JPS6335540A - Method for optical resolution of chrysanthemum-monocarboxylic acid - Google Patents
Method for optical resolution of chrysanthemum-monocarboxylic acidInfo
- Publication number
- JPS6335540A JPS6335540A JP18124986A JP18124986A JPS6335540A JP S6335540 A JPS6335540 A JP S6335540A JP 18124986 A JP18124986 A JP 18124986A JP 18124986 A JP18124986 A JP 18124986A JP S6335540 A JPS6335540 A JP S6335540A
- Authority
- JP
- Japan
- Prior art keywords
- trans
- cis
- chrysanthemum
- acid
- 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
- 230000003287 optical effect Effects 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 24
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 title abstract 6
- 239000002253 acid Substances 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 8
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical compound CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZICDZTXDTPZBKH-UHFFFAOYSA-N 2-(4-methylphenyl)-1-phenylethanamine Chemical compound C1=CC(C)=CC=C1CC(N)C1=CC=CC=C1 ZICDZTXDTPZBKH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 241000723353 Chrysanthemum Species 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 235000007516 Chrysanthemum Nutrition 0.000 claims description 15
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 51
- 150000003839 salts Chemical class 0.000 abstract description 19
- 239000013078 crystal Substances 0.000 abstract description 17
- 238000001914 filtration Methods 0.000 abstract description 8
- 150000002148 esters Chemical class 0.000 abstract description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012452 mother liquor Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 2
- 230000000749 insecticidal effect Effects 0.000 abstract description 2
- XLOPRKKSAJMMEW-SFYZADRCSA-N (+)-trans-chrysanthemic acid Chemical compound CC(C)=C[C@@H]1[C@@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-SFYZADRCSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 33
- 238000003756 stirring Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 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 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 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
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical class N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940024113 allethrin Drugs 0.000 description 1
- 239000007864 aqueous solution 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
- 239000001273 butane Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 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
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 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
- 239000002728 pyrethroid Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はｄｌ−トランス−第−期成またはｄｌ−シス／
トランス−混合筒−期成の光学分割法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to dl-trans-phase or dl-cis/
This article relates to an optical separation method for trans-mixing tube formation.
更に詳しくは光学分割剤として光学活性α−フェニル−
β−パラトリルエチルアミン（以下、ＰＴＥと略す）ま
たは光学活性α−フェニルエチルアミン（以下、ＰＥＡ
と略す）を用い、かつ、光学分割溶媒として疎水性有機
溶媒を用いるｄｌ−１−ランス−第−期成またはｄｌ−
シス／トランス−混合筒−期成の光学分割法に関する。More specifically, optically active α-phenyl-
β-paratolylethylamine (hereinafter abbreviated as PTE) or optically active α-phenylethylamine (hereinafter referred to as PEA)
dl-1-lance-first phase formation or dl-1-lance-phase formation or dl-
This invention relates to an optical resolution method for cis/trans mixing cylinder phase formation.
〈従来の技術〉
第−期成はピレスリン、アレスリン、フタルスリンなど
の所謂ピレスロイドと称される低毒速効性殺虫剤エステ
ルの酸成分を構成するものであり、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。<Prior art> Phase 1 forms the acid component of esters of low toxicity, fast-acting insecticides called pyrethroids, such as pyrethrin, allethrin, and phthalthrin, and is useful as a raw material for these pyrethroid insecticides. It is.
ところで第−期成には不斉炭素が２個あり４種類の異性
体が存在する。By the way, there are two asymmetric carbons in the -stage formation, and there are four types of isomers.
−ｉに第−期成のエステルに関しては、殺虫効力がシス
体のエステルよりもトランス体のエステルの方が強く、
また、１体のエステルよりも６体のエステルが強いこと
が知られていることから、工業的により有利なｄ−）ラ
ンス体またはｄ−シス／トランス混合体の取得法の開発
が望まれている。Regarding the esters formed in the -i stage, the insecticidal efficacy of the trans-form esters is stronger than that of the cis-form esters;
In addition, since it is known that six esters are stronger than one ester, it is desired to develop a method for obtaining the d-)trans isomer or the d-cis/trans mixture that is industrially more advantageous. There is.
