JPH02243651A - Method for racemizing dihalovinylcyclopropanecarboxylic acid halide - Google Patents
Method for racemizing dihalovinylcyclopropanecarboxylic acid halideInfo
- Publication number
- JPH02243651A JPH02243651A JP1065448A JP6544889A JPH02243651A JP H02243651 A JPH02243651 A JP H02243651A JP 1065448 A JP1065448 A JP 1065448A JP 6544889 A JP6544889 A JP 6544889A JP H02243651 A JPH02243651 A JP H02243651A
- Authority
- JP
- Japan
- Prior art keywords
- acid halide
- dihalo
- boron
- racemizing
- optically active
- 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
- 150000004820 halides Chemical class 0.000 title claims abstract description 24
- 239000002253 acid Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 11
- YMEKEHSRPZAOGO-UHFFFAOYSA-N boron triiodide Chemical compound IB(I)I YMEKEHSRPZAOGO-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000002917 insecticide Substances 0.000 abstract description 4
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 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 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- -1 cyclopropanecarboxylic acid halide Chemical class 0.000 description 4
- 239000000243 solution Substances 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002728 pyrethroid Substances 0.000 description 3
- 230000006340 racemization Effects 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
- 241001465754 Metazoa Species 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
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 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
- 230000000694 effects Effects 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-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
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000005946 Cypermethrin Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-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
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 1
- KAATUXNTWXVJKI-UHFFFAOYSA-N cypermethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-UHFFFAOYSA-N 0.000 description 1
- 229960005424 cypermethrin Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 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
- 239000007787 solid Substances 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (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〉
本発明は式（１）
（式中、Ｘ、Ｙはハロゲン原子を、＊は不斉炭素を表わ
す、）
で示される光学活性ジハロ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
徴とするへロビニルシクロプロパンカルボン酸ハライド
のラセミ化方法に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to optically active dihalovinyl represented by formula (1) (wherein, X and Y represent halogen atoms, and * represents an asymmetric carbon). The present invention relates to a method for racemizing herovinylcyclopropanecarboxylic acid halide, which comprises reacting cyclopropanecarboxylic acid halide with boron iodide.
〈従来の技術、発明が解決しようとする課題〉式（１）
においてＹが水酸基に相当するジハロとニルシクロプロ
パンカルボン酸すなわち２．２−ジメチル−３−（２，
２−ジハロビニル）−シクロプロパンカルボン酸（以下
、ジハロ酸と略称する。）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低毒性
殺虫剤ベルメスリン、サイペルメスリン等の酸成分を構
成するものである。ジハロ酸ハライドはこれ等の殺虫剤
の中間体として有用である。<Prior art, problem to be solved by invention> Formula (1)
dihalo and nylcyclopropanecarboxylic acid in which Y corresponds to a hydroxyl group, i.e. 2,2-dimethyl-3-(2,
2-Dihalovinyl)-cyclopropanecarboxylic acid (hereinafter abbreviated as dihaloacid) is an acid used in low-toxicity insecticides such as vermethrin and cypermethrin, which are highly effective not only for household use and epidemic prevention, but also against agricultural pests and forest pests. It constitutes the ingredients. Dihaloacid halides are useful as intermediates for these insecticides.
前記式（１）で示されるジハロ酸ハライドにはシス、ト
ランスの幾何異性体があり、またその各々に（＋）およ
び（−）の光学異性体があることから、合計４種の異性
体が存在する。一般に、これらの異性体の中、（＋）体
から導かれるピレスロイド系のエステル類は対応する（
−）体から導びかれるピレスロイド系エステル類よりも
強い殺虫活性を示し、また温血動物に対する安全性はト
ランス体のエステル類が対応するシス体のエステル類に
比し遥かに高いことが知られている（例えばＮａｔｕｒ
ｅ ２４４，４５６（１９７３）） 。The dihaloacid halide represented by the above formula (1) has cis and trans geometric isomers, and each of them has (+) and (-) optical isomers, so there are a total of four types of isomers. exist. Generally, among these isomers, pyrethroid esters derived from the (+) isomer have the corresponding (
-) It is known that trans-esters exhibit stronger insecticidal activity than pyrethroid esters derived from the body, and that trans-esters are much safer for warm-blooded animals than the corresponding cis-esters. (e.g. Natur
e 244, 456 (1973)).
