JPH0253429B2 - - Google Patents
Info
- Publication number
- JPH0253429B2 JPH0253429B2 JP56169666A JP16966681A JPH0253429B2 JP H0253429 B2 JPH0253429 B2 JP H0253429B2 JP 56169666 A JP56169666 A JP 56169666A JP 16966681 A JP16966681 A JP 16966681A JP H0253429 B2 JPH0253429 B2 JP H0253429B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- trans
- cis
- chrysanthemum
- isomer
- 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 38
- 241000723353 Chrysanthemum Species 0.000 claims description 32
- 235000007516 Chrysanthemum Nutrition 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 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 5
- 230000003287 optical effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000000749 insecticidal effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000002728 pyrethroid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride 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
- 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
- DZPCYXCBXGQBRN-UHFFFAOYSA-N 2,5-Dimethyl-2,4-hexadiene Chemical compound CC(C)=CC=C(C)C DZPCYXCBXGQBRN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 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
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940024113 allethrin Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- YVPJCJLMRRTDMQ-UHFFFAOYSA-N ethyl diazoacetate Chemical compound CCOC(=O)C=[N+]=[N-] YVPJCJLMRRTDMQ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003389 potentiating effect Effects 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
- 238000003385 ring cleavage reaction 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
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は光学活性トランス第一菊酸の製造法に
関し、さらに詳しくは下記式（）で示される
（−）−シス第一菊酸を200℃〜260℃に加熱して、
式（）で示される（＋）−トランス第一菊酸に
変換させることを特徴とする（＋）−トランス第
一菊酸の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing optically active trans-dairy chrysanthemum acid, and more specifically, by heating (-)-cis-dairy chrysanthemum acid represented by the following formula () to 200°C to 260°C. hand,
The present invention relates to a method for producing (+)-trans primary chrysanthemum acid, which is characterized in that it is converted to (+)-trans primary chrysanthemum acid represented by the formula ().
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。 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.
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コの異性体が存在する。これら４コ
の異性体の中で（＋）体からなるピレスロイド系
エステルに殺虫活性があり、さらに（＋）−トラ
ンス体からなるエステルが一般に最も強い活性を
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。それに対して、（−）体はシス
体、トランス体ともほとんど効力がなく無価値な
ものとしか標価されない。 The carboxylic acid has cis and trans geometric isomers and each of them has (+) and (-) optical isomers, for a total of four isomers. It is known that among these four isomers, pyrethroid esters consisting of the (+) isomer have insecticidal activity, and esters consisting of the (+)-trans isomer generally exhibit the strongest activity. By the way, the primary chrysanthemum acid ester contained in naturally occurring pyrethrum is the (+)-trans form. On the other hand, the (-) isomer, both cis and trans, has almost no efficacy and is marked as worthless.
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。 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, and (+)-trans form, and these are (1R, 3S), (1S, 3R) (1R,
3R) (1S, 3S).
従来、シス第一菊酸類からトランス第一菊酸類
の製造法としては次のような方法が知られてい
る。例えば、シス第一菊酸のアルキルエステルに
対してある種の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）、またシス第一菊酸クロリドを高温に加熱す
る方法（特公昭47−26778号公報）あるいは、シ
ス第一菊酸を180℃以上の温度にて加熱する方法
（特開昭49−126650号公報）等が挙げられる。し
かしながらこれらの方法はシス、トランスの異性
化方法、換言すれば、ラセミシス第一菊酸類から
ラセミトランス体へ変換する方法があり、４つの
異性体の中のある異性体から、より有用な他の異
性体へ選択的に立体変換させるという技術内容を
も含むものではない。 Conventionally, the following method is known as a method for producing trans primary chrysanthemum acids from cis primary chrysanthemum acids. For example, there are methods in which alkyl esters of cis-dairy chrysanthemum acid are treated with certain basic catalysts (Japanese Patent Publication No. 18495/1983, Japanese Patent Publication No. 18496/1983, etc.), and a method of treating alkyl esters of cis-dairy chrysanthemum acid with Examples include a method of heating to a high temperature (Japanese Patent Publication No. 47-26778), a method of heating cis-daisyl chrysanthemum acid at a temperature of 180° C. or higher (Japanese Patent Application Laid-open No. 126650/1982). However, these methods include cis and trans isomerization methods, in other words, methods of converting racemic cis-primary chrysanthemum acids to racemic trans isomers, and from one of the four isomers to another more useful one. It does not even include the technical contents of selective stereoconversion into isomers.