従来、ｄｌ−トランス−第−期成またはｄｌ−シス／ト
ランス−混合筒−期成の代表的な光学分割法としては、
光学活性なＰＴＥを用いる方法が知られている（特公昭
４６−２０３８２号公報および特公昭５４−３７１３０
号公報）。Conventionally, typical optical separation methods for dl-trans-phase formation or dl-cis/trans-mixing tube-phase formation include:
A method using optically active PTE is known (Japanese Patent Publication No. 46-20382 and Japanese Patent Publication No. 37130-1982).
Publication No.).
〈発明が解決しようとする問題点〉
しかしながら、上記の方法では分割溶媒としてアルコー
ル類、アセトン、テトラヒドロフラン、ジオキサン等の
親水性溶媒を用いることから、目的の光学活性な第−期
成を単離または回収するために、新たに疎水性有機溶媒
を使用しなければならない。また、晶析分離された塩は
、通常これに鉱酸、苛性アルカリなどの水溶液を作用さ
せることにより、目的の光学活性な第−期成を取得する
ことから、使用した親水性溶媒を水から回収する操作も
必要となり、特に工業的規模での実施時には煩雑な操作
を要することになる。<Problems to be Solved by the Invention> However, since the above method uses hydrophilic solvents such as alcohols, acetone, tetrahydrofuran, and dioxane as the separation solvent, it is difficult to isolate or isolate the desired optically active first-phase product. For recovery, a new hydrophobic organic solvent must be used. In addition, since the crystallized salt is usually treated with an aqueous solution such as mineral acid or caustic alkali to obtain the desired optically active phase, the hydrophilic solvent used can be removed from water. A recovery operation is also required, which is particularly complicated when implemented on an industrial scale.
さらに、上記方法により得られた第−期成は、その光学
純度の点において充分に満足できるものとは言い難い。Furthermore, the first-stage product obtained by the above method cannot be said to be fully satisfactory in terms of its optical purity.
く問題点を解決するための手段〉
本発明者らは、光学活性なＰＴＥまたはＰＥＡを用いた
トランス−第−期成またはシス／トランス−混合筒−期
成の光学分割法について上述の問題点を解消すべく鋭意
検討を重ねた結果、分割溶媒として疎水性有機溶媒を用
いることにより、高い光学純度の第−期成が容易に得ら
れることを見出し本発明に至った。Means for Solving the Problems> The present inventors have solved the above-mentioned problems regarding the optical resolution method of trans-phase phase formation or cis/trans-mixing cylinder phase formation using optically active PTE or PEA. As a result of extensive studies aimed at solving the problem, it was discovered that by using a hydrophobic organic solvent as a splitting solvent, a first phase formation with high optical purity can be easily obtained, leading to the present invention.
即ち本発明は、ｄｌ−）ランス−第−期成またはｄｌ−
シス／トランス−混合筒−期成を光学活性ＰＴＥまたは
光学活性ＰＥＡを用いて光学分割する方法において、上
記第−期成と光学活性ＰＴＥまたは光学活性ＰＥＡとの
反応、および一方の光学活性なトランス−第−期成また
は光学活性なシス／トランス−混合筒−期成と該アミン
との塩を晶出させ、これを母液から分離する晶析分だ工
程を、疎水性有機溶媒中で行うことによるトランス−第
−期成またはシス／トランス−混合筒−期成の光学分割
法を提供するものである。That is, the present invention provides dl-) lance-stage formation or dl-
In a method for optically resolving a cis/trans-mixing cylinder phase using optically active PTE or optically active PEA, the reaction between the above-mentioned phase and optically active PTE or optically active PEA, and one of the optically active trans - Performing a crystallization step of crystallizing the salt of the first stage or the optically active cis/trans mixing cylinder stage and the amine and separating it from the mother liquor in a hydrophobic organic solvent. The present invention provides an optical resolution method for trans-phase phase formation or cis/trans mixed cylinder phase formation.
本発明方法によれば得られる第−期成の光学純度が高い
ことに加え、使用した溶媒の回収が容易で、しかも得ら
れる第−期成のＰＴＥまたはＰＥＡの塩の結晶の濾過性
が良好であることから、工業的規模でめ製造において有
利であり、また、原料として用いる第−期成のシス／ト
ランス比に影うされることなく光学分割が達成できる。According to the method of the present invention, in addition to the high optical purity of the first-stage product obtained, the used solvent can be easily recovered, and the obtained first-stage PTE or PEA salt crystals have good filterability. Therefore, it is advantageous in producing rice on an industrial scale, and optical resolution can be achieved without being affected by the cis/trans ratio of the first stage used as a raw material.
