethane, under stirring,
2゜4-dichlorotoluene 16.1g (0.1 mol)
The same operation as in Reference Example 3 was carried out except that a mixed solution of 19.1 g of 1,2-dichloroethane and 1,2-dichloroethane was added dropwise.
CT24.3g (purity 70.2%, yield 61.3%)
I got it. Unreacted 2,4-dichlorotoluene was not detected in this crude DCTCT, and DCBM was detected as a by-product.
only was detected.
参考例５
無水塩化アルミニウム２７．０ｇ （０，２０３モル）
と四塩化炭素１００．０ ｇの混合液中に、攪拌下２゜
５−ジクロロトルエン１６．１ｇ（０，１モル）と四塩
化炭素５４ｇ（合計１．０モル）の混合溶液を５０〜５
２゛Ｃ１２時間で滴下し、さらに２時間攪拌反応させた
。放冷後、氷水１０００ ｍｌに反応液を注ぎ室温下攪
拌し塩化アルミニウムを除いた。水層を四塩化炭素で抽
出し、集めた有機層を無水塩化カルシウムで乾燥し、溶
媒を減圧留去して粗Ｌ） ＣＴ ＣＴ ２４．１ｇを得
た。これをガスクロマトグラフィーで分析したところ２
．５−ジクロロ−４−トリクロロメチルトルエンが７２
．１ｗｔ％（収率６２．４％） 、ＤＣＢＭが２７．９
ｗｔ％（収率３３．３％）含有されており未反応のジク
ロロトルエンは検出されなかった。Reference example 5 Anhydrous aluminum chloride 27.0g (0,203 mol)
A mixed solution of 16.1 g (0.1 mol) of 2°5-dichlorotoluene and 54 g (total 1.0 mol) of carbon tetrachloride was added to a mixed solution of 50 to 50 g of carbon tetrachloride (total 1.0 mol) under stirring.
The mixture was added dropwise at 2°C for 12 hours, and the mixture was stirred and reacted for an additional 2 hours. After cooling, the reaction solution was poured into 1000 ml of ice water and stirred at room temperature to remove aluminum chloride. The aqueous layer was extracted with carbon tetrachloride, the collected organic layer was dried over anhydrous calcium chloride, and the solvent was distilled off under reduced pressure to obtain 24.1 g of crude L) CT. When this was analyzed by gas chromatography, 2
．． 5-dichloro-4-trichloromethyltoluene is 72
．． 1wt% (yield 62.4%), DCBM 27.9
wt% (yield 33.3%) and unreacted dichlorotoluene was not detected.
粗Ｄ ＣＴ ＣＴ ２５．５ｇをｎ−へキサン５０ｍ
ｌに加えて非溶解物を除去後、口演を減圧濃縮、減圧蒸
留することにより、純度９９．２％のＤＣＴＣＴｌｌ、
５ｇ （０，０４１０モル、収率４１．０％）を得た（
融点４１．６〜４２．５℃）。構造はマススペクトル（
Ｍ＋２７３ ） 、Ｈ−ＮＭＲスペクトル（ＣＤＣＩ、
溶媒、６２．３９ Ｈ（ＣＢ、） Ｓ、 ７．
４０ １Ｈ（３−Ｈ） Ｓ、 ８゜１３ １Ｈ（６
−Ｈ”） Ｓ ）により確認した。25.5 g of crude D CT CT was added to 50 m of n-hexane.
After removing undissolved matter in addition to L, by vacuum concentration and vacuum distillation, DCTCTll with a purity of 99.2%,
5g (0,0410 mol, yield 41.0%) was obtained (
melting point 41.6-42.5°C). The structure is mass spectrum (
M+273), H-NMR spectrum (CDCI,
Solvent, 62.39 H(CB,)S, 7.
40 1H (3-H) S, 8゜13 1H (6
-H”)S).
