JPH0248546A - Production of trans-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acid halide - Google Patents
Production of trans-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acid halideInfo
- Publication number
- JPH0248546A JPH0248546A JP63199156A JP19915688A JPH0248546A JP H0248546 A JPH0248546 A JP H0248546A JP 63199156 A JP63199156 A JP 63199156A JP 19915688 A JP19915688 A JP 19915688A JP H0248546 A JPH0248546 A JP H0248546A
- Authority
- JP
- Japan
- Prior art keywords
- trans
- cis
- boron
- dichlorovinyl
- dimethyl
- 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
- -1 trans-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acid halide Chemical class 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- YMEKEHSRPZAOGO-UHFFFAOYSA-N boron triiodide Chemical compound IB(I)I YMEKEHSRPZAOGO-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical class N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002917 insecticide Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 3
- 229910052796 boron Inorganic materials 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical group 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- 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 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical class ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
- KGANAERDZBAECK-UHFFFAOYSA-N (3-phenoxyphenyl)methanol Chemical compound OCC1=CC=CC(OC=2C=CC=CC=2)=C1 KGANAERDZBAECK-UHFFFAOYSA-N 0.000 description 1
- AFEOKIGLYCQHAZ-UHFFFAOYSA-N (5-benzylfuran-3-yl)methanol Chemical compound OCC1=COC(CC=2C=CC=CC=2)=C1 AFEOKIGLYCQHAZ-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は一般式（［）
（式中、Ｘはハロゲン原子を表わす、）で示されるシス
２，２−ジメチル−３−（２，２−ジクロルビニル）−
シクロプロパンカルボン酸ハライドをトランス化せしめ
ることによるトランス−２，２−ジメチル−３−（２，
２−ジクロルビニル）−シクロプロパンカルボン酸ハラ
イドの製法に関する。Detailed Description of the Invention The present invention provides cis-2,2-dimethyl-3-(2,2-dichlorovinyl)-
trans-2,2-dimethyl-3-(2,
The present invention relates to a method for producing 2-dichlorovinyl)-cyclopropanecarboxylic acid halide.
〈従来の技術０発明が解決しようとする課題〉２．２−
ジメチル−３−（２，２−ジクロルビニル）−シクロプ
ロパンカルボン酸（以下、ジクロル酸と略称する。）は
家庭用、防疫用のみならず農業害虫あるいは森林害虫に
も優れた効力を示す殺虫剤ベルメスリン、サイベルメス
リン等の酸成分を構成するものである。ジクロル酸ハラ
イドはこれ等の殺虫剤の中間体と・して宵月である。<Conventional technology 0 Problems to be solved by the invention> 2.2-
Dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acid (hereinafter abbreviated as dichloroic acid) is an insecticide known as vermethrin, which is highly effective not only for household use and epidemic prevention, but also against agricultural pests and forest pests. , Cybelmethrin, etc., constitutes the acid component. Dichloric acid halide is used as an intermediate for these insecticides.
ジクロル酸ハライドには三員環に基づくシス、トランス
の幾何異性体が存在するが、シス体からＭＲされるエス
テルよりもトランス体から誘導されるエステルの方が温
血動物に対し低毒性であることが知られている。（Ｎａ
ｔｕｒｅ、２４４．４５６（１９７３）） 。Dichloric acid halide has cis and trans geometric isomers based on a three-membered ring, but esters derived from the trans isomer are less toxic to warm-blooded animals than esters derived from the cis isomer. It is known. (Na
ture, 244.456 (1973)).
しかしながら、ジクロル酸ハライドはトランス体とシス
体の混合物として製造される。従って、シス体をトラン
ス体に変換させることは工業的に重要な意義を持つ。However, dichloroacid halide is produced as a mixture of trans and cis forms. Therefore, converting the cis form to the trans form has important industrial significance.
これ迄、ジクロル酸ハライドのシス体をトランス体に変
換する方法としては１６０°Ｃ下に加熱する方法が知ら
れている（特開昭５０−１３１９５３号公報）。Hitherto, a method of heating to 160° C. has been known as a method for converting the cis form of dichloroacid halide into the trans form (Japanese Patent Application Laid-open No. 131953/1983).
しかしながら、この方法では高温を必要とするという問
題があり、例えばｔｏｏ’ｃではほとんどトランス化は
進行しない。However, this method has the problem of requiring high temperatures, and for example, trans conversion hardly progresses in too'c.