次に本発明方法につき詳しく説明する１本発明において
用いられる疎水性有機溶媒としては、例えばベンゼン、
トルエン、キシレン等の芳香族炭化水素、ヘキサン、ヘ
プタン、オクタン等の脂肪族炭化水素などが挙げられる
。Next, the method of the present invention will be explained in detail.1 Hydrophobic organic solvents used in the present invention include, for example, benzene,
Examples include aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as hexane, heptane and octane.
かかる溶媒の使用については、多すぎると生産効率が低
下し、また得られるｄ−１−ランス第−期成またはｄ−
シス／トランス−混合筒−期成の光学純度が低下し、一
方、溶媒量が少なすぎると反応溶液の濃度が高くなり攪
拌が不充分になり、また生成する結晶の濾過性も悪くな
り、ひいては得られるｄ−）ランス第−期成またはｄ−
シス／トランス−混合筒−期成の光学純度が低下するこ
となどから、溶媒量は用いるｄｌ−トランス第−期成ま
たはｄｌ−シス／トランス−混合筒−期成に対して通常
２．５〜６重量倍、好ましくは３〜５重量倍の範囲であ
る。Regarding the use of such a solvent, if the amount is too large, the production efficiency will decrease, and the resulting d-1-lance stage formation or d-
The optical purity of the cis/trans mixing cylinder phase will decrease, and on the other hand, if the amount of solvent is too small, the concentration of the reaction solution will be high and stirring will be insufficient, and the filterability of the formed crystals will also be poor. obtained d-) lance stage formation or d-
Since the optical purity of the cis/trans-mixing cylinder phase decreases, the amount of solvent is usually 2.5 to 2.5% for the dl-trans phase formation or the dl-cis/trans-mixing cylinder phase formation. The amount is 6 times by weight, preferably 3 to 5 times by weight.
また、光学分割剤のＰＴＥまたはＰＥＡとしては、通常
（＋）ＰＴＥまたは（−）ＰＥＡが用いられ、中でも、
得られるｄ−トランス第−期成またはｄ−シス／トラン
ス−混合筒−期成の光学純度の点で（＋）ＰＴＥの使用
がより好ましい。かかる光学分割剤の使用量は、好まし
くは用いるｄｌ−トランス第−期成またはｄｌ−シス／
トランス−混合第−期成１モルに対して０．２〜０．６
モルの範囲、より好ましくは０．３〜０．５モルの範囲
が望ましい。In addition, as the optical resolution agent PTE or PEA, (+) PTE or (-) PEA is usually used, and among them,
From the viewpoint of the optical purity of the resulting d-trans phase formation or d-cis/trans mixed cylinder phase formation, it is more preferable to use (+)PTE. The amount of such optical resolving agent used is preferably determined depending on the dl-trans stage or dl-cis/
0.2 to 0.6 per mole of trans-mixed phase formation
A molar range, more preferably a range of 0.3 to 0.5 molar is desirable.
造塩時の反応温度に関しては、反応温度が低すぎると、
得られるｄ−）ランス第−期成またはｄ−シス／トラン
ス−混合筒−期成の光学純度が悪いのみならず、反応液
の攪拌が困難となり、一方、反応温度が高すぎると第−
期成塩の結晶の析出が非常におそくなることから、反応
温度は５０〜７５℃の範囲が好ましい。Regarding the reaction temperature during salt formation, if the reaction temperature is too low,
Not only is the optical purity of the resulting d-) lance phase formation or d-cis/trans mixing cylinder phase formation poor, but it also becomes difficult to stir the reaction solution.On the other hand, if the reaction temperature is too high, the
The reaction temperature is preferably in the range of 50 to 75°C, since precipitation of crystals of the nascent salt becomes very slow.
尚、本発明方法において、水分がｄｌ−）ランス第−期
成またはｄｌ−シス／トランス−混合筒−期成に対して
１重量％程度存在すると収率や結晶の濾過性の低下をき
たすことから系内の水分量はできるだけ少ないことが望
ましいが０．２重量％以下であれば何ら支障は生じない
、従って本発明方法において通常の原料として使用され
る有８１溶媒は、そのまま分割溶媒として使用すること
ができる。In addition, in the method of the present invention, if water is present in an amount of about 1% by weight based on the dl-) lance phase formation or the dl-cis/trans mixing cylinder phase formation, the yield and filterability of the crystals may be reduced. Therefore, it is desirable that the amount of water in the system is as low as possible, but if it is 0.2% by weight or less, no problems will occur. Therefore, the 81 solvent used as a normal raw material in the method of the present invention can be used as it is as a dividing solvent. can do.