参考例６
無水塩化アルミニウム２７．０ｇ （０，２０３モル）
と四塩化炭素３１．５ｇ （０，２０５モル）と、１，
２−ジクロロエタン５０．５ｇの混合液中に、攪拌下、
２゜５−ジクロロトルエン１６．１ｇ （０，１モル）
と１．２＝ジクロロエタン１９．１ｇの混合溶液を滴下
する以外は参考例５と同様の操作をおこない、粗ＤＣＴ
Ｃ’１’ ２５．２ｇ （純度７８．８％、収率７１
．３％）を得た。この粗ＤＣＴＣＴ中には未反応の２，
５−ジクロロトルエンは検出されず、副生成物としては
ＤＣＢＭのみが検出された。Reference example 6 Anhydrous aluminum chloride 27.0g (0,203 mol)
and 31.5 g (0,205 mol) of carbon tetrachloride, and 1,
In a mixed solution of 50.5 g of 2-dichloroethane, under stirring,
2゜5-dichlorotoluene 16.1g (0.1 mol)
The same operation as in Reference Example 5 was performed except that a mixed solution of 19.1 g of 1.2=dichloroethane was added dropwise, and crude DCT was obtained.
C'1' 25.2g (purity 78.8%, yield 71
．． 3%). This crude DCTCT contains unreacted 2,
5-dichlorotoluene was not detected, and only DCBM was detected as a by-product.
参考例７
無水塩化アルミニウム２７．０ｇ （０，２０３モル）
と四塩化炭素３１．５ｇ （０，２０５モル） ト１．
２−ジクロロエタン５０．５ｇの混合液中に、攪拌下２
，６−ジクロロトルエン１６．１ｇ （０，１モル）と
１．２−ジクロロエタン１９．１ｇの混合溶液を５０〜
５２℃、２時間で滴下し、さらに２時間攪拌反応させた
。放冷後、氷水１０００ ｓｉｔに反応液を注ぎ室温下
攪拌し塩化アルミニウムを除いた。水層を四塩化炭素で
抽出し、集めた有機層を水酸化ナトリウム水溶液で洗浄
し、無水塩化カルシウムで乾燥し、溶媒を減圧留去して
粗ＤＣＴＣＴ２６．Ｏｇを得た。これをガスクロマトグ
ラフィーで分析したところ２．６−ジクロロ−３−トリ
クロロメチルトルエンが８８．４ｗｔ％（収率８２．７
％） 、ＤＣＢＭが１１．６ｗｔ％（収率１５．０％）
含有されており未反応のＤＣ’Ｉ”は検出されなかった
。Reference example 7 Anhydrous aluminum chloride 27.0g (0,203 mol)
and carbon tetrachloride 31.5g (0,205 mol) 1.
In a mixed solution of 50.5 g of 2-dichloroethane, 2
A mixed solution of 16.1 g (0.1 mol) of ,6-dichlorotoluene and 19.1 g of 1,2-dichloroethane was added to the
The mixture was added dropwise at 52°C for 2 hours, and the mixture was stirred and reacted for an additional 2 hours. After cooling, the reaction solution was poured into 1000 sit of ice water and stirred at room temperature to remove aluminum chloride. The aqueous layer was extracted with carbon tetrachloride, the collected organic layer was washed with an aqueous sodium hydroxide solution, dried over anhydrous calcium chloride, and the solvent was distilled off under reduced pressure to obtain crude DCTCT26. Obtained Og. When this was analyzed by gas chromatography, 2,6-dichloro-3-trichloromethyltoluene was found to be 88.4 wt% (yield: 82.7
%), DCBM is 11.6 wt% (yield 15.0%)
Contained and unreacted DC'I'' was not detected.
実施例１
参考例２で得られた粗ＤＣＴＣＴ１０２ｇとフッ化水素
１０９ｇを３００ｍ１のステンレス製オートクレーブに
仕込み反応温度９５〜１００℃で加熱しながら攪拌し、
反応圧が８ｋｇ ／−となるように還流塔上部から一次
圧調整弁を用いて副反応生成物である塩化水素ガスを連
続的に抜き出した。Example 1 102 g of crude DCTCT obtained in Reference Example 2 and 109 g of hydrogen fluoride were charged into a 300 ml stainless steel autoclave and stirred while heating at a reaction temperature of 95 to 100°C.
Hydrogen chloride gas, a side reaction product, was continuously extracted from the upper part of the reflux column using a primary pressure regulating valve so that the reaction pressure was 8 kg/-.