また菊酸ハライドのトランス化触媒として、ホウ素の塩
化物、臭化物が知られている（特開昭５４１２３５０号
公報）が、これ等をジクロル酸ハライドに用いてもトラ
ンス化は殆ど進行しない。Furthermore, boron chlorides and bromides are known as trans-conversion catalysts for chrysanthemum halide (Japanese Patent Application Laid-Open No. 5412350), but even when these are used for dichloroacid halide, trans conversion hardly proceeds.
〈課題を解決するための手段〉
本発明者らはジクロル酸ハライドのシス体をトランス化
することによるトランス体のより優れた製造方法を見出
すべく鋭意検討を重ねた結果、ホウ素のヨウ化物等が意
外にも好都合に、温和な条件下でもシス体をトランス化
せしめることを見出すとともに、更に種々の検討を加え
本発明を完成した。<Means for Solving the Problems> The present inventors have conducted intensive studies to find a better method for producing the trans form by converting the cis form of dichloroacid halide into trans form, and as a result, it has been found that boron iodide, Surprisingly, the inventors discovered that the cis isomer can be trans-converted even under mild conditions, and after further various studies, the present invention was completed.
すなわち本発明は（１）−船式（＋）
Ｃ！
（式中、Ｘはハロゲン原子を表わす、）で示されるシス
またはシス／トランス混合ジクロル酸ハライドにホウ素
のヨウ化物を作用させることを特徴とする工業的に優れ
たトランス−ジクロル酸ハライドの製造方法を提供する
ものである。That is, the present invention is (1)-ship type (+) C! (In the formula, X represents a halogen atom) An industrially excellent method for producing trans-dichloroic acid halide, which comprises reacting cis or cis/trans mixed dichloroic acid halide with boron iodide. It provides:
次に本発明方法について詳細に説明する。Next, the method of the present invention will be explained in detail.
本発明の原料であるジクロル酸ハライド（１）としでは
例えば、ジクロル酸クロライド、ジクロル酸ブロマイド
等が挙げられるが、工業的には取扱い易さ、価格等の面
からクロライドが通常使用される。Examples of dichloroyl halide (1) which is a raw material of the present invention include dichloroyl chloride and dichlorobromide, but chloride is usually used industrially from the viewpoint of ease of handling and price.
またジクロル酸ハライドはシス体単独あるいはトランス
体と任意の割合の混合物であっても良いが、本発明の目
的から考えてシス体単独もしくはシス体に冨むジクロル
酸ハライドを用いる場合にその意義を発揮することは言
うまでもない。In addition, dichloroyl halide may be used alone in the cis form or as a mixture with the trans form in any proportion; however, from the perspective of the purpose of the present invention, it is important to use dichloric acid halide in the cis form alone or in the cis form. Needless to say, it will be effective.
本発明で使用されるホウ素のヨウ化物としては、代表的
には三ヨウ化ホウ素が挙げられ、その使用量は被処理ジ
クロル酸ハライドに対して通常１７２００〜１モル倍、
好ましくは１／１００〜１１５モル倍である。The boron iodide used in the present invention is typically boron triiodide, and the amount used is usually 17,200 to 1 times the mole of dichlorohalide to be treated.
Preferably it is 1/100 to 115 times the mole.
反応は通常９溶媒の存在下に実施される。用いられる溶
媒としては、反応を阻害しないものであれば良く、例え
ばベンゼン、トルエン、キシレン、クメン、トリメチル
ベンゼン、ニトロベンゼン等の芳香族炭化水素、クロロ
ホルム、四塩化炭素、ジクロルエタン、クロルベンゼン
、０−シクロルヘンゼン、ブロムベンゼン等のハロゲン
化炭化水素、アセトニトリル、プロピオニトリル、ブチ
ロニトリル等のニトリル類が挙げられるが好ましくはハ
ロゲン化炭化水素である。The reaction is usually carried out in the presence of 9 solvents. The solvent used may be one that does not inhibit the reaction, such as aromatic hydrocarbons such as benzene, toluene, xylene, cumene, trimethylbenzene, and nitrobenzene, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, and 0-cyclohenzene. , halogenated hydrocarbons such as bromobenzene, and nitriles such as acetonitrile, propionitrile, butyronitrile, etc., but halogenated hydrocarbons are preferred.