菊酸の４ケの異性体は、例えば２，５−ジメチ
ル−２，４−ヘキサジエンとジアゾ酢酸エチルを
銅触媒で反応させて得られるシス、トランス混合
ラセミカルボン酸エステルを加水分解して誘導さ
れるカルボン酸を、光学活性アミンで分割するこ
とによつて純粋に取得できる（特開昭49−125342
号公報、特公昭51−23497号公報、特公昭54−
37130号公報等）。かくして得られる異性体の中
で、無効な（−）体を有効な（＋）体に立体変換
させて有用化をはかることは工業的に重要なこと
である。 The four isomers of chrysanthemum acid are derived, for example, by hydrolyzing a cis and trans mixed racemic carboxylic acid ester obtained by reacting 2,5-dimethyl-2,4-hexadiene with ethyl diazoacetate using a copper catalyst. A pure carboxylic acid can be obtained by splitting it with an optically active amine (Japanese Patent Application Laid-Open No. 125342-1989).
Publication No. 51-23497, Special Publication No. 54-
37130, etc.). Among the isomers thus obtained, it is industrially important to stereoconvert the ineffective (-) isomer to the effective (+) isomer to make it useful.
前述のシス、トランスの異性化方法の中で、シ
ス第一菊酸アルキルエステルを塩基触媒で処理す
る方法あるいはシス第一菊酸クロリドを高温に加
熱する方法によるトランス体への変換はC1位の
立体配置の変換であることが知られているが、
（−）−シス菊酸に適用するには一旦エステル化す
るか又は酸クロリドに誘導する必要がある。 Among the above-mentioned cis and trans isomerization methods, conversion to the trans isomer by treating a cis-synchronous alkyl ester with a base catalyst or heating a cis-synchronous acid chloride to a high temperature converts the C 1 -position to the trans isomerization method. It is known that it is a transformation of the configuration of
In order to apply it to (-)-cis chrysanthemum acid, it is necessary to esterify it or induce it into an acid chloride.
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（±）−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方法で優れた方法で
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。 In addition, a method is known in which a Lewis acid is applied to each acid halide of the four isomers to obtain a racemic form, that is, a (±)-form, and this method starts from any of the four isomers. can be racemized, especially (−)−
This is an excellent method as it can racemize the trans isomer, but when the (-)-cis isomer is used as the raw material, the (±)-trans is obtained.
従つて、（−）−シス第一菊酸から直接的に
（＋）−トランス体へ変換する効率的な方法が望ま
れる。 Therefore, an efficient method for directly converting (-)-cis primary chrysanthemum acid into the (+)-trans form is desired.
このような状況の下に、本発明者らは（−）−
シス第一菊酸から他の官能基に化学変化させるこ
となく選択的に立体変換させることにより（＋）
−トランス体を効率よく製造することについて鋭
意検討した結果、（−）−シス第一菊酸を200°〜
260℃に加熱することにより効率よく目的を達成
できることを解明し、本発明を完成した。 Under these circumstances, the present inventors (-)-
(+) by selective stereoconversion from cis-dairylic acid to other functional groups without chemical change.
- As a result of intensive studies on how to efficiently produce the trans isomer, we found that (-)-cis Daichic acid was
They discovered that the objective could be achieved efficiently by heating to 260°C, and completed the present invention.
以下に本発明方法につき詳しく説明する。 The method of the present invention will be explained in detail below.
