JPH04338369A - Production of substituted phenoxycarboxylic acid anilide - Google Patents
Production of substituted phenoxycarboxylic acid anilideInfo
- Publication number
- JPH04338369A JPH04338369A JP10940291A JP10940291A JPH04338369A JP H04338369 A JPH04338369 A JP H04338369A JP 10940291 A JP10940291 A JP 10940291A JP 10940291 A JP10940291 A JP 10940291A JP H04338369 A JPH04338369 A JP H04338369A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- acid anilide
- substituted
- solvent
- general 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.)
- Pending
Links
- XVNKRRXASPPECQ-UHFFFAOYSA-N phenyl n-phenylcarbamate Chemical class C=1C=CC=CC=1OC(=O)NC1=CC=CC=C1 XVNKRRXASPPECQ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- -1 phenol compound Chemical class 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 19
- 150000002989 phenols Chemical class 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000003756 stirring Methods 0.000 abstract description 4
- 239000000706 filtrate Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 150000003931 anilides Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- BWWXKHHVIAJJFM-UHFFFAOYSA-N 2-chloro-n-phenylpropanamide Chemical compound CC(Cl)C(=O)NC1=CC=CC=C1 BWWXKHHVIAJJFM-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003613 toluenes Chemical class 0.000 description 5
- BDQWWOHKFDSADC-UHFFFAOYSA-N 2-(2,4-dichloro-3-methylphenoxy)-n-phenylpropanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C)OC1=CC=C(Cl)C(C)=C1Cl BDQWWOHKFDSADC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GIXSFSVVKULPEK-UHFFFAOYSA-N 2,4-dichloro-3-methylphenol Chemical compound CC1=C(Cl)C=CC(O)=C1Cl GIXSFSVVKULPEK-UHFFFAOYSA-N 0.000 description 2
- AQJFATAFTQCRGC-UHFFFAOYSA-N 2-Chloro-4-methylphenol Chemical compound CC1=CC=C(O)C(Cl)=C1 AQJFATAFTQCRGC-UHFFFAOYSA-N 0.000 description 2
- JEQDSBVHLKBEIZ-UHFFFAOYSA-N 2-chloropropanoyl chloride Chemical compound CC(Cl)C(Cl)=O JEQDSBVHLKBEIZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229940051881 anilide analgesics and antipyretics Drugs 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- YSBUANSGDLZTKV-UHFFFAOYSA-N n-phenylcarbamoyl chloride Chemical compound ClC(=O)NC1=CC=CC=C1 YSBUANSGDLZTKV-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LHJGJYXLEPZJPM-UHFFFAOYSA-N 2,4,5-trichlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C=C1Cl LHJGJYXLEPZJPM-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- PPUKKDDQKNVMQJ-UHFFFAOYSA-N 2-(2,4-dichlorophenoxy)-n-phenylacetamide Chemical compound ClC1=CC(Cl)=CC=C1OCC(=O)NC1=CC=CC=C1 PPUKKDDQKNVMQJ-UHFFFAOYSA-N 0.000 description 1
- QPWNBJYOBTUXBH-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)-n-phenylpropanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C)OC1=CC=C(Cl)C=C1C QPWNBJYOBTUXBH-UHFFFAOYSA-N 0.000 description 1
- 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
- SYZRZLUNWVNNNV-UHFFFAOYSA-N 2-bromoacetyl chloride Chemical compound ClC(=O)CBr SYZRZLUNWVNNNV-UHFFFAOYSA-N 0.000 description 1
- PMUTYIACIXXOGC-UHFFFAOYSA-N 2-bromopentanoyl chloride Chemical compound CCCC(Br)C(Cl)=O PMUTYIACIXXOGC-UHFFFAOYSA-N 0.000 description 1
- ILLHORFDXDLILE-UHFFFAOYSA-N 2-bromopropanoyl bromide Chemical compound CC(Br)C(Br)=O ILLHORFDXDLILE-UHFFFAOYSA-N 0.000 description 1
- OZGMODDEIHYPRY-UHFFFAOYSA-N 2-bromopropanoyl chloride Chemical compound CC(Br)C(Cl)=O OZGMODDEIHYPRY-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- VDLGLFVMQUNFST-UHFFFAOYSA-N 2-phenoxy-n-phenylacetamide Chemical compound C=1C=CC=CC=1NC(=O)COC1=CC=CC=C1 VDLGLFVMQUNFST-UHFFFAOYSA-N 0.000 description 1
- CDIIZULDSLKBKV-UHFFFAOYSA-N 4-chlorobutanoyl chloride Chemical compound ClCCCC(Cl)=O CDIIZULDSLKBKV-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 244000038559 crop plants Species 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N hexane carboxylic acid Natural products CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002672 m-cresols Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000002883 o-cresols Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002931 p-cresols Chemical class 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、有用植物保護剤、特に
除草剤として有用な化合物群置換フェノキシカルボン酸
アニリドの工業的製造法の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in an industrial process for producing compound-substituted phenoxycarboxylic acid anilides useful as useful plant protection agents, particularly herbicides.
