JPS6351137B2 - - Google Patents
Info
- Publication number
- JPS6351137B2 JPS6351137B2 JP4781781A JP4781781A JPS6351137B2 JP S6351137 B2 JPS6351137 B2 JP S6351137B2 JP 4781781 A JP4781781 A JP 4781781A JP 4781781 A JP4781781 A JP 4781781A JP S6351137 B2 JPS6351137 B2 JP S6351137B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- chrysanthemum
- ester
- trans
- cis
- 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
Links
- 239000002253 acid Substances 0.000 claims description 40
- 241000723353 Chrysanthemum Species 0.000 claims description 39
- 235000007516 Chrysanthemum Nutrition 0.000 claims description 39
- 150000002148 esters Chemical class 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 125000005907 alkyl ester group Chemical group 0.000 claims description 11
- 230000003287 optical effect Effects 0.000 claims description 11
- 239000002841 Lewis acid Substances 0.000 claims description 10
- 150000007517 lewis acids Chemical class 0.000 claims description 10
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 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 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000006345 epimerization reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 239000002728 pyrethroid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000126 substance Substances 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
- IVGYSSJKFLEVIX-UHFFFAOYSA-N (-(E)-Pyrethrolone Natural products CC1=C(CC=CC=C)C(=O)CC1O IVGYSSJKFLEVIX-UHFFFAOYSA-N 0.000 description 1
- UIWNHGWOYRFCSF-KTERXBQFSA-N (1r,3r)-3-[(e)-3-methoxy-2-methyl-3-oxoprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound COC(=O)C(\C)=C\[C@@H]1[C@@H](C(O)=O)C1(C)C UIWNHGWOYRFCSF-KTERXBQFSA-N 0.000 description 1
- IVGYSSJKFLEVIX-SNAWJCMRSA-N (E)-pyrethrolone Chemical compound CC1=C(C\C=C\C=C)C(=O)CC1O IVGYSSJKFLEVIX-SNAWJCMRSA-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UIWNHGWOYRFCSF-UHFFFAOYSA-N Pyrethric acid Natural products COC(=O)C(C)=CC1C(C(O)=O)C1(C)C UIWNHGWOYRFCSF-UHFFFAOYSA-N 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
- 240000004460 Tanacetum coccineum Species 0.000 description 1
- ROVGZAWFACYCSP-MQBLHHJJSA-N [2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(C\C=C/C=C)C(=O)C1 ROVGZAWFACYCSP-MQBLHHJJSA-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
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940024113 allethrin Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- -1 chlorobenzene Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 229940015367 pyrethrum Drugs 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
本発明は光学活性なシス第一菊酸のアルキルエ
ステルの異性化方法に関する。
さらに詳しくは一般式（）
〔式中、Ｒはアルキル基を表わす。〕
で示される光学活性シス第一菊酸エステル、また
はそれを含む第一菊酸エステルに特定のルイス酸
を作用させ、用いたエステルと同一の旋光性を示
す一般式（）
〔式中、Ｒは前述と同じ意味を有する。〕
で示される光学活性トランス第一菊酸エステル、
またはそれを含む第一菊酸エステルに変換させる
ことを特徴とする光学活性シス第一菊酸エステル
類の異性化方法に関する。
第一菊酸はピレトリン、アレスリン、フタルス
リンなどのいわゆるピレスロイドと称される低毒
速効性の殺虫性エステルの酸成分を構成する重要
な化合物である。
当該カルボン酸にはシス、トランスの幾何異性
体およびその各々に（＋）、（−）の光学異性体が
あり、合計４ケの異性体が存在する。これら４ケ
の異性体の中でもトランス体からなるピレスロイ
ド系エステル類はシス体からなるエステル類より
強い効力を示し、さらに（＋）体の方が対応する
（−）体よりも遥かに高い活性を示すことが知ら
れている。ちなみに天然に産する除虫菊に含まれ
る第一菊酸エステルは（＋）トランス体である。
また（＋）トランス第一菊酸は光学活性アミンの
分割剤としても有用である。
上述したように第一菊酸にはそのC1位および
C3位に２ケの不斉炭素があり、合計４ケの異性
体が存在する。即ち、（＋）―シス体、（−）―シ
ス体、（＋）―トランス体、（−）―トランス体の
４種の異性体であり、これらはそれぞれ、（1R，
3S）、（1S，3R）、（1R，3R）、（1S，3S）の絶対
配置を有する。
第一菊酸類の異性化方法としては、C1位の立
体配置を変換する方法、即ちC1エピ化が知られ
ており、例えばシス第一菊酸のアルキルエステル
を特殊な塩基性触媒で処理する方法（特公昭53−
18495号公報、特公昭53−18496号公報など）や、
ピレトリン酸クロリドを高温下に加熱する方法
（特公昭46―24694号公報）が知られている。これ
らは何れもC1位の立体配置の交換方法であつて、
（＋）―シス第一菊酸を原料として適用した場合
には、そのピレスロイド系エステルとしては殆ん
ど殺虫活性のない（−）―トランス体が得られる
ことになる。
また、４種の異性体の各酸ハライドにルイス酸
を作用させて、ラセミ体、即ち（±）一体を得る
方法が知られており、この方法は４種の異性体の
何れから出発してもラセミ化でき、特に（−）―
トランス体をラセミ化できる点で優れた方法であ
るが、（＋）―シス体を原料とした場合には（±）
―トランスが得られることになる。
このように、第一菊酸類のC1エピ化およびラ
セミ化については既にいくつかの方法が知られて
はいるが、これまでC3位の立体配置を変換（C3
エピ化）させてトランス体を合成する方法は全く
知られておらず、それゆえ（＋）―シス体から
（＋）―トランス体を得る効率的な方法はなかつ
た。
しかるに、本発明者らはC3エピ化させること
により、（＋）―シス体から（＋）―トランス体
を得る方法について鋭意検討した結果、当該カル
