JPH0477738B2 - - Google Patents
Info
- Publication number
- JPH0477738B2 JPH0477738B2 JP59031861A JP3186184A JPH0477738B2 JP H0477738 B2 JPH0477738 B2 JP H0477738B2 JP 59031861 A JP59031861 A JP 59031861A JP 3186184 A JP3186184 A JP 3186184A JP H0477738 B2 JPH0477738 B2 JP H0477738B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- reaction
- chrysanthemum
- optically active
- trans
- 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.)
- Expired - Lifetime
Links
- 239000002253 acid Substances 0.000 claims description 22
- 241000723353 Chrysanthemum Species 0.000 claims description 20
- 235000007516 Chrysanthemum Nutrition 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 11
- 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 10
- 239000002904 solvent Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002728 pyrethroid Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000006340 racemization Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000749 insecticidal effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- SJWFXCIHNDVPSH-QMMMGPOBSA-N (2S)-octan-2-ol Chemical compound CCCCCC[C@H](C)O SJWFXCIHNDVPSH-QMMMGPOBSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 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 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZCVAOQKBXKSDMS-AQYZNVCMSA-N (+)-trans-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-AQYZNVCMSA-N 0.000 description 1
- XLOPRKKSAJMMEW-HTQZYQBOSA-N (-)-cis-chrysanthemic acid Chemical compound CC(C)=C[C@@H]1[C@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-HTQZYQBOSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FMTFEIJHMMQUJI-NJAFHUGGSA-N 102130-98-3 Natural products CC=CCC1=C(C)[C@H](CC1=O)OC(=O)[C@@H]1[C@@H](C=C(C)C)C1(C)C FMTFEIJHMMQUJI-NJAFHUGGSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229940024113 allethrin Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- VIMXTGUGWLAOFZ-NXEZZACHSA-N ethyl (1s,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CCOC(=O)[C@H]1[C@@H](C=C(C)C)C1(C)C VIMXTGUGWLAOFZ-NXEZZACHSA-N 0.000 description 1
- VIMXTGUGWLAOFZ-UHFFFAOYSA-N ethyl 2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CCOC(=O)C1C(C=C(C)C)C1(C)C VIMXTGUGWLAOFZ-UHFFFAOYSA-N 0.000 description 1
- PNFFNTLWIUCQOA-UHFFFAOYSA-N ethyl 2-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CCOC(=O)C1CC1C=C(C)C PNFFNTLWIUCQOA-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- -1 isobutenyl group Chemical group 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 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 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CXBMCYHAMVGWJQ-UHFFFAOYSA-N tetramethrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OCN1C(=O)C(CCCC2)=C2C1=O CXBMCYHAMVGWJQ-UHFFFAOYSA-N 0.000 description 1
- 229960005199 tetramethrin Drugs 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical group OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 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)
Description
【発明の詳細な説明】
本発明は第一菊酸誘導体のラセミ化方法に関
し、さらに詳しくは一般式（）
（式中、Ｒは水素原子、炭素数１〜20のアルキ
ル基、シクロアルキル基、アラルキル基を表わ
し、＊は不斉炭素を表わす。）
で示される光学活性な第一菊酸誘導体に臭化ホウ
素を作用させることを特徴とする光学活性第一菊
酸誘導体のラセミ方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for racemizing primary chrysanthemum derivatives, and more specifically, to (In the formula, R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, or an aralkyl group, and * represents an asymmetric carbon.) This invention relates to a racemic method for optically active chrysanthemum derivatives, which is characterized by the action of boron.
第一菊酸は、低毒速効性殺虫剤として有用なピ
レトリン、アレスリン、フタルスリンなどのいわ
ゆるピレスロイド系殺虫剤としてよく知られてい
るエステル類の酸成分を構成するものであり、前
記一般式（）で示される第一菊酸誘導体は、こ
れらのピレスロイド系殺虫剤の原料として有用で
ある。 Daiichichrysanthemum acid constitutes the acid component of esters that are well known as so-called pyrethroid insecticides such as pyrethrin, allethrin, and phthalthrin, which are useful as low-toxicity and fast-acting insecticides, and has the general formula () The primary chrysanthemum acid derivative represented by is useful as a raw material for these pyrethroid insecticides.
