JPS62185060A - Production of chloroacetanilide derivative - Google Patents
Production of chloroacetanilide derivativeInfo
- Publication number
- JPS62185060A JPS62185060A JP2391686A JP2391686A JPS62185060A JP S62185060 A JPS62185060 A JP S62185060A JP 2391686 A JP2391686 A JP 2391686A JP 2391686 A JP2391686 A JP 2391686A JP S62185060 A JPS62185060 A JP S62185060A
- Authority
- JP
- Japan
- Prior art keywords
- buten
- formula
- cis
- compound
- catalyst
- 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
- VONWPEXRCLHKRJ-UHFFFAOYSA-N 2-chloro-n-phenylacetamide Chemical class ClCC(=O)NC1=CC=CC=C1 VONWPEXRCLHKRJ-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- NEEDEQSZOUAJMU-UHFFFAOYSA-N but-2-yn-1-ol Chemical compound CC#CCO NEEDEQSZOUAJMU-UHFFFAOYSA-N 0.000 claims abstract description 9
- WCASXYBKJHWFMY-IHWYPQMZSA-N 2-buten-1-ol Chemical compound C\C=C/CO WCASXYBKJHWFMY-IHWYPQMZSA-N 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000000010 aprotic solvent Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- BFAKENXZKHGIGE-UHFFFAOYSA-N bis(2,3,5,6-tetrafluoro-4-iodophenyl)diazene Chemical compound FC1=C(C(=C(C(=C1F)I)F)F)N=NC1=C(C(=C(C(=C1F)F)I)F)F BFAKENXZKHGIGE-UHFFFAOYSA-N 0.000 claims description 2
- SIIVGPQREKVCOP-UHFFFAOYSA-N but-1-en-1-ol Chemical compound CCC=CO SIIVGPQREKVCOP-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 230000002363 herbicidal effect Effects 0.000 abstract description 4
- 239000004009 herbicide Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- DBAMUTGXJAWDEA-UHFFFAOYSA-N Butynol Chemical compound CCC#CO DBAMUTGXJAWDEA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101150041968 CDC13 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011981 lindlar catalyst Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、除草性化合物としＣ極めて有利なりロロアセ
トアニリド誘導体の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a process for producing roloacetanilide derivatives which are highly advantageous as herbicidal compounds.
クロロアセトアニリド誘導体Ｈ１（１１プロトン性生成
させた後、精製＃留して浴媒などを除き、ｃｉｓ −２
−ブテン−１−オールを単離する工程（Ｊ、 Ａｍ、
Ｃｈｅｍ、 Ｓｏｃ、、 ７２ 、７２７ （１９５
Ｕ））および（２）
で示される化合物（ＲおよびＲ′は同一または相異なる
低級アルキル基）を非プロトン性ｍ媒にとかし、ｃｉｓ
−’ｌ−ブテンー１−オールを〃０えて反応させる工
程（特開昭５８−１０３３５１号公＠）により製造され
る。Chloroacetanilide derivative H1 (11) After the protic formation, purification #distillation was performed to remove the bath medium, etc., and cis -2
- step of isolating buten-1-ol (J, Am,
Chem, Soc, 72, 727 (195
The compounds represented by U)) and (2) (R and R' are the same or different lower alkyl groups) are dissolved in an aprotic medium, and cis
-' It is produced by a step of adding and reacting l-buten-1-ol (Japanese Unexamined Patent Publication No. 103351/1983).