本発明方法を実施するにあたっては、通常、ジクロル酸
ハライドを溶媒に溶解し、ホウ素のヨウ化物を加えるこ
とにより実施される。The method of the present invention is usually carried out by dissolving dichloroacid halide in a solvent and adding boron iodide.
反応温度はホウ素のヨウ化物の使用量、溶媒の種類等に
よっても変化するが、通常４０〜１５０’Ｃ。The reaction temperature varies depending on the amount of boron iodide used, the type of solvent, etc., but is usually 40-150'C.
好ましくは６０〜１２０ ’Ｃである。Preferably it is 60-120'C.
また反応時間もホウ素のヨウ化物の使用量、溶媒の種類
等によっても変化するが通常３０分〜２０時間程度であ
る。The reaction time also varies depending on the amount of boron iodide used, the type of solvent, etc., but is usually about 30 minutes to 20 hours.
反応の進行度は反応液の一部をサンプリングし、ガスク
ロマトグラフィー、ＮＭＲ等による分析により求めるこ
とができる。The progress of the reaction can be determined by sampling a portion of the reaction solution and analyzing it by gas chromatography, NMR, or the like.
反応後、例えば反応マスから触媒を除去した後蒸留等の
手段によりトランス体に冨んだジクロル酸ハライドが得
られる。また単離することなしに反応マスへ、３−フェ
ノキシベンジルアルコール、５−ベンジル−３−フリル
メチルアルコール等を加えて直接反応させることにより
低毒性殺虫剤へ誘導することもできる。After the reaction, for example, after removing the catalyst from the reaction mass, a dichloroacid halide enriched in the trans isomer can be obtained by means such as distillation. It is also possible to derive a low toxicity insecticide by adding 3-phenoxybenzyl alcohol, 5-benzyl-3-furylmethyl alcohol, etc. to the reaction mass and reacting directly without isolation.
また反応マスへエタノール等を加えて直接エステル化し
、生化学的光学分割用原料として供することもできるし
、常法に従いアルカリ性水溶液等を加えて加水分解する
ことにより遊離の酸に誘導することもできる。It is also possible to directly esterify the reaction mass by adding ethanol etc. and use it as a raw material for biochemical optical resolution, or it can also be derived into a free acid by adding an alkaline aqueous solution etc. and hydrolyzing it according to a conventional method. .
〈発明の効果〉
かくして目的とするトランス−ジクロル酸ハライドが製
造されるが、本発明方法によれば公知法に比し極めて緩
和な条件でトランス体を製造し得る。<Effects of the Invention> In this way, the desired trans-dichloroacid halide is produced, and according to the method of the present invention, the trans isomer can be produced under extremely mild conditions compared to known methods.
〈実施例〉
次に実施例によって本発明を更に詳細に説明するが、本
発明はこれらのみに限定されるものではない。<Examples> Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these.
実施例１
シス体９６．３％、トランス体３．７％よりなるジクロ
ル酸クロライド゛２．Ｏｇをクロルベンゼン１８ｇに溶
解した後、窒素雰囲気下これに三ヨウ化ホウ素１１０ｍ
ｇを加えて１００℃で３時間撹拌した。Example 1 Dichloroyl chloride consisting of 96.3% cis isomer and 3.7% trans isomer 2. After dissolving Og in 18 g of chlorobenzene, 110 m of boron triiodide was added to it under a nitrogen atmosphere.
g was added thereto, and the mixture was stirred at 100°C for 3 hours.
反応後、室温まで冷却し、エタノール４４０Ｌ１ｇとピ
リジン７７０ｍｇを加え、室温下１時間撹拌した後水洗
、溶媒留去を行った。 得られた溶液を蒸留し、沸点８
８〜９０℃／１ｍｄｇの留分２．Ｏｇを得た。After the reaction, the mixture was cooled to room temperature, 1 g of ethanol (440 L) and 770 mg of pyridine were added, and the mixture was stirred at room temperature for 1 hour, followed by washing with water and distilling off the solvent. The resulting solution was distilled to a boiling point of 8
8-90°C/1mdg fraction 2. Obtained Og.