ボン酸のアルキルエステルに特定のルイス酸を作
用させることにより、緩和な条件下に効率よく目
的を達成できることを見出し、さらに種々の検討
を加え本発明を完成するに至つた。
本発明に関する立体変換を図示すれば以下のよ
うである。
The present invention relates to a method for isomerizing optically active alkyl esters of cis-dairy chrysanthemum acid. For more details, please refer to the general formula () [In the formula, R represents an alkyl group. ] General formula () which shows the same optical rotation as the ester used by reacting a specific Lewis acid with the optically active cis-stochrylate ester represented by or the stochastic ester containing it [In the formula, R has the same meaning as above. ] Optically active trans primary chrysanthemum acid ester represented by
The present invention relates to a method for isomerizing optically active cis-carboxylic acid esters, which comprises converting the optically active cis-carboxylic acid esters into primary chrysanthemum esters containing the same. Chrysanthemum acid is an important compound that constitutes the acid component of low-toxicity, fast-acting insecticidal esters called pyrethroids, such as pyrethrin, allethrin, and phthalthrin. The carboxylic acid has cis and trans geometric isomers and each of them has (+) and (-) optical isomers, for a total of four isomers. Among these four isomers, pyrethroid esters consisting of the trans isomer show stronger potency than esters consisting of the cis isomer, and the (+) isomer has much higher activity than the corresponding (-) isomer. known to show. By the way, the primary chrysanthemum acid ester contained in naturally occurring pyrethrum is the (+) trans form.
(+) Trans-synthetic acid is also useful as a resolving agent for optically active amines. As mentioned above, Daichic acid has its C1 position and
There are two asymmetric carbon atoms at the C3 position, and a total of four isomers exist. That is, there are four isomers: (+)-cis form, (-)-cis form, (+)-trans form, and (-)-trans form, and these are (1R,
3S), (1S, 3R), (1R, 3R), (1S, 3S). As a method for isomerizing primary chrysanthemum acids, a method of converting the configuration at the C 1 position, that is, C 1 epimerization, is known. For example, an alkyl ester of cis primary chrysanthemum acid is treated with a special basic catalyst. How to do it (Tokuko Showa 53-
18495 Publication, Special Publication No. 18496, etc.),
A method is known in which pyrethric acid chloride is heated to a high temperature (Japanese Patent Publication No. 46-24694). These are all methods of exchanging the configuration at the C1 position,
When (+)-cis primary chrysanthemum acid is used as a raw material, the (-)-trans form of its pyrethroid ester having almost no insecticidal activity is obtained. Furthermore, a method is known in which a Lewis acid is applied to each of the acid halides of the four isomers to obtain a racemic form, that is, a (±) unit, and this method starts from any of the four isomers. can also be racemized, especially (-)-
This method is excellent in that it can racemize the trans isomer, but if the (+)-cis isomer is used as the raw material, the (±)
-You will get a trance. As described above, although several methods are already known for C 1 epimerization and racemization of primary chrysanthemum acids, until now the C 3 configuration has been changed (C 3
There is no known method for synthesizing the trans isomer by epimerization, and therefore there has been no efficient method to obtain the (+)-trans isomer from the (+)-cis isomer. However, as a result of extensive research into a method for obtaining the (+)-trans form from the (+)-cis form by C3 epimerization, the present inventors found that a specific Lewis acid was applied to the alkyl ester of the carboxylic acid. The inventors discovered that the objective could be efficiently achieved under mild conditions by doing so, and after further various studies, the present invention was completed. The steric transformation related to the present invention is illustrated as follows.