ジハロ＊ｇは通常シス体、トランス体の混合したラセミ
体、即ち（±）体として製造され、酸の場合はこれを光
学活性な有機塩類を用いて光学分割することにより、ま
たエステルの場合は酵素などを用いて不斉加水分解する
ことにより（＋）体が得られ、より高活性な殺虫性化合
物の製造に使用されている。ここで光学分割された残り
の（−）体はそのピレスロイド系のエステルとしての活
性が殆んどなく、従ってこの有用性のない（−）体を効
率よくラセミ化し、より有効な（±）体に変換すること
は、特に工業的規模でのピレスロイド系エステルの生産
時においては大きな！！！！題となる。Dihalo*g is usually produced as a racemic mixture of cis and trans forms, that is, (±) form, and in the case of acids, it is produced by optically resolving it using optically active organic salts, and in the case of esters, it is produced by optically resolving it using optically active organic salts. The (+) form is obtained by asymmetric hydrolysis using enzymes, etc., and is used in the production of more highly active insecticidal compounds. The remaining (-) isomer optically resolved here has almost no activity as a pyrethroid ester, and therefore this useless (-) isomer can be efficiently racemized to create a more effective (±) isomer. The conversion to ! ! ! It becomes a problem.
しかしながら、前８己のように、式（＋）で示されるシ
クロプロパンカルボン酸類にはＣ１位と６１位に２個の
不斉炭素を有するため、そのラセミ化には種々の困難を
伴なう。However, as shown in the previous example, the cyclopropanecarboxylic acids represented by the formula (+) have two asymmetric carbon atoms at the C1 and 61 positions, so their racemization is accompanied by various difficulties. .
これ迄、ジハロ酸類をラセミ化する方法としてはジハロ
酸を光増感剤の存在下に光盟射する方法が知られている
（特開昭５０−１６０２４２号）。Until now, as a method for racemizing dihaloacids, a method in which dihaloacids are irradiated with light in the presence of a photosensitizer has been known (Japanese Patent Application Laid-open No. 160242/1983).
しかしながら、この方法では光化学反応用の特殊な装置
を必要とするうえ電力の消費も大きいなど、工業的に実
施するには種々の難点があった。However, this method has various difficulties in industrial implementation, such as requiring special equipment for photochemical reactions and high power consumption.
本発明者らは、光学活性ジハロ酸類をラセミ化させる工
業的により優れた方法を見出すべ（、鋭意検討を重ねた
結果、前記式（りで示される光学活性ジハロ酸ハライド
にホウ素のヨウ化物等を作用させることにより意外にも
好都合にラセミ化反応が進行す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。The present inventors have discovered an industrially superior method for racemizing optically active dihaloacids. They discovered that the racemization reaction progresses in a surprisingly favorable manner by acting on the compound, and completed the present invention by further conducting various studies.
く課題を解決するための手段〉
すなわち本発明は
式（口
（式中、Ｘ、Ｙはハロゲン原子を、本は不斉炭素を表わ
す、）
で示される光学活性なジハロ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
特徴とする工業的に優れたジノ＼ロビニｌレジクロプロ
パンカルボン酸ハライドのラセミ化方法を提供するもの
である。Means for Solving the Problems> That is, the present invention provides an optically active dihalovinylcyclopropanecarboxylic acid represented by the formula: The present invention provides an industrially excellent method for racemizing dichloropropanecarboxylic acid halide, which is characterized by reacting boron iodide with the halide.
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光学活性ジハロ酸ハライド（１）と
しては、例えばジクロル酸クロライド、ジクロル酸ブロ
マイド、ジブロム酸クロライド、ジブロム酸ブロマイド
等の光学活性体が挙げられる。工業的には取扱い昌さ、
′価格等の面からジハロ酸ハライドが通常使用される。Examples of the optically active dihaloyl halide (1) which is a raw material of the present invention include optically active substances such as dichloroyl chloride, dichlorobromide, dibromic acid chloride, and dibromic acid bromide. Industrially, it is easy to handle,
'Dihaloacid halides are usually used from the viewpoint of cost.
ジハロ酸ハライドには、前述のように４種類の異性体が
存在する。その中の１種単独であっても、これらの任意
の割合の混合物であっても、用いることができるが、本
発明の目的から考えて（−）体または（−）体に冨むジ
ハロ酸ハライドを用いる時に、その意義を発揮すること
は言うまでもない。As mentioned above, dihaloacid halides exist in four types of isomers. It is possible to use either one of them alone or a mixture of these in any proportion, but from the perspective of the purpose of the present invention, dihaloacids in the (-) form or in the (-) form may be used. Needless to say, when using halide, its significance is demonstrated.