本発明方法は、標準的には次のような操作により実施さ
れる。The method of the present invention is typically carried out by the following operations.
先ず、ｄｌ−トランス第−期成またはｄｌ−シス／トラ
ンス−混合筒−期成を前記溶媒中で（＋）ＰＴＥまたは
（−）ＰＥＡと反応させ対応する塩を生成させる。この
時の温度は５０〜７５℃であり、反応時間は通常は１〜
３時間である。First, the dl-trans stage or dl-cis/trans mixed cylinder stage is reacted with (+)PTE or (-)PEA in the above solvent to generate the corresponding salt. The temperature at this time is 50-75℃, and the reaction time is usually 1-75℃.
It is 3 hours.
次に、この反応液を４〜１５時間を要し、徐々に１０〜
２０℃まで冷却する。この時、さらに１〜２時間同温度
に保ちｄ−）ランス第−期成またはｄ−ラス／トランス
−混合期成菊酸の塩の結晶の熟成を図ることが望ましい
。Next, this reaction solution was mixed for 4 to 15 hours, and gradually 10 to 15 hours.
Cool to 20°C. At this time, it is desirable to maintain the same temperature for an additional 1 to 2 hours to ripen the d-) lance-stage or d-las/trans-mixed chrysanthemum acid salt crystals.
引続き、このようにして析出させたｄ−トランス第−期
成またはｄ−シス／トランス−混合筒−期成の塩の結晶
を母液より分離する。Subsequently, the salt crystals of the d-trans phase or the d-cis/trans mixed tube phase thus precipitated are separated from the mother liquor.
尚、この時当然ながら母液中に含まれるトランス第−期
成またはシス／トランス−混合・第−期成は１体に富む
。Incidentally, at this time, naturally, the mother liquor contains only one trans phase formation or cis/trans mixed phase formation.
上記のようにして得られる塩の結晶は鳴これを塩酸、硫
酸等の酸または水酸化ナトリウム、水酸化カリウム等の
アルカリを用いる塩分群の常法により、目的の光学活性
なｄ−１−ランス第−期成またはｄ−シス／トランス−
混合筒−期成を得ることができる。The salt crystals obtained in the above manner are crystallized to form the desired optically active d-1-lance by a conventional salt group method using an acid such as hydrochloric acid or sulfuric acid or an alkali such as sodium hydroxide or potassium hydroxide. Phase formation or d-cis/trans-
Mixing cylinder - phase formation can be obtained.
〈実施例〉
以下、実施例を用いて本発明を更に詳細に説明するが、
本発明はこれらに限定されるものではない。<Examples> The present invention will be explained in more detail using Examples below.
The present invention is not limited to these.
実施例１
旧−トランス第−期成（ｄｌ１・４７．５１５２．５
、シス／トランス−〇／１００） １００ｇにトルエン
１７０ｇを加えて攪拌溶解した。Example 1 Old-trans phase formation (dl1・47.5152.5
, cis/trans-○/100) 170 g of toluene was added to 100 g and dissolved with stirring.
次いで、これに（＋）ＰＴＥ （光学純度９６％）５７
．０ｇをトルエン１７０ｇに溶かした液を３０分を要し
撹拌下に滴下した。Then, (+)PTE (optical purity 96%) 57
．． A solution prepared by dissolving 0 g in 170 g of toluene was added dropwise over 30 minutes with stirring.
尚、滴下時の温度は５０〜６０℃であり、また、この反
応液の水分は３００ｐｐｍであった。The temperature during the dropwise addition was 50 to 60°C, and the water content of this reaction solution was 300 ppm.
滴下終了後１時間同温度で保温攪拌し、次いで１０時間
で１５℃まで撹拌冷却し、さらに１５℃で１時間攪拌し
た。After the completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour, then cooled to 15°C with stirring for 10 hours, and further stirred at 15°C for 1 hour.