上記の従来法では、ｃｉａ−２−ブテン−１−オールを
単離して用い℃いるので、接触還元後、メタノール、エ
タノールの如きグロトン性浴媒などから分離精製するた
めに、時間と手間のかかる蒸留工程を必要とする。Ｃｉ
ｓ −２−ブテン−１−オールは、低沸点で揮発しやす
く失いやすいうえにｚｒａｎｓ −２−ブテン−１−オ
ールの不安定異性体であるので、ｔｒａｎｓ型に異性化
てる危険１にはらんでいる。′ ゛ −・
２事実、前記文献（Ｊ、 Ａｍ、 Ｏｈｅｍ、 Ｓｏ
（！、１７２ｒ ７２７（１９５０））の方法では１番
良い場合でもｃｉｓ： ｔｒａｎｓ ＝８８ ： １２
の混合物となってしまい、高純度の０１θ体を得るため
には、メタノールの如きプロトン性溶媒中で、新たに砕
いた水酸化カリウムを加え熱し、加圧下、還元を行なわ
なければならない。そしてこれを追試した文献では真空
蒸留を２回繰返して、収率４４％と報告されている（
Ｊ、Ｏｒｇ、 Ｏｈｅｍ、、 ４６．３９７０ （１９
８１） ）。In the above-mentioned conventional method, cia-2-buten-1-ol is isolated and used at °C, so it is time-consuming and labor-intensive to separate and purify it from a grotonic bath medium such as methanol or ethanol after catalytic reduction. Requires a distillation process. Ci
Since s-2-buten-1-ol has a low boiling point and is volatile and easily lost, it is also an unstable isomer of zrans-2-buten-1-ol, so it does not fall under the risk of isomerization to the trans form. I'm here. ′ ゛ −・
2 Facts, the above literature (J, Am, Ohem, So
(!, 172r 727 (1950)), even in the best case cis: trans = 88: 12
In order to obtain a highly pure 01θ form, freshly crushed potassium hydroxide must be added and heated in a protic solvent such as methanol, and reduction must be carried out under pressure. In a literature review of this, the vacuum distillation was repeated twice and the yield was reported to be 44% (
J,Org,Ohem,, 46.3970 (19
81) ).
本発明者らは、製造法上、きわめて好ましくない蒸留工
程を必要とせず、しかも、誦純度で収率風（Ｏｌｓ −
２−ブテン−１−オールが得られるという方法を開発す
べく、鋭意研究を行ない本発明の方法を見い出した。The present inventors have discovered that the manufacturing method does not require an extremely unfavorable distillation step, and that the yield rate is as high as the purity (Ols-
In order to develop a method for obtaining 2-buten-1-ol, we conducted extensive research and discovered the method of the present invention.
―噛−
〔問題点を解決するだめの手段〕
不発９３ｒＸ、下記工根によるクロロアセトアニリド誘
導体の製造法である。-Say- [Means to solve the problem] This is a method for producing chloroacetanilide derivatives using the following process using the unexploded 93rX.
（１１第１工程：非プロトン性浴媒中で、触媒の存在下
、２−ブチン−１−オールｔ−接触還元し℃、ｃｉｓ
−２−ブテン−１−オールの溶液を得る工程。(11 First step: t-catalytic reduction of 2-butyn-1-ol in the presence of a catalyst in an aprotic bath medium at °C, cis
- Obtaining a solution of 2-buten-1-ol.
（２１第２工程：第１工程で得られたｃｉｇ −２−ブ
テン−１−オールの浴淑と、一般式
（式中、ＲおよびＲ’に、同一または相異なる低級アル
キル基である。）
で示される化合物と全混合し反応させて、一般式
（式中、Ｒおよび白り同一または相異なる低級アルキル
基である。）
で示されるクロロアセトアニリド誘導体を得る工程。(21 2nd step: The cig-2-buten-1-ol obtained in the 1st step is mixed with the general formula (wherein R and R' are the same or different lower alkyl groups.) A step of obtaining a chloroacetanilide derivative represented by the general formula (wherein R and white are the same or different lower alkyl groups) by completely mixing and reacting with the compound represented by:
本発明の方法によって製造される化合物ＩＮニ、除重活
性ｔ−有する有用な化合物である。特に、式ｌにおいて
、ＲおよびＷがエチル基である化合物は、水田用の選択
性除草剤として著名である。本化合物の特徴は、分子中
に特殊なｃｉａ −２−ブテン−１−オール残基を有す
ることであり、従ってこのアルコールをいかに製造し、
そして分子中に導入するかが製造上きわめてに要なこと
である。The compound IN prepared by the method of the present invention is a useful compound having de-weighting activity. In particular, compounds in which R and W are ethyl groups in formula 1 are well-known as selective herbicides for paddy fields. The feature of this compound is that it has a special cia-2-buten-1-ol residue in the molecule, so how to produce this alcohol,
Introducing it into the molecule is extremely important in manufacturing.