３時間後、反応圧の上昇が認められない時点でフッ素化
が終了したと判断し反応生成物をオートクレーブから取
り出し、水酸化ナトリウム水溶液で洗浄し未反応のフッ
化水素を除去した後、減圧蒸留することにより、純度９
８．３％の２゜３−ジクロロ−４−トリフルオロメチル
トルエン（以下ＤＣＴＦＴ■という） ７．４２ｇ （
０，０３１９モル、収率１６．６％、沸点１１５〜１１
８℃／ ３５ｍｍＨｇ）を、純度９９．２％の２．３−
ジクロロ−６−トリフルオロメチルトルエン（以下ＤＣ
ＴＦＴ■という）７．〜４５ｇ （０，０３２３モル、
収率２８．３％、沸点１０８〜１１０℃／ ３５＋＋ｕ
ａＨｇ）を得た。ＤＣＴＦＴ■の構造はマススペクトル
（Ｍ ２２８ ） 、Ｈ−ＮＭＲスペクトル（ＣＤＣ
Ｉ、溶媒、６２．４８ ３Ｈ（ＣＩ（、） Ｓ、７゜２
４ １８（６−Ｈ） Ｓ、７．５２ １）１（５−Ｈ）
Ｓ） 、Ｆ−ＮＭＲスペクトル（ＣＤＣｌ 、溶媒、
６１．５ｐｐｍ ３Ｆ （ＣＦ。After 3 hours, when no rise in reaction pressure was observed, it was judged that the fluorination was complete, and the reaction product was taken out of the autoclave, washed with an aqueous sodium hydroxide solution to remove unreacted hydrogen fluoride, and then distilled under reduced pressure. Purity 9
7.42 g of 8.3% 2゜3-dichloro-4-trifluoromethyltoluene (hereinafter referred to as DCTFT) (
0,0319 mol, yield 16.6%, boiling point 115-11
8°C/35mmHg) with a purity of 99.2%.
Dichloro-6-trifluoromethyltoluene (hereinafter referred to as DC
(referred to as TFT■)7. ~45g (0,0323 mol,
Yield 28.3%, boiling point 108-110℃/35++u
aHg) was obtained. The structure of DCTFT■ is shown in the mass spectrum (M 228 ) and H-NMR spectrum (CDC
I, solvent, 62.48 3H (CI(,) S, 7°2
4 18(6-H) S, 7.52 1) 1(5-H)
S), F-NMR spectrum (CDCl, solvent,
61.5ppm 3F (CF.
）Ｓ基準物質ＣＦＣＩ ）により確認した。) Confirmed using S reference material CFCI).
同様にＤＣＴＦＴ■の構造はマススペクトル（Ｍ ２
２８ ） 、Ｈ−ＮＭＲスペクトル（ＣＤＣ１３溶媒、
δ２．５８３ Ｈ（ＣＩ、） Ｓ 、 ７．４８ ２８
（４，５−Ｈ） Ｓ”） 、Ｆ−ＮＭＲスペクトル（
ＣＤＣＩｓ溶媒、６３．３ｐｐｍ３Ｆ （ＣＦｍ ）
Ｓ 、基準物質ＣＦＣＩ ｓ ）により確認した。Similarly, the structure of DCTFT■ has a mass spectrum (M 2
28), H-NMR spectrum (CDC13 solvent,
δ2.583 H(CI,) S, 7.48 28
(4,5-H)S”), F-NMR spectrum (
CDCIs solvent, 63.3 ppm F (CFm)
S, reference material CFCIs).
丸施例２
参考例３で得られた粗Ｄ ＣＴ ＣＴ ２４．３ｇとフ
フ化水素１０．０ｇを１００ｍ ｌのステンレス製オー
トクレーブに仕込み反応温度９５〜１０２℃で加熱しな
がら攪拌し、反応圧が８ｋｇ／ｃｆｆｌとなるように還
−原基上部から一次圧調整弁を用いて副反応生成物であ
る塩化水素ガスを連続的に抜き出した。Circle Example 2 24.3 g of the crude DCT CT obtained in Reference Example 3 and 10.0 g of hydrogen fluoride were placed in a 100 ml stainless steel autoclave and stirred while heating at a reaction temperature of 95 to 102°C. Hydrogen chloride gas, which is a side reaction product, was continuously extracted from the upper part of the reduced primordium using a primary pressure regulating valve so that the amount of hydrogen chloride gas was 8 kg/cffl.