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
は三ヨウ化ホウ素などが挙げられる。The boron iodide used in the present invention typically includes boron triiodide.
その使用量は被処理ジハロ酸ハライドに対して通常１
／２００〜１モル倍、好ましくはｌ ／１００〜１／３
モル倍である。The amount used is usually 1 part per dihalo acid halide to be treated.
/200 to 1 mole, preferably l /100 to 1/3
It is twice as many moles.
反応は通常、溶媒の存在下に実施される。溶媒としては
、反応を阻害しないものであれば良（、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、クロルベンゼン、０−ジクロルベンゼン、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 a solvent. The solvent may be one that does not inhibit the reaction (for example, benzene, toluene, xylene, cumene, trimethylbenzene,
Examples include aromatic hydrocarbons such as nitrobenzene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, chlorobenzene, 0-dichlorobenzene, bromobenzene, and nitriles such as acetonitrile, propionitrile, butyronitrile, but preferably It is a halogenated hydrocarbon.
本発明を実施するにあたっては、通常、ジハロ酸ハライ
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 present invention is generally carried out by dissolving dihaloacid 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、種類等によって
も変化するが、通常４０〜１５０℃、好ましくは８０〜
１２０℃である。The reaction temperature varies depending on the amount and type of boron iodide used, but is usually 40-150°C, preferably 80-150°C.
The temperature is 120°C.
また反応時間もホウ素のヨウ化物の使用量、種類によっ
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 and type of boron iodide used, 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、目的物は例えば、反応マスから触媒を除去した
後、蒸留等の手段により単離することができる。After the reaction, the target product can be isolated by means such as distillation after removing the catalyst from the reaction mass.
また、本発明によれば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。According to the present invention, it is also possible to add
3-phenoxybenzyl alcohol, 5-benzyl-3
- It is also possible to induce a low toxicity insecticide by adding furyl methyl alcohol or the like and causing a direct reaction.
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。Alternatively, it is possible to directly esterify the reaction mass by adding ethanol or the like and use it as a raw material for biochemical optical resolution, or it can be induced into a free acid by adding an alkaline aqueous solution or the like and hydrolyzing it according to a conventional method. can.
〈発明の効果〉
本発明によれば特殊な反応装置を必要とせず、しかも効
率良くラセミ−ジハロａｍを製造、し得る。<Effects of the Invention> According to the present invention, racemic dihalo am can be efficiently produced without requiring a special reaction apparatus.
また、本発明によるラセミ化生成物は温血動物に対しよ
り低毒性のトランス体に冨み、本発明はこの点において
も有利である。Furthermore, the racemization product according to the present invention is rich in trans isomers that are less toxic to warm-blooded animals, and the present invention is also advantageous in this respect.
〈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
発明は何らこれら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 thereto.
実施例１
左旋性ジクロル酸クロライド（（＋）−シス体＝３．０
％、（−）−シス体：２．９％、（＋）−）ランス体：
１４．１％、（−）−トランス体＝８０．０％よりなる
）１．２１ｇをクロルベンゼン２２ｇに溶解した後、窒
素雰囲気下に三ヨウ化ホウ素２９０ｍｇを加え１００°
Ｃで８時間撹拌した。Example 1 Levorotatory dichloroyl chloride ((+)-cis form = 3.0
%, (-)-cis form: 2.9%, (+)-) lance form:
After dissolving 1.21 g of (-14.1%, (-)-trans isomer = 80.0%) in 22 g of chlorobenzene, 290 mg of boron triiodide was added under a nitrogen atmosphere, and the mixture was heated at 100°.
The mixture was stirred at C for 8 hours.
反応液をサンプリングし、（＋）−２−オクタツールの
エステルに導いた後、ガスクロマトグラフィーにより分
析した結果、光学異性体比は（＋）−シス体７１１．４
％、（−）−シス体＝７．２％、（＋）−）ランス体：
２８．６％、（〜）−トランス体： ５２．８％であ
った。After sampling the reaction solution and converting it into an ester of (+)-2-octatool, analysis by gas chromatography revealed that the optical isomer ratio was (+)-cis form 711.4
%, (-)-cis form = 7.2%, (+)-) lance form:
28.6%, (~)-trans form: 52.8%.