【０００２】0002
【従来の技術】置換フェノキシカルボン酸アニリド、特
に有用性の高いα−（置換フェノキシ）カルボン酸アニ
リドの製造方法としては、従来より置換フェノ−ルとα
−ハロカルボン酸誘導体とからα−（置換フェノキシ）
カルボン酸誘導体を合成し、これを塩化チオニル等の試
薬を用いα−（置換フェノキシ）カルボン酸クロリドと
した後、アニリンと反応せしめる方法が知られている。[Prior Art] As a method for producing substituted phenoxycarboxylic acid anilides, particularly useful α-(substituted phenoxy)carboxylic acid anilides, there has conventionally been a method for producing substituted phenoxycarboxylic acid anilides using substituted phenols and α-(substituted phenoxy)carboxylic acid anilides.
-halocarboxylic acid derivative and α-(substituted phenoxy)
A method is known in which a carboxylic acid derivative is synthesized, converted into α-(substituted phenoxy)carboxylic acid chloride using a reagent such as thionyl chloride, and then reacted with aniline.
【０００３】これに対して、特開昭６３−１７０３４６
号公報には、クロロカルボン酸クロリドとアニリンより
クロロカルボン酸アニリドを合成し、これに置換フェノ
−ルを無機塩基の存在下有機溶媒中で反応せしめる方法
が改良法として提案されている。この方法は、従来の方
法に比べ工程数が減少された上に、酸クロリド合成工程
で塩化水素廃ガスの処理設備等の特殊な設備を必要とし
ない利点があり、更にフェノ−ル類を用いるのが最終工
程である為、特に高価な置換フェノ−ル類を用いる場合
原材料費として有利となる優れた方法である。[0003] On the other hand, Japanese Patent Application Laid-Open No. 170346/1983
The publication proposes an improved method in which a chlorocarboxylic acid anilide is synthesized from a chlorocarboxylic acid chloride and aniline, and a substituted phenol is reacted with the synthesized chlorocarboxylic acid anilide in an organic solvent in the presence of an inorganic base. This method has the advantage that the number of steps is reduced compared to the conventional method, does not require special equipment such as hydrogen chloride waste gas treatment equipment in the acid chloride synthesis process, and also uses phenols. Since this is the final step, it is an excellent method that is advantageous in terms of raw material costs, especially when expensive substituted phenols are used.
【０００４】しかしながら、この方法での欠点としては
、事前にハロカルボン酸アニリドを合成しそれを単離し
ておく必要があることである。このハロカルボン酸アニ
リド製造の反応は、一般的な収率の良い反応であるが、
その単離工程に於ける中間体自身および溶媒損失や工程
操作上の手間による生産性の低下という問題点がある。However, a drawback of this method is that it is necessary to synthesize and isolate the halocarboxylic acid anilide in advance. This reaction for producing halocarboxylic acid anilide is a general reaction with good yield, but
There is a problem in that productivity decreases due to loss of the intermediate itself and solvent during the isolation process and due to the labor involved in process operations.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、工程操作が
簡略化され、原料費等のコストが低減された工業的に極
めて有利な置換フェノキシカルボン酸アニリドを効率的
に製造する方法を提供することを目的としている。OBJECTS OF THE INVENTION The present invention provides a method for efficiently producing substituted phenoxycarboxylic acid anilides, which is industrially extremely advantageous and which simplifies process operations and reduces costs such as raw material costs. The purpose is to
【０００６】[0006]
【課題を解決するための手段】本発明によれば、下記一
般式（１）：[Means for Solving the Problems] According to the present invention, the following general formula (1):
【０００７】[0007]
【化３】[C3]
【０００８】（但し、式中Ｘはハロゲン族原子または低
級アルキル基を、ｎは０または１〜５の整数を、Ａは直
鎖または分枝の低級アルキレン基を表す。）で表わされ
る置換フェノキシカルボン酸アニリドを製造する際に、
下記一般式（２）：
Ｙ−Ａ−Ｃ（＝Ｏ）−Ｚ 一
般式（２）（但し、式中Ａは直鎖または分枝の低級アル
キレン基を、ＹおよびＺは各々ハロゲン族原子を表す。
）で表わされるハロカルボン酸ハライドとアニリンとを