３時間後、反応圧の上昇が認められない時点でフッ素化
が終了したと判断し反応生成物をオートクレーブから取
り出し、水酸化ナトリウム水溶液で洗浄し未反応のフッ
化水素を除去した後、減圧蒸留することにより、純度９
８．２％の２゜４−シクロロー５−トリフルオロメチル
トルエン１２．３ｇ （０，０５２７モル、収率８６．
０％、沸点８３〜８５℃／ ６ ｍｍＨｇ）を得た。構
造はマススペクトル（Ｍ”２２８ ） 、Ｈ−ＮＭＲス
ペクトル（ＣＤＣＩ３溶媒、δ２゜３６３８ （ＣＨ
，） Ｓ、 ７．４３ １８（６−Ｈ） Ｓ、 ７．５
０ＩＨ（３−Ｈ） Ｓ ） 、Ｐ−ＮＭＲスペクトル（
ＣＤＣＩ、溶媒、６２．８ｐｐ慣３Ｆ （ＣＦｓ ）
Ｓ 、基準物質ＣＦＣＩ、 ）により確認した。After 3 hours, when no rise in reaction pressure was observed, it was judged that the fluorination was complete, and the reaction product was taken out of the autoclave, washed with an aqueous sodium hydroxide solution to remove unreacted hydrogen fluoride, and then distilled under reduced pressure. Purity 9
12.3 g of 8.2% 2°4-cyclo-5-trifluoromethyltoluene (0,0527 mol, yield 86.
0%, boiling point 83-85°C/6 mmHg). The structure is mass spectrum (M”228), H-NMR spectrum (CDCI3 solvent, δ2°3638 (CH
,) S, 7.43 18(6-H) S, 7.5
0IH(3-H)S), P-NMR spectrum (
CDCI, solvent, 62.8 pp standard 3F (CFs)
Confirmed by S, reference material CFCI, ).
実施例３
参考例５で得られた粗ＤｃＴｃＴ２４．１ｇとフッ化水
素１０．０ｇを１００ｍ１のステンレス製オートクレー
ブに仕込み反応温度９５〜１０２℃で加熱しながら攪拌
し、反応圧が８ｋｇ ／ｃｄとなるように還流塔上部か
ら一次圧調整弁を用いて副反応生成物である塩化水素ガ
スを連続的に抜き出した。Example 3 24.1 g of crude DcTcT obtained in Reference Example 5 and 10.0 g of hydrogen fluoride were placed in a 100 ml stainless steel autoclave and stirred while heating at a reaction temperature of 95 to 102°C, resulting in a reaction pressure of 8 kg/cd. Hydrogen chloride gas, a side reaction product, was continuously extracted from the upper part of the reflux column using a primary pressure regulating valve.
３時間後、反応圧の上昇が認められない時点でフッ素化
が終了したと判断し反応生成物をオートクレーブから取
り出し、水酸化ナトリウム水溶液で洗浄し未反応のフッ
化水素を除去した後、減圧蒸留することにより、純度９
７．８％の２゜５−ジクロロ−４−トリフルオロメチル
トルエン１１．３ｇ （０，０４８３モル、収率７７．
３％、沸点８３〜８５℃／ ６ ｍｍＨｇ）を得た。構
造はマススペクトル（Ｍ”２２８ ”） 、Ｆｌ−ＮＭ
Ｒスペクトル＜ＣＤＣ１１溶媒、δ２゜３５３Ｈ（ＣＨ
ｓ）Ｓ、７．３２ １１（（３−Ｈ）Ｓ、７．６１１Ｈ
（６−Ｈ） Ｓ ”） 、Ｆ−ＮＭＲスペクトル（ＣＤ
ＣＩ、溶媒、６３．ｌｐｐｍ ３Ｆ （ＣＦｓ ） Ｓ
、基準物質ｃｐｃｔ、 ）により確認した。After 3 hours, when no rise in reaction pressure was observed, it was judged that the fluorination was complete, and the reaction product was taken out of the autoclave, washed with an aqueous sodium hydroxide solution to remove unreacted hydrogen fluoride, and then distilled under reduced pressure. Purity 9
11.3 g (0,0483 mol, yield 77.8%) of 2°5-dichloro-4-trifluoromethyltoluene.