本発明において出発原料である（−）−シス第
一菊酸とは（−）−シス体単独もしくはそれに富
む第一菊酸であり、該出発原料は既述したよう
に、ラセミ第一菊酸の光学分割法によつて得るこ
とができる。従つて、本発明の方法はこれらの技
術と組み合わせることにより、殺虫効力の最も高
い成分である（＋）−トランス体が極めて効率よ
く得られることになる。 In the present invention, (-)-cis primary chrysanthemum acid, which is a starting material, is (-)-cis primary chrysanthemum alone or enriched in the (-)-cis form, and as mentioned above, the starting material is racemic primary chrysanthemum acid. It can be obtained by the optical resolution method. Therefore, by combining the method of the present invention with these techniques, the (+)-trans isomer, which is the component with the highest insecticidal efficacy, can be obtained extremely efficiently.
反応を行なうに際しては原料を200℃以上に加
熱するのみでよいが、300℃以上では環開裂反応
が起つてパイロシンが生成するので、温度範囲は
200〜260℃の範囲であり、この範囲では10時間以
内で充分に目的を達することができる。 To carry out the reaction, it is only necessary to heat the raw materials above 200°C, but at temperatures above 300°C a ring cleavage reaction occurs and pyrosine is produced, so the temperature range is limited.
The temperature is in the range of 200 to 260°C, and within 10 hours the purpose can be fully achieved within this range.
また、本反応に際し、溶媒は必須ではないが、
必要に応じ反応を阻害しない溶媒を用いることも
可能であり、また通常は窒素、アルゴン等の不活
性ガス雰囲気下で実施する。 Additionally, although a solvent is not essential for this reaction,
If necessary, it is possible to use a solvent that does not inhibit the reaction, and the reaction is usually carried out under an inert gas atmosphere such as nitrogen or argon.
また、本発明方法を実施するに際し、反応の形
式はバツチ形式あるいは連続形式の何れの形式で
も行うことができ、原料の（−）−シス第一菊酸
を反応容器に一括して入れる方法あるいは反応の
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。 Furthermore, when carrying out the method of the present invention, the reaction can be carried out either batchwise or continuously. Either method of adding continuously or intermittently depending on the progress of the reaction can be adopted.
反応の進行度は旋光度の測定あるいは光学活性
アルコールと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による分析などにより知る
ことができる。 The progress of the reaction can be determined by measuring the optical rotation or by analyzing diastereoisomers with the optically active alcohol using gas chromatography.
また本発明方法は減圧下または加圧下で実施す
ることができるが、常圧下でも容易に目的を達す
ることができる。 Although the method of the present invention can be carried out under reduced pressure or increased pressure, the purpose can be easily achieved even under normal pressure.
以上のようにして反応が終了した反応液はC1
位がエビ化されて生成した（＋）−トランス第一
菊酸、またはそれに富むトランス第一菊酸として
得られる。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。 The reaction solution that completed the reaction as described above is C 1
It is obtained as (+)-trans primary chrysanthemum acid, which is produced by the conversion of the trans primary chrysanthemum position, or as trans primary chrysanthemum acid enriched therein. Furthermore, it can be purified by distillation, chromatography, etc., if necessary.
このようにして得られた（＋）−トランス第一
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。 The (+)-trans primary chrysanthemum acid thus obtained can be used for various purposes. For example, (+)-trans primary chrysanthemum acid is called a pyrethroid alcohol represented by pyrethrolone and allethrone. Reaction with a group of alcohols can lead to highly potent insecticidal compounds.
次に実施例によつて本発明の方法を説明する。 The method of the invention will now be explained by way of examples.