、芳香族炭化水素を溶媒とし塩基の存在下で反応せしめ
た後、得られた反応生成物を単離することなく、塩基の
存在下同一溶媒中で、下記一般式（３）：A substituted phenoxy represented by When producing carboxylic acid anilide,
General formula (2) below: Y-A-C(=O)-Z General formula (2) (wherein A represents a straight-chain or branched lower alkylene group, and Y and Z each represent a halogen group atom) ) and aniline are reacted in an aromatic hydrocarbon as a solvent in the presence of a base, and then the reaction product is reacted with the same solvent in the presence of a base without isolating the resulting reaction product. Among them, the following general formula (3):
【０００９】[0009]
【化４】[C4]
【００１０】（但し、式中Ｘはハロゲン族原子または低
級アルキル基を、ｎは０または１〜５の整数を表す。）
で表わされる置換フェノ−ルと反応せしめることを特徴
とする置換フェノキシカルボン酸アニリドの製造法が提
供される。(However, in the formula, X represents a halogen group atom or a lower alkyl group, and n represents 0 or an integer from 1 to 5.)
Provided is a method for producing a substituted phenoxycarboxylic acid anilide, which comprises reacting it with a substituted phenol represented by:
【００１１】ここで、一般式（１）、（２）及び（３）
において、Ｘで表わされるハロゲン族原子とは、弗素、
塩素、臭素、沃素のハロゲン族原子の何れかであり、低
級アルキル基とは、炭素数１〜４までの飽和炭化水素基
であり、例えばメチル基、エチル基、イソプロピル基、
第２級ブチル基、第３級ブチル基等を例示できる。また
、Ｘｎとして、ｎが２以上の場合、これらのハロゲン族
原子と低級アルキル基が混在していてもよい。Here, general formulas (1), (2) and (3)
In, the halogen group atom represented by X is fluorine,
A halogen group atom such as chlorine, bromine, or iodine, and a lower alkyl group is a saturated hydrocarbon group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group,
Examples include secondary butyl group and tertiary butyl group. Furthermore, when n is 2 or more, these halogen group atoms and lower alkyl groups may be present together.
【００１２】また、Ａで表わされる直鎖または分枝の低
級アルキレン基とは、炭素数１〜６の２価の飽和炭化水
素基であり、例えばメチレン基、エチレン基、エチリデ
ン基、１，２−プロピレン基、１，１−プロピリデン基
、２，２−プロピリデン基、１，１−ｎ−ブチリデン基
、１，３−ブチレン基、１，１−ｎ−ヘキシリデン基等
を例として挙げることが出来る。さらに、Ｙ及びＺで表
わされるハロゲン族原子とは、弗素、塩素、臭素、沃素
であり、それらの中で、特に塩素、臭素が好ましい。The linear or branched lower alkylene group represented by A is a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, such as methylene group, ethylene group, ethylidene group, 1,2 Examples include -propylene group, 1,1-propylidene group, 2,2-propylidene group, 1,1-n-butylidene group, 1,3-butylene group, 1,1-n-hexylidene group, etc. . Further, the halogen group atoms represented by Y and Z include fluorine, chlorine, bromine, and iodine, and among them, chlorine and bromine are particularly preferred.
【００１３】これらの置換基により構成される一般式（
１）の置換フェノキシカルボン酸アニリドとしては、具
体的には、例えば、フェノキシ酢酸アニリド、α−（ｐ
−クロロフェノキシ）プロピオン酸アニリド、２，４−
ジクロロフェノキシ酢酸アニリド、α−（２−メチル−
４−クロロフェノキシ）プロピオン酸アニリド、α−（
２，４−ジクロロ−３−メチルフェノキシ）プロピオン
酸アニリド、β−（２，４−ジクロロフェノキシ）プロ
ピオン酸アニリド、α−（２−メチル−４−クロロフェ
ノキシ）吉草酸アニリド、α−（２，４−ジクロロ−３
メチルフェノキシ）ヘプタン酸アニリド等を挙げること
が出来る。The general formula (
Specifically, the substituted phenoxycarboxylic acid anilide of 1) is, for example, phenoxyacetic acid anilide, α-(p
-chlorophenoxy)propionic acid anilide, 2,4-
Dichlorophenoxyacetic acid anilide, α-(2-methyl-
4-chlorophenoxy)propionic acid anilide, α-(
2,4-dichloro-3-methylphenoxy)propionic acid anilide, β-(2,4-dichlorophenoxy)propionic acid anilide, α-(2-methyl-4-chlorophenoxy)valeric acid anilide, α-(2, 4-dichloro-3
Examples include methylphenoxy)heptanoic acid anilide.
