JPS63270631A - Novel dichlorotrichloromethyltoluene and production thereof - Google Patents
Novel dichlorotrichloromethyltoluene and production thereofInfo
- Publication number
- JPS63270631A JPS63270631A JP10656987A JP10656987A JPS63270631A JP S63270631 A JPS63270631 A JP S63270631A JP 10656987 A JP10656987 A JP 10656987A JP 10656987 A JP10656987 A JP 10656987A JP S63270631 A JPS63270631 A JP S63270631A
- Authority
- JP
- Japan
- Prior art keywords
- dichlorotoluene
- mol
- dichlorotrichloromethyltoluene
- solvent
- dctct
- 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
- 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 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- -1 aluminum halide Chemical class 0.000 claims abstract description 12
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- DMEDNTFWIHCBRK-UHFFFAOYSA-N 1,3-dichloro-2-methylbenzene Chemical compound CC1=C(Cl)C=CC=C1Cl DMEDNTFWIHCBRK-UHFFFAOYSA-N 0.000 claims abstract 2
- RYMMNSVHOKXTNN-UHFFFAOYSA-N 1,3-dichloro-5-methyl-benzene Natural products CC1=CC(Cl)=CC(Cl)=C1 RYMMNSVHOKXTNN-UHFFFAOYSA-N 0.000 claims abstract 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 34
- 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 claims 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 22
- 239000002904 solvent Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000006227 byproduct 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
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 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 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012044 organic layer Substances 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
- GWLKCPXYBLCEKC-UHFFFAOYSA-N 1,2-dichloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1Cl GWLKCPXYBLCEKC-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XFEKIQFBJSDMQB-UHFFFAOYSA-N 2,2,2-trichloroethylbenzene Chemical class ClC(Cl)(Cl)CC1=CC=CC=C1 XFEKIQFBJSDMQB-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 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
- 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000035484 reaction time Effects 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
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using 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・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クロロメチルトルエン
（以下ＤＣＴＣＴ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 Application Field] The present invention is directed to a novel dichlorotrichloromethyltoluene ( (hereinafter abbreviated as DCTCT) and its manufacturing method.
［従来の技術］
トリクロロメチルトルエン誘導体の製造法としては、以
下のものが知られている。[Prior Art] The following methods are known as methods for producing trichloromethyltoluene derivatives.
しかしながら、２，３−ジクロロトルエン、２．４−ジ
クロロトルエン、２．５−ジクロロトルエンに関するト
リクロロメチルトルエン誘導体は皆無であった。However, there were no trichloromethyltoluene derivatives related to 2,3-dichlorotoluene, 2.4-dichlorotoluene, and 2.5-dichlorotoluene.
［問題点を解決するための手段］
本発明者らは、２．３−１２．４−および２．５−ジク
ロロトルエンのトリクロロメチル化について検討の結果
、新規なりＣＴＣＴを効率良く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 studies on trichloromethylation of 2.3-12.4- and 2.5-dichlorotoluene, the present inventors discovered that a novel CTCT can be efficiently produced. We have arrived at the present invention.
すなわち本発明は新規なジクロロトリクロロメチルトル
エン（２，６−ジクロロ−３−トリクロロメチルトルエ
ンを除く）およびその製造法であり、製造法は、ジクロ
ロトルエン（ただし２．６−ジクロロトルエンを除く）
をハロゲン化アルミニウムの存在下で四塩化炭素と反応
させることを特徴とするジクロロトリクロロメチルトル
エンの製造法である。That is, the present invention is a novel dichlorotrichloromethyltoluene (excluding 2,6-dichloro-3-trichloromethyltoluene) and a method for producing the same;
This is a method for producing dichlorotrichloromethyltoluene, which is characterized by reacting dichlorotrichloromethyltoluene with carbon tetrachloride in the presence of aluminum halide.
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。In this reaction, carbon tetrachloride is used in an amount of 1 to 10 moles based on dichlorotoluene as a raw material, and may be used as a solvent.
本反応における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
れる。ハロゲン化アルミニウム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。Examples of the aluminum halide in this reaction include anhydrous aluminum chloride and anhydrous aluminum bromide. The amount of aluminum halide used is 1 to 6 mol, preferably 1 to 3 mol, based on dichlorotoluene as a raw material.
ハロゲン化アルミニウムはＤＣＴＣＴと下式に示すよう
な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
に生成する。Aluminum halide forms a complex with DCTCT as shown in the formula below, so if aluminum halide is insufficient, dichlorobis(dichloromethylphenyl)
A by-product called methane (hereinafter referred to as DCBM) is selectively produced.
また、ハロゲン化アルミニウムを過剰に使用してもＤＣ
ＴＣＴの選択率は増加しない。Also, even if aluminum halide is used excessively, DC
TCT selectivity does not increase.