実施例 １
（−）−シス第一菊酸10.0ｇを耐圧硝子アンプ
ルに入れ、窒素ガスで系内を置換した後、250℃
の油浴に１時間浸漬した。冷後反応液をトルエン
50mlに溶解し、５％苛性ソーダ水溶液で抽出し
た。水層を硫酸酸性とし、１，２−ジクロロエタ
ン50mlで抽出、水洗した後硫酸マグネシウムで乾
燥した。この溶液をガスクロマトグラフイーで分
析すると、（−）−シス体12.9％、（＋）−トランス
体87.1％であつた。Example 1 10.0g of (-)-cis-daisy chrysanthemum acid was placed in a pressure-resistant glass ampoule, and after purging the system with nitrogen gas, the temperature was increased to 250°C.
immersed in an oil bath for 1 hour. After cooling, add toluene to the reaction solution.
The solution was dissolved in 50 ml and extracted with a 5% aqueous solution of caustic soda. The aqueous layer was acidified with sulfuric acid, extracted with 50 ml of 1,2-dichloroethane, washed with water, and dried over magnesium sulfate. When this solution was analyzed by gas chromatography, it was found that the (-)-cis form was 12.9% and the (+)-trans form was 87.1%.
この溶液に0.25ｇの塩化亜鉛を加え、60〜65℃
に２時間加熱撹拌した。冷後、水洗し５％苛性ソ
ーダ水溶液で抽出した。水層を硫酸酸性とし、ト
ルエン50mlを加えて抽出、水洗した後、減圧下に
溶媒を留去し、蒸留するとb.p.95〜98℃／0.3mm
Hgの油状物8.1ｇが得られた。 Add 0.25g of zinc chloride to this solution and heat at 60-65℃.
The mixture was heated and stirred for 2 hours. After cooling, it was washed with water and extracted with a 5% aqueous solution of caustic soda. The aqueous layer was acidified with sulfuric acid, extracted with 50 ml of toluene, washed with water, and the solvent was distilled off under reduced pressure.
8.1 g of Hg oil was obtained.
このもののIRスペクトル、NMRスペクトルは
標準品の（＋）−トランス第一菊酸と一致した。
また、このものの旋光度は〔α〕24 D＋14.1゜（ｃ＝
0.9、エタノール）であつた。 The IR spectrum and NMR spectrum of this product matched that of the standard product (+)-trans Daisichroic acid.
Also, the optical rotation of this object is [α] 24 D +14.1° (c=
0.9, ethanol).
実施例 ２
実施例１で用いた（−）−シス第一菊酸1.0ｇを
耐圧硝子アンプルに入れ、窒素ガスで系内を置換
したのち、密封し220℃で５時間加熱した。Example 2 1.0 g of (-)-cis primary chrysanthemum acid used in Example 1 was placed in a pressure-resistant glass ampoule, and after purging the inside of the system with nitrogen gas, the ampoule was sealed and heated at 220° C. for 5 hours.
反応後内容物を取出しトルエン10mlに溶解し、
５％苛性ソーダ水溶液で抽出し、水層を酸析、ト
ルエン抽出、水洗したのち、減圧下に溶媒を留去
すると0.91ｇの第一菊酸を得た。このものをガス
クロマトグラフイーで分析すると（−）−シス体
11.7％（＋）−トランス体88.8％であつた。次い
でこれをクロロホルム５mlに溶し、25mgの塩化亜
鉛を加え、以後実施例１と同様に処理すると、
0.80ｇの（＋）−トランス第一菊酸が得られた。
このものの旋光度は〔α〕25 D＋14.1゜（ｃ＝1.5、エ
タノール）であつた。 After the reaction, take out the contents and dissolve in 10ml of toluene.
After extraction with a 5% caustic soda aqueous solution, the aqueous layer was precipitated with acid, extracted with toluene, washed with water, and the solvent was distilled off under reduced pressure to obtain 0.91 g of Daiichi chrysanthemum acid. When this substance is analyzed by gas chromatography, it shows (-)-cis form.
It was 11.7% (+) - 88.8% trans isomer. Next, this was dissolved in 5 ml of chloroform, 25 mg of zinc chloride was added, and the process was then carried out in the same manner as in Example 1.
0.80 g of (+)-trans primary chrysanthemum acid was obtained.
The optical rotation of this product was [α] 25 D +14.1° (c=1.5, ethanol).
