JPS625137B2 - - Google Patents
Info
- Publication number
- JPS625137B2 JPS625137B2 JP4786978A JP4786978A JPS625137B2 JP S625137 B2 JPS625137 B2 JP S625137B2 JP 4786978 A JP4786978 A JP 4786978A JP 4786978 A JP4786978 A JP 4786978A JP S625137 B2 JPS625137 B2 JP S625137B2
- Authority
- JP
- Japan
- Prior art keywords
- bromide
- magnesium
- mol
- reaction
- chlorobenzotrifluoride
- 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
Links
- DGRVQOKCSKDWIH-UHFFFAOYSA-N 1-chloro-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1Cl DGRVQOKCSKDWIH-UHFFFAOYSA-N 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- FBRJYBGLCHWYOE-UHFFFAOYSA-N 2-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(F)(F)F FBRJYBGLCHWYOE-UHFFFAOYSA-N 0.000 claims description 7
- 150000001347 alkyl bromides Chemical class 0.000 claims description 6
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical group CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RWXUNIMBRXGNEP-UHFFFAOYSA-N 1-bromo-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1Br RWXUNIMBRXGNEP-UHFFFAOYSA-N 0.000 description 2
- UPSXAPQYNGXVBF-UHFFFAOYSA-N 2-bromobutane Chemical compound CCC(C)Br UPSXAPQYNGXVBF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
本発明は農業用薬剤などの中間原料として有用
なＯ−トリフルオロメチル安息香酸の製造法に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing O-trifluoromethylbenzoic acid, which is useful as an intermediate raw material for agricultural drugs and the like.
Ｏ−トリフルオロメチル安息香酸の製法として
はＯ−ブロムベンゾトリフルオライドをエーテル
中マグネシウムと反応させた後、炭酸化する方法
（J.A.C.S.、69、2349、1947）およびベンゾトリ
フルオライドをリチウムと反応された後、炭酸化
する方法（J.A.C.S.、68、1658、1946）が知らせ
ているが、しかし、工業的に大量製造するに当つ
ては、Ｏ−ブロムベンゾトリフルオライドの使用
は高価な資材であり、適当な方法ではない。 Methods for producing O-trifluoromethylbenzoic acid include a method in which O-bromobenzotrifluoride is reacted with magnesium in ether and then carbonated (JACS, 69, 2349, 1947), and a method in which benzotrifluoride is reacted with lithium. However, in industrial large-scale production, the use of O-bromobenzotrifluoride is an expensive material and is not appropriate. Not in a good way.
また有機金属リチウムで金属化し、炭酸化する
方法も、資材の高価な点の他にも、オルトおよび
メター異性体の混入もあつて有利な方法とは言え
ない。 Furthermore, the method of metallization with organometallic lithium and carbonation is not an advantageous method because of the expensive materials and the contamination of ortho and meta isomers.
本発明者らは出発原料として比較的安価なＯ−
クロルベンゾトリフルオライドを用いる方法につ
いて種々研究、検討を重ねた結果、収率良好でか
つ、経済的な方法を見いだし、本発明を完成し
た。 The present inventors used relatively inexpensive O- as a starting material.
As a result of various studies and studies on methods using chlorobenzotrifluoride, an economical method with good yield was discovered and the present invention was completed.
すなわちＯ−クロルベンゾトリフルオライドを
低級アルキルブロマイドの存在下にマグネシウム
と反応させた後、炭酸化する方法である。 That is, this is a method in which O-chlorobenzotrifluoride is reacted with magnesium in the presence of a lower alkyl bromide, and then carbonated.
この方法によつてＯ−クロルベンゾトリフルオ
ライドから好収率でＯ−トリフルオロメチル安息
香酸を得ることができる。 By this method, O-trifluoromethylbenzoic acid can be obtained from O-chlorobenzotrifluoride in good yield.
ここに本反応に用いられる低級アルキルブロマ
イドは炭素数２〜４のものであり、たとえばエチ
ルブロマイド、イソプロピルブロマイド、セカン
ダリーブチルブロマイド、エチレンブロマイドな
ど常温常圧で取り扱い易いものが挙げられるが、
特にイソプロピルブロマイドが好ましい。 The lower alkyl bromides used in this reaction have 2 to 4 carbon atoms, and include those that are easy to handle at room temperature and pressure, such as ethyl bromide, isopropyl bromide, secondary butyl bromide, and ethylene bromide.
Isopropyl bromide is particularly preferred.
本反応に用いられる溶媒はテトラハイドロフラ
ンが最もよく、テトラハイドロピラン、２−メチ
ルテトラハイドロフランも用いることができる。 The best solvent used in this reaction is tetrahydrofuran, and tetrahydropyran and 2-methyltetrahydrofuran can also be used.
反応温度は20℃から120℃の範囲から適宜選択
することができるが、特に50℃から60℃の温度範
囲内で反応を行うことが好ましい。 Although the reaction temperature can be appropriately selected from the range of 20°C to 120°C, it is particularly preferable to carry out the reaction within the temperature range of 50°C to 60°C.
低級アルキルブロマイドはＯ−クロル−ベンゾ
トリフルオライドに対し、通常のグリニヤール反
応で用いられる触媒量以上であればよいが特にの
ぞましくは当モルおよび当モルの近傍の量であ
る。 The amount of lower alkyl bromide relative to O-chloro-benzotrifluoride may be at least the catalytic amount used in the usual Grignard reaction, but it is particularly preferable to use an equimolar amount or an amount close to the equimolar amount.
また、マグネシウムはＯ−クロル−ベンゾトリ
フルオライド及び低級アルキルブロマイドの合算
モル以上の量であるのがのぞましい。 Further, the amount of magnesium is preferably greater than the total mole of O-chloro-benzotrifluoride and lower alkyl bromide.
炭酸化試剤としては炭酸ガス、ドライアイスの
いづれでも良い。反応終了後、常法に従つて反応
物より目的物を分離すればよい。 As the carbonation reagent, either carbon dioxide gas or dry ice may be used. After the reaction is completed, the target product may be separated from the reactant according to a conventional method.
本発明の目的物であるＯ−トリフルオロメチル
安息香酸はこれを原料の１つとして誘導される
種々の化合物の出発原料として有用であり、たと
えば、Ｏ−トリフルオロメチル安息香酸をｍ−ア
ルコキシ−アニリンと反応させて得られるm′−
アルコキシ−Ｏ−トリフルオロメチルアニリド類
は農園芸用殺菌剤殊に稲の紋枯病防除剤として有
用である。 O-trifluoromethylbenzoic acid, which is the object of the present invention, is useful as a starting material for various compounds derived from it as one of the raw materials. m′− obtained by reacting with aniline
Alkoxy-O-trifluoromethylanilides are useful as agricultural and horticultural fungicides, particularly as agents for controlling rice sheath blight.
以下若干の実施例を示すが、本願発明はこれら
に限定されるものではない。 Some examples will be shown below, but the present invention is not limited thereto.
実施例 １
無水Ｏ−クロルベンゾトリフルオライド181ｇ
（１モル）と無水イソプロピルブロマイド123ｇ
（１モル）とをテトラハイドロフラン750mlにとか
す。この溶液50mlを、よく乾燥させた２の丸底
フラスコに取つた粉末マグネシウム49ｇ（２モ
ル）に滴下、反応を開始させる。反応開始後、撹
拌下に残りのテトラハイドロフラン溶液を反応温
度が55〜60℃に保つように滴下する。滴下後２時
間撹拌し、室温に冷却する。この反応液を粉砕し
たドライアイス１Kgと１のエーテル混合物中に
ゆつくりと撹拌注加する。一夜放置後これに6N
−HCI500mlを冷却下に加えエーテル層を分取す
る。エーテル層に25％NaOH400mlを加え振りま
ぜ水層を分取する。この水層を再び6N−HCl500
mlを加え酸性とし、エーテルで抽出する。エーテ
ル層を水洗、乾燥してエーテルを留去し、Ｏ−ト
リフルオロメチル安息香酸170ｇを得る。Example 1 181 g of anhydrous O-chlorobenzotrifluoride
(1 mol) and 123 g of anhydrous isopropyl bromide
(1 mol) and dissolved in 750 ml of tetrahydrofuran. 50 ml of this solution was added dropwise to 49 g (2 mol) of powdered magnesium in a well-dried round-bottomed flask to initiate the reaction. After the reaction starts, the remaining tetrahydrofuran solution is added dropwise while stirring so as to maintain the reaction temperature at 55-60°C. After the addition, the mixture was stirred for 2 hours and cooled to room temperature. This reaction solution was slowly stirred and poured into a mixture of 1 kg of crushed dry ice and 1 kg of ether. 6N after leaving it overnight
- Add 500 ml of HCI under cooling and separate the ether layer. Add 400ml of 25% NaOH to the ether layer, shake and separate the aqueous layer. Add 6N−HCl500 to this aqueous layer again.
ml to acidify and extract with ether. The ether layer was washed with water, dried, and the ether was distilled off to obtain 170 g of O-trifluoromethylbenzoic acid.
m.p.110℃ 収率90％
実施例 ２
実施例１と同様にして、無水クロルベンゾトリ
フルオライド181ｇ（１モル）、エチルブロマイド
109ｇ（１モル）およびマグネシウム49ｇ（２モ
ル）からＯ−トリフルオロメチル安息香酸152ｇ
を得る。mp110℃ Yield 90% Example 2 In the same manner as in Example 1, 181 g (1 mol) of anhydrous chlorobenzotrifluoride and ethyl bromide were added.
152 g O-trifluoromethylbenzoic acid from 109 g (1 mol) and 49 g (2 mol) magnesium
get.
m.p.110℃ 収率80％
実施例 ３
実施例１と同様にして、無水Ｏ−クロルベンゾ
トリフルオライド181ｇ（１モル）、セカンダリー
ブチルブロマイド137ｇ（１モル）およびマグネ
シウム49ｇ（２モル）からＯ−トリフルオロメチ
ル安息香酸155ｇを得る。mp 110°C Yield 80% Example 3 In the same manner as in Example 1, O-trifluoride was prepared from 181 g (1 mol) of anhydrous O-chlorobenzotrifluoride, 137 g (1 mol) of secondary butyl bromide, and 49 g (2 mol) of magnesium. 155 g of methylbenzoic acid are obtained.
m.p.110℃ 収率82％m.p.110℃ yield 82%
Claims (1)
アルキルブロマイドの存在下にマグネシウムと反
応させた後、炭酸化することを特徴とするＯ−ト
リフルオロメチル安息香酸の製造方法。 ２ 低級アルキルブロマイドがイソプロピルブロ
マイドである特許請求の範囲第１項記載の製造方
法。 ３ Ｏ−クロル−ベンゾトリフルオライドを当モ
ルのイソプロピルブロマイドの存在下に、２倍モ
ル以上のマグネシウムと反応されることからなる
特許請求の範囲第１項又は第２項記載の製造方
法。 ４ 溶媒がテトラハイドロフランである特許請求
の範囲第１項又は第３項記載の製造方法。[Scope of Claims] 1. A method for producing O-trifluoromethylbenzoic acid, which comprises reacting O-chlorobenzotrifluoride with magnesium in the presence of a lower alkyl bromide, followed by carbonation. 2. The manufacturing method according to claim 1, wherein the lower alkyl bromide is isopropyl bromide. 3. The manufacturing method according to claim 1 or 2, wherein 3 O-chloro-benzotrifluoride is reacted with at least twice the mole of magnesium in the presence of the same mole of isopropyl bromide. 4. The manufacturing method according to claim 1 or 3, wherein the solvent is tetrahydrofuran.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4786978A JPS54141748A (en) | 1978-04-24 | 1978-04-24 | Preparation of o-trifluoromethylbenzoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4786978A JPS54141748A (en) | 1978-04-24 | 1978-04-24 | Preparation of o-trifluoromethylbenzoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54141748A JPS54141748A (en) | 1979-11-05 |
| JPS625137B2 true JPS625137B2 (en) | 1987-02-03 |
Family
ID=12787373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4786978A Granted JPS54141748A (en) | 1978-04-24 | 1978-04-24 | Preparation of o-trifluoromethylbenzoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54141748A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1243410B (en) * | 1990-12-17 | 1994-06-10 | Donegani Guido Ist | PROCEDURE FOR THE FUNCTIONALIZATION OF TRIFLUOROMETILBENZENI |
| JP4641839B2 (en) * | 2005-03-23 | 2011-03-02 | セントラル硝子株式会社 | Process for producing 4-methyl-3-trifluoromethylbenzoic acid |
-
1978
- 1978-04-24 JP JP4786978A patent/JPS54141748A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54141748A (en) | 1979-11-05 |
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