次に、析出した結晶を濾取し、該結晶を８７ｇのトルエ
ンで２回洗浄後、乾燥しｄ−）ランス第一筒酸の（＋）
ＰＴＥ塩６９．９ｇを得た。Next, the precipitated crystals were collected by filtration, washed twice with 87 g of toluene, and dried.
69.9 g of PTE salt was obtained.
収率 ６５．３％（対 ｄ−第一筒酸）光学純度
９６．６％
実施例２
ｄｌ−シス／トランス混合第一菊酸（ｄ／ｌ・５０１５
０、シス／トランス＝ １／９９） １００ｇ にｎ
−へブタン１３６ｇを加えて攪拌溶解した。Yield: 65.3% (based on d-synthetic acid) Optical purity
96.6% Example 2 dl-cis/trans mixed primary chrysanthemum acid (d/l・5015
0, cis/trans = 1/99) n in 100g
- 136 g of hebutane was added and dissolved with stirring.
次いで、これに（＋）ＰＴＥ （光学純度９６％）４４
．３８をｎ−へブタン１３６ｇに熔かした液を３０分を
要し攪拌下に滴下した。Then, (+)PTE (optical purity 96%) 44
．． A solution prepared by dissolving No. 38 in 136 g of n-hebutane was added dropwise over 30 minutes with stirring.
尚、滴下時の温度は７０〜７２℃であり、また、この反
応液の水分は２００ｐｐｍであった。The temperature during the dropwise addition was 70 to 72°C, and the water content of this reaction liquid was 200 ppm.
滴下終了後７５℃で１時間保温攪拌し、次いで６時間で
２０℃まで攪拌冷却し、さらに２０℃で１時間攪拌した
。After the completion of the dropwise addition, the mixture was stirred at 75°C for 1 hour, then cooled to 20°C with stirring for 6 hours, and further stirred at 20°C for 1 hour.
次に、析出した結晶を濾取し、該結晶を６８ｇのｎ−へ
ブタンで２回洗浄後、乾燥しｄ−シス／トランス混合第
一菊酸の（＋）ＰＴＥ塩６３．２ｇを得た。Next, the precipitated crystals were collected by filtration, washed twice with 68 g of n-hebutane, and then dried to obtain 63.2 g of (+) PTE salt of d-cis/trans mixed daisies chrysanthemum acid. .
収率 ５６．０％（対 ｄ−第一筒酸）光学純度
９７．０％
シス／トランス＝０．１／９９．９
実施例３
ｄｌ−シス／トランス混合第一菊酸（ｄ／ ｌ・４７１
５３、シス／トランス＝２３／７７） １００ｇ に
トルエン２００ｇを加えて攪拌溶解した。Yield: 56.0% (based on d-synthetic acid) Optical purity
97.0% cis/trans=0.1/99.9 Example 3 dl-cis/trans mixed chlorinated acid (d/l・471
53, cis/trans = 23/77) 200 g of toluene was added to 100 g and dissolved with stirring.
次いで、これに（＋）ＰＴＥ （光学純度９６％）５７
．０ｇをトルエン２００ｇに溶かした液を３０分を要し
攪拌下に滴下した。Then, (+)PTE (optical purity 96%) 57
．． A solution prepared by dissolving 0 g in 200 g of toluene was added dropwise over 30 minutes with stirring.
尚、滴下時の温度は５０〜６０℃であり、また、この反
応液の水分は３００ｐｐｍであった。The temperature during the dropwise addition was 50 to 60°C, and the water content of this reaction solution was 300 ppm.
滴下終了後１時間同温度で保温攪拌し、次いで１０時間
で１５℃まで攪拌冷却し、さらに１５℃で１時間攪拌し
た。After the completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour, then cooled to 15°C with stirring for 10 hours, and further stirred at 15°C for 1 hour.
次に、析出した結晶を濾取し、該結晶を９０ｇのトルエ
ンで２回洗浄後、乾燥しｄ−シス／トランス混合第一菊
酸の（＋）ＰＴＥ塩５９．１ｇを得た。Next, the precipitated crystals were collected by filtration, washed twice with 90 g of toluene, and then dried to obtain 59.1 g of (+) PTE salt of d-cis/trans mixed chrysanthemum acid.
