JPS63310855A - 5-(1-butyn-3-yl)oxy-4-chloro-2-fluoroacetanilide and production thereof - Google Patents
5-(1-butyn-3-yl)oxy-4-chloro-2-fluoroacetanilide and production thereofInfo
- Publication number
- JPS63310855A JPS63310855A JP62146561A JP14656187A JPS63310855A JP S63310855 A JPS63310855 A JP S63310855A JP 62146561 A JP62146561 A JP 62146561A JP 14656187 A JP14656187 A JP 14656187A JP S63310855 A JPS63310855 A JP S63310855A
- Authority
- JP
- Japan
- Prior art keywords
- chloro
- formula
- fluoro
- compound
- butyn
- 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 description 12
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical class CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 p- toluenesulfonyloxy Chemical group 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000005948 methanesulfonyloxy group Chemical group 0.000 claims abstract description 3
- GVRKNSAEOVXHOS-UHFFFAOYSA-N n-(4-chloro-2-fluorophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1F GVRKNSAEOVXHOS-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000002363 herbicidal effect Effects 0.000 abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 4
- 239000004009 herbicide Substances 0.000 abstract description 3
- 239000004480 active ingredient Substances 0.000 abstract description 2
- HQFWVSGBVLEQGA-UHFFFAOYSA-N 4-aminobenzoic acid 3-(dibutylamino)propyl ester Chemical class CCCCN(CCCC)CCCOC(=O)C1=CC=C(N)C=C1 HQFWVSGBVLEQGA-UHFFFAOYSA-N 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- BTQIJXHWQVDZJL-UHFFFAOYSA-N (2-chloro-4-fluoro-5-nitrophenyl) methyl carbonate Chemical compound COC(=O)OC1=CC([N+]([O-])=O)=C(F)C=C1Cl BTQIJXHWQVDZJL-UHFFFAOYSA-N 0.000 description 1
- RVNOLDUNQMDIBG-UHFFFAOYSA-N (5-amino-2-chloro-4-fluorophenyl) methyl carbonate Chemical compound COC(=O)OC1=CC(N)=C(F)C=C1Cl RVNOLDUNQMDIBG-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- TXQCFWXPBBCRTP-UHFFFAOYSA-N 2-chloro-2-fluoro-n-phenylacetamide Chemical compound FC(Cl)C(=O)NC1=CC=CC=C1 TXQCFWXPBBCRTP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000012345 acetylating agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
くＭ楽土の利用分野〉
本発明は式［１１
％式％
で示される５−（１−ブチン−８−イル）オキシ−４−
クロロ−２−フルオロアセトアニリド（以下、本発明化
合物と記す。）およびその製造法に関する。[Detailed Description of the Invention] Field of Application of KuM Rakudo> The present invention provides 5-(1-butyn-8-yl)oxy-4-
The present invention relates to chloro-2-fluoroacetanilide (hereinafter referred to as the compound of the present invention) and a method for producing the same.
さらに詳しくは、除草剤の有効成分として有用な式「Ｉ
［」
で示される化合物の製造中間体を提供するものである。More specifically, the formula “I” is useful as an active ingredient in herbicides.
The present invention provides an intermediate for producing the compound represented by [''.
〈従来の技術〉
式［１［］で示される化合物は欧州特許第６１７４１号
明細書に記載の除草活性を有する化合物である。<Prior Art> The compound represented by formula [1] is a compound having herbicidal activity as described in European Patent No. 61741.
〈発明が解決しようとする問題点〉
従来より知られている式［１１］で示される化合物の製
造法では、生成物の純度や収率において必ずしも満足で
きるものではなかった。<Problems to be Solved by the Invention> Conventionally known methods for producing the compound represented by formula [11] have not always been satisfactory in terms of product purity and yield.
く問題点を解決するための手段〉
本発明者らは、除草剤として有用な式［１［］で示され
る化合物の工業的にも有利な優れた製造法について検討
した結果、本発明化合物が重要な製造中間体となり得る
ことを見い出し、本発明化合物より下記の経路によって
高純度の式［ＩＩ］で示される化合物が高収率で得られ
ることを明らかにして本発明を完成した。Means for Solving Problems〉 The present inventors have investigated an excellent industrially advantageous manufacturing method for the compound represented by the formula [1] which is useful as a herbicide, and have found that the compound of the present invention is The present invention was completed by discovering that the compound of the present invention can be used as an important production intermediate, and by demonstrating that a highly purified compound represented by formula [II] can be obtained in high yield from the compound of the present invention by the following route.