3%, boiling point 83-85°C/6 mmHg). The structure is mass spectrum (M"228"), Fl-NM
R spectrum < CDC11 solvent, δ2°353H (CH
s)S, 7.32 11((3-H)S, 7.611H
(6-H)S”), F-NMR spectrum (CD
CI, solvent, 63. lppm 3F (CFs) S
, reference material cpct, ).
実施例４
参考例７で得た粗ＤＣＴＣＴ２６．０ｇとフッ化水素１
０．０ｇを１００ａ＋１のステンレス製オートクレーブ
に仕込み反応温度９５〜１０２℃で加熱しながら攪拌し
、反応圧が１３ｋｇ／ａＪとなるように還流塔上部から
一次圧Ｗｉｔ整弁を用いて副反応生成物である塩化水素
ガスを連続的に抜き出した。３時間後、反応圧の上昇が
認められない時点でフッ素化が終了したと判断し反応生
成物をオートクレーブから取り出し、水酸化ナトリウム
水溶液で洗浄し未反応のフッ化水素を除去した後、減圧
蒸留することにより、純度９８．７％の２．６−ジクロ
ロ−３−トリフルオロメチルトルエン１６．６ｇ（０，
０５２７モル、収率８７．８％、沸点８３〜８５℃／８
ｍｍＨｇ）を得た。構造はマススペクトル（Ｍ２２８
） 、Ｈ−ＮＭＲスペクトル（ＣＤＣ１ｇ溶媒、δ２．
５８３ＨＣＣＨｓ ） Ｓ、 ７．３３ １１（（５−
Ｈ） Ｓ、 ７．４３１）＋ （４−）１ ） Ｓ ）
、Ｆ−ＮＭＩ？スペクト ル（ＣＤＣＩ３溶媒、６２
．８ｐｐｍ ３Ｆ （ＣＦＳ ） Ｓ、基準 物質ＣＦ
ＣＩｍ）により確認した。Example 4 26.0 g of crude DCTCT obtained in Reference Example 7 and 1 hydrogen fluoride
0.0g was charged into a 100a+1 stainless steel autoclave, stirred while heating at a reaction temperature of 95 to 102℃, and the side reaction products were removed from the top of the reflux column using the primary pressure regulator Wit so that the reaction pressure was 13kg/aJ. Hydrogen chloride gas was extracted continuously. After 3 hours, when no rise in reaction pressure was observed, it was judged that the fluorination was complete, and the reaction product was taken out of the autoclave, washed with an aqueous sodium hydroxide solution to remove unreacted hydrogen fluoride, and then distilled under reduced pressure. By doing this, 16.6 g of 2,6-dichloro-3-trifluoromethyltoluene (0,
0527 mol, yield 87.8%, boiling point 83-85°C/8
mmHg) was obtained. The structure is mass spectrum (M228
), H-NMR spectrum (CDC1g solvent, δ2.
583HCCHs)S, 7.33 11((5-
H) S, 7.431)+ (4-)1) S)
, F-NMI? Spectrum (CDCI3 solvent, 62
．． 8ppm 3F (CFS) S, standard substance CF
Confirmed by CIm).
［発明の効果］
本発明の新規なジクロロトリフルオロメチルトルエンは
容易且つ収率良く製造することができ、医・農薬の中間
体として有用なアミノトリフルオロメチルトルエン誘導
体の製造原料として極めて有用である。[Effects of the Invention] The novel dichlorotrifluoromethyltoluene of the present invention can be produced easily and with high yield, and is extremely useful as a raw material for producing aminotrifluoromethyltoluene derivatives useful as intermediates for medicines and agricultural chemicals. .
特許出願人 セントラル硝子株式会社 ℃−ｊPatent applicant: Central Glass Co., Ltd. ℃−j
Claims (2)
，４−ジクロロ−６−トリフルオロメチルトルエンを除
く）。(1) Dichlorotrifluoromethyltoluene (however, 3
, 4-dichloro-6-trifluoromethyltoluene).