【表】
このようにして得られる第一菊酸のアルキルエ
ステルは、常法により容易に第一菊酸に導くこと
ができ、また出発物質である光学活性なシス―体
は（±）―シス第一菊酸の光学分割法（特開昭49
−125342号公報）、あるいは光学活性ジヒドロク
リサンセモラクトンから誘導する方法（特開昭47
−30669号公報）などによつて得られる。従つて、
これらの技術と本発明の方法を組み合わせること
により、（＋）―トランス体が極めて効率よく得
られることになる。
本発明はまた同様に、一般式（）
〔式中、Ｒは前述と同じ意味を有する。〕
で示される光学活性シス第一菊酸エステル、また
はそれを含む第一菊酸エステルに特定のルイス酸
を作用させ、用いたエステルと同一の旋光性を示
す一般式（）
〔式中、Ｒは前述と同じ意味を有する。〕
で示される光学活性トランス第一菊酸エステル、
またはそれを含む第一菊酸エステルに変換させる
方法をも提供するものであり、本方法を経由して
得られる（−）―トランス―第一菊酸は光学分割
剤して有用である。
次に本発明方法についてさらに詳しく説明する
と、光学活性シス―第一菊酸のアルキルエステ
ル、またはそれを含む第一菊酸のアルキルエステ
ルに三フツ化ホウ素、塩化鉄、塩化アルミニウム
から選ばれるルイス酸またはこれらの錯体と接触
させることにより、C3エピ化が外圧に関係なく
容易に進行し、目的とする光学活性トランス―第
一菊酸のアルキルエステル、またはそれを含む第
一菊酸エステルに変換することができる。
原料として用いる光学活性シス―第一菊酸エス
テルはシス―体単独またはそれと同一旋光性を有
するトランス―体との任意の割合の混合物でもよ
く、さらにその光学純度はどの程度のものであつ
ても差しつかえはないが、生成物の実用性から考
えて何れか一方の旋光性を有する光学活性なエス
テル、またはそれに富むエステルを使用すること
が好ましい。
本発明において、一般式（）〜（）で示さ
れるエステルの置換基Ｒとしてはメチル基、エチ
ル基、プロピル基、ブチル基、ヘキシル基、メン
チル基などの炭素数１〜10のアルキル基を挙げる
ことができる。
また反応を行なうに際しては、本質的に反応を
阻害しない溶媒を用いることが好ましく、溶媒と
してはヘキサン、ヘプタン、シクロヘキサン、オ
クタンなどの飽和炭化水素、クロルベンゼンなど
のハロゲン置換芳香族炭化水素またはエーテルな
どを挙げるとができ、ヘキサン、ヘプタンなどの
飽和炭化水素がより好ましい。
用いるルイス酸の量は特に限定されるものでは
ないが、原料エステル１モルに対し、1/200モル
〜当モル、好ましくは1/100〜1/2モルの範囲であ
る。
反応温度は、著しく高いとシクロプロパン環の
開裂および他の副反応などが生じることから、通
常−70℃〜150℃、好ましくは−30℃〜100℃の範
囲である。
反応に要する時間は用いるルイス酸の量および
反応温度によつて変わるが、通常１分〜20時間で
目的を達することができる。尚、反応の進行度は
旋光度の測定、あるいはカルボン酸のジアステレ
オアイソマーとしてガスクロマトグラフイーなど
により知ることができる。
また、本発明方法は減圧下または加圧下でも実
施することができるが、常圧下で容易に目的を達
することができる。さらに、より確実に行なうた
めには、不活性ガスの雰囲気下で行なえばよい。
尚、本発明方法を実施するに際しては、バツチ
形式あるいは連続形式の何れの形式でも行なうこ
とができ、また仕込み方法も、原料のエステルを
ルイス酸と共に反応容器に一括して入れる方式、
あるいは反応の進行に応じて連続的に、または断
続的に入れる方式の何れの方法をも採用すること
ができる。
以上のようにして反応が終了した反応液から、
ルイス酸を除去し濃縮すれば、C3位がエピ化さ
れて生成した光学活性トランス―第一菊酸エステ
ル、またはそれに富む第一菊酸エステルが得られ
る。これを常法に従がい、アルカリ性水溶液を加
えて加水分解することにより、光学活性なトラン
ス―第一菊酸、またはそれに富む第一菊酸が容易
に得られ、さらには必要に応じこれを蒸留、クロ
マトグラフイーなどにより精製することもでき
る。
このようにして得られた光学活性な第一菊酸は
それぞれの用途に供することができ、例えば
（＋）―トランス第一菊酸はピレスロロン、アレ
スロロンに代表されるピレスロイドアルコールと
称される一群のアルコールと反応させることによ
り、効力の高い殺虫性化合物に導くことができ
る。
次に実施例によつて本発明を説明するが、本発
明は何らこれらに限定されるものではない。
実施例 １
200ml容のフラスコに、窒素雰囲気下（＋）―
シス―第一菊酸エチルエステル4.0ｇとｎ―ヘプ
タン100mlを仕込み、これに塩化アルミニウム
1.36ｇを加え、70℃で３時間撹拌した。次に、反
応液に水を加え塩化アルミニウムを分解除去し、
有機層を水洗後、濃縮し4.0ｇの濃縮残渣が得ら
れた。
このものの赤外吸収スペクトルを測定するとト
ランス―第一菊酸エチルエステルのそれを示し
た。
この濃縮残渣を蒸留し、沸点106〜116℃／20mm
Hgの油状物3.5ｇを得た。
次いでこれに20％苛性ソーダ水6.2ｇを加え100
℃で2.5時間撹拌し加水分解し、反応液をトルエ
ンで抽出し、中性部を除いた後、希塩酸で中和、
酸析すると、（＋）―トランス―第一菊酸88.4％、
（−）―トランス―第一菊酸1.1％、（＋）―シス
―第一菊酸10.5％（ガスクロマトグラフイーによ
る分析値）の組成を有するトランス―体に富む第
一菊酸が2.4ｇ得られた。
実施例 ２
100ml容のフラスコに（−）―シス体3.6％、
（＋）―シス体19.1％、（−）―トランス体10.5
％、（＋）―トランス体66.9％の組成を有する第
一菊酸エチルエステル2.0ｇとｎ―ヘプタン18.0
ｇを入れ溶解し、これに塩化アルミニウム0.7ｇ
を加え70℃で３時間撹拌した。次に反応液に水を
加えて塩化アルミニウムを分解し、分液後、有機
層をとり、溶媒を除去し、次いでこれに10％苛性
ソーダ水溶液6.1ｇを加え100℃で2.5時間撹拌し
加水分解した。反応液にトルエンを加えて中性物
質を抽出除去後、硫酸酸性にしトルエンで抽出
し、トルエン層を水洗、乾燥後、溶媒を留去し次
いで減圧蒸留して沸点110〜116℃／２mmHgのト
ランス―第一菊酸1.32ｇを得た。
このものの光学異性体比をガスクロマトグラフ
イーで分析すると、（−）―シス体0.9％、（＋）
―シス体6.3％、（−）―トランス体12.4％、（＋）
―トランス体80.4％であつた。
実施例 ３〜６
実施例２で用いた第一菊酸と同じ組成を有する
第一菊酸の下表に記載のアルキルエステルを用