本発明者らは、第２工程で盛装とされる非プロトン性溶
媒を用いて、第１工稲の還元反応を鋭意検討した。その
結果、プロトン性俗媒を用いなくても、反応の終点付近
で注意深く水素吸収を行なわせねば、高純度のｃｉｓ
−２−ブテン−１−オールを得ることができることを見
出し、本発明を完成し、た。本発明によれば、非プロト
ン性溶媒にｍ解した状態で高純度のｃｉｓ〜２−ブテン
−１−オールが得られるので、手間のかかる精留操作を
必要とせ丁、直ちに第２工根を行なうことができる。The present inventors have intensively investigated the reduction reaction of the first cultivated rice using the aprotic solvent used in the second step. As a result, even without using a protic medium, high purity cis
They discovered that -2-buten-1-ol can be obtained and completed the present invention. According to the present invention, since highly pure cis-2-buten-1-ol can be obtained in a state dissolved in an aprotic solvent, the second root can be immediately removed without the need for a time-consuming rectification operation. can be done.
（第１工程 還元工程）
第１工程および第２工程において共通して用いる非プロ
トン性触媒としＣは、ベンゼン、トルエン、キンシン、
シクロヘキサン、オクタンの如き炭化水素糸爵媒および
テトラヒドロフラン、ジインフロビルエーテルの如きエ
ーテル糸溶媒を挙げることができるが、反応性、ｋｋ性
、安全性などを８慮すると、トルエンが望ましい。用い
る触媒は、２−ブチン−１−オールの三１結合ｔ ｃｉ
ａの二１結合に選択的に変換できるものであり、パラジ
ウム・炭酸カルシウム、パラジウム・炭酸カルシクム・
鉛（リンドラ−触＃、）の如ぎパ２ゾクム糸の触媒およ
びラネーニッケルの如きニッケル糸の触＆’に挙げるこ
とができる。(First step reduction step) C is an aprotic catalyst commonly used in the first step and the second step, and C is benzene, toluene, quincin,
Examples include hydrocarbon thread solvents such as cyclohexane and octane, and ether thread solvents such as tetrahydrofuran and diinflobil ether, but toluene is preferable in consideration of reactivity, kk properties, safety, and the like. The catalyst used is 31 bonds of 2-butyn-1-ol, t ci
It can be selectively converted into the 21 bond of a, palladium/calcium carbonate, palladium/calcicum carbonate/
Mention may be made of catalysts for Pazoku threads such as lead (Lindler's catalyst) and catalysts for nickel threads such as Raney nickel.
２−ブチン−１−オールを非プロトン性溶媒に俗かし、
触媒をＵ口えて、水素下で攪拌、反応を行なう。水素圧
は、常圧以下および常圧以上の広い範１で用いることが
できるが、常圧ないしやや加圧＠＆が操作上好ましい。Using 2-butyn-1-ol as an aprotic solvent,
The catalyst was placed in a U-mouth, and the mixture was stirred and reacted under hydrogen. The hydrogen pressure can be used in a wide range from below normal pressure to above normal pressure, but normal pressure to slightly elevated pressure@& is preferable for operation.
２−ブチン−１−オールの消失ないし消失近くで反応を
終了する。この反応液ハその１ま第２工程に用いること
ができるが、好ましくは、濾過などの操作により触媒を
除去回収して得た溶液を仄工柱で用いる。The reaction is terminated when 2-butyn-1-ol disappears or almost disappears. This reaction solution alone can be used in the second step, but preferably, a solution obtained by removing and recovering the catalyst by an operation such as filtration is used in the secondary step.
（第２工程 合成工程）
第１工程で得られた浴故に、式Ｉで示される化合物を加
えて反応全行なう。必要に応じ、東に、同一または異な
る非プロトン性溶媒′に那えて反応を行なうこともでき
る。(Second Step Synthesis Step) To the bath obtained in the first step, the compound represented by formula I is added and the entire reaction is carried out. If necessary, the reaction can also be carried out in the same or different aprotic solvent.
本工程を実施するに当つＣは、塩基の使用が望ましく、
トリエチルアミン、ビリシンの如き有機塩基、および炭
酸水素ナトリウム、炭酸ナトリウムの如き無機塩基を用
いることができるが、収率の点で有機塩基が好ましい。In carrying out this step, it is preferable to use a base as C.
Organic bases such as triethylamine and bilicin, and inorganic bases such as sodium bicarbonate and sodium carbonate can be used, but organic bases are preferred from the viewpoint of yield.
