JPH02255649A - Production of 4'-chloro-2'-trifluoromethylpropoxy acetanilide - Google Patents
Production of 4'-chloro-2'-trifluoromethylpropoxy acetanilideInfo
- Publication number
- JPH02255649A JPH02255649A JP1076468A JP7646889A JPH02255649A JP H02255649 A JPH02255649 A JP H02255649A JP 1076468 A JP1076468 A JP 1076468A JP 7646889 A JP7646889 A JP 7646889A JP H02255649 A JPH02255649 A JP H02255649A
- Authority
- JP
- Japan
- Prior art keywords
- phosphorus
- formula
- chloro
- phosphorus oxychloride
- phosphorus trichloride
- 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 abstract description 7
- PRFIIMLQPHQGOC-UHFFFAOYSA-N n-[4-chloro-2-(trifluoromethyl)phenyl]-2-propoxyacetamide Chemical compound CCCOCC(=O)NC1=CC=C(Cl)C=C1C(F)(F)F PRFIIMLQPHQGOC-UHFFFAOYSA-N 0.000 title claims 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 18
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000005494 condensation Effects 0.000 claims abstract 3
- 238000009833 condensation Methods 0.000 claims abstract 3
- SGUYGLMQEOSQTH-UHFFFAOYSA-N 2-propoxyacetic acid Chemical compound CCCOCC(O)=O SGUYGLMQEOSQTH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 4
- RVUYACAXXOCJAH-UHFFFAOYSA-N propyl ethaneperoxoate Chemical compound CCCOOC(C)=O RVUYACAXXOCJAH-UHFFFAOYSA-N 0.000 abstract 3
- CVINWVPRKDIGLL-UHFFFAOYSA-N 4-chloro-2-(trifluoromethyl)aniline Chemical compound NC1=CC=C(Cl)C=C1C(F)(F)F CVINWVPRKDIGLL-UHFFFAOYSA-N 0.000 abstract 1
- 239000003905 agrochemical Substances 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000003931 anilides Chemical class 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- -1 benzene-toluene Chemical compound 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000011282 treatment 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)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は農業中間体として重要な式
４′−クロロー２１−トリフルオロメチル・プロポキシ
アセトアニリド（以下アニリドという、）の新規な製造
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel method for producing 4'-chloro-21-trifluoromethyl propoxyacetanilide (hereinafter referred to as anilide), which is important as an agricultural intermediate.
（従来の技術）
一般的な置換アニリドの製造方法としては、カルボン酸
の酸無水物、酸クロリド等と置換アニリンとを反応させ
る方法、あるいはカルボン酸と置換アニリンとを縮合剤
の存在下に縮合する方法等が知られている。(Prior art) A general method for producing a substituted anilide is to react a carboxylic acid anhydride, acid chloride, etc. with a substituted aniline, or to condense a carboxylic acid and a substituted aniline in the presence of a condensing agent. There are known methods to do this.
しかしながら本発明の如（置換基としてトリフルオロメ
チル基を有する場合は、その電子吸引性のため、縮合反
応が完結しなかったり、トリフルオロメチル基が加水分
解され、フン化水素が副生し、反応容器の腐食がおこる
等の問題点を有していた。However, as in the present invention (when a trifluoromethyl group is included as a substituent), due to its electron-withdrawing property, the condensation reaction may not be completed, or the trifluoromethyl group may be hydrolyzed, and hydrogen fluoride may be produced as a by-product. This method had problems such as corrosion of the reaction vessel.
本発明者等はアニリドの製造方法を種々検針した結果、
三塩化リンスはオキシ塩化リンを縮合剤に用いることに
より比較的低温で反応が完結するため、トリフルオロメ
チル基の加水分解によるフン化水素の副生を抑制できる
ことを見い出し本発明を完成した。As a result of testing various methods for producing anilide, the present inventors found that
The inventors of the present invention have discovered that trichloride rinse uses phosphorus oxychloride as a condensing agent and completes the reaction at a relatively low temperature, thereby suppressing the by-product of hydrogen fluoride due to hydrolysis of trifluoromethyl groups.
即ち、本発明は
一α、α、α−トリフルオロオルトトルイジン（以下ア
ニリンという、）とプロポキシ酢酸とを三塩化リン又は
オキシ塩化リンにより、縮合させることを特徴とするア
ニリドの製造法である。That is, the present invention is a method for producing an anilide characterized by condensing -α,α,α-trifluoroorthotoluidine (hereinafter referred to as aniline) and propoxyacetic acid with phosphorus trichloride or phosphorus oxychloride.
