JPH0588703B2 - - Google Patents
Info
- Publication number
- JPH0588703B2 JPH0588703B2 JP1076468A JP7646889A JPH0588703B2 JP H0588703 B2 JPH0588703 B2 JP H0588703B2 JP 1076468 A JP1076468 A JP 1076468A JP 7646889 A JP7646889 A JP 7646889A JP H0588703 B2 JPH0588703 B2 JP H0588703B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- water
- toluene
- aniline
- formula
- 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.)
- Expired - Fee Related
Links
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 8
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 5
- SGUYGLMQEOSQTH-UHFFFAOYSA-N 2-propoxyacetic acid Chemical compound CCCOCC(O)=O SGUYGLMQEOSQTH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 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 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 150000003931 anilides Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- -1 Fluorine ions Chemical class 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229940051881 anilide analgesics and antipyretics Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- 238000004458 analytical method Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000001424 substituent group Chemical group 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)
Description
〔産業上の利用分野〕
本発明は農業中間体として重要な式
[Industrial Application Field] The present invention is applicable to formulas important as agricultural intermediates.
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
ド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。
しかしながら本発明の如く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つたり、トリフル
オロメチル基が加水分解され、フツ化水素が副生
し、反応容器の腐食がおこる等の問題点を有して
いた。
〔課題を解決するための手段〕
本発明者等はアニリドの製造方法を種々検討し
た結果、三塩化リン又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
ツ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。
即ち、本発明は
(1) 式
Common methods for producing substituted anilides include a method in which a carboxylic acid anhydride, acid chloride, etc. are reacted with a substituted anilide, or a method in which a carboxylic acid and a substituted aniline are condensed in the presence of a condensing agent. It is being However, when a trifluoromethyl group is used as a substituent as in the present invention, due to its electron-withdrawing property, the condensation reaction may not be completed, or the trifluoromethyl group may be hydrolyzed and hydrogen fluoride is produced as a by-product. There were problems such as corrosion of the container. [Means for Solving the Problems] As a result of studying various methods for producing anilides, the present inventors found that using phosphorus trichloride or phosphorus oxychloride as a condensing agent allows the reaction to be completed at a relatively low temperature. The present invention was completed by discovering that it is possible to suppress the by-product of hydrogen fluoride due to hydrolysis of methyl groups. That is, the present invention is based on formula (1)
次に実施例を挙げ、本発明を更に詳細に説明す
る。
実施例 １
温度計、還流冷却器、共沸脱水用検水管、滴下
ロートおよびガラス缶攪拌機のついた３フラス
コにアニリン（250ｇ 1.28モル）、プロポキシ酢
酸（151ｇ 1.28モル）およびトルエン１を入
れ、50℃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。滴下後塩酸の発生
がなくなつたら冷却し水を加えて攪拌洗浄し水層
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373ｇ（収率98.8％）を得た。
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ツ素イ
オンは1.3m-npl（原料のアニリンの分解率として
0.034モル％）であつた。またこの実験を30回く
り返して攪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、0.024mm／Ｙと
なつた。0.024mm／Ｙという数値は実用上充分な
値で一般的には0.05mm／Ｙ以下であれば、ほぼ完
全耐食と考えられている。
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
（250ｇ 1.28モル）、プロポキシ酢酸（151ｇ
1.28モル）およびトルエン１を入れ50℃に加熱
したあと、オキシ塩化リン（78.5ｇ 0.51モル）
を徐々に滴下する。滴下後塩酸の発生がなくなつ
たら冷却し、水を加えて攪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。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ツ素イオンは
1.1npl（原料のアニリンの分解率として0.029モル
％）であつた。またこの実験を25回くり返して攪
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0.018mm／Ｙとなつた。
実施例 ３
実施例１と同じ装備をした３フラスコにアニ
リン（250ｇ 1.28モル）、プロポキシ酢酸（150
ｇ 1.28モル）および四塩化炭素１を加え50℃
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。滴下後塩酸の発生がなくなつ
たら冷却し、水を加え攪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。反応中発生する
塩酸ガスは水に吸収させた。吸収後及び水洗水中
のフツ素イオンを分析したところ、総フツ素イオ
ン量は0.07m-npl（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又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ツ
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。
Next, the present invention will be explained in more detail with reference to Examples. Example 1 Aniline (250 g, 1.28 mol), propoxyacetic acid (151 g, 1.28 mol), and toluene 1 were placed in three flasks equipped with a thermometer, reflux condenser, azeotropic dehydration test tube, dropping funnel, and glass can stirrer, and 50 g of toluene was added. After heating to ℃, add phosphorus trichloride (70g
0.51 mol) was gradually added dropwise. After dropping, when no more hydrochloric acid is generated, cool, add water, stir and wash, and separate the aqueous layer. Toluene was distilled off from the toluene layer under reduced pressure to obtain 373 g (yield 98.8%) of the desired anilide.
Waste gases such as hydrochloric acid gas generated during the reaction are absorbed into water and recovered. Fluorine ions in the washing water and waste gas absorption water are 1.3 m -npl (as the decomposition rate of the raw material aniline)
0.034 mol%). This experiment was repeated 30 times to check the weight loss of the glass blades used in the stirrer, and the amount of corrosion in one year was 0.024 mm/Y. The numerical value of 0.024 mm/Y is a sufficient value for practical use, and generally, if it is 0.05 mm/Y or less, it is considered to be almost completely corrosion resistant. Example 2 Aniline (250 g 1.28 mol) and propoxyacetic acid (151 g
After adding 1.28 mol) and 1 toluene and heating to 50℃, add phosphorus oxychloride (78.5 g 0.51 mol).
Gradually drip. After dropping, when no more hydrochloric acid is generated, cool, add water, stir and wash, and separate the aqueous layer. Toluene was distilled off from the toluene layer under reduced pressure to obtain 374 g (yield 99.0%) of the desired anilide. Waste gases such as hydrochloric acid gas generated during the reaction are absorbed into water and recovered. Fluorine ions in washing water and waste gas absorption water
It was 1.1 npl (0.029 mol% as the decomposition rate of the raw material aniline). This experiment was repeated 25 times to check the weight loss of the glass blades used in the stirrer, and the amount of corrosion in one year was 0.018 mm/Y. Example 3 Aniline (250 g 1.28 mol) and propoxyacetic acid (150 g
g 1.28 mol) and carbon tetrachloride 1 and heated to 50°C.
After heating to , phosphorus trichloride (70g 0.51mol)
Gradually drip. After dropping, when no more hydrochloric acid is generated, cool, add water, stir and wash, and separate the aqueous layer. The carbon tetrachloride layer was distilled off under reduced pressure to obtain 374 g (yield 99%) of the desired anilide. Hydrochloric acid gas generated during the reaction was absorbed into water. Analysis of fluorine ions in the water after absorption and washing revealed that the total amount of fluorine ions was 0.07 m -npl (decomposition rate of aniline was 0.0018
(mol%) [Effects of the Invention] As is clear from the above examples, the production method of the present invention uses phosphorus trichloride or phosphorus oxychloride as a condensing agent, so that the reaction is completed at a relatively low temperature. This is an industrially excellent production method because the generation of hydrogen fluoride due to hydrolysis of groups is suppressed.
Claims (1)
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
【式】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。[Claims] 1. A formula characterized by condensing 4-chloro-α, α, α-trifluoroorthotoluidine represented by the formula [Formula] and propoxyacetic acid with phosphorus trichloride or phosphorus oxychloride. A method for producing 4'-chloro-2'-trifluoromethylpropoxyacetanilide represented by the formula:
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 JPH02255649A (en) | 1990-10-16 |
| JPH0588703B2 true 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105289A (en) * | 2019-04-11 | 2019-08-09 | 江苏禾本生化有限公司 | A kind of fluorine bacterium azoles raw medicine and preparation method thereof |
-
1989
- 1989-03-30 JP JP1076468A patent/JPH02255649A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105289A (en) * | 2019-04-11 | 2019-08-09 | 江苏禾本生化有限公司 | A kind of fluorine bacterium azoles raw medicine and preparation method thereof |
| CN110105289B (en) * | 2019-04-11 | 2022-04-26 | 江苏禾本生化有限公司 | Triflumizole technical and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02255649A (en) | 1990-10-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081224 Year of fee payment: 15 |
|
| LAPS | Cancellation because of no payment of annual fees |