反応龜度は、呈龜ないし２υＵ℃を用い得るが、室温で
は反応が遅く高温でｒｉ漸色および副生物の生成を伴な
いやすいので、５０〜１５Ｌｌ’Ｃが望ましい。反応時
間は、温度によるが、数時間ないし十数時間である。The reaction temperature may range from about 1 to 2υU°C, but is preferably from 50 to 15Ll'C because the reaction is slow at room temperature and tends to cause ri discoloration and by-product formation at high temperatures. The reaction time varies from several hours to more than ten hours depending on the temperature.
ｃ＝ｓ −２−ブテン−１−オールは、化合物１に対し
等モルないしやや過剰に用いる。c=s -2-Buten-1-ol is used in equimolar to slightly excess amount relative to compound 1.
式Ｉまたは…におけるＲおよびビは、同一または相異な
るメチル、エチル、プロピル、イソプロピル、ブチル、
Ｌ−ブチルの如き低級アルキル基である。R and Bi in formula I or... are the same or different methyl, ethyl, propyl, isopropyl, butyl,
It is a lower alkyl group such as L-butyl.
以下、実施例により史に評しく脱明する。 Hereinafter, the explanation will be explained with reference to examples.
実施例１
２−ブチ７−１−、ｔ−ル（１，４＆、２Ｌ１ｍモル）
をトルエン（２０＋ｆｉε）にとかし、リンドラ−触媒
〔５％Ｐｄ−ＣａＣＯ３（Ｐｄ １％宮有〕、７５ｍｙ
Ｊｋｎｕえて、やや陽圧の水素雰囲気下で撹拌した。１
．ｇ当量前後の水素を吸収した時点から反応液を少量採
取し、がスクロマトグラフイー（５％Ｔｈｅｒｍｏｎ−
ろｔＪ ＬＩ Ｌｌ ／ Ｇａｓ Ｃｈｒｏｍ Ｑ 、
カラム長２．１ｍ。Example 1 2-buty7-1-, t-ru (1,4 &, 2L 1 mmol)
was dissolved in toluene (20+fiε) and treated with Lindlar catalyst [5% Pd-CaCO3 (Pd 1% Miyaari)], 75 my
The mixture was then stirred under a slightly positive hydrogen atmosphere. 1
．． A small amount of the reaction solution was collected from the point at which about 100 g of hydrogen was absorbed, and subjected to chromatography (5% Thermon-
RotJ LI Ll / Gas Chrom Q,
Column length 2.1m.
９０°０）（以下、ＧＯと略す）で反応を追跡し、２−
ブチン−１−オールがほとんど消失した時点で反応を終
了したｚ （Ｇｃにより、ｃｉｓ −２−ブテン−１−
オール１００に対し、ｔｒａｎｓ−異性体２．６．ブタ
ノール０．８．２−ブチン−１−オール０であった。）
、ｇＭを用いて触媒を濾別し、得ら・れた濾液に化合物
１（Ｒ＝Ｒ’＝エチル基）（４，１１、ｙ、１５ｍモル
）およびトリエチルアミン（１，６７９，１６，５ｍモ
ル）を加えて、１００℃で６時間、攪拌反応した。冷却
後、水を加え振とうし、有機層を分離した。有機層を脱
水、凝縮、および約８０℃で真空下、低沸点物質を除去
してクロロアセトアニリド誘導体［（Ｒ＝Ｒ’士エチル
基）（４，１８Ｎ、９０チ）を得た。90°0) (hereinafter abbreviated as GO), 2-
The reaction was terminated when butyn-1-ol had almost disappeared (by Gc, cis-2-butene-1-
per 100 of the trans-isomer 2.6. Butanol: 0.8, 2-butyn-1-ol: 0. )
, gM to remove the catalyst, and the resulting filtrate contained Compound 1 (R=R'=ethyl group) (4,11,y, 15 mmol) and triethylamine (1,679,16,5 mmol). ) was added thereto, and the mixture was stirred and reacted at 100°C for 6 hours. After cooling, water was added and shaken, and the organic layer was separated. The organic layer was dehydrated, condensed, and low-boiling materials were removed under vacuum at about 80° C. to obtain a chloroacetanilide derivative [(R=R′ethyl group) (4,18N, 90%).