前記一般式（）で示される第一菊酸誘導体に
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、トランス体から導びかれる
ピレスロイド系のエステル類は対応するシス体か
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、さらに（＋）体のエステル類
が対応する（−）体のエステル類よりも遥かに高
い活性を示すことが知られている。 The primary chrysanthemum acid derivative represented by the general formula () has cis and trans geometric isomers, and each of them has (+) and (-) optical isomers, so there are a total of four types of isomers. A body exists. in general,
Among these isomers, pyrethroid esters derived from the trans isomer exhibit stronger insecticidal activity than the corresponding pyrethroid esters derived from the cis isomer, and the (+) esters also exhibit stronger insecticidal activity. It is known that it exhibits much higher activity than (-) esters.
第一菊酸は通常の製造法ではシス体、トランス
体の混合したラセミ体、即ち（±）体として合成
され、これを光学活性な有機塩基を用いて光学分
割することにより（＋）体がられ、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、従つて
この有用性のない（−）体を効率よくラセミ化
し、上記の光学分割の原料として供し得るように
することは、特に工業的規模での（＋）体の生産
時においては大きな課題となる。 Daiichichrysanthemum acid is synthesized as a racemic mixture of cis and trans forms, i.e. (±) form, by the usual production method, and the (+) form is obtained by optically resolving this using an optically active organic base. and are 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 is efficiently racemized and used as the raw material for the above optical resolution. This poses a major challenge, especially when producing (+) bodies on an industrial scale.
しかしながら、前記のように、一般式（）で
示されるシクロプロパンカルボン酸にはC1位と
C3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 mentioned above, cyclopropanecarboxylic acid represented by the general formula () has a C1 position and
Since it has two asymmetric carbon atoms at the C3 position, its racemization is accompanied by various difficulties.
これ迄、第一菊酸類のラセミ化方法としては、
（−）トランス第一菊酸のC3位のイソブテニル基
を酸化してケトアルコール基に導いた後、C1位
のカルボン酸をエステル化し、これをアルカリ金
属アルコレートと溶媒の存在下に加熱反応させる
方法（特公昭39−15977号公報）、あるいは（−）
−トランス−第一菊酸を光増感剤の存在下に紫外
線を照射する方法（特公昭47−30697号公報）が
知られているが、前者は多くの反応工程を要する
こと、また後者は反応率が劣るうえ光源の電力消
費量が大きく、また光源の寿命も比較的短いこと
など工業的に実施するには種々の問題点を有す
る。 Until now, the racemization methods for primary chrysanthemum acids were as follows:
After oxidizing the isobutenyl group at the C3 position of (-)trans-dairy chrysanthemum acid to form a keto alcohol group, the carboxylic acid at the C1 position is esterified, and this is heated in the presence of an alkali metal alcoholate and a solvent. Reaction method (Special Publication No. 39-15977) or (-)
A method is known in which -trans-daisy chrysanthemum acid is irradiated with ultraviolet rays in the presence of a photosensitizer (Japanese Patent Publication No. 47-30697), but the former requires many reaction steps, and the latter There are various problems in industrial implementation, such as poor reaction rate, high power consumption of the light source, and relatively short life of the light source.
さらに光学活性第一菊酸を酸ハライドとして、
これにルイス酸を触媒として作用させることによ
るラセミ化方法（特公昭53−37858号公報、特開
昭52−144651号公報、）、
あるいは光学活性なシクロプロパンカルボン酸
の無水物にヨウ素、四塩化スズ、塩化鉄等のルイ
ス酸を作用させることによるラセミ化方法も知ら
れている（特開昭57−163341号公報）。 Furthermore, optically active chrysanthemum acid is used as an acid halide,
A racemization method in which a Lewis acid acts as a catalyst (Japanese Patent Publication No. 53-37858, Japanese Unexamined Patent Publication No. 52-144651), or an anhydride of optically active cyclopropanecarboxylic acid with iodine and tetrachloride. A racemization method using a Lewis acid such as tin or iron chloride is also known (Japanese Unexamined Patent Publication No. 163341/1983).