い、次に示す条件で反応を行つた。
結果は下表の通りである。[Table] The alkyl ester of primary chrysanthemum acid obtained in this way can be easily converted to primary chrysanthemum acid by a conventional method, and the starting material, optically active cis-isomer, is (±)-cis Optical resolution method of Daiichi chrysanthemum acid
-125342) or a method of deriving from optically active dihydrochrysansemolactone (Japanese Unexamined Patent Publication No. 125342)
-30669 Publication) etc. Therefore,
By combining these techniques with the method of the present invention, the (+)-trans isomer can be obtained extremely efficiently. The present invention also relates to the general formula () [In the formula, R has the same meaning as above. ] General formula () which shows the same optical rotation as the ester used by reacting a specific Lewis acid with the optically active cis-stochrylate ester represented by or the stochastic ester containing it [In the formula, R has the same meaning as above. ] Optically active trans primary chrysanthemum acid ester represented by
The present invention also provides a method for converting the compound into a primary chrysanthemum acid ester containing the same, and the (-)-trans-carboxylic acid obtained through this method is useful as an optical resolution agent. Next, to explain the method of the present invention in more detail, an optically active cis-alkyl ester of chrysanthemum acid or an alkyl ester of chrysanthemum acid containing the same is combined with a Lewis acid selected from boron trifluoride, iron chloride, and aluminum chloride. Or, by contacting with these complexes, C 3 epimerization easily proceeds regardless of external pressure and is converted to the target optically active alkyl ester of trans-daisy chrysanthemum acid or a primary chrysanthemum acid ester containing it. can do. The optically active cis-primary chrysanthemum acid ester used as a raw material may be the cis-isomer alone or a mixture of the trans-isomer and the trans-isomer having the same optical rotation in any proportion, and the optical purity thereof may be any level. Although there is no problem, in view of the practicality of the product, it is preferable to use an optically active ester having one of the optical rotations, or an ester rich in the same. In the present invention, examples of the substituent R of the esters represented by general formulas () to () include alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, hexyl group, and menthyl group. be able to. In addition, when carrying out the reaction, it is preferable to use a solvent that does not essentially inhibit the reaction, such as saturated hydrocarbons such as hexane, heptane, cyclohexane, and octane, halogen-substituted aromatic hydrocarbons such as chlorobenzene, or ethers. Saturated hydrocarbons such as hexane and heptane are more preferred. The amount of Lewis acid used is