ｉ磁気共鳴（ＮＭＲ）スペクトル（ＣＤＣ１３）δ：ｔ
、２２（６Ｈ，ｔ、Ｊ＝７ａｚ）、１．６３ （３Ｈ。i Magnetic resonance (NMR) spectrum (CDC13) δ:t
, 22 (6H, t, J=7az), 1.63 (3H.
ｃｌ、Ｊ＝５）１ｚ）、２．５７ （４Ｈ、ｑ 、 Ｊ
＝７Ｈｚ）、６．６６（２Ｈ、Ｓ ）、４．２０Ｃ２Ｈ
、ｍ ）、４．９３ （２Ｈ、Ｓ ）、５．１５〜５．
８５ Ｃ２Ｈ）、７．１５（３Ｈ，ｍ）。cl, J = 5) 1z), 2.57 (4H, q, J
=7Hz), 6.66 (2H, S), 4.20C2H
, m), 4.93 (2H, S), 5.15-5.
85 C2H), 7.15 (3H, m).
赤外線吸収（ＩＲ）スペクトル（液膜）：２９７０．１
６８０．１４６０．１０７５ｃｍ−” 。Infrared absorption (IR) spectrum (liquid film): 2970.1
680.1460.1075cm-”.
実施例２
２−ブチン−１−オーｋ （１−４ｆｌ −、２０ｍモ
ル）をトルエン（２０１１４）にとかし、触媒（５チＰ
（１−（３ａＣＯ３，１００ｑ）を加えて、水素下で攪
拌した。Example 2 2-Butyne-1-oak (1-4 fl -, 20 mmol) was dissolved in toluene (20114) and the catalyst (5
(1-(3aCO3,100q) was added and stirred under hydrogen.
０、ｇ当を前後の水素を吸収した時点から反応液を少量
採取し、ａＣで反応を追跡し、２−ブチン−１−オール
がほとんど消失した時点で反応を終了したｐ （Ｇ Ｏ
により、ｃｉｓ −’ｌ−ブテンー１−オール１００に
対し、ｔｒａｎｓ−異性体１゛、４、シタノール０．６
．２−ブチン−１−オール２．２であった。A small amount of the reaction solution was collected from the point at which hydrogen was absorbed around 0.0 g, and the reaction was followed by aC, and the reaction was terminated when most of the 2-butyn-1-ol disappeared.
According to 100% of cis-'l-buten-1-ol, 1% of trans-isomer, 4% of trans-isomer, 0.6% of citanol.
．． 2-butyn-1-ol was 2.2.
ａｔ紙を用いて触媒を濾別し、得られた濾液に、化合物
１（Ｒ＝Ｒ’＝エチル基）（４，３８ｇ、１６ｍモル）
およびトリエチルアミン（１，７８，９゜１７．６ｍ％
ル）ｆｔ加えて、９０℃で１５時間攪拌反応した。以下
、実施例１と同様に処理して、クロロアセトアニリド誘
導体１（Ｒ＝Ｒ’−エチル基）（４，５１ｇ、９１チ）
を得た。The catalyst was filtered off using at paper, and compound 1 (R=R'=ethyl group) (4.38 g, 16 mmol) was added to the obtained filtrate.
and triethylamine (1,78,9°17.6m%
ft) and stirred and reacted at 90°C for 15 hours. Hereinafter, the same treatment as in Example 1 was carried out to obtain chloroacetanilide derivative 1 (R=R'-ethyl group) (4.51 g, 91 thi).
I got it.