本発明者らはその後さらに研究を重ねた結果、
前記一般式（）で示される光学活性第一菊酸誘
導体、即ち、その分子内に２ケの不斉炭素を有し
ている光学活性な第一菊酸そのもの、あるいはそ
のエステルに、特殊なハロゲン化ホウ素であるる
臭化ホウ素を作用させることにより、意外にも極
めて好都合に、ラセミ化が進行することを見出
し、これに種々の検討を加えて、本発明を完成す
るに至つた。 As a result of further research by the present inventors,
A special halogen is added to the optically active chrysanthemum acid derivative represented by the general formula (), that is, the optically active chrysanthemum acid itself having two asymmetric carbon atoms in its molecule, or its ester. It was discovered that racemization progresses in a surprisingly favorable manner by the action of boron bromide, which is a boron compound, and after making various studies on this, the present invention was completed.
本発明方法によれば、他の誘導体に導くことは
なしに、光学活性第一菊酸そのもの、あるいはそ
のエステルのままでラセミ化させることができる
ことから、極めて有利であり、さらに従来の種々
の光学分割法（例えば、光学分割剤による物理化
学的分割法、酵素による生化学的分割法）におい
て分離除去される（−）−第一菊酸誘導体を直接、
効率よく有効利用することが可能となる。 The method of the present invention is extremely advantageous because it is possible to racemize optically active dichroic acid itself or its ester without leading to other derivatives. The (-)-primary chrysanthemum acid derivative that is separated and removed in a method (e.g., physicochemical resolution method using an optical resolving agent, biochemical resolution method using an enzyme),
It becomes possible to use it efficiently and effectively.
以下に本発明の方法について詳細に説明する。 The method of the present invention will be explained in detail below.
本発明において原料として用いる光学活性第一
菊酸誘導体は４種の異性体の中の１種単独、また
はこれらの任意の割合の混合物を用いることがで
き、また光学純度はどの程度のものでも差しつか
えないが、本発明の目的から考えて（−）体また
は（−）体に富むカルボン酸誘導体を用いる時
に、その意義を発揮することは言うまでもない。 The optically active chrysanthemum acid derivative used as a raw material in the present invention can be used alone among the four isomers, or a mixture of these in any proportion, and any degree of optical purity can be used. Although it is not useful, it goes without saying that, considering the purpose of the present invention, its significance is exhibited when using the (-) isomer or a carboxylic acid derivative rich in the (-) isomer.
また、反応を行なうに際しては不活性溶媒を使
用することが好ましく、そのような溶媒としては
飽和炭化水素、芳香族炭化水素及びこれらのハロ
ゲン化物、エーテル類などを挙げることができ
る。 Further, when carrying out the reaction, it is preferable to use an inert solvent, and examples of such solvents include saturated hydrocarbons, aromatic hydrocarbons, their halides, and ethers.
用いる臭化ホウ素の量は被処理第一菊酸誘導体
１モルに対し1/1000〜1/2モル、好ましくは1/200
〜1/4モルの範囲である。 The amount of boron bromide used is 1/1000 to 1/2 mole, preferably 1/200 to 1 mole of the chrysanthemum acid derivative to be treated.
~1/4 mole range.
また反応温度は通常−30℃〜当該第一菊酸誘導
体の沸点（溶媒を使用する場合は用いる溶媒の沸
点）の範囲で任意であるが、通常−30℃〜130℃
の範囲である。 The reaction temperature is usually -30°C to the boiling point of the primary chrysanthemum acid derivative (if a solvent is used, the boiling point of the solvent used), but is usually -30°C to 130°C.
is within the range of
反応に要する時間は用いる臭化ホウ素の量や反
応温度によつても変わり得るが通常10分〜20時間
で充分その目的を達成することができる。尚反応
の進行度は反応液の一部をサンプリングして旋光
度を測定するかガスクロマトグラフイー等による
分析で求めることができる。 The time required for the reaction may vary depending on the amount of boron bromide used and the reaction temperature, but usually 10 minutes to 20 hours is sufficient to achieve the purpose. The degree of progress of the reaction can be determined by sampling a portion of the reaction solution and measuring the optical rotation, or by analysis using gas chromatography or the like.
上記のようにして得られるラセミ化された第一
菊酸誘導体は種々のピレストロイドアルコールと
のエステル化反応により殺虫性エステルに導くこ
とができる。 The racemized primary chrysanthemum acid derivative obtained as described above can be converted into an insecticidal ester by an esterification reaction with various pyrethroid alcohols.