収率 ５５．．７％（対 ｄ−第一筒酸）光学純度
９６．６％
ソス／トランス＝１７．５／８２．５
実施例４
旧−シス／トランス混合第一菊酸（ｄ／ｌ・５０１５０
、シス／トランス＝３５／６５） １００ｇ にトル
エン１７０ｇを加えて攪拌溶解した。Yield 55. ．． 7% (relative to d-synthetic acid) Optical purity 96.6% Sos/trans = 17.5/82.5 Example 4 Old-cis/trans mixed stochastic acid (d/l・50150
, cis/trans = 35/65) and 170 g of toluene was added and dissolved with stirring.
次いで、これに（＋）ＰＴＥ （光学純度９７％）５７
．０ｇをトルエン１７０ｇに溶かした液を３０分を要し
攪拌下に滴下した。Then, (+)PTE (optical purity 97%) 57
．． A solution prepared by dissolving 0 g in 170 g of toluene was added dropwise over 30 minutes with stirring.
尚、滴下時の温度は５０〜５５℃であり、また、この反
応液の水分は２ｓｏｐｐ＋ｍであった。The temperature during the dropwise addition was 50 to 55°C, and the water content of this reaction solution was 2sopp+m.
滴下終了後６０℃で１時間保温攪拌し、次いで６時間で
１５℃まで攪拌冷却し、さらに１５℃で２時間攪拌した
。After completion of the dropwise addition, the mixture was stirred at 60° C. for 1 hour while stirring, then cooled to 15° C. over 6 hours with stirring, and further stirred at 15° C. for 2 hours.
次に、析出した結晶を濾取し、該結晶を８０ｇのトルエ
ンで２回洗浄後、乾燥しｄ−シス／トランス混合第一菊
酸の（＋）ＰＴＥ塩４８．０ｇを得た。Next, the precipitated crystals were collected by filtration, washed twice with 80 g of toluene, and then dried to obtain 48.0 g of (+) PTE salt of d-cis/trans mixed chrysanthemum acid.
収率 ４３．２％（対 ｄ−第一筒酸）光学純度
９６．６％
シス／トランス＝３４／６６
実施例５
ｄｌ−シス／トランス混合第一菊酸（ｄ／ ＋＝４７１
５３、シス／トランス＝２３／７７） １００ｇ に
ｎ ／’％ブタン１３６ｇを加えて攪拌溶解した。Yield: 43.2% (based on d-synthetic acid) Optical purity
96.6% cis/trans=34/66 Example 5 dl-cis/trans mixed chlorinated acid (d/+=471
53, cis/trans=23/77) 136 g of n/'% butane was added to 100 g and dissolved with stirring.
次いで、これに（＋）ＰＴＥ （光学純度９６％）４４
．３８をＱ−ヘプタン１３６ｇに溶かした液を３０分を
要し攪拌下に滴下した。Then, (+)PTE (optical purity 96%) 44
．． A solution prepared by dissolving No. 38 in 136 g of Q-heptane was added dropwise over 30 minutes with stirring.
尚、滴下時の温度は７０〜７２℃であり、また、この反
応液の水分は２５０ｐｐｍであった。The temperature during the dropwise addition was 70 to 72°C, and the water content of this reaction solution was 250 ppm.
滴下終了後７５℃で１時間保温攪拌し、次いで６時間で
２０℃まで撹拌冷却し、さらに２０℃で１時間攪拌した
。After completion of the dropwise addition, the mixture was stirred at 75°C for 1 hour while stirring, then cooled to 20°C over 6 hours with stirring, and further stirred at 20°C for 1 hour.
次に、析出した結晶を濾取し、該結晶を７０８のｎ−へ
ブタンで２回洗浄後、乾燥しｄ−シス／トランス混合第
一菊酸の（＋）ＰＴＥＴＥ１０１ｇを得た。Next, the precipitated crystals were collected by filtration, washed twice with 708 g of n-hebutane, and dried to obtain 101 g of d-cis/trans mixed (+) PTETE of chrysanthemum acid.
収率 ５７．７％（対 ｄ−第一菊ｒＩ１．）光学
純度 ９７．０％
シス／トランス−１７／８３
実施例６
ｄｌ−シス／トランス混合第一菊酸（ｄ／Ｉ・４７．８
１５２．２ 、シス／トランス−３，８／９６．２）
１００ｇにトルエン１７５ｇを加えて攪拌溶解した。Yield 57.7% (vs. d-Daichichrysanthemum rI1.) Optical purity 97.0% cis/trans-17/83 Example 6 dl-cis/trans mixed Daiichichrysanthemum acid (d/I・47.8
152.2, cis/trans-3,8/96.2)
175 g of toluene was added to 100 g and dissolved with stirring.