実施例６
２−ブチン−１−オー＃（１，４＃％ ２０ｍ−ｆ−ル
）をシクロヘキサン（２Ｑｍ６）に加え、更に触媒（５
％ Ｆｉｌ（３ａＣ０３，１５０１１１９）を加えて、
水素下で攪拌した。０１ｇ当量前後の水素を吸収した時
点から反応液を少量採取し、Ｇｏで反応を追跡し、２−
ブチン−１−オールがほとんど消失した時点で反応を終
了した。濾紙を用いて触媒を濾別し、得られた濾液にト
ルエン（１０１１）を加え、更に化合物１（Ｒ＝Ｒ’＝
エチル基）（３，８４Ｎ、１４ｍモｌＬ／）およびトリ
エチルアミン（１，５６ｇ、１５．４ ｍモル）を加え
て、１００℃で５時間、攪拌反応した。以下、実施例１
と同様に処理して、化合物１（Ｒ＝Ｒ’＝エチル基）（
１，９４ｇ、９１Ｓ＞ｔ−得た。Example 6 2-Butyn-1-oh# (1,4#% 20 m-f-ole) was added to cyclohexane (2Qm6) and further catalyst (5
Add % Fil (3aC03,1501119),
Stir under hydrogen. A small amount of the reaction solution was collected from the time when around 0.1 g equivalent of hydrogen was absorbed, the reaction was tracked with Go, and 2-
The reaction was terminated when butyn-1-ol almost disappeared. The catalyst was filtered out using filter paper, toluene (1011) was added to the obtained filtrate, and compound 1 (R=R'=
Ethyl group) (3.84 N, 14 mmol/L/) and triethylamine (1.56 g, 15.4 mmol) were added and reacted with stirring at 100° C. for 5 hours. Below, Example 1
Compound 1 (R=R'=ethyl group) (
1.94 g, 91S>t- was obtained.
実施例４
実施例１と同様に第１工程を行ない反応濾液を得た。こ
の濾液に、化合物［（Ｒ＝エチル基、Ｒ′＝メチル基）
（３−９，！ｉ’、 １５＋ｎモル）およびトリエチ
ルアミン（１−６７＆、１６．５ｍモル）ｔ−加えて、
１００”Ｃで６時間、撹拌反応した。冷却後、水を加え
振とうし、有機層を分離した。有機層を脱水、濃縮、お
よび約８０℃で真空下、低沸点物質を除去して、クロロ
アセトアニリド誘導体１（Ｒ＝エチル基、Ｒ′＝メチル
基）（４，３４，９゜８９慢）を得た。Example 4 The first step was carried out in the same manner as in Example 1 to obtain a reaction filtrate. To this filtrate, the compound [(R=ethyl group, R'=methyl group)
(3-9,!i', 15+n mol) and triethylamine (1-67&, 16.5 mmol) t-additionally,
The reaction was stirred at 100"C for 6 hours. After cooling, water was added and shaken, and the organic layer was separated. The organic layer was dehydrated, concentrated, and low-boiling substances were removed under vacuum at about 80"C. Chloroacetanilide derivative 1 (R = ethyl group, R' = methyl group) (4,34,9°89) was obtained.
本発明の方法により、除草性化合物として有用なりロロ
アセトアニリｒｖＩ導体を容易にかつ高収率で製造でき
る。By the method of the present invention, roloacetanyl rvI conductors useful as herbicidal compounds can be easily produced in high yield.
Claims (1)
、２−ブチン−１−オールを接触還元して、ｃｉｓ−２
ブテン−１−オールの浴液を得る工程。 （２）第２工程：第１工程で得られたｃｉｓ−２−ブテ
ン−１−オールの溶液と、一般式 ▲数式、化学式、表等があります▼ （式中、ＲおよびＲ′は、同一または相異なる低級アル
キル基である。） で示される化合物とを混合して反応させて、一般式 ▲数式、化学式、表等があります▼ （式中、ＲおよびＲ′は、同一または相異なる低級アル
キル基である。） で示されるクロロアセトアニリド誘導体を得る工程。[Claims] A method for producing a chloroacetanilide derivative by the following steps. (1) First step: In an aprotic solvent, in the presence of a catalyst, 2-butyn-1-ol is catalytically reduced to give cis-2
Obtaining a bath solution of buten-1-ol. (2) Second step: The solution of cis-2-buten-1-ol obtained in the first step and the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R and R' are the same or different lower alkyl groups) are mixed and reacted to form the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein R and R' are the same or different lower alkyl groups). A step of obtaining a chloroacetanilide derivative represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2391686A JPS62185060A (en) | 1986-02-07 | 1986-02-07 | Production of chloroacetanilide derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2391686A JPS62185060A (en) | 1986-02-07 | 1986-02-07 | Production of chloroacetanilide derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62185060A true JPS62185060A (en) | 1987-08-13 |
Family
ID=12123817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2391686A Pending JPS62185060A (en) | 1986-02-07 | 1986-02-07 | Production of chloroacetanilide derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62185060A (en) |
-
1986
- 1986-02-07 JP JP2391686A patent/JPS62185060A/en active Pending
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