このものは赤外線吸収スペクトルよりジクロル酸エチル
エステルであることを確認した。ガスクロマトグラフィ
ーで分析した結果シス体２１．１％トランス体７８．９
％であった。This product was confirmed to be dichloroic acid ethyl ester by infrared absorption spectrum. Analysis by gas chromatography shows that the cis form is 21.1% and the trans form is 78.9%.
%Met.
実施例２
シス体４５．０％、トランス体５５．０％よりなるジク
ロル酸クロライド３．０８ｇをクロルベンゼン２４ｇに
溶解した後、窒素雰囲気下これに三ヨウ化ホウ素４４０
ｍｇ加えて８０°Ｃで６時間撹拌した。Example 2 After dissolving 3.08 g of dichloroyl chloride consisting of 45.0% cis isomer and 55.0% trans isomer in 24 g chlorobenzene, 440 g of boron triiodide was added to this under a nitrogen atmosphere.
mg and stirred at 80°C for 6 hours.
反応後、室温まで冷却した後１５％水酸化ナトリウム水
溶液を用いて加水分解後、７０％硫酸で酸性にしトルエ
ンで抽出した。トルエンを留去すると白色の固体が２．
６４ｇ得られた。このものは赤外線吸収スペクトルより
ジクロル酸であることをＲｉＵした。After the reaction, the mixture was cooled to room temperature, hydrolyzed using a 15% aqueous sodium hydroxide solution, acidified with 70% sulfuric acid, and extracted with toluene. When the toluene was distilled off, a white solid was obtained.
64g was obtained. This product was determined to be dichloroic acid by RiU based on its infrared absorption spectrum.
一部をサンプリングし常法によりエチルエステルとした
後、ガスクロマトグラフィーにより分析した結果、シス
体２０．７％、トランス体７９．３％であった。A portion was sampled and converted into ethyl ester using a conventional method, and then analyzed by gas chromatography. As a result, the cis isomer was 20.7% and the trans isomer was 79.3%.
実施例３
シス体９６．６％、トランス体３，４％よりなるジクロ
ル酸クロライド１．１９ ｇをトルエン１７．４ ｇに
熔解した後、窒素雰囲気下、三ヨウ化ホウ素３２０ｍｇ
を加えて１００°Ｃで８時間撹拌した。Example 3 After dissolving 1.19 g of dichloroyl chloride consisting of 96.6% cis form and 3.4% trans form in 17.4 g of toluene, 320 mg of boron triiodide was dissolved in a nitrogen atmosphere.
was added and stirred at 100°C for 8 hours.
反応後実施例１と同様な方法で処理し、１．９３ｇのジ
クロル酸エチルエステルを得た。After the reaction, the reaction mixture was treated in the same manner as in Example 1 to obtain 1.93 g of ethyl dichloroate.
分析結果はシス体２９．７％、トランス体７０．３％で
あった。The analysis results were 29.7% cis isomer and 70.3% trans isomer.
実施例４
実施例３で用いたと同じジクロル酸クロライド１．２１
ｇを１．２−ジクロルエタン２５ｇに溶解した後、窒
素雰囲気下これに三ヨウ化ホウ素３２０＋ｗｇを加えて
８０°Ｃで４時間撹拌した。Example 4 Same dichloroyl chloride used in Example 3 1.21
g was dissolved in 25 g of 1,2-dichloroethane, 320+ wg of boron triiodide was added thereto under a nitrogen atmosphere, and the mixture was stirred at 80°C for 4 hours.
反応後実施例１と同様な方法で処理して１．１３ｇのジ
クロル酸エチルを得た。 分析結果はシス体１８．１％
、トランス体８１．９％であった。After the reaction, the reaction mixture was treated in the same manner as in Example 1 to obtain 1.13 g of ethyl dichlorate. The analysis result is cis isomer 18.1%
, 81.9% was trans isomer.
実施例５
実施例１で用いたと同じジクロル酸クロライド２．２１
ｇをア七ト二トリル２６ｇに溶解した後、窒素雰囲気
下これに三ヨウ化ホウ素２２０ｎ＋ｇを加えて５０°Ｃ
で９時間撹拌した。Example 5 Same dichloroyl chloride used in Example 1 2.21
After dissolving g in 26 g of a7tonitrile, 220 n+g of boron triiodide was added thereto under a nitrogen atmosphere, and the mixture was heated at 50°C.
The mixture was stirred for 9 hours.