not particularly limited, but is in the range of 1/200 mole to the equivalent mole, preferably 1/100 to 1/2 mole, per mole of raw material ester. The reaction temperature is generally in the range of -70°C to 150°C, preferably -30°C to 100°C, since cleavage of the cyclopropane ring and other side reactions will occur if the reaction temperature is extremely high. The time required for the reaction varies depending on the amount of Lewis acid used and the reaction temperature, but the objective can usually be achieved in 1 minute to 20 hours. The degree of progress of the reaction can be determined by measuring the optical rotation or by gas chromatography as diastereoisomers of carboxylic acids. Although the method of the present invention can be carried out under reduced pressure or increased pressure, the purpose can be easily achieved under normal pressure. Furthermore, in order to carry out the process more reliably, it may be carried out under an inert gas atmosphere. The method of the present invention can be carried out either batchwise or continuously, and the charging method may include charging the raw material ester together with the Lewis acid into a reaction vessel all at once;
Alternatively, it is possible to adopt either a method of adding continuously or intermittently depending on the progress of the reaction. From the reaction solution that has completed the reaction as described above,
By removing the Lewis acid and concentrating it, optically active trans-primary chrysanthemum esters produced by epilation at the C3 position, or primary chrysanthemum esters enriched therein can be obtained. By hydrolyzing this by adding an alkaline aqueous solution in accordance with a conventional method, optically active trans-daisy chrysanthemum acid or Daisichichrysanthic acid rich in it can be easily obtained, and if necessary, this can be distilled. It can also be purified by chromatography, etc. The optically active chrysanthemum acid thus obtained can be used for various purposes. For example, (+)-trans chrysanthemum acid is a group of pyrethroid alcohols represented by pyrethrolone and allethrone. Reaction with alcohol can lead to highly effective insecticidal compounds. Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. Example 1 In a 200 ml flask, under nitrogen atmosphere (+) -
Prepare 4.0 g of cis-1 chrysanthemum acid ethyl ester and 100 ml of n-heptane, and add aluminum chloride to this.
1.36g was added and stirred at 70°C for 3 hours. Next, water was added to the reaction solution to decompose and remove aluminum chloride.
After washing the organic layer with water, it was concentrated to obtain 4.0 g of a concentrated residue. When the infrared absorption spectrum of this product was measured, it showed that of trans-phenol chrysanthemum acid ethyl ester. This concentrated residue is distilled to a boiling point of 106-116℃/20mm.