【００１４】一般式（２）のハロカルボン酸ハライドと
しては、クロロ酢酸クロリド、ブロモ酢酸クロリド、α
−クロロプロピオン酸クロリド、α−ブロモプロピオン
酸クロリド、α−ブロモプロピオン酸ブロミド、γ−ク
ロロ酪酸クロリド、α−ブロモ吉草酸クロリド等を挙げ
ることが出来る。Examples of the halocarboxylic acid halide of general formula (2) include chloroacetic acid chloride, bromoacetic acid chloride, α
Examples include -chloropropionic acid chloride, α-bromopropionic acid chloride, α-bromopropionic acid bromide, γ-chlorobutyric acid chloride, α-bromovaleric acid chloride, and the like.
【００１５】一般式（３）の置換フェノ−ル類としては
、無置換のフェノ−ル、ｏ−クロロフェノ−ル、ｐ−ク
ロロフェノ−ル、ｏ−，ｍ−，ｐ−の各クレゾ−ル、２
，４−ジクロロフェノ−ル、２，４，５−トリクロロフ
ェノ−ル、２−クロロ−４−メチルフェノ−ル、２，４
−ジクロロ−３−メチルフェノ−ル等を挙げることが出
来る。The substituted phenols of general formula (3) include unsubstituted phenol, o-chlorophenol, p-chlorophenol, o-, m-, and p-cresols, 2
, 4-dichlorophenol, 2,4,5-trichlorophenol, 2-chloro-4-methylphenol, 2,4
-dichloro-3-methylphenol and the like can be mentioned.
【００１６】本発明の第１工程、即ち一般式（２）のハ
ロカルボン酸ハライドとアニリンとの反応は、有機また
は無機の塩基存在下，不活性な溶媒を用い、適切な方法
と条件を選択することにより定量的に進行するが、本発
明の目的から第２工程の溶媒と共通化させ、途中の余分
な操作を省略することを種々検討し、以下の手法が最適
であることを見いだした。The first step of the present invention, that is, the reaction of the halocarboxylic acid halide of general formula (2) with aniline, is carried out by selecting an appropriate method and conditions using an inert solvent in the presence of an organic or inorganic base. However, for the purpose of the present invention, we conducted various studies on using the same solvent as the second step and omitting unnecessary operations during the process, and found that the following method was optimal.
【００１７】第１工程、第２工程に共通の溶媒としては
芳香族炭化水素類、特にトルエン、キシレン等が好まし
い。その理由は、第１、第２両工程を通じて不活性で余
分な副反応もなく、第２工程終了後も特開昭６３−１７
０３４６号公報に記載のように、熱反応液に水を加えな
がら晶析する事により簡便に目的とする置換フェノキシ
カルボン酸アニリドを得ることが出来るからである。[0017] As the solvent common to the first step and the second step, aromatic hydrocarbons, particularly toluene, xylene, etc. are preferable. The reason for this is that it is inert during both the first and second steps, there are no unnecessary side reactions, and even after the second step is completed,
This is because the desired substituted phenoxycarboxylic acid anilide can be easily obtained by crystallizing while adding water to the hot reaction solution, as described in Japanese Patent No. 0346.
【００１８】実際の手法としては、第１工程では上記芳
香族炭化水素を溶媒とし、脱酸剤として塩基を用い反応
を行なう。塩基としては、通常用いられる無機塩基、例
えば水酸化ナトリウム、水酸化カリウム、炭酸カリウム
、炭酸ナトリウムおよびそれらの水溶液等を挙げること
が出来る。また、反応に供試する一般式（２）のハロカ
ルボン酸ハライドはアニリン１モルに対し０．５から２
モル、実用上好ましくは１．０から１．２モルが適切で
ある。反応温度としては、５０℃以下、実用上好ましく
は−１０〜３０℃程度である。As an actual method, in the first step, the reaction is carried out using the above-mentioned aromatic hydrocarbon as a solvent and a base as a deoxidizing agent. Examples of the base include commonly used inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, and aqueous solutions thereof. Furthermore, the amount of halocarboxylic acid halide of general formula (2) to be used in the reaction is 0.5 to 2% per mole of aniline.