反応後実施例１と同様な方法で処理し、分析したところ
シス体４８％、トランス体５２％であった。After the reaction, the reaction mixture was treated in the same manner as in Example 1 and analyzed, and found to be 48% cis-isomer and 52% trans-isomer.
比較例１
実施例１で用いたと同じジクロル酸クロライド１．０５
ｇをクロルベンゼン１６ｇに溶解した後、窒素雰囲気下
１００°Ｃで８時間撹拌した。Comparative Example 1 Same dichloroyl chloride as used in Example 1 1.05
g was dissolved in 16 g of chlorobenzene, and the mixture was stirred at 100°C for 8 hours under a nitrogen atmosphere.
分析結果はシス体９４．７％、トランス体５．３％であ
った。The analysis results were 94.7% cis isomer and 5.3% trans isomer.
比較例２
実施例１において、三ヨウ化ホウ素に代えて三臭化ホウ
素７０＋ｇ用いる以外は実施例１と同様に実施した。Comparative Example 2 The same procedure as in Example 1 was carried out except that 70+g of boron tribromide was used in place of boron triiodide.
分析結果はシス体９５．１％、トランス体４．９％であ
った。The analysis results were 95.1% cis isomer and 4.9% trans isomer.
比較例３
実施例１において、三ヨウ化ホウ素に代えて三塩化ホウ
素３３ｍｇ用いる以外は実施例１と同様に実施した。Comparative Example 3 The same procedure as in Example 1 was carried out except that 33 mg of boron trichloride was used instead of boron triiodide.
分析結果はシス体９６．３％、トランス体３．７％であ
った。The analysis results were 96.3% cis isomer and 3.7% trans isomer.
Claims (1)
チル−３−（２，２−ジクロルビニル）−シクロプロパ
ンカルボン酸ハライドにホウ素のヨウ化物を作用させる
ことを特徴とするトランス−２，２−ジメチル−３−（
２，２−ジクロルビニル）−シクロプロパンカルボン酸
ハライドの製造方法[Claims] Cis or cis/trans mixed 2,2-dimethyl-3-(2, Trans-2,2-dimethyl-3-(2-dichlorovinyl)-cyclopropanecarboxylic acid halide is treated with boron iodide.
Method for producing 2,2-dichlorovinyl)-cyclopropanecarboxylic acid halide
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63199156A JP2629862B2 (en) | 1988-08-09 | 1988-08-09 | Method for producing racemic-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid halide |
| US07/349,056 US4962233A (en) | 1988-05-19 | 1989-05-09 | Process for preparing racemic dihalovinylcyclopropane carboxylic acid halides |
| DE8989304662T DE68905073T2 (en) | 1988-05-19 | 1989-05-09 | METHOD FOR PRODUCING RACEMIC CYCLOPROPANCARBONIC ACID HALOGENIDES. |
| EP89304662A EP0342843B1 (en) | 1988-05-19 | 1989-05-09 | Process for preparing racemic dihalovinylcyclopropane carboxylic acid halides |
| HU892485A HU205597B (en) | 1988-05-19 | 1989-05-18 | Process for producing and converting raceme dihalogeno-vinyl-cyclopropane-carboxylic acid halogenides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63199156A JP2629862B2 (en) | 1988-08-09 | 1988-08-09 | Method for producing racemic-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid halide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0248546A true JPH0248546A (en) | 1990-02-19 |
| JP2629862B2 JP2629862B2 (en) | 1997-07-16 |
Family
ID=16403087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63199156A Expired - Lifetime JP2629862B2 (en) | 1988-05-19 | 1988-08-09 | Method for producing racemic-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid halide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2629862B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02243651A (en) * | 1989-03-16 | 1990-09-27 | Sumitomo Chem Co Ltd | Method for racemizing dihalovinylcyclopropanecarboxylic acid halide |
| US10729795B2 (en) | 2004-01-12 | 2020-08-04 | Veltek Associates, Inc. | Method for mixing and dispensing |
-
1988
- 1988-08-09 JP JP63199156A patent/JP2629862B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02243651A (en) * | 1989-03-16 | 1990-09-27 | Sumitomo Chem Co Ltd | Method for racemizing dihalovinylcyclopropanecarboxylic acid halide |
| US10729795B2 (en) | 2004-01-12 | 2020-08-04 | Veltek Associates, Inc. | Method for mixing and dispensing |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2629862B2 (en) | 1997-07-16 |
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