以上、詳述したように本発明方法により、前記
一般式（）で示される第一菊酸誘導体の（−）
体、またはそれに富む第一菊酸誘導体を工業的規
模で、効率よく有用なラセミ体に変換させること
が可能となり、さらにこれを各種の光学分割方法
と組み合わせることにより、より有用な（＋）体
に変換させることも可能となり、その果たす役割
は極めて大きいものがある。 As detailed above, by the method of the present invention, (-) of the primary chrysanthemum acid derivative represented by the general formula ()
It is now possible to efficiently convert the polyhydric acid derivatives or primary chrysanthemum derivatives rich in the same into useful racemic forms on an industrial scale, and by combining this with various optical resolution methods, more useful (+) forms can be obtained. It has also become possible to convert it into , and it plays an extremely important role.
また、本発明方法において得られるラセミ体
は、そのエステルとしてより有効なトランス体に
富み、この点においても本発明方法は有利であ
る。 Furthermore, the racemate obtained by the method of the present invention is rich in the trans form, which is more effective as an ester, and the method of the present invention is advantageous in this respect as well.
次に、実施例によつて、本発明をさらに詳細に
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。 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
50ml容の反応容器に、窒素雰囲気下で（−）−
シス−２，２−ジメチル−３−（２−メチル−１
−プロペニル）シクロプロパン−１−カルボン酸
2.0ｇとｎ−ヘキサン18.0ｇを入れ、これに三臭
化ホウ素0.3ｇを滴下し、15℃で１時間撹拌した。Example 1 In a 50 ml reaction vessel, (-)-
cis-2,2-dimethyl-3-(2-methyl-1
-propenyl)cyclopropane-1-carboxylic acid
2.0 g and 18.0 g of n-hexane were added, and 0.3 g of boron tribromide was added dropwise thereto, followed by stirring at 15° C. for 1 hour.
反応後、氷水を加えて撹拌、触媒を失活除去し
た。分液後、有機層を4.8ｇの10％カセイソーダ
水溶液で２回抽出し、得られる水層を塩酸酸性に
してトルエンで２回抽出した。トルエン層を水洗
し、硫酸ソーダで乾燥したのち減圧下に溶媒を留
去し、1.45ｇの残留液を得た。該残留液を蒸留
し、沸点110〜119℃／2.5mmHgの留分1.38ｇが得
られた、このものは赤外線吸収スペクトルより
２，２−ジメチル−３−（２−メチル−１−プロ
ペニル）シクロプロパン−１−カルボン酸である
ことが確認され、この一部をサンプリングし
（＋）−２−オクタノールとのエステルに導いた
後、ガスクロマトグラフイーによりその光学異性
体比率を求めたところ、（＋）シス体：3.3％，、
（−）シス体：4.4％、，（＋）トランス体：45.7
％、，（−）トランス体：46.6％であつた。 After the reaction, ice water was added and stirred to deactivate and remove the catalyst. After separation, the organic layer was extracted twice with 4.8 g of 10% caustic soda aqueous solution, and the resulting aqueous layer was acidified with hydrochloric acid and extracted twice with toluene. The toluene layer was washed with water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 1.45 g of residual liquid. The residual liquid was distilled to obtain 1.38 g of a fraction with a boiling point of 110-119°C/2.5 mmHg, which was determined by infrared absorption spectrum to be 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclo It was confirmed that it was propane-1-carboxylic acid, and a part of it was sampled and converted into an ester with (+)-2-octanol, and its optical isomer ratio was determined by gas chromatography. ) Cis form: 3.3%,,
(-) cis form: 4.4%, (+) trans form: 45.7
%, (-) trans form: 46.6%.
実施例 ２
50ml容の反応容器に窒素雰囲気で（−）−シス
−２，２−ジメチル−３−（２−メチル−１−プ
ロペニル）シクロプロパン−１−カルボン酸エチ
ルエステル2.0ｇとｎ−ヘプタン18.0ｇを入れ、
これに三臭化ホウ素0.26ｇを滴下し、15℃で３時
間撹拌した。Example 2 2.0 g of (-)-cis-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropane-1-carboxylic acid ethyl ester and n-heptane were placed in a 50 ml reaction vessel under nitrogen atmosphere. Add 18.0g,
0.26 g of boron tribromide was added dropwise to this, and the mixture was stirred at 15°C for 3 hours.