また反応液を室温まで冷却し、エタノール２７０ｍｇと
ピリジン４６０ａ＋ｇを加え室温下１時間撹拌した後、
水洗、溶媒留去し、次いで蒸留することにより、沸点８
８〜９０°Ｃ／１＋ｕ＋ｌ１ｇの留分１．１３ｇを得た
。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６１ｍした。In addition, the reaction solution was cooled to room temperature, 270 mg of ethanol and 460 a+g of pyridine were added, and the mixture was stirred at room temperature for 1 hour.
By washing with water, removing the solvent, and then distilling, the boiling point is 8.
1.13 g of a fraction of 8-90°C/1+u+l1g was obtained. This product was determined to be dichloroic acid ethyl ester by infrared absorption spectrum.
実施例２
実施例１において、ヨウ化ホウ素を５４０１ｍｇ、クロ
ルベンゼンを６ｇ用いる以外は、実施例１と同様に実施
し１．０７ｇのジクロル酸エチルエステルを得た。Example 2 The same procedure as in Example 1 was carried out except that 5401 mg of boron iodide and 6 g of chlorobenzene were used to obtain 1.07 g of ethyl dichloroate.
光学異性体比は（＋）−シス体＝９．９％、（−）−シ
ス体＝７．６％、（＋）−トランス体： ３８．２％、
（−）−トランス体： ４４．３％であった。The optical isomer ratio is (+)-cis form = 9.9%, (-)-cis form = 7.6%, (+)-trans form: 38.2%,
(-)-Trans form: 44.3%.
実施例３
左旋性ジクロル酸クロライド（（＋）−シス体： １８
．６％、（−）−シス体： ７８．０％、（＋）−）ラ
ンス体二１，６％、（＝）−トランス体：１．８％より
なる）１．２１ ｇを１．２−ジクロルエタン２５ｇに
溶解した後、窒素雰囲気下に三ヨウ化ホウ素３２０ｍｇ
を加え８０°Ｃで８時間撹拌した。Example 3 Levorotatory dichloroyl chloride ((+)-cis form: 18
．． 6%, (-)-cis form: 78.0%, (+)-) lance form: 1.6%, (=)-trans form: 1.8%) 1.21 g to 1.2 - 320 mg of boron triiodide after dissolving in 25 g of dichloroethane under nitrogen atmosphere
was added and stirred at 80°C for 8 hours.
反応後室温まで冷却した後１５％水酸化ナトリウム水溶
液で加水分解後、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Ｉｇ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
あることを確認した。After the reaction, the mixture was cooled to room temperature, hydrolyzed with a 15% aqueous sodium hydroxide solution, acidified with 70% sulfuric acid, and extracted with toluene. When toluene was distilled off, white solid Ig was obtained. This substance was confirmed to be dichloroic acid by infrared absorption spectrum.
一部をサンプリングし、常法により（＋）−２−オクチ
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、光学異性体比は（＋）−シス体：６．４％
、（−）−シス体： １２．２％、（＋）−トランス体
：５４．１％、（−）−）ランス体： ２７．３％であ
った。A portion was sampled and converted into (+)-2-octyl ester using a conventional method, and then analyzed by gas chromatography. As a result, the optical isomer ratio was (+)-cis form: 6.4%
, (-)-cis form: 12.2%, (+)-trans form: 54.1%, and (-)-) lance form: 27.3%.
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１．１９
ｇを＋ルエン１７．４ ｇに溶解した後、舊素雰囲気下
に三ヨウ化ホウ素を３２０ｍｇ加えて１００℃で８時間
撹拌した。Example 4 Same dichloroyl chloride used in Example 3 1.19
g was dissolved in 17.4 g of toluene, 320 mg of boron triiodide was added in a fluorine atmosphere, and the mixture was stirred at 100° C. for 8 hours.
反応後、実施例１と同様な方法で処理し１．０９ｇのジ
クロル酸エチルエステルを得た。光学異性体比は （＋
）−シス体ニア、６％、（−）−シス体：ｚｔ、ｉ％、
（＋）−）ランス体： ５０，９％、（−）−）ラ
ンス体； ２０．４％であった。After the reaction, the reaction mixture was treated in the same manner as in Example 1 to obtain 1.09 g of ethyl dichloroate. The optical isomer ratio is (+
)-cis form near, 6%, (-)-cis form: zt, i%,
(+)-) lance form: 50.9%, (-)-) lance form: 20.4%.
