JPH0588704B2 - - Google Patents
Info
- Publication number
- JPH0588704B2 JPH0588704B2 JP1076469A JP7646989A JPH0588704B2 JP H0588704 B2 JPH0588704 B2 JP H0588704B2 JP 1076469 A JP1076469 A JP 1076469A JP 7646989 A JP7646989 A JP 7646989A JP H0588704 B2 JPH0588704 B2 JP H0588704B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- formula
- aniline
- reaction
- toluene
- 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
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 2
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 159000000007 calcium salts Chemical class 0.000 claims 1
- 159000000003 magnesium salts Chemical class 0.000 claims 1
- 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
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- 239000011592 zinc chloride Substances 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 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 150000003931 anilides Chemical class 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- -1 fluorine ions Chemical class 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229940051881 anilide analgesics and antipyretics Drugs 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction 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
- 239000002912 waste gas Substances 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 focuses on 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
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。
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、さらに反応系
内にある種の塩類を存在させることにより、副生
するフツ化水素量をさらに減少できることを見い
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 aniline, 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. We have completed the present invention by discovering that it is possible to suppress the by-product of hydrogen fluoride due to hydrolysis of methyl groups, and that the amount of hydrogen fluoride by-produced can be further reduced by the presence of a certain kind of salt in the reaction system. 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（150
ｇ 1.28モル）、粒状無水塩化カルシウム25ｇ、
およびトルエン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。トルエン層
は減圧にて留去し、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
0.09m-npl（アニリンの分解率として0.0023モル％）
であつた。この実験を30回くり返して、攪拌機に
つけたガラス羽の減量を測定したが、減量は、１
年間の腐食量に換算して、0.001mm／Ｙとなつた。
0.001mm／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（150ｇ
1.28モル）、粉末状ケイ酸カルシウム30ｇ、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、不溶分を
濾過後、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してトルエンを留去し目
的のアニリド371ｇ（収率98.2％）を得た。反応
中の廃ガス及び水洗水は実施例２のように回収処
理した。分析の結果生成フツ素イオンの総量は
0.095m-npl（原料のアニリンの分解率として0.0025
モル％）であつた。この実験を20回繰返して攪拌
機につけたガラス羽の減量を測定したが減量は１
年間の腐食量に換算して0.001mm／Ｙとなり充分
な耐食を示した。
実施例 ３
温度計、還流冷却器、共沸脱水用検水管、滴下
ロート、および攪拌機のついた３フラスコにア
ニリン（250ｇ 1.28モル）、プロポキシ酢酸
（150ｇ 1.28モル）、粒状無水塩化カルシウム25
ｇ、およびトルエン１を加え50℃に加熱したあ
と、オキシ塩化リン（78ｇ 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。トルエ
ンは減圧にて留去し、目的のアニリド372ｇ（収
率98.5％）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
0.08m-nplであつた。（原料のアニリンの分解率と
して0.002モル％）
実施例 ４〜９
以下、同様の実験を塩類にかえ行なつた。
結果を次表に示す。
Next, the present invention will be explained in more detail with reference to Examples. Example 1 Aniline (250 g 1.28 mol) and propoxyacetic acid (150 g
g 1.28 mol), granular anhydrous calcium chloride 25 g,
After adding 1 mol of toluene and heating to 50°C, phosphorus trichloride (70 g 0.51 mol) was gradually added dropwise. After dropping, when hydrochloric acid is no longer generated, cool it down.
Add water, stir and wash, and separate the aqueous layer. The toluene layer was distilled off under reduced pressure to obtain 374 g of the desired anilide (yield:
99.0%). 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
0.09m -npl (0.0023 mol% as decomposition rate of aniline)
It was hot. This experiment was repeated 30 times and the weight loss of the glass blade attached to the stirrer was measured.
The amount of corrosion per year was 0.001mm/Y.
The numerical value of 0.001 mm/Y is a practically sufficient value, and it is generally considered that a value of 0.05 mm/Y or less is almost completely corrosion resistant. Example 2 Aniline (250 g 1.28 mol) and propoxyacetic acid (150 g
1.28 mol), 30 g of powdered calcium silicate, and 1 part of toluene were heated to 50°C, and then phosphorus trichloride (70 g, 0.51 mol) was gradually added dropwise. After the dropwise addition, when no more hydrochloric acid is generated, the mixture is cooled, the insoluble matter is filtered, water is added, the mixture is stirred and washed, and the aqueous layer is separated. The toluene layer was reduced in pressure and toluene was distilled off to obtain 371 g (yield 98.2%) of the desired anilide. The waste gas and washing water during the reaction were collected and treated as in Example 2. The total amount of fluorine ions produced as a result of the analysis is
0.095m -npl (0.0025 as decomposition rate of raw material aniline
(mol%). This experiment was repeated 20 times and the weight loss of the glass blade attached to the stirrer was measured, but the weight loss was 1.
The annual corrosion amount was 0.001 mm/Y, indicating sufficient corrosion resistance. Example 3 Aniline (250 g 1.28 mol), propoxyacetic acid (150 g 1.28 mol), and granular anhydrous calcium chloride 25 were placed in three flasks equipped with a thermometer, reflux condenser, azeotropic dehydration test tube, dropping funnel, and stirrer.
After adding 1 g and 1 mol of toluene and heating to 50°C, phosphorus oxychloride (78 g 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 under reduced pressure to obtain 372 g of the desired anilide (yield 98.5%). 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
It was 0.08m -npl . (0.002 mol % as the decomposition rate of aniline as a raw material) Examples 4 to 9 Similar experiments were conducted using salts instead. The results are shown in the table below.
前記実施例からも明らかなように本発明製造方
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、更に塩類を添加する
ことによりフツ化水素の発生をほぼ完全におさえ
られることから、グラスライニング反応槽が使用
可能となる等、工業的に優れた製造方法である。
As is clear from the above examples, the production method of the present invention uses phosphorus trichloride or phosphorus oxychloride as the condensing agent, and the reaction is completed at a relatively low temperature. This is an industrially excellent production method, as it can suppress the generation of hydrogen fluoride and, by adding salts, almost completely suppress the generation of hydrogen fluoride, making it possible to use a glass-lined reaction tank.
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、縮合させる際に、カルシウム塩、マグネシウ
ム塩、アンモニウム塩及び塩化亜鉛から選ばれる
１種又は２種以上の塩類を存在させることを特徴
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
トアニリドの製造方法。[Claims] 1. When condensing 4-chloro-α, α, α-trifluoro-orthotoluidine represented by the formula [formula] and propoxyacetic acid with phosphorus trichloride or phosphorus oxychloride, a calcium salt, A method for producing 4'-chloro-2'-trifluoromethylpropoxyacetanilide represented by the formula [Formula], characterized by the presence of one or more salts selected from magnesium salts, ammonium salts, and zinc chloride. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1076469A JPH02255650A (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 |
|---|---|---|---|
| JP1076469A JPH02255650A (en) | 1989-03-30 | 1989-03-30 | Production of 4'-chloro-2'-trifluoromethylpropoxy acetanilide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02255650A JPH02255650A (en) | 1990-10-16 |
| JPH0588704B2 true JPH0588704B2 (en) | 1993-12-24 |
Family
ID=13606029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1076469A Granted JPH02255650A (en) | 1989-03-30 | 1989-03-30 | Production of 4'-chloro-2'-trifluoromethylpropoxy acetanilide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02255650A (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 JP1076469A patent/JPH02255650A/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 |
|---|---|
| JPH02255650A (en) | 1990-10-16 |
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