４−ジクロロ−６−トリクロロメチルトルエンを除く）
をフッ化水素と反応させることを特徴とするジクロロト
リフルオロメチルトルエンの製造法。(2) Dichlorotrichloromethyltoluene (3,
(excluding 4-dichloro-6-trichloromethyltoluene)
A method for producing dichlorotrifluoromethyltoluene, which comprises reacting with hydrogen fluoride.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10657087A JPS63270632A (en) | 1987-04-30 | 1987-04-30 | Novel dichlorotrifluoromethyltoluene and production thereof |
| US07/084,019 US4876404A (en) | 1986-08-13 | 1987-08-11 | Preparation of dichlorotrifluoromethyltoluenes including novel isomers |
| GB8719063A GB2194235B (en) | 1986-08-13 | 1987-08-12 | Dichlorotrifluoromethyltoluenes and preparation thereof |
| FR878711502A FR2602764B1 (en) | 1986-08-13 | 1987-08-12 | DICHLOROTRIFLUOROMETHYLTOLUENES COMPOUNDS AND PROCESS FOR THE PREPARATION THEREOF |
| DE19873726890 DE3726890A1 (en) | 1986-08-13 | 1987-08-12 | METHOD FOR THE PRODUCTION OF DICHLORTRIFLUORMETHYLTOLUOLS AND NEW ISOMERS PRODUCED BY THE METHOD |
| IT8721651A IT1228929B (en) | 1986-08-13 | 1987-08-13 | PREPARATION OF DICHLOROTRIFLUOROMETILTOLUENI, INCLUDING ISOMERS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10657087A JPS63270632A (en) | 1987-04-30 | 1987-04-30 | Novel dichlorotrifluoromethyltoluene and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63270632A true JPS63270632A (en) | 1988-11-08 |
Family
ID=14436913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10657087A Pending JPS63270632A (en) | 1986-08-13 | 1987-04-30 | Novel dichlorotrifluoromethyltoluene and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63270632A (en) |
-
1987
- 1987-04-30 JP JP10657087A patent/JPS63270632A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7799959B2 (en) | Process for producing 1,2,3,4-tetrachlorohexafluorobutane | |
| EP0462514A1 (en) | Process for preparing 1-chloro-2,2,2-trifluoroethane | |
| JPH06219987A (en) | Production of alpha-fluoro-beta-dicarbonyl compound | |
| JP4641839B2 (en) | Process for producing 4-methyl-3-trifluoromethylbenzoic acid | |
| JPH03184938A (en) | Preparation of ethylenic ketone | |
| JPS63270632A (en) | Novel dichlorotrifluoromethyltoluene and production thereof | |
| US4876404A (en) | Preparation of dichlorotrifluoromethyltoluenes including novel isomers | |
| US4117006A (en) | Selective chlorination of benzoyl chloride | |
| RU2748928C1 (en) | Method for producing perfluoroalkyliodes | |
| JP7385141B2 (en) | Method for producing a composition containing a purified fluorine-containing ether compound | |
| JP2672012B2 (en) | Method for producing 1-chloro-3,4-difluorobenzene | |
| JP4283174B2 (en) | Fluorine-containing benzal chloride and method for producing the same | |
| JP2000159700A (en) | Production of bisdifluoromethylbenzene | |
| JP2000212104A (en) | Production of bis (trifluoromethyl)monobromobenzene | |
| JP3531039B2 (en) | 1,4-difluorobenzene derivative | |
| JPH0474340B2 (en) | ||
| WO1992003397A1 (en) | Process for producing trifluorinated hydrocarbon compound | |
| JP2016169192A (en) | Method of producing 7-octenyl halide | |
| JPH0476977B2 (en) | ||
| JPH05132446A (en) | Preparation of beta-halogeno-tert-alkylcarboxy- lic acid chlorides | |
| JPS63270644A (en) | Novel dichlorotrifluoromethylnitrotoluene and production thereof | |
| JPH07165638A (en) | New fluorobenzotrichloride compound | |
| JPS63270631A (en) | Novel dichlorotrichloromethyltoluene and production thereof | |
| JPH03169830A (en) | Production of allylbromides | |
| JPH11246465A (en) | Production of chlorinated acetone |