実施例５
実施例３で用いたと同じジクロル酸クロライド１．３５
ｇをアセトニトリル１５．７ ｇに溶解した後、窒素雰
囲気下に三ヨウ化ホウ素３９０ｍｇを加えて、８０°Ｃ
で１０時間撹拌した。Example 5 Same dichloroyl chloride used in Example 3 1.35
g was dissolved in 15.7 g of acetonitrile, 390 mg of boron triiodide was added under a nitrogen atmosphere, and the mixture was heated at 80°C.
The mixture was stirred for 10 hours.
反応後、実施例１と同様な方法で処理し１．１６ｇのジ
クロル酸エチルエステルを得た。光学異性体比は （＋
）−シス体：５．２％、（−）−シス体：９．６％、
（＋）−）ランス体７５７．４％、（−）−）ランス
体：２７．８％であった。After the reaction, the reaction mixture was treated in the same manner as in Example 1 to obtain 1.16 g of ethyl dichloroate. The optical isomer ratio is (+
)-cis form: 5.2%, (-)-cis form: 9.6%,
(+)-) lance form: 757.4%, (-)-) lance form: 27.8%.
比較例！
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１９０１ｇを用いる以外は実施例１と同様に実施した
。Comparative example! Example 1 was carried out in the same manner as in Example 1 except that 1901 g of boron tribromide was used in place of boron triiodide.
光学異性体比は（＋）−シス体＝３．９％、（−）−シ
ス体：３．７％、（＋）−トランス体： １５．７％、
（−）−トランス体： ７６．７％であった。The optical isomer ratio is (+)-cis form = 3.9%, (-)-cis form: 3.7%, (+)-trans form: 15.7%,
(-)-Trans form: 76.7%.
比較例２
実施例１においで、三ヨウ化ホウ素に代えて三塩化ホウ
素１９０ ｍｇを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 190 mg of boron trichloride was used instead of boron triiodide.
光学異性体比は（＋）、シス体８３．０％、（−）−シ
ス体：３．０％、（＋）−）ランス体： １４．０％、
（−）トランス体： ８０．０％であった。The optical isomer ratio is (+), cis form: 83.0%, (-)-cis form: 3.0%, (+)-) lance form: 14.0%,
(-) trans form: 80.0%.
Claims (1)
す。） で示される光学活性なジハロ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
特徴とするジハロシクロプロパンカルボン酸ハライドの
ラセミ化方法。(1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X and Y represent halogen atoms, and * represents an asymmetric carbon.) Optically active dihalovinylcyclopropanecarboxylic acid halide 1. A method for racemizing dihalocyclopropanecarboxylic acid halide, which comprises reacting with boron iodide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1065448A JP2629950B2 (en) | 1989-03-16 | 1989-03-16 | Method for racemizing dihalovinylcyclopropanecarboxylic acid halides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1065448A JP2629950B2 (en) | 1989-03-16 | 1989-03-16 | Method for racemizing dihalovinylcyclopropanecarboxylic acid halides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02243651A true JPH02243651A (en) | 1990-09-27 |
| JP2629950B2 JP2629950B2 (en) | 1997-07-16 |
Family
ID=13287431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1065448A Expired - Lifetime JP2629950B2 (en) | 1989-03-16 | 1989-03-16 | Method for racemizing dihalovinylcyclopropanecarboxylic acid halides |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2629950B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52144651A (en) * | 1976-05-24 | 1977-12-02 | Sumitomo Chem Co Ltd | Racemization of optical active 2,2-dimethyl-3-(1-alkenyl)-cyclopropane-1-carboxylic acid |
| JPS5337858A (en) * | 1976-09-20 | 1978-04-07 | Nippon Mektron Kk | Terminal structure for flexible circuit and method of producing same |
| JPH0248546A (en) * | 1988-08-09 | 1990-02-19 | Sumitomo Chem Co Ltd | Production of trans-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acid halide |
-
1989
- 1989-03-16 JP JP1065448A patent/JP2629950B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52144651A (en) * | 1976-05-24 | 1977-12-02 | Sumitomo Chem Co Ltd | Racemization of optical active 2,2-dimethyl-3-(1-alkenyl)-cyclopropane-1-carboxylic acid |
| JPS5337858A (en) * | 1976-09-20 | 1978-04-07 | Nippon Mektron Kk | Terminal structure for flexible circuit and method of producing same |
| JPH0248546A (en) * | 1988-08-09 | 1990-02-19 | Sumitomo Chem Co Ltd | Production of trans-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acid halide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2629950B2 (en) | 1997-07-16 |
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