反応後、反応液に氷水を加えて撹拌し、触媒を
失活除去した。分液後、有機相を減圧下に溶媒留
去し、1.96ｇの残留液を得た。これを10％水酸化
ナトリウム水溶液10.2ｇと共に３時間加熱還流し
たのち、トルエンを加えて分液し、トルエン層と
して中性物を除去した。水層を塩酸酸性にした後
トルエン抽出し、有機層を水洗後、無水硫酸ソー
ダを加えて乾燥し、これを減圧下に溶媒留去する
と1.6ｇの残留液が得られた。該残留液を蒸留し、
沸点110〜119℃／2.5mmHgの留分1.53ｇを得た。
このものは赤外線吸収スペクトルより、２，２−
ジメチル−３−（２−メチル−１−プロペニル）
シクロプロパンカルボン酸であることが確認され
た。このものの一部をサンプリングし（＋）−２
−オクタノールとのエステルに導いた後、ガスク
ロマトグラフイーによりその光学異性体比率を求
めたところ、（＋）シス体：3.3％、（−）シス
体：4.3％、（＋）トランス体：46.1％、（−）ト
ランス体：46.3であつた。 After the reaction, ice water was added to the reaction solution and stirred to deactivate and remove the catalyst. After separation, the solvent of the organic phase was distilled off under reduced pressure to obtain 1.96 g of residual liquid. After heating and refluxing this with 10.2 g of a 10% aqueous sodium hydroxide solution for 3 hours, toluene was added to separate the layers, and neutral substances were removed to form a toluene layer. The aqueous layer was acidified with hydrochloric acid and then extracted with toluene. The organic layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 1.6 g of residual liquid. Distilling the residual liquid,
1.53 g of a fraction with a boiling point of 110-119°C/2.5 mmHg was obtained.
From the infrared absorption spectrum, this substance is 2,2-
Dimethyl-3-(2-methyl-1-propenyl)
It was confirmed to be cyclopropanecarboxylic acid. Sample part of this (+)-2
- After leading to an ester with octanol, the optical isomer ratio was determined by gas chromatography. (+) cis form: 3.3%, (-) cis form: 4.3%, (+) trans form: 46.1%. , (-) trans isomer: 46.3.
実施例 ３
50ml容の反応容器に窒素雰囲気で（＋）シス
体：2.5％、（−）シス体：16.8％、（＋）トラン
ス体：12.3％、（−）トランス体：68.4％よりな
る２，２−ジメチル−３−（２−メチル−１−プ
ロペニル）シクロプロパン−１−カルボン酸エチ
ルエステル2.0ｇとｎ−ヘプタン18.0ｇを入れた。Example 3 2 consisting of (+) cis form: 2.5%, (-) cis form: 16.8%, (+) trans form: 12.3%, (-) trans form: 68.4% in a 50 ml reaction vessel in a nitrogen atmosphere , 2-dimethyl-3-(2-methyl-1-propenyl)cyclopropane-1-carboxylic acid ethyl ester (2.0 g) and n-heptane (18.0 g) were added.
これに三臭化ホウ素0.26ｇを滴下して、15℃で
３時間撹拌した。反応後、氷水を加えて撹拌、触
媒を失活、除去した。分液後、有機相を硫酸ソー
ダを加えて乾燥したのち、減圧下に溶媒留去して
1.95ｇの残留液を得た。該残留液を蒸留し、沸点
85〜88℃／10mmHgの留分1.77ｇを得た。このも
のは赤外線吸収スペクトルより２，２−ジメチル
−３−（２−メチル−１−プロペニル）シクロプ
ロパン−１−カルボン酸エチルエステルであるこ
とが確認され、その一部を常法により加水分解し
得られたカルボン酸を（＋）−２−オクタノール
とのエステルに導いた後ガスクロマトグラフイー
によりその光学異性体比率を求めたところ、（＋）
シス体：2.7％、（−）シス体：3.0％、（＋）トラ
ンス体：46.6％、（−）トランス体：47.7％であ
つた。 0.26 g of boron tribromide was added dropwise to this, and the mixture was stirred at 15°C for 3 hours. After the reaction, ice water was added and stirred to deactivate and remove the catalyst. After separation, the organic phase was dried by adding sodium sulfate, and the solvent was distilled off under reduced pressure.