［ｌｌ ［ｍｌ ［Ｉ
［］次に、本発明化合物の製造法について述べる。[ll [ml [I
[] Next, a method for producing the compound of the present invention will be described.
本発明化合物は４−クロロ−２−フルオロ−６−ヒトロ
キシアセトアニリドと一般式［ｆｆ〕ＣＨｍＣＨＣ＝Ｃ
Ｈ［！／］
Ｅ式中、ｘはハロゲン原子、メタンスルホニルオキシ基
またはｐ−トルエンスルホニルオキシ基を表わす。〕
で示されるブチン誘導体とを塩基の存在下に反応させる
ことにより製造される。The compound of the present invention is 4-chloro-2-fluoro-6-hydroxyacetanilide and has the general formula [ff]CHmCHC=C
H [! /] E In the formula, x represents a halogen atom, a methanesulfonyloxy group or a p-toluenesulfonyloxy group. ] It is produced by reacting the butyne derivative shown in the following in the presence of a base.
該反応は、通常４−クロロ−２−フルオロ−５−ヒドロ
キシアセトアニリド１当量に対して、一般式［１で示さ
れるブチン易導体は１．０〜２．０当量、好ましくは１
．１〜１．８当澁、塩基は１．０〜２、０当λ、好まし
くは１．０〜１．８当量用いられる。In this reaction, the butyne easy conductor represented by the general formula [1] is usually used in an amount of 1.0 to 2.0 equivalents, preferably 1 equivalent to 1 equivalent of 4-chloro-2-fluoro-5-hydroxyacetanilide.
．． The base is used in an amount of 1.0 to 2.0 equivalents, preferably 1.0 to 1.8 equivalents.
反応は通常不活性溶媒中、室温から使用する溶媒の沸点
までの温度、万ましくは５０〜９０゛Ｃの温度で通常０
．５〜２４時間かけて行われる。The reaction is usually carried out in an inert solvent at a temperature ranging from room temperature to the boiling point of the solvent used, preferably at a temperature of 50 to 90°C.
．． It takes 5 to 24 hours.
用いられる溶媒としてはメタノール、エタノール、イソ
プロパツール等のアルコール類、ベンゼン、トルエン、
キシレン等の芳香族炭化水素類、ジクロロエタン、四塩
化炭素、クロロベンゼン等のハロゲン化炭化水素、アセ
トレ、メチルイソブチルケトン等のケトン類、ジエチル
エーテル、テトラヒドロフラン、ジオキサン等のエーテ
ル類、アセトニトリル等めニトリル類、ヘキサン、ヘプ
タン等の脂肪族炭化水素、ジメチルスルホキシド、ジメ
チルホルムアミド、水等あるいはそれらの混合物が挙げ
られ、通常、アルコール類、ニトリル類、ジメチルホル
ムアミド等の極性溶媒が用いられる。用いられる塩基と
しては水酸化ナトリウム、水酸化カリウム等のアルカリ
金属の水酸化物、炭酸ナトリウム、炭酸カリウム等のア
ルカリ金属の炭酸塩、炭酸水素ナトリウム等のアルカリ
金属の重炭酸塩、水素化ナトリウム等のアルカリ金属の
水素化物、ナトリウムメトキシド等の金属アルコキシド
、トリエチルアミン、ピリジン、ジメチルアミノピリジ
ン等の有機塩基等が挙げられる。上記の反応は触媒の存
在下に行うこともでき、触媒としては臭化ナトリウム、
臭化カリウム、ヨウ化ナトリウム、ヨウ化カリウム等の
塩類、テトラブチルアンモニウムクロリド等の四級アン
モニウム塩等が挙げられ、４−クロロ−２−フルオロ−
５−ヒドロキシアセトアニリド１当量に対して、通常０
．０１〜０．２当量用いられる。Solvents used include alcohols such as methanol, ethanol, isopropanol, benzene, toluene,
Aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as dichloroethane, carbon tetrachloride, and chlorobenzene, ketones such as acetre and methyl isobutyl ketone, ethers such as diethyl ether, tetrahydrofuran, and dioxane, nitriles such as acetonitrile, Examples include aliphatic hydrocarbons such as hexane and heptane, dimethyl sulfoxide, dimethylformamide, water, and mixtures thereof, and polar solvents such as alcohols, nitriles, and dimethylformamide are usually used. Examples of bases that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate, sodium hydride, etc. Examples include alkali metal hydrides, metal alkoxides such as sodium methoxide, and organic bases such as triethylamine, pyridine, and dimethylaminopyridine. The above reaction can also be carried out in the presence of a catalyst, including sodium bromide,
Examples include salts such as potassium bromide, sodium iodide, potassium iodide, quaternary ammonium salts such as tetrabutylammonium chloride, and 4-chloro-2-fluoro-
Usually 0 per equivalent of 5-hydroxyacetanilide
．． 01 to 0.2 equivalents are used.
反応終了後は、反応液を水で希釈し、生じる結晶をＰ取
するか、あるいは有機溶媒で抽出し濃縮するなどの通常
の後処理を行なうことにより本発明化合物を得ることが
できる。After the reaction is completed, the compound of the present invention can be obtained by diluting the reaction solution with water and performing usual post-treatments such as removing P from the resulting crystals or extracting with an organic solvent and concentrating.
尚、一般式［ｆｌで示されるブチン誘導体は１−プチン
ー８−オールを塩化チオニル、三臭化リン等のハロゲン
化剤または塩化メタンスル本ニル、塩化ｐ−トルエンス
ルホニル等のスルホニル化剤と反応させることにより得
ることができる。また、４−クロロ−２−フルオロ−５
−ヒドロキシアセトアニリドは下記の経路により製造す
ることができる。The butyne derivative represented by the general formula [fl is obtained by reacting 1-putyn-8-ol with a halogenating agent such as thionyl chloride or phosphorus tribromide, or a sulfonylating agent such as methanesulfonyl chloride or p-toluenesulfonyl chloride. This can be obtained by Also, 4-chloro-2-fluoro-5
-Hydroxyacetanilide can be produced by the following route.
［ｖｌ ［ｓｓｌ
［■］上記の式［Ｖ］で示される化合物は特開昭
５８−７９９６０号公報に記載の化合物である。該化合
物は、通常芳香席上のニトロ基をアミノ基に還元する際
に用いられる方法、例えば硫化ナトリウムや鉄粉を使用
する方法、接触還元方法等により式（”Ｊ］で示さｎる
化合物に導かれる。[vl [ssl
[■] The compound represented by the above formula [V] is a compound described in JP-A-58-79960. The compound can be converted into a compound represented by formula (J) by a method normally used to reduce a nitro group on an aromatic site to an amino group, such as a method using sodium sulfide or iron powder, or a catalytic reduction method. be guided.
得られた式１１で示される化合物は無水酢酸、塩化アセ
チル、酢酸等通常のアセチル化剤を用いてアセチル化す
ることにより式［■〕で示される化合物に導かれ、さら
に水酸化ナトリウム水溶液等を用いてアルカリ条件下に
加水分解を行なうことにより、本発明化合物の製造原料
である式［■］で示される化合物、即ち、４−クロロ−
２−フルオロ−５−ヒドロキシアセトアニリドを得るこ
とができる。The obtained compound represented by formula 11 is acetylated using a common acetylating agent such as acetic anhydride, acetyl chloride, acetic acid, etc. to give a compound represented by formula [■], and further treated with an aqueous solution of sodium hydroxide, etc. The compound represented by formula [■], which is the raw material for producing the compound of the present invention, is hydrolyzed under alkaline conditions using
2-fluoro-5-hydroxyacetanilide can be obtained.
本発明化合物は、酸性条件下で加水分解することにより
、前記式［ＤＩ］で示されるアニリン誘導体に導くこと
ができ、次いで８．４．５．６ −テトラヒドロフタル
酸無水物を反応させることにより式〔１Ｋ〕で示される
除草活性を有する化合物に導くことができる。The compound of the present invention can be led to the aniline derivative represented by the above formula [DI] by hydrolysis under acidic conditions, and then by reacting with 8.4.5.6-tetrahydrophthalic anhydride. This can lead to a compound having herbicidal activity represented by formula [1K].
〈実施例゛〉 次に本発明化合物の製造例を示す。<Example> Next, production examples of the compounds of the present invention will be shown.
製造例１
４−クロロ−２−フルオロ−５−ヒドロキシアセトアニ
リド２００ｐ、８−メタンスルホニルオキシ−１−ブチ
ン１７５ ｆ、無水炭酸カリウム１８６ｆおよびヨウ化
カリウム８、１５１をジメチルホルムアミド１０００Ｆ
に加え、７０〜７５°Ｃにて８時間攪拌した。Production Example 1 200p of 4-chloro-2-fluoro-5-hydroxyacetanilide, 175f of 8-methanesulfonyloxy-1-butyne, 186f of anhydrous potassium carbonate, and 8,151f of potassium iodide were added to 1000F of dimethylformamide.
and stirred at 70-75°C for 8 hours.
反応液を室温に冷却した後、冷水２．５Ｅを加えて１時
間攪拌し、生成した結晶をＰ取、水洗、次いで乾燥する
ことにより２８９ｆの本発明化合物を得た。（収率９５
．０％）融点 １２６〜１２８”Ｃ
ＮＭＲスペクトル（ＣＤＣ１ａ溶媒、ＴＭＳ内部標準）
δ値（ｐＩ）ｍ） ８．８０（ＩＨ，ｄ、Ｊ＝８．０Ｈ
ｚ）、７．６５（ＩＨ。After cooling the reaction solution to room temperature, 2.5E of cold water was added and stirred for 1 hour, and the resulting crystals were removed from P, washed with water, and then dried to obtain 289f of the present compound. (Yield 95
．． 0%) Melting point 126-128”C NMR spectrum (CDC1a solvent, TMS internal standard)
δ value (pI) m) 8.80 (IH, d, J = 8.0H
z), 7.65 (IH.
ｂｒｓ）、７．１５ （ＩＨ，ｄ 、 Ｊ＝１０）ｉＺ
）、４．９０（１）１．ｑｄＪ＝６Ｈｚ、２Ｈｚ）、
２．５８（１）１．ｄ、Ｊ＝２Ｈｚ）、２．２２（８）
ｉ、８）、１．６９ （８Ｈ，ｄ 、 Ｊ＝６Ｈｚ ）
製造例２
４−クロロ−２−フルオロ−５−ヒドロキシアセトアニ
リド６、Ｏｆ、８−ブロモ−１−ブチン５．１１および
無水炭酸カリウム４．１１をジメチルホルムアミド８０
ｇに加え、６０〜６５℃にて８時間攪拌した。反応液を
室温に冷却した後、冷水１００ｇＩｔを加え、生成した
結晶をＰ取、水洗、次いで乾燥することによｌ） ７．
０８９の本発明化合物を得た。（収率９４．０％ ）
製造例８
４−クロロ−２−フルオロ−５−ヒドロキシアセトアニ
リド４．０７ｆ、無水炭酸カリウム８．８２Ｆおよびヨ
ウ化カリウム０．０７ダをジメチルホルムアミド１２．
１ｇに加え７５゛Ｃに加温した。８−１−）ルエンスル
ホニルオキシー１−ブチン５．８８ｆをトルエン１２．
２Ｖに溶かした液を１５分間かけて滴下し、さらに１５
時間７６”Ｃに保った。反応液を室温に冷却した後、水
５０Ｆを加え、トルエン１００ｇで抽出した。トルエン
層を水洗、無水硫酸マグネシウムで乾燥、次いで減圧下
に溶媒を留去することにより４．９１１の本発明化合物
を得た。（収率９６．０％）
上記の製造例で得られた本発明化合物はイソプロピルア
ルコールより再結晶することによって融点１８１″Ｃの
無色結晶になるが、式（Ｔ１］で示される化合物の製造
原料として用いる場合、特に精製等の操作は必要としな
い。brs), 7.15 (IH, d, J=10)iZ
), 4.90(1)1. qdJ=6Hz, 2Hz),
2.58(1)1. d, J=2Hz), 2.22(8)
i, 8), 1.69 (8H, d, J=6Hz)
Production Example 2 4-chloro-2-fluoro-5-hydroxyacetanilide 6,Of,8-bromo-1-butyne 5.11 and anhydrous potassium carbonate 4.11 were dissolved in dimethylformamide 80
g and stirred at 60 to 65°C for 8 hours. After cooling the reaction solution to room temperature, 100 g of cold water was added, and the resulting crystals were removed from P, washed with water, and then dried. 7.
089 of the compound of the present invention was obtained. (Yield: 94.0%) Production Example 8 4.07f of 4-chloro-2-fluoro-5-hydroxyacetanilide, 8.82f of anhydrous potassium carbonate, and 0.07f of potassium iodide were mixed with 12.0f of dimethylformamide.
1 g and heated to 75°C. 8-1-) 5.88f of luenesulfonyloxy-1-butyne was added to 12.8f of toluene.
Drop the solution dissolved at 2V over 15 minutes, and then
The temperature was maintained at 76"C for a period of time. After the reaction solution was cooled to room temperature, 50F of water was added and extracted with 100g of toluene. The toluene layer was washed with water, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. 4.911 of the present compound was obtained. (Yield 96.0%) The present compound obtained in the above production example became colorless crystals with a melting point of 181"C by recrystallization from isopropyl alcohol. When used as a raw material for producing the compound represented by formula (T1), no particular operations such as purification are required.
次に、本発明化合物より式［ｍｌで示される化合物を経
由して、式［Ｉ［〕で示される化合物を製造する例を参
考例１および参考例２にて示す。Next, reference examples 1 and 2 show examples of producing a compound represented by formula [I] from the compound of the present invention via a compound represented by formula [ml].
参考例１
本発明化合物１１．０ｆＳ！塩酸８，７ｆ、ｘタノール
２０ｆおよびトルエン７０Ｆを混合し、４時間加熱還流
した。室温まで冷却した後、５％水酸化ナトリウム水溶
液を加えて中和し、トルエン層を分取した。トルエン層
を水洗、無水硫酸マグネシウムで乾燥、次いで減圧下に
溶媒を留去して式［１１１１で示される４−クロロ−２
−フルオロ−５−（１−ブチン−８−イル）オキシアニ
リン９．０９１を得た。Reference Example 1 Compound of the present invention 11.0 fS! 8.7f of hydrochloric acid, 20f of x-tanol and 70f of toluene were mixed and heated under reflux for 4 hours. After cooling to room temperature, 5% aqueous sodium hydroxide solution was added to neutralize, and the toluene layer was separated. The toluene layer was washed with water, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 4-chloro-2 represented by the formula [1111].
-Fluoro-5-(1-butyn-8-yl)oxyaniline 9.091 was obtained.
（収率９８．９％、純度９６．７％）―点７２〜７６℃
得られた式［ｍｌで示される化合物はヘキサンより再結
晶することによって融点７８〜７９”Ｃの無色針状晶に
なるが、式［Ｉ［〕で示される化合物を製造する際は、
特に精製等の操作を行うことなく、下記の参考例２に例
示される工程の原料として用いられる。(Yield 98.9%, purity 96.7%) - Point 72-76°C The compound represented by the formula [ml] was recrystallized from hexane to form colorless needle-like crystals with a melting point of 78-79"C. However, when producing the compound represented by the formula [I[],
It can be used as a raw material in the process exemplified in Reference Example 2 below without any particular purification or other operations.
参考例２
４−クロロ−２−フルオロ−５−（１−ブチン−８−イ
ル〕オキシアニリン６、Ｏｆ、８゜４．５．６−チトラ
ヒドロフタル酸無水物５．１２１および酢酸２４ｆの混
合物を８６〜９０℃にて８時間攪拌した。反応液を室温
に冷却した後、水４８１とメタノール１２１を加え、生
成した結晶をｐ取、水洗、次いで乾燥することにより、
式［１」で示されるへ−［４−クロロ−２−フルオロ−
５−（１−ブチン−８−イル）オキシフェニル］−８，
４，５，６−チトラヒドロフタルイ電ド９．１６ ’ｉ
を結晶として得た。（収率９Ｓ、８％、純度９６．８％
）次に、本発明化合物を製造する際に出発原料となる４
−クロロ−２−フルオロ−６−ヒドロキシアセトアニリ
ドの製造例を参考例８にて示す。Reference Example 2 4-chloro-2-fluoro-5-(1-butyn-8-yl)oxyaniline 6, Of, 8° 4.5.6-Titrahydrophthalic anhydride 5.121 and acetic acid 24f mixture was stirred at 86 to 90°C for 8 hours. After cooling the reaction solution to room temperature, 481 parts of water and 12 parts of methanol were added, and the formed crystals were collected, washed with water, and then dried.
He-[4-chloro-2-fluoro- represented by formula [1]
5-(1-butyn-8-yl)oxyphenyl]-8,
4,5,6-titrahydrophthalide 9.16'i
was obtained as a crystal. (Yield 9S, 8%, purity 96.8%
) Next, 4, which is the starting material when producing the compound of the present invention, is
An example of the production of -chloro-2-fluoro-6-hydroxyacetanilide is shown in Reference Example 8.
参考例８
４−クロロ−２−フルオロ−５−メトキシカルボニルオ
キシニトロベンゼン１００ｆをトルエン４００ｆに溶解
し、１０％パラジウム−炭素１．Ｏｆを加え、オートク
レーブ中５０〜７０℃にて５〜１０ ｋｇ／ｃｄの圧力
で水素ガスを導入した。水素ガスの吸収が止んだ後、触
媒をＰ去し、Ｆ液中の水層を分液操作で除いた。トルエ
ン層を無水硫酸マグネシウムで乾燥後、減圧下に溶媒を
除去する仁とにより４−クロロ−２−フルオロ−５−メ
トキシカルボニルオキシアニリン８６．２Ｆを得た。Reference Example 8 100f of 4-chloro-2-fluoro-5-methoxycarbonyloxynitrobenzene was dissolved in 400f of toluene, and 10% palladium-carbon 1. Hydrogen gas was introduced into the autoclave at a pressure of 5 to 10 kg/cd at 50 to 70°C. After hydrogen gas absorption stopped, the catalyst was removed and the aqueous layer in the F solution was removed by liquid separation. After drying the toluene layer over anhydrous magnesium sulfate, the solvent was removed under reduced pressure to obtain 4-chloro-2-fluoro-5-methoxycarbonyloxyaniline 86.2F.
（収率９８％）融点８７〜９０℃
ＮＭＲスペクトル（ＣＤＣｊｉ＠溶媒、ＴＭＳ内部標準
）δ値（ｐＩ）ｍ） ７．０１（ＩＨ，ｄ、Ｊ＝１０
Ｈｚ）、６．５８（ＩＨ，ｄ、Ｊ＝５Ｈｚ）、４．１０
〜８．８８（２Ｈ。(Yield 98%) Melting point 87-90°C NMR spectrum (CDCji@solvent, TMS internal standard) δ value (pI) m) 7.01 (IH, d, J = 10
Hz), 6.58 (IH, d, J=5Hz), 4.10
~8.88 (2H.
ｍ）、８．８８（８）１．ｓ）
上記で得られた４−クロロ−２−フルオロ−５−メトキ
シカルボニルオキシアセトアニリド１６１を酢酸４０ｊ
Ｆに溶解し、５０〜６０”ＣＩζて無水酢酸１１１１を
加え同温度で２時間攪拌した。次に室温まで冷却し氷水
１５０ｍｇを加えて析出した結晶をＰ取、水洗、乾燥し
４−クロロ−２−フルオロ−６−メトキシカルボニルオ
キシアセトアニリド１８．９Ｆを得た。（収率９９％）
融点１６７へ１６９°ＣＮｌ１ｄＲスペクトル（ＣＤ
Ｃ１ｓ溶媒、ＴＭＳ内部標準）δ値（１）ｐｍ） ９
．６０ （ＩＨ，ｂｒｓ ）、８．２０（１）１．ｄ、
Ｊ＝６）ｉｚ）、７．２５（ＩＨ，ｄ、Ｊ＝１０Ｈｚ）
、８．９０＜８Ｈ，ｓ）、２．１６（８Ｈ，８）上記で
得られた４−クロロ−２−フルオロ−５−メトキシカル
ボニルオキシアセトアニリド１８．５Ｆをメタノール６
０ｆに溶解し、２０％水酸化ナトリウム水溶液４６９を
加え、４０〜４５℃にて８時間攪拌した。反応液を氷水
に注ぎ、濃塩酸で中和して生じた結晶をＰ取、水洗、乾
燥して目的の４−クロロ−２−フルオロ−５−ヒドロキ
シアセトアニリド１８．９Ｎを得た。（収率９６％）融
点１１８〜１１４℃
ＮＭＲスペクトルＣＤＭＳＯ−ｄａ溶媒、ＴＭＳ内部標
準）δ値（ｐｐｍ） １０．１０〜９．８０（２Ｈ，
ｍ）、７．７９（ＩＨ。m), 8.88(8)1. s) 4-chloro-2-fluoro-5-methoxycarbonyloxyacetanilide 161 obtained above was dissolved in acetic acid 40j
4-chloro- 2-Fluoro-6-methoxycarbonyloxyacetanilide 18.9F was obtained. (Yield 99%)
melting point 167 to 169°CNl1dR spectrum (CD
C1s solvent, TMS internal standard) δ value (1) pm) 9
．． 60 (IH, brs), 8.20 (1) 1. d,
J=6)iz), 7.25(IH,d, J=10Hz)
, 8.90 < 8H, s), 2.16 (8H, 8) 4-chloro-2-fluoro-5-methoxycarbonyloxyacetanilide 18.5F obtained above was dissolved in methanol 6
0f, 20% aqueous sodium hydroxide solution 469 was added, and the mixture was stirred at 40 to 45°C for 8 hours. The reaction solution was poured into ice water and neutralized with concentrated hydrochloric acid, and the resulting crystals were collected with P, washed with water, and dried to obtain 18.9N of 4-chloro-2-fluoro-5-hydroxyacetanilide. (Yield 96%) Melting point 118-114°C NMR spectrum CDMSO-da solvent, TMS internal standard) δ value (ppm) 10.10-9.80 (2H,
m), 7.79 (IH.
ｄ 、 Ｊ＝７）ｉｚ ）、７．０’ｌＣ１）１．ｄ、
Ｊ＝１１Ｈｚ）、２．１１（８Ｈ，Ｓ）d, J=7)iz), 7.0'lC1)1. d,
J=11Hz), 2.11(8H,S)
Claims (1)
−２−フルオロアセトアニリド。 ２）４−クロロ−２−フルオロ−５−ヒドロキシアセト
アニリドと一般式 ▲数式、化学式、表等があります▼ 〔式中、Ｘはハロゲン原子、メタンスルホ ニルオキシ基またはｐ−トルエンスルホニ ルオキシ基を表わす。〕 で示されるブチン誘導体を塩基の存在下に反応させるこ
とを特徴とする５−（１−ブチン−３−イル）オキシ−
４−クロロ−２−フルオロアセトアニリドの製造方法。[Claims] 1) 5-(1-butyn-8-yl)oxy-4-chloro-2-fluoroacetanilide. 2) 4-Chloro-2-fluoro-5-hydroxyacetanilide and general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, X represents a halogen atom, a methanesulfonyloxy group, or a p-toluenesulfonyloxy group. ] 5-(1-butyn-3-yl)oxy-, which is characterized by reacting a butyne derivative represented by the formula in the presence of a base.
A method for producing 4-chloro-2-fluoroacetanilide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62146561A JPH0768194B2 (en) | 1987-06-11 | 1987-06-11 | 5- (1-butyn-3-yl) oxy-4-chloro-2-fluoroacetanilide and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62146561A JPH0768194B2 (en) | 1987-06-11 | 1987-06-11 | 5- (1-butyn-3-yl) oxy-4-chloro-2-fluoroacetanilide and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63310855A true JPS63310855A (en) | 1988-12-19 |
| JPH0768194B2 JPH0768194B2 (en) | 1995-07-26 |
Family
ID=15410458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62146561A Expired - Lifetime JPH0768194B2 (en) | 1987-06-11 | 1987-06-11 | 5- (1-butyn-3-yl) oxy-4-chloro-2-fluoroacetanilide and process for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0768194B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0554894A2 (en) * | 1992-02-07 | 1993-08-11 | Sumitomo Chemical Company Limited | Imine derivatives and process for production thereof |
| WO1994021597A1 (en) * | 1993-03-22 | 1994-09-29 | Sumitomo Chemical Company, Ltd. | Aniline derivative and process for producing the same |
| JPH08225497A (en) * | 1995-12-26 | 1996-09-03 | Sagami Chem Res Center | Substituted phenyl carbonate derivative |
-
1987
- 1987-06-11 JP JP62146561A patent/JPH0768194B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0554894A2 (en) * | 1992-02-07 | 1993-08-11 | Sumitomo Chemical Company Limited | Imine derivatives and process for production thereof |
| WO1994021597A1 (en) * | 1993-03-22 | 1994-09-29 | Sumitomo Chemical Company, Ltd. | Aniline derivative and process for producing the same |
| JPH08225497A (en) * | 1995-12-26 | 1996-09-03 | Sagami Chem Res Center | Substituted phenyl carbonate derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0768194B2 (en) | 1995-07-26 |
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