A mole, preferably 1.0 to 1.2 mole is suitable in practice. The reaction temperature is 50°C or less, preferably about -10 to 30°C in practical terms.
【００１９】反応終了後、水溶液塩基を用いた場合は分
液および水洗により、無水の塩基を用いた場合は濾過ま
たは水を加えて溶解し分液する方法の一方または両方を
併用する事により粗製のハロカルボン酸アニリドの溶液
を得ることが出来る。なお、溶媒の量は最終製品の合成
反応および晶析に適切な量で実施する事が好ましいが、
上記分液または濾過時には溶解していることが必要であ
り、場合によっては室温から１１０℃の範囲で加温し操
作することも可能である。After completion of the reaction, when an aqueous base is used, it is separated and washed with water, and when an anhydrous base is used, it is filtrated or dissolved by adding water and separated, or both of these methods are used in combination. A solution of halocarboxylic acid anilide can be obtained. In addition, it is preferable to use an appropriate amount of solvent for the synthesis reaction and crystallization of the final product.
It is necessary to dissolve the liquid at the time of the liquid separation or filtration, and in some cases, it is possible to perform the operation by heating in a range from room temperature to 110°C.
【００２０】第２工程では、上記のようにして調製され
た粗製のハロカルボン酸アニリドの溶液を分析し、得ら
れたハロカルボン酸アニリド１モルに対し０．７から１
．３モル、好ましくは０．９から１．０５モルの一般式
（３）で表わされる置換フェノ−ル類を用いる。反応に
用いる脱酸剤としての塩基は、前記引用特許（特開昭６
３−１７０３４６号）に例示記載されているものが好ま
しく、特に炭酸カリウムを原料の置換フェノ−ル１モル
に対し１〜２モル程度使用するのが最も好ましい。In the second step, the solution of the crude halocarboxylic acid anilide prepared as described above is analyzed, and 0.7 to 1
．． 3 moles, preferably 0.9 to 1.05 moles of substituted phenols represented by general formula (3) are used. The base as a deoxidizing agent used in the reaction is described in the cited patent (Japanese Patent Laid-open No. 6
3-170346) are preferred, and in particular, it is most preferred to use about 1 to 2 moles of potassium carbonate per mole of substituted phenol as a raw material.
【００２１】反応温度としては５０℃〜１５０℃程度が
好ましく、トルエン、キシレンを用いる場合はその還流
温度を採用する事が出来る。反応時間としては特に限定
はないが通常３乃至４８時間で終了することが出来、好
ましい条件では６乃至２４時間程度で終了させることが
出来る。反応終了後、水を加え晶析の為冷却するに当た
っては４０℃以下、好ましくは３０℃以下にする。The reaction temperature is preferably about 50°C to 150°C, and when toluene or xylene is used, its reflux temperature can be used. There is no particular limitation on the reaction time, but it can usually be completed in 3 to 48 hours, and under preferable conditions, it can be completed in about 6 to 24 hours. After the reaction is completed, water is added to cool the mixture for crystallization at a temperature of 40°C or lower, preferably 30°C or lower.
【００２２】本反応は第１工程も第２工程も殆ど副反応
の無い定量的な反応であるので、反応による原料の損失
は極めて少なく、第２工程の後の晶析精製に於ける製品
置換フェノキシカルボン酸アニリドの溶解分が最大の損
失である。従って、一度使用した溶媒をそのまま次回の
第１工程に再使用する手法を適用することで、晶析に於
ける溶解分は溶媒と共に第１及び第２の反応系中を経由
した後、再度晶析工程で回収する方法を適用することに
より回収効率が向上することを確認した。別の表現をす
れば、２回目以降では、既に晶析条件に於ける目的生成
物の飽和溶解量を含有した溶媒を用いて反応および晶析
を行なっていることになるとも言え、反応収量分の殆ど
全部をロス無く製品として回収できることになる。[0022] Since this reaction is a quantitative reaction with almost no side reactions in both the first and second steps, the loss of raw materials due to the reaction is extremely small, and product replacement during crystallization and purification after the second step The greatest loss is in the dissolved phenoxycarboxylic acid anilide. Therefore, by applying a method in which the solvent used once is reused in the next first step, the dissolved matter during crystallization passes through the first and second reaction systems together with the solvent, and then is crystallized again. It was confirmed that the recovery efficiency was improved by applying a method of recovering in the analysis process. In other words, from the second time onwards, it can be said that the reaction and crystallization are already carried out using a solvent that contains the saturated amount of dissolved target product under the crystallization conditions, and the reaction yield is Almost all of this can be recovered as a product without loss.
【００２３】この様にして再使用する溶媒の回数の限界
は、製品の一般式（１）の置換フェノキシカルボン酸ア
ニリドの要求純度によるが、使用する一般式（２）のハ
ロカルボン酸ハライドと一般式（３）の置換フェノ−ル
の純度によっても決まる。即ち高純度の原料を用いれば
再使用する溶媒中には殆ど不純物が混入しないため相当
回数再使用できる。しかしながら工業的に入手し得る原
料を用いた場合その不純物の種類、組成により一概には
言えないが、工業的に有意な回数として２回から１０回
程度は可能である。The limit on the number of times the solvent can be reused in this manner depends on the required purity of the product substituted phenoxycarboxylic acid anilide of general formula (1), but it depends on the required purity of the product substituted phenoxycarboxylic acid anilide of general formula (2) and the halocarboxylic acid halide of general formula (2) used. It also depends on the purity of the substituted phenol in (3). That is, if high-purity raw materials are used, there will be almost no impurities in the reused solvent, so it can be reused a considerable number of times. However, if industrially available raw materials are used, it is possible to carry out the process 2 to 10 times as an industrially significant number of times, although this cannot be said unconditionally depending on the type and composition of impurities.
【００２４】[0024]
【実施例】［実施例１］内容積１．５リットルガラス製
反応器に１３７ｇの１０％の水酸化ナトリウム水溶液と
３０．４ｇのアニリンおよび３５４ｍｌのトルエンを入
れ、０℃に冷却し滴下ロ−トより４１．１ｇのα−クロ
ロプロピオン酸クロリドを滴下した。滴下中反応系内の
温度は０〜１０℃に保ち、滴下には約１時間をかけた。
なお、反応途中より、有機層に生成したα−クロロプロ
ピオン酸アニリドが結晶として析出し固液混合状態とな
った。滴下終了後、更に５℃で３０分間撹拌し反応を完
結させた。[Example 1] 137 g of 10% aqueous sodium hydroxide solution, 30.4 g of aniline, and 354 ml of toluene were placed in a 1.5-liter glass reactor, cooled to 0°C, and dropped using a dropping funnel. 41.1 g of α-chloropropionic acid chloride was added dropwise from the top. The temperature inside the reaction system was maintained at 0 to 10°C during the dropwise addition, and the dropwise addition took about 1 hour. During the reaction, α-chloropropionic acid anilide produced in the organic layer precipitated as crystals and became a solid-liquid mixed state. After the dropwise addition was completed, the mixture was further stirred at 5° C. for 30 minutes to complete the reaction.
【００２５】次に、反応液を５０℃に加温し析出したα
−クロロプロピオン酸アニリドの結晶を溶解した後、分
液により水層を除去した。更に、新たに１％の希硫酸で
洗浄した後、この液の一部を内部標準法を用いたガスク
ロマトグラフィ−にて分析したところ、このトルエン溶
液には５９．４ｇのα−クロロプロピオン酸アニリドが
含有していることが判明した。Next, the reaction solution was heated to 50°C and the precipitated α
- After dissolving the crystals of chloropropionic acid anilide, the aqueous layer was removed by liquid separation. Furthermore, after freshly washing with 1% dilute sulfuric acid, a part of this solution was analyzed by gas chromatography using an internal standard method, and it was found that 59.4 g of α-chloropropionic acid anilide was present in this toluene solution. It was found that it contained.
【００２６】このトルエン溶液に５４．５ｇの２，４−
ジクロロ−３−メチルフェノ−ルと６３．８ｇの炭酸カ
リウムを加え、撹拌しながら油浴にてトルエンが還流す
るまで昇温した。この時還流管にディ−ン・スタ−ク式
の水分分離器を備え第１工程での分液で溶解または混入
した水分を除去した。加熱反応は約２０時間で終了し、
撹拌しながら放冷し、１００℃になった時点で約８００
ｍｌの水を投入したところ結晶が析出した。更に６時間
放冷した後、結晶を濾別し水と少量のトルエンで洗浄し
、乾燥したところ、８９．０ｇのα−（２，４−ジクロ
ロ−３−メチルフェノキシ）プロピオン酸アニリドを得
た。[0026] 54.5 g of 2,4-
Dichloro-3-methylphenol and 63.8 g of potassium carbonate were added, and the mixture was heated in an oil bath while stirring until the toluene refluxed. At this time, the reflux tube was equipped with a Dean-Stark type water separator to remove water dissolved or mixed in during the liquid separation in the first step. The heating reaction was completed in about 20 hours,
Leave to cool while stirring, and when the temperature reaches 100°C, it will be about 800°C.
When ml of water was added, crystals were precipitated. After cooling for further 6 hours, the crystals were filtered, washed with water and a small amount of toluene, and dried to obtain 89.0 g of α-(2,4-dichloro-3-methylphenoxy)propionic acid anilide. .
【００２７】［実施例２］実施例１の濾過操作でのトル
エン／水混合の濾液及び洗液を合わせ分液し、得られた
トルエン層に若干のトルエンを加え３５４ｍｌとした。
これに１３７ｇの１０％の水酸化ナトリウム水溶液と３
０．４ｇのアニリンを入れ、０℃に冷却し滴下ロ−トよ
り４１．１ｇのα−クロロプロピオン酸クロリドを滴下
した。滴下中、反応系内の温度は０から１０℃に保ち、
滴下には約１時間をかけた。[Example 2] The toluene/water mixed filtrate and washing liquid obtained in the filtration operation of Example 1 were combined and separated, and a small amount of toluene was added to the obtained toluene layer to make 354 ml. Add 137 g of 10% aqueous sodium hydroxide solution and 3
0.4 g of aniline was added, the mixture was cooled to 0° C., and 41.1 g of α-chloropropionic acid chloride was added dropwise from the dropping funnel. During the dropping, the temperature in the reaction system was maintained at 0 to 10°C.
The dropping process took about 1 hour.
【００２８】なお、反応途中より、有機層に生成したα
−クロロプロピオン酸アニリドが結晶として析出し固液
混合状態となった。滴下終了後、更に５℃で３０分間撹
拌した後、５０℃に加温し析出したα−クロロプロピオ
ン酸アニリドの結晶を溶解し分液により水層を除去した
。It should be noted that α generated in the organic layer during the reaction
-Chloropropionic acid anilide precipitated as crystals and became a solid-liquid mixture. After the addition was completed, the mixture was further stirred at 5°C for 30 minutes, then heated to 50°C to dissolve the precipitated crystals of α-chloropropionic acid anilide, and the aqueous layer was removed by liquid separation.
【００２９】更に、新たに１％の希硫酸で洗浄した後、
この液の一部を内部標準法を用いたガスクロマトグラフ
ィ−にて分析したところこのトルエン溶液には５９．１
ｇのα−クロロプロピオン酸アニリドが含有しているこ
とが判明した。このトルエン溶液に５４．３ｇの２，４
−ジクロロ−３−メチルフェノ−ルと６３．５ｇの炭酸
カリウムを加え撹拌しながら油浴にてトルエンが還流す
るまで昇温した。実施例１と同様にディ−ン・スタ−ク
式の水分分離器により水分を除去し、約２０時間で反応
は終了した。実施例１と全く同様に処理し、乾燥したと
ころ９６．９ｇのα−（２，４−ジクロロ−３−メチル
フェノキシ）プロピオン酸アニリドを得た。Furthermore, after washing with 1% dilute sulfuric acid,
When a part of this liquid was analyzed by gas chromatography using an internal standard method, this toluene solution contained 59.1
It was found that the sample contained g of α-chloropropionic acid anilide. Add 54.3g of 2,4 to this toluene solution.
-Dichloro-3-methylphenol and 63.5 g of potassium carbonate were added, and while stirring, the temperature was raised in an oil bath until toluene refluxed. As in Example 1, water was removed using a Dean-Stark water separator, and the reaction was completed in about 20 hours. It was treated in exactly the same manner as in Example 1 and dried to obtain 96.9 g of α-(2,4-dichloro-3-methylphenoxy)propionic acid anilide.
【００３０】この濾液も同様に分液しそのトルエン層を
溶媒として３５４ｍｌに調製し前記と同量の原料を仕込
み同様に反応し、ガスクロマトグラフィ−にて分析した
ところ、このトルエン溶液には５９．４ｇのα−クロロ
プロピオン酸アニリドが含有していることが判明した。
このトルエン溶液に５４．５ｇの２，４−ジクロロ−３
−メチルフェノ−ルと６３．８ｇの炭酸カリウムを加え
晶析単離したところ、９７．７ｇのα−（２，４−ジク
ロロ−３−メチルフェノキシ）プロピオン酸アニリドを
得た。This filtrate was separated in the same manner, and the toluene layer was used as a solvent to prepare 354 ml, and the same amount of raw materials as above were charged and reacted in the same manner. Analysis by gas chromatography revealed that this toluene solution contained 59. It was found to contain 4 g of α-chloropropionic acid anilide. Add 54.5 g of 2,4-dichloro-3 to this toluene solution.
-Methylphenol and 63.8 g of potassium carbonate were added and crystallized and isolated to obtain 97.7 g of α-(2,4-dichloro-3-methylphenoxy)propionic acid anilide.
【００３１】[0031]
【発明の効果】本発明は、第１および第２工程で共通の
芳香族炭化水素溶媒を使用するので、中間体のハロカル
ボン酸アニリドを単離せずに反応溶液ごと次工程で利用
することができ、単離操作による中間体の単離ロスを無
くすと共に、操作の簡便化と溶剤の回収ロスの大幅減少
を図ることができる。[Effects of the Invention] Since the present invention uses a common aromatic hydrocarbon solvent in the first and second steps, the intermediate halocarboxylic acid anilide can be used in the next step together with the reaction solution without isolating it. In addition to eliminating isolation loss of intermediates due to isolation operations, it is possible to simplify operations and significantly reduce recovery losses of solvents.
Claims (2)
を、ｎは０または１〜５の整数を、Ａは直鎖または分枝
の低級アルキレン基を表す。）で表わされる置換フェノ
キシカルボン酸アニリドを製造する際に、下記一般式（
２）： Ｙ−Ａ−Ｃ（＝Ｏ）−Ｚ 一
般式（２）（但し、式中Ａは直鎖または分枝の低級アル
キレン基を、ＹおよびＺは各々ハロゲン族原子を表す。 ）で表わされるハロカルボン酸ハライドとアニリンとを
、芳香族炭化水素を溶媒とし塩基の存在下で反応せしめ
た後、得られた反応生成物を単離することなく、塩基の
存在下同一溶媒中で、下記一般式（３）： 【化２】 （但し、式中Ｘはハロゲン族原子または低級アルキル基
を、ｎは０または１〜５の整数を表す。）で表わされる
置換フェノ−ルと加熱反応せしめることを特徴とする置
換フェノキシカルボン酸アニリドの製造法。Claim 1: The following general formula (1): [Formula 1] (wherein, represents a lower alkylene group), when producing a substituted phenoxycarboxylic acid anilide represented by the following general formula (
2): Y-A-C(=O)-Z with the general formula (2) (wherein A represents a linear or branched lower alkylene group, and Y and Z each represent a halogen group atom). After reacting the represented halocarboxylic acid halide with aniline in the presence of a base using an aromatic hydrocarbon as a solvent, the reaction product obtained was reacted with the following in the same solvent in the presence of a base without isolating the reaction product. General formula (3): [Formula 2] (However, in the formula, X represents a halogen group atom or a lower alkyl group, and n represents 0 or an integer of 1 to 5.) A heated reaction is performed with a substituted phenol represented by the following formula: A method for producing a substituted phenoxycarboxylic acid anilide, characterized in that:
酸アニリドが回収除去された反応溶媒を、次の反応に再
使用する請求項１記載の方法。2. The method according to claim 1, wherein after the reaction is completed, the reaction solvent from which the substituted phenoxycarboxylic acid anilide has been recovered and removed is reused for the next reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10940291A JPH04338369A (en) | 1991-05-14 | 1991-05-14 | Production of substituted phenoxycarboxylic acid anilide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10940291A JPH04338369A (en) | 1991-05-14 | 1991-05-14 | Production of substituted phenoxycarboxylic acid anilide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04338369A true JPH04338369A (en) | 1992-11-25 |
Family
ID=14509340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10940291A Pending JPH04338369A (en) | 1991-05-14 | 1991-05-14 | Production of substituted phenoxycarboxylic acid anilide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04338369A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012012454A (en) * | 2010-06-30 | 2012-01-19 | Nissan Chem Ind Ltd | Method for producing poly(5-(meth)acryloyl-2-azaadamantane-n-oxyl) |
-
1991
- 1991-05-14 JP JP10940291A patent/JPH04338369A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012012454A (en) * | 2010-06-30 | 2012-01-19 | Nissan Chem Ind Ltd | Method for producing poly(5-(meth)acryloyl-2-azaadamantane-n-oxyl) |
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