本反応の反応温度は０〜１００℃であり、望ましくは２
０〜８０℃である。The reaction temperature of this reaction is 0 to 100°C, preferably 2
The temperature is 0 to 80°C.
また、本発明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、最も好ましい。Further, in the present invention, it is preferable to use a solvent,
As the solvent, for example, methylene chloride, tetrachloroethane, fluorocarbons, etc. can be used, but 1,2-dichloroethane is the most preferred solvent because it can significantly improve the selectivity of DCTCT.
本反応の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、目的のＤＣＴＣＴを得る。The reaction time of this reaction cannot be absolutely specified, but it is from 20 minutes to
It is 4 hours. Water is added to the reaction product thus obtained to decompose the complex and obtain the desired DCTCT.
本反応においては、原料として２．３−ジクロロ ：
トルエンを用いた場合にはトリクロロメチル基の導入位
置は４および６であり、その比率は略６：４である。In this reaction, 2,3-dichloro as a raw material:
When toluene is used, the trichloromethyl groups are introduced at positions 4 and 6, and the ratio is approximately 6:4.
また、２．４−ジクロロトルエンの場合は５の位置に選
択的に導入され、２．５−ジクロロトルエンの場合は４
の位置に選択的に導入される。In addition, in the case of 2,4-dichlorotoluene, it is selectively introduced at the 5 position, and in the case of 2,5-dichlorotoluene, it is introduced at the 4 position.
selectively introduced into the position.
本発明の新規化合物であるＤＣＴＣＴ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。DCTCT, 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.
（ｆｆ〕（ＤＯＴ！ＰＩ’〕（ＤＯＴＦＮＴ）以下本発
明を実施例により詳細に説明する。(ff] (DOT! PI') (DOTFNT) The present invention will be described in detail below with reference to Examples.
丸施例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）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 ｍｌ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
ＤＣＴＣ７２４，５ｇ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訂％（
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（ＤＣ
ＢＭ）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。Circle Example 1 Anhydrous aluminum chloride 27.0g (0,203 mol)
A mixed solution of 16.1 g (0.1 mol) of 2゜3-dichlorotoluene (0.1 mol) and 54 g of carbon tetrachloride (total 1.0 mol) was added under stirring to a mixed solution of 100.0 g of carbon tetrachloride.
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 ml 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 724.5 g of crude DCTC. When this was analyzed by gas chromatography, 2,3-dichloro-4-trichloromethyltoluene (DCTCT) was found to be 42.8% (
Yield 37.6%), 2.3-dichloro-6-trichloromethyltoluene (DCTCT■) was 27.1wt% (
yield 23.8%) and dichlorobis(2,3-dichloro-4-methylphenyl)methane and dichlorobis(
2-Methyl-3,4-dichlorophenyl)methane (DC
BM) was contained at 30.1 wt% (yield 36.6%), and unreacted dichlorotoluene was not detected.
粗Ｄ ＣＴ Ｃ７２５，２ｇをｆｉ −ヘキサン５０
ｍ１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■＋
ＤＣＴＣＴ■１０．５ｇ （０，０３７７モル、収率３
７．７％）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１２０〜１
２５℃／ ３ｍｍＨｇ ）を０．１５ｇおよび純度９９
．０％のＤ Ｃ’Ｉ’ ＣＴ■（沸点１０９〜１１５℃
／ ３ ｍｎ＋Ｈｇ）を０．１２ｇに分離した。ＤＣＴ
ＣＴ■の構造はマススペクトル（Ｍ ２７６）、Ｈ−
ＮＭＲスペクトル（ＣＤＣ１，溶媒、６２．８０ ３Ｈ
（ＣＨｓ ） Ｓ、 ？、９９１Ｈ（５ＪＩ） Ｓ、
７．３８ １Ｈ（６−）１）Ｓ）により確認した。2g of crude DCT C725 in fi-hexane 50
After removing undissolved substances in addition to m1, the oral mixture is concentrated under reduced pressure and distilled under reduced pressure to obtain DCTCT■+ with a purity of 99.2%.
DCTCT ■ 10.5 g (0,0377 mol, yield 3
7.7%). From this, using gas chromatography, DCTCT■ with a purity of 99.5% (boiling point 120-1
0.15g (25℃/3mmHg) and purity 99
．． 0% D C'I' CT■ (boiling point 109-115℃
/3 mn+Hg) was separated into 0.12 g. DCT
The structure of CT■ is shown in the mass spectrum (M 276), H-
NMR spectrum (CDC1, solvent, 62.80 3H
(CHs) S,? , 991H (5JI) S,
7.38 1H(6-)1)S).