3.5 g of Hg oil was obtained. Next, add 6.2g of 20% caustic soda water to this and make 100%
Stir at ℃ for 2.5 hours for hydrolysis, extract the reaction solution with toluene, remove the neutral part, neutralize with dilute hydrochloric acid,
When precipitated with acid, (+)-trans-daisyl chrysanthemum acid 88.4%,
Obtained 2.4g of trans-rich chrysanthemum-rich acid having a composition of (-)-trans-daisy chrysanthemum acid 1.1% and (+)-cis-daisy chrysanthemum acid 10.5% (analysis value by gas chromatography). It was done. Example 2 In a 100 ml flask, (-)-cis isomer 3.6%,
(+)-cis form 19.1%, (-)-trans form 10.5%
%, 2.0 g of primary chrysanthemum acid ethyl ester with a composition of 66.9% (+)-trans form and 18.0 g of n-heptane.
Add 0.7 g of aluminum chloride and dissolve it.
was added and stirred at 70°C for 3 hours. Next, water was added to the reaction solution to decompose aluminum chloride, and after separation, the organic layer was taken and the solvent was removed. Next, 6.1 g of a 10% caustic soda aqueous solution was added thereto, and the mixture was stirred at 100°C for 2.5 hours for hydrolysis. . After adding toluene to the reaction solution and extracting and removing neutral substances, it was made acidic with sulfuric acid and extracted with toluene. The toluene layer was washed with water, dried, the solvent was distilled off, and then distilled under reduced pressure to obtain a trans-container with a boiling point of 110-116℃/2mmHg. -1.32 g of Daiichi Chrysanthemum acid was obtained. When the optical isomer ratio of this substance was analyzed by gas chromatography, it was found that (-)-cis isomer 0.9%, (+)
-cis form 6.3%, (-) -trans form 12.4%, (+)
- 80.4% was trans-isomer. Examples 3 to 6 Using the alkyl esters of the primary chrysanthemum acid listed in the table below having the same composition as the primary chrysanthemum acid used in Example 2, a reaction was carried out under the following conditions. The results are shown in the table below.
Claims (1)
またはそれを含む第一菊酸のアルキルエステルに
三フツ化ホウ素、塩化鉄、塩化アルミニウムから
選ばれるルイス酸を作用させ、用いたエステルと
同一の旋光性を有する光学活性トランス第一菊酸
のアルキルエステル、またはそれを含む第一菊酸
のアルキルエステルに変換させることを特徴とす
る光学活性第一菊酸エステルの異性化方法。1 Alkyl ester of optically active cis-dairy chrysanthemum acid,
Or an optically active trans alkyl ester of chrysanthemum acid containing the same is reacted with a Lewis acid selected from boron trifluoride, iron chloride, and aluminum chloride, and the alkyl ester of fluorous chrysanthemum acid has the same optical rotation as the ester used. 1. A method for isomerizing an optically active chrysanthemum ester, which comprises converting it into an ester or an alkyl ester of chrysanthemum containing the same.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4781781A JPS57163344A (en) | 1981-03-30 | 1981-03-30 | Isomerization of optically active chrysanthemum- monocarboxylic acid ester |
| US06/359,319 US4473703A (en) | 1981-03-30 | 1982-03-18 | Method of epimerization of alkyl chrysanthemate |
| EP82301470A EP0062979B1 (en) | 1981-03-30 | 1982-03-22 | A method of epimerization of alkyl chrysanthemate |
| DE8282301470T DE3268358D1 (en) | 1981-03-30 | 1982-03-22 | A method of epimerization of alkyl chrysanthemate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4781781A JPS57163344A (en) | 1981-03-30 | 1981-03-30 | Isomerization of optically active chrysanthemum- monocarboxylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57163344A JPS57163344A (en) | 1982-10-07 |
| JPS6351137B2 true JPS6351137B2 (en) | 1988-10-13 |
Family
ID=12785901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4781781A Granted JPS57163344A (en) | 1981-03-30 | 1981-03-30 | Isomerization of optically active chrysanthemum- monocarboxylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57163344A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57176930A (en) * | 1981-04-24 | 1982-10-30 | Sumitomo Chem Co Ltd | Preparation of trans-chrysanthemumic acid alkyl ester |
| JP4876339B2 (en) * | 2001-06-20 | 2012-02-15 | 住友化学株式会社 | Process for producing trans-vinyl substituted cyclopropanecarboxylic acid esters |
-
1981
- 1981-03-30 JP JP4781781A patent/JPS57163344A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57163344A (en) | 1982-10-07 |
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