次いで、これに（＋）ＰＴＥ （光学純度９６％）５７
．０ｇをトルエン１７５ｇに溶かした液を３０分を要し
攪拌下に滴下した。Then, (+)PTE (optical purity 96%) 57
．． A solution prepared by dissolving 0 g in 175 g of toluene was added dropwise over 30 minutes with stirring.
尚、滴下時の温度は５０〜６０℃であり、また、この反
応液の水分は３００ｐｐｍであった。The temperature during the dropwise addition was 50 to 60°C, and the water content of this reaction solution was 300 ppm.
滴下終了後７５℃で１時間保温攪拌し、次いで１２時間
で１５℃まで攪拌冷却し、さらに１５℃で１時間撹拌し
た。After the completion of the dropwise addition, the mixture was stirred at 75°C for 1 hour, then cooled to 15°C with stirring for 12 hours, and further stirred at 15°C for 1 hour.
次に、析出した結晶を濾取し、該結晶を８０ｇのトルエ
ンで２回洗浄後、乾燥しｄ−シス／トランス混合第一菊
酸の（＋）ＰＴＥ塩６９．２ｇを得た。Next, the precipitated crystals were collected by filtration, washed twice with 80 g of toluene, and then dried to obtain 69.2 g of (+) PTE salt of d-cis/trans mixed chrysanthemum acid.
収率 ６４．２％（対 ｄ−第一期成）光学純度
９６．６％
シス／トランス＝２／９８
実施例７
ｄｌ−シス／トランス混合第一菊酸（ｄ／１＝４７１５
３、シス／トランス、２３／７７） １００ｇ にｎ
−へブタン６８ｇとトルエン６８ｇを加えて攪拌溶解し
た。Yield 64.2% (vs. d-1st stage formation) Optical purity
96.6% cis/trans=2/98 Example 7 dl-cis/trans mixed daisies chrysanthemum acid (d/1=4715
3, cis/trans, 23/77) n in 100g
- 68 g of hebutane and 68 g of toluene were added and dissolved with stirring.
次いで、これに（−）ＰＥＡ （光学純度９７％）２５
．４ｇをｎ−ヘプタン６８ｇとトルエン６８ｇに７容か
した液を３０分を要し攪拌下に滴下した。Next, (-)PEA (optical purity 97%) 25
．． A solution prepared by adding 4g of 4g to 68g of n-heptane and 68g of toluene in 7 volumes was added dropwise over 30 minutes with stirring.
尚、滴下時の温度は６５〜７０℃であり、また、この反
応液の水分は２００ｐｐｍであった。The temperature during the dropwise addition was 65 to 70°C, and the water content of this reaction solution was 200 ppm.
滴下終了後７５℃で１時間保温攪拌し、次いで１４時間
で２０℃まで攪拌冷却し、さらに２０℃で１時間攪拌し
た。After completion of the dropwise addition, the mixture was stirred at 75°C for 1 hour while being kept warm, then cooled to 20°C with stirring for 14 hours, and further stirred at 20°C for 1 hour.
次に、析出した結晶を濾取し、該結晶を３５ｇのｎ−へ
ブタンと３５ｇのトルエンの混合液で２回洗浄後、乾燥
しｄ−シス／トランス混合第一菊酸の（−）ＰＥＡ塩４
０．４ｇを得た。Next, the precipitated crystals were collected by filtration, washed twice with a mixed solution of 35 g of n-hebutane and 35 g of toluene, and dried. salt 4
0.4g was obtained.
収率 ５０，０％（対 ｄ−第一期成）光学純度
９３．０％
シス／トランス−２０／８０
〈発明の効果〉
本発明方法によればｄｌ−）ランス−第−期成またはｄ
ｌ−シス／トランス−混合筒−期成を光学活性ＰＴＥま
たは光学活性ＰＥＡを用いて光学分割する方法において
、疎水性有機溶媒を用いることにより、得られる第−期
成の光学純度が高いことに加え、使用した溶媒の回収が
容易で、しかも得られる第−期成のＰＴＥまたはＰＥＡ
の塩の結晶の濾過性が良好であることから、工業的規模
での製造において有利であることが見出された。Yield 50.0% (vs. d-1st stage formation) Optical purity
93.0% cis/trans-20/80 <Effects of the Invention> According to the method of the present invention, dl-) lance-stage formation or d
In the method of optically resolving the l-cis/trans-mixing tube phase using optically active PTE or optically active PEA, the optical purity of the obtained first phase is high by using a hydrophobic organic solvent. In addition, the used solvent can be easily recovered, and the PTE or PEA in the first stage can be obtained.