＋
ＤＣＴＣＴ■の構造はマススペクトル（Ｍ２７６ ）
、Ｈ−ＮＭＲスペクトル（ＣＤＣ１ｍ溶媒、６２．４７
３８ （ｃｕｌ） Ｓ、？、２２ １Ｈ（４−Ｈ）
ｓ、 ７゜９０ １Ｈ（５−Ｈ） Ｓ ）により確認
した。+ The structure of DCTCT■ is mass spectrum (M276)
, H-NMR spectrum (CDC1m solvent, 62.47
38 (cul) S,? , 22 1H (4-H)
s, 7°90 1H(5-H)S).
実施例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５
０〜５２℃、３０分間で滴下しさらに２時間攪拌反応さ
せ、放冷後、氷水１００抛１に反応液を注ぐ以外は実施
例１と同様の操作をおこない、粗Ｄ ＣＴ ＣＴ １０
２ｇ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５１．５ｗｔ％（収率４６．８％
’） 、ＤＣＴＣＴ■が３０．４ｗｔ％（収率２７．６
％）およびＤＣＢＭがｉｓ、ｓｗｔ％（収率２７６６％
）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。Example 2 108 g (0,812 mol) of anhydrous aluminum chloride
and 125 g (0,812 mol) of carbon tetrachloride; 1.
In a mixed solution of 205 g of 2-dichloroethane, 2
A mixed solution of 65.4 g (0,406 mol) of ゜3-dichlorotoluene and 78.0 g of 1゜2-dichloroethane was
The mixture was added dropwise at 0 to 52°C for 30 minutes, stirred and reacted for 2 hours. After cooling, the same procedure as in Example 1 was performed except that the reaction solution was poured into 100 μl of ice water.
2g was obtained. When this was analyzed by gas chromatography, DCTCT■ was found to be 51.5 wt% (yield 46.8%).
), DCTCT■ was 30.4 wt% (yield 27.6
%) and DCBM is, swt% (yield 2766%
), and unreacted 2,3-dichlorotoluene was not detected.
実施例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 ｍｌ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７０．２ｗｔ％（収率６１．３
％）、ＤＣＢＭが２９．８４％（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。Example 3 Anhydrous aluminum chloride 27.0 g (0,203 mol)
A mixed solution of 16.1 g (0.1 mol) of 2°4-dichlorotoluene and 54 g (total 1.0 mol) of carbon tetrachloride was added to a mixed solution of 100.0 g of carbon tetrachloride and 50 g of carbon tetrachloride 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 ml 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 70.2 wt% (yield 61.3
%), DCBM was contained at 29.84% (yield 35.9%), and unreacted dichlorotoluene was not detected.
粗Ｄ Ｃ’ｌ’ ＣＴ ２５．３ｇをｎ−ヘキサン５０
＊１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ＤＣＴＣ７１３
，８ｇ （０，０４９６モル、収率４９．６％）を得た
（触子
点７９．０〜８０．２℃）、構造はマススペクトル（Ｍ
２７３ ） 、）Ｉ−ＮＭＲスペクトル（ＣＤＣ１ｍ溶
媒、δ ２．６０ Ｈ（Ｃ）ｌ” ）Ｓ、７．７２
１Ｈ（６−Ｈ） Ｓ、８゜２１ １Ｈ（３−）１ ）’
）により確認した。25.3 g of crude D C'l' CT was added to 50 g of n-hexane.
*In addition to 1, after removing undissolved substances, the oral material is concentrated under reduced pressure and distilled under reduced pressure to obtain DCTC713 with a purity of 98.7%.
, 8g (0,0496 mol, yield 49.6%) (touch point 79.0-80.2°C), whose structure was determined by mass spectrometry (M
273),) I-NMR spectrum (CDC1m solvent, δ 2.60 H(C)l'')S, 7.72
1H(6-H) S, 8゜21 1H(3-)1 )'
) was confirmed.
実施例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１６．１ ｇ （０，１モ
ル）と１．２−ジクロロエタン１９．１ｇの混合溶液を
滴下する以外は実施例３と同様の操作をおこない、粗Ｄ
ＣＴＣＴ２４．３ｇ （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ＤＣ
ＢＭのみが検出された。Example 4 27.0 g (0,203 mol) of anhydrous aluminum chloride, 31.5 g (0,205 mol) of carbon tetrachloride, and 1
．． Example except that a mixed solution of 16.1 g (0.1 mol) of 2°4-dichlorotoluene and 19.1 g of 1,2-dichloroethane was added dropwise to a mixed solution of 50.5 g of 2-dichloroethane under stirring. Perform the same operation as step 3 to obtain coarse D.
CTCT24.3g (purity 70.2%, yield 61.3
%) was obtained. This crude DCTCT contained unreacted 2.4-
Dichlorotoluene was not detected, and DC as a by-product
Only BM was detected.
実施例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〜
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 ｖｓｌ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、集めた有機層を無水塩化カルシウムで乾燥し、
溶媒を減圧留去して粗Ｄ Ｃ’ｒ’ 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．
９ｗｔ％（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。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 under stirring to a mixed solution of 100.0 g of carbon tetrachloride and 100.0 g of carbon tetrachloride.