反応は有機溶媒中、５０℃〜１１０℃、好ましくは６０
゛Ｃ〜７０°Ｃで塩酸の発生がなくなるまで行なう。The reaction is carried out in an organic solvent at 50°C to 110°C, preferably at 60°C.
The process is carried out at 70°C to 70°C until no hydrochloric acid is generated.
有機溶媒としては、四塩化炭素、クロロホルム等の塩素
系溶媒、ベンゼントルエン等の芳香族系溶媒等が使用で
きるが、溶媒の回収効率、毒性等の点からトルエンが好
ましい。As the organic solvent, chlorine-based solvents such as carbon tetrachloride and chloroform, aromatic solvents such as benzene-toluene, etc. can be used, but toluene is preferred from the viewpoint of solvent recovery efficiency, toxicity, etc.
反応のモル比はアニリン１モルに対し、プロポキシ酢酸
０．５〜２．０モル、通常は等モル前後、三塩化リン、
オキシ塩化リンは０．３モル〜０．５モル好ましくは０
．３３モル〜０，４モルである。The molar ratio of the reaction is 1 mole of aniline to 0.5 to 2.0 moles of propoxyacetic acid, usually around the same mole, phosphorus trichloride,
Phosphorus oxychloride is 0.3 mol to 0.5 mol, preferably 0
．． 33 moles to 0.4 moles.
反応終了後は通常の後処理を行なうことにより目的のア
ニリドを好収率で得ることができる。After the reaction is completed, the desired anilide can be obtained in good yield by carrying out usual post-treatments.
（実施例） 次に実施例を挙げ、本発明を更に詳細に説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
実施例１
温度計、連流冷却器、共沸脱水用検水管、滴下ロートお
よびガラス缶撹拌機のついた３２フラスコにアニリン（
２５０ｇ １．２８モル） プロポキシ酸ａｌ （１
５１ｇ １．２８モル）およびトルエン１２を入れ、５
０″Ｃに加熱したあと、三塩化リン（７０ｇ ０．５１
モル）を徐々に滴下する０滴下後場酸の発生がなくな
ったら冷却し水を加えて撹拌洗浄し水層を分液する。ト
ルエン層は減圧にてトルエンを留去し目的のアニリド３
７３ｇ（収率９８．８％）を得た９反応中発生する塩酸
ガス等の廃ガスは水に吸収し回収する。水洗水及び廃ガ
ス吸収水中のフッ素イオンは１．３ ｍ−ｍｏｌ（原料
のアニリンの分解率として０．０３４モル％）であった
、またこの実験を３０回くり返して撹拌機に使用したガ
ラス羽の減量をみたが、１年間の腐食量に換算して、０
．０２４膿／Ｙとなった。Example 1 Aniline (
250g 1.28 mol) Propoxy acid al (1
51g (1.28 mol) and toluene 12,
After heating to 0″C, phosphorus trichloride (70g 0.51
After the addition of 0 drops, when no acid is generated, the mixture is cooled, water is added, and the mixture is stirred and washed, and the aqueous layer is separated. The toluene layer is distilled off under reduced pressure to obtain the desired anilide 3.
Waste gases such as hydrochloric acid gas generated during the 9 reactions yielding 73 g (yield 98.8%) are absorbed into water and recovered. The amount of fluorine ions in the washing water and waste gas absorption water was 1.3 mmol (0.034 mol% as a decomposition rate of the raw material aniline). We looked at the weight loss, but when converted to the amount of corrosion per year, it was 0.
．． It became 024 pus/Y.
０、０２４■／Ｙという数値は実用上充分な値で一般的
には０．０５鴎／Ｙ以下であれば、はぼ完全耐食と考え
られている。The value of 0.024/Y is a practically sufficient value, and generally, if it is 0.05/Y or less, it is considered to be completely corrosion resistant.
実施例２
実施例１と同じ装備をしたフラスコにアニリン（２５０
ｇ １．２８モル）、プロポキシ酢酸（１５１ｇ １，
２８モル）およびトルエン１２を入れ５０°Ｃに加熱し
たあと、オキシ塩化リン（７８，５ｇｏ、５１モル）を
徐々に滴下する０滴下後場酸の発生がなくなったら冷却
し、水を加えて撹拌洗浄し水層を分液する。トルエン層
は減圧にてトルエンを留去し目的のアニリド３７４ｇ（
収率９９．０％）を得た０反応中発生する塩酸ガス等の
廃ガスは水に吸収し回収する。水洗水及び廃ガス吸収水
中のフッ素イオンは１．１ｓ＋ｏｌ（原料のアニリンの
分解率として０．０２９モル％）であった。Example 2 Aniline (250
g 1.28 mol), propoxyacetic acid (151 g 1,
After adding 28 mol) and toluene 12 and heating to 50°C, gradually add phosphorus oxychloride (78.5 go, 51 mol) dropwise. When no acid is generated after 0 drops, cool, add water and stir and wash. Separate the aqueous layer. The toluene layer was distilled off under reduced pressure to obtain 374 g of the desired anilide (
Waste gas such as hydrochloric acid gas generated during the reaction (yield 99.0%) is absorbed into water and recovered. Fluorine ions in the washing water and waste gas absorption water were 1.1 s+ol (0.029 mol % as decomposition rate of aniline as a raw material).
またこの実験を２５回くり返して撹拌機に使用したガラ
ス羽の減量をみたが、１年間の腐食量に換算して０．０
１８ ｍ ／ Ｙとなった。In addition, this experiment was repeated 25 times to check the weight loss of the glass blades used in the stirrer, which was calculated to be 0.0 in terms of the amount of corrosion per year.
The distance was 18 m/Y.
実施例３
実施例１と同じ装備をした３１フラスコにアニリン（２
５０ｇ １．２８モル）、プロポキシ酢酸（１５０ｇ
１．２８モル）および四塩化炭素１１を加え５０℃に
加熱したあと、三塩化リン（７０ｇ０．５１モル）を徐
りに滴下する０滴下後場酸の発生がなくなったら冷却し
、水を加え撹拌洗浄し水層を分液する。四塩化炭素層は
減圧にて留去し、目的のアニリド３７４ｇ（収率９９％
）を得た０反応中発生する塩酸ガスは水に吸収させた。Example 3 Aniline (2
50g 1.28mol), propoxyacetic acid (150g
Add 1.28 mol) and 11 carbon tetrachloride and heat to 50°C, then gradually add dropwise phosphorus trichloride (70 g 0.51 mol). When no acid is generated after the drop, cool, add water and stir. Wash and separate the aqueous layer. The carbon tetrachloride layer was distilled off under reduced pressure to obtain 374 g of the desired anilide (yield 99%).
) The hydrochloric acid gas generated during the reaction was absorbed into water.
吸収後及び水洗水中のフッ素イオンを分析したところ、
総フッ素イオン量は０．０７ ｍ−５ｏｌ （アニリン
の分解率として０．００１８モル％）〔発明の効果〕
前記実施例からも明らかなように本発明製造法は縮合剤
に三塩化リンスはオキシ塩化リンを用いることにより、
比較的低温で反応が完結するため、トリフルオロメチル
基の加水分解によるフン化水素の発生がおさえられ、工
業的に優れた製造法である。Analysis of fluoride ions in the water after absorption and washing revealed that
The total amount of fluorine ions was 0.07 m-5 ol (0.0018 mol% as the decomposition rate of aniline) [Effects of the invention] As is clear from the above examples, the production method of the present invention uses oxychloride as the condensing agent. By using phosphorus chloride,
Since the reaction is completed at a relatively low temperature, the generation of hydrogen fluoride due to hydrolysis of the trifluoromethyl group is suppressed, making it an excellent production method industrially.
Claims (1)
ロ ロ−α，α，α−トリフルオロオルトトルイジンとプロ
ポキシ酢酸とを三塩化リン又はオキシ塩化リンにより、
縮合させることを特徴とする式▲数式、化学式、表等が
あります▼で表わされる４′− クロロ−２′−トリフルオロメチルプロポキシアセトア
ニリドの製造法。(1) 4-chloro-α,α,α-trifluoro-orthotoluidine represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and propoxyacetic acid are mixed with phosphorus trichloride or phosphorus oxychloride.
A method for producing 4'-chloro-2'-trifluoromethylpropoxyacetanilide, which is characterized by condensation and is represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1076468A JPH02255649A (en) | 1989-03-30 | 1989-03-30 | Production of 4'-chloro-2'-trifluoromethylpropoxy acetanilide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1076468A JPH02255649A (en) | 1989-03-30 | 1989-03-30 | Production of 4'-chloro-2'-trifluoromethylpropoxy acetanilide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02255649A true JPH02255649A (en) | 1990-10-16 |
| JPH0588703B2 JPH0588703B2 (en) | 1993-12-24 |
Family
ID=13606002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1076468A Granted JPH02255649A (en) | 1989-03-30 | 1989-03-30 | Production of 4'-chloro-2'-trifluoromethylpropoxy acetanilide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02255649A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105289B (en) * | 2019-04-11 | 2022-04-26 | 江苏禾本生化有限公司 | Triflumizole technical and preparation method thereof |
-
1989
- 1989-03-30 JP JP1076468A patent/JPH02255649A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0588703B2 (en) | 1993-12-24 |
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