It has been found that the salt crystals have good filterability and are therefore advantageous in production on an industrial scale.
Claims (1)
ランス−混合第一菊酸を光学活性α−フェニル−β−パ
ラトリルエチルアミンまたは光学活性α−フェニルエチ
ルアミンを用いて光学分割する方法において、ｄｌ−ト
ランス−第一菊酸またはｄｌ−シス／トランス−混合第
一菊酸と光学活性α−フェニル−β−パラトリルエチル
アミンまたは光学活性α−フェニルエチルアミンとの反
応、および一方の光学活性なトランス−第一菊酸または
光学活性なシス／トランス−混合第一菊酸と該アミンと
の塩を晶出させ、これを母液から分離する晶析分離工程
を、疎水性有機溶媒中で行うことを特徴とするトランス
−第一菊酸またはシス／トランス−混合第一菊酸の光学
分割法。 （２）疎水性有機溶媒が芳香族炭化水素および脂肪族炭
化水素からなる群より選ばれる一種以上の溶媒である特
許請求の範囲第１項に記載の光学分割法。 （３）溶媒をｄｌ−トランス−第一菊酸またはｄｌ−シ
ス／トランス−混合第一菊酸に対して、２．５〜６重量
倍用いる特許請求の範囲第１項または第２項に記載の光
学分割法。（４）光学活性α−フェニル−β−パラトリ
ルエチルアミンまたは光学活性α−フェニルエチルアミ
ンをｄｌ−トランス−第一菊酸またはｄｌ−シス／トラ
ンス−混合第一菊酸１モルに対し、０．３〜０．５モル
反応させる特許請求の範囲第１項、第２項または第３項
に記載の光学分割法。 （５）ｄｌ−トランス−第一菊酸またはｄｌ−シス／ト
ランス−混合第一菊酸と光学活性α−フェニル−β−パ
ラトリルエチルアミンまたは光学活性α−フェニルエチ
ルアミンとを５０℃〜７５℃の温度で反応させる特許請
求の範囲第１項、第２項、第３項または第４項に記載の
光学分割法。 （６）光学活性α−フェニル−β−パラトリルエチルア
ミンを用いる特許請求の範囲第１項、第２項、第３項、
第４項または第５項に記載の光学分割法。[Scope of Claims] (1) dl-trans- primary chrysanthemum acid or dl-cis/trans-mixed primary chrysanthemum acid is used with optically active α-phenyl-β-paratolylethylamine or optically active α-phenylethylamine. In the method of optical resolution, the reaction of dl-trans-stochylachianic acid or dl-cis/trans-mixed stochastic acid with optically active α-phenyl-β-paratolylethylamine or optically active α-phenylethylamine, A hydrophobic 1. An optical resolution method for trans- primary chrysanthemum acid or cis/trans mixed primary chrysanthemum acid, characterized in that it is carried out in an organic solvent. (2) The optical resolution method according to claim 1, wherein the hydrophobic organic solvent is one or more solvents selected from the group consisting of aromatic hydrocarbons and aliphatic hydrocarbons. (3) Claim 1 or 2 in which the solvent is used in a range of 2.5 to 6 times the weight of dl-trans-daisy chrysanthemum acid or dl-cis/trans-mixed chrysanthemum acid. optical resolution method. (4) Optically active α-phenyl-β-paratolylethylamine or optically active α-phenylethylamine is added to 1 mole of dl-trans-daisylchrysanthemum acid or dl-cis/trans-mixed chrysanthemum acid at 0.3 The optical resolution method according to claim 1, 2 or 3, wherein the reaction is carried out by 0.5 mol. (5) dl-trans- primary chrysanthemum acid or dl-cis/trans mixed primary chrysanthemum acid and optically active α-phenyl-β-paratolylethylamine or optically active α-phenylethylamine at 50°C to 75°C