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 vsl 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 with anhydrous calcium chloride,
The solvent was distilled off under reduced pressure to obtain 24.1 g of crude D C'r' CT.
I got it. When this was analyzed by gas chromatography, 2.5-dichloro-4-trichloromethyltoluene was 72.1 wt% (yield 62.4%), and DCBM was 27.5 wt%.
Unreacted dichlorotoluene, which contained 9 wt% (yield 33.3%), was not detected.
粗ＤＣＴＣＴ２５．５ｇをｎ−ヘキサン５０１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Ｄ ＣＴ ＣＴ１１．５ｇ
（０，０４１０モル、収率４１．０％）を得た（融点４
１．６〜４２．５℃）。構造はマススペクトル（Ｍ＋２
７３ ） 、Ｈ−ＮＭＲスヘクト／［’ （Ｃ［１ＣＩ
ｊ溶媒、６２．３９ Ｈ（Ｃ）ｉｎ） Ｓ、７．
４０ １１１（３−）１） Ｓ、 ８゜１３ １Ｈ（
６−Ｅｌ ）Ｓ ’）により確認した。After adding 25.5 g of crude DCTCT to 501 n-hexane and removing undissolved substances, the liquid was concentrated under reduced pressure and distilled under reduced pressure to obtain 11.5 g of DCTCT with a purity of 99.2%.
(0,0410 mol, yield 41.0%) (melting point 4
1.6-42.5°C). The structure is mass spectrum (M+2
73), H-NMR spectrum/['(C[1CI
j solvent, 62.39 H(C)in)S, 7.
40 111(3-)1) S, 8゜13 1H(
6-El)S').
実施例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
する以外は実施例５と同様の操作をおこない、粗ＤＣＴ
ｃＴ２５．２ｇ （純度７８．８％、収率７１．３％）
を得たｅ ；−（Ｄ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Ｄ
ＣＢＭのみが検出された。Example 6 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゜5-dichlorotoluene 16.1g (0.1 mol)
The same operation as in Example 5 was carried out except that a mixed solution of 19.1 g of 1,2-dichloroethane and 19.1 g of crude DCT was added dropwise.
cT25.2g (purity 78.8%, yield 71.3%)
The obtained e ;-(D contains unreacted 2.5
-Dichlorotoluene was not detected, and D as a by-product
Only CBM was detected.
［発明の効果］
本発明の新規なジクロロトリクロロメチルトルエンは対
応するジクロロトルエンから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 dichlorotrichloromethyltoluene of the present invention can be easily produced from the corresponding dichlorotoluene with good yield, and can be used as a raw material for producing aminotrifluoromethyltoluene derivatives useful as intermediates for medicines and agricultural chemicals. Extremely useful.
Claims (2)
６−ジクロロ−３−トリクロロメチルトルエンは除く）
。(1) Dichlorotrifluoromethyltoluene (but 2,
(excluding 6-dichloro-3-trichloromethyltoluene)
.
エンを除く）をハロゲン化アルミニウムの存在下で四塩
化炭素と反応させることを特徴とするジクロロトリクロ
ロメチルトルエンの製造法。(2) A method for producing dichlorotrichloromethyltoluene, which comprises reacting dichlorotoluene (excluding 2,6-dichlorotoluene) with carbon tetrachloride in the presence of aluminum halide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10656987A JPS63270631A (en) | 1987-04-30 | 1987-04-30 | Novel dichlorotrichloromethyltoluene and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10656987A JPS63270631A (en) | 1987-04-30 | 1987-04-30 | Novel dichlorotrichloromethyltoluene and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63270631A true JPS63270631A (en) | 1988-11-08 |
Family
ID=14436889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10656987A Pending JPS63270631A (en) | 1987-04-30 | 1987-04-30 | Novel dichlorotrichloromethyltoluene and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63270631A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03161450A (en) * | 1989-11-17 | 1991-07-11 | Asahi Glass Co Ltd | Production of novel fluorobenzotrichloride compound and fluorobenzoic acids |
| JP2010001300A (en) * | 2006-01-13 | 2010-01-07 | Dow Agrosciences Llc | 6-(poly-substituted aryl)-4-aminopicolinate and its use as herbicide |
-
1987
- 1987-04-30 JP JP10656987A patent/JPS63270631A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03161450A (en) * | 1989-11-17 | 1991-07-11 | Asahi Glass Co Ltd | Production of novel fluorobenzotrichloride compound and fluorobenzoic acids |
| JP2010001300A (en) * | 2006-01-13 | 2010-01-07 | Dow Agrosciences Llc | 6-(poly-substituted aryl)-4-aminopicolinate and its use as herbicide |
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