1.95g of residual liquid was obtained. The residual liquid was distilled and the boiling point
1.77 g of a fraction of 85-88°C/10 mmHg was obtained. This substance was confirmed to be 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropane-1-carboxylic acid ethyl ester by infrared absorption spectrum, and a part of it was hydrolyzed by a conventional method. After the obtained carboxylic acid was converted into an ester with (+)-2-octanol, the optical isomer ratio was determined by gas chromatography, and it was found that (+)
Cis form: 2.7%, (-) cis form: 3.0%, (+) trans form: 46.6%, and (-) trans form: 47.7%.
実施例 ４
50ml容の反応容器に窒素雰囲気で実施例３で用
いた光学異性体比率を有する２，２−ジメチル−
３−（２−メチル−１−プロペニル）シクロプロ
パン−１−カルボン酸エチルエステル2.0ｇとジ
オキサン18.0ｇを入れ、これに三臭化ホウ素0.26
ｇを滴下し、15℃で４時間撹拌した。Example 4 2,2-dimethyl- having the optical isomer ratio used in Example 3 was placed in a 50 ml reaction vessel in a nitrogen atmosphere.
Add 2.0 g of 3-(2-methyl-1-propenyl)cyclopropane-1-carboxylic acid ethyl ester and 18.0 g of dioxane, and add 0.26 g of boron tribromide.
g was added dropwise, and the mixture was stirred at 15°C for 4 hours.
反応後、反応液の一部をサンプリングし実施例
２と同様にして加水分解し得られたカルボン酸を
（＋）−２−オクタノールとのエステルに導いた
後、ガスクロマトグラフイーにより、光学異性体
比率を求めたところ、（＋）シス体：2.4％、（−）
シス体：2.6％、（＋）トランス体：46.2％、（−）
トランス体：48.8％であつた。 After the reaction, a part of the reaction solution was sampled and hydrolyzed in the same manner as in Example 2. The resulting carboxylic acid was converted into an ester with (+)-2-octanol, and then the optical isomers were separated by gas chromatography. When the ratio was calculated, (+) cis form: 2.4%, (-)
Cis form: 2.6%, (+) Trans form: 46.2%, (-)
Trans form: 48.8%.
Claims (1)
ル基、シクロアルキル基、アラルキル基を表わ
し、＊は不斉炭素を表わす。） で示される光学活性第一菊酸誘導体に臭化ホウ素
を作用させることを特徴とする光学活性第一菊酸
誘導体のラセミ化方法。[Claims] 1. General formula (In the formula, R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, or an aralkyl group, and * represents an asymmetric carbon.) Boron bromide is added to the optically active chrysanthemum acid derivative represented by 1. A method for racemizing an optically active chrysanthemum acid derivative, which is characterized by acting on an optically active chrysanthemum derivative.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59031861A JPS60174744A (en) | 1984-02-22 | 1984-02-22 | Method for racemizing chrysanthemum-monocarboxylic acid derivative |
| EP85301065A EP0155765B1 (en) | 1984-02-22 | 1985-02-18 | Method for racemization of chrysanthemic acid or its ester |
| DE8585301065T DE3565397D1 (en) | 1984-02-22 | 1985-02-18 | Method for racemization of chrysanthemic acid or its ester |
| US06/702,599 US4644080A (en) | 1984-02-22 | 1985-02-19 | Method for racemization of chrysanthemic acid or its ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59031861A JPS60174744A (en) | 1984-02-22 | 1984-02-22 | Method for racemizing chrysanthemum-monocarboxylic acid derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60174744A JPS60174744A (en) | 1985-09-09 |
| JPH0477738B2 true JPH0477738B2 (en) | 1992-12-09 |
Family
ID=12342829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59031861A Granted JPS60174744A (en) | 1984-02-22 | 1984-02-22 | Method for racemizing chrysanthemum-monocarboxylic acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60174744A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114539045B (en) * | 2020-11-18 | 2023-07-21 | 中国科学院大连化学物理研究所 | Racemization method of trans-L-chrysanthemic acid |
-
1984
- 1984-02-22 JP JP59031861A patent/JPS60174744A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60174744A (en) | 1985-09-09 |
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