実施例 ３
（−）−シス体90.0％、（−）−トランス体10.0
％から成る第一菊酸10.0ｇをオートクレープに入
れ、窒素ガスで系内を置換した後、密栓し、250
℃で40分間加熱した。冷後反応液をトルエン50ml
に溶解し、５％苛性ソーダ水溶液で抽出し、水層
を硫酸酸性とし、１，２−ジクロルエタン50mlで
抽出した。水洗後硫酸マグネシウムで乾燥し、塩
化第二鉄0.3ｇを加えて、２時間加熱撹拌した。
以下、実施例１と同様に処理して、（＋）−トラン
ス体90.0％（−）−トランス体10.0％から成る
（＋）−トランス体に富む第一菊酸8.2ｇが得られ
た。Example 3 (-)-cis form 90.0%, (-)-trans form 10.0%
Put 10.0 g of Daiichi Chrysanthemum acid consisting of
Heat at ℃ for 40 minutes. After cooling, add 50ml of toluene to the reaction solution.
The aqueous layer was acidified with sulfuric acid and extracted with 50 ml of 1,2-dichloroethane. After washing with water, it was dried over magnesium sulfate, 0.3 g of ferric chloride was added, and the mixture was heated and stirred for 2 hours.
Thereafter, the same treatment as in Example 1 was carried out to obtain 8.2 g of (+)-trans isomer-enriched Daishu chrysanthemum acid, which was composed of 90.0% of the (+)-trans isomer and 10.0% of the (-)-trans isomer.
実施例 ４
（−）−シス体91.2％、（＋）−シス体8.8％から
成る第一菊酸10.0ｇをオートクレープに入れ、実
施例３と同様にして240℃で２時間反応した。冷
後実施例３と同様に処理して（＋）−トランス体
91.2％、（−）−トランス体8.8％から成る（＋）−
トランス体に富む第一菊酸8.2ｇが得られた。Example 4 10.0 g of Daishu chrysanthemum acid consisting of 91.2% of (-)-cis isomer and 8.8% of (+)-cis isomer was placed in an autoclave, and reacted in the same manner as in Example 3 at 240°C for 2 hours. After cooling, it was treated in the same manner as in Example 3 to obtain the (+)-trans isomer.
91.2%, (+)- consisting of 8.8% (-)- trans isomer
8.2 g of daichusic acid rich in trans isomer was obtained.
Claims (1)
囲で加熱することを特徴とする（＋）−トランス
第一菊酸の製造法。1. A method for producing (+)-trans primary chrysanthemum acid, which comprises heating (-)cis primary chrysanthemum acid in a temperature range of 200° to 260°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16966681A JPS5869831A (en) | 1981-10-22 | 1981-10-22 | Preparation of (+)-trans chrysanthemum-monocarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16966681A JPS5869831A (en) | 1981-10-22 | 1981-10-22 | Preparation of (+)-trans chrysanthemum-monocarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5869831A JPS5869831A (en) | 1983-04-26 |
| JPH0253429B2 true JPH0253429B2 (en) | 1990-11-16 |
Family
ID=15890665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16966681A Granted JPS5869831A (en) | 1981-10-22 | 1981-10-22 | Preparation of (+)-trans chrysanthemum-monocarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5869831A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0619855U (en) * | 1992-03-06 | 1994-03-15 | 旭サナック株式会社 | Coating material spraying device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49126650A (en) * | 1973-04-17 | 1974-12-04 | ||
| JPS5077346A (en) * | 1973-11-12 | 1975-06-24 |
-
1981
- 1981-10-22 JP JP16966681A patent/JPS5869831A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49126650A (en) * | 1973-04-17 | 1974-12-04 | ||
| JPS5077346A (en) * | 1973-11-12 | 1975-06-24 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0619855U (en) * | 1992-03-06 | 1994-03-15 | 旭サナック株式会社 | Coating material spraying device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5869831A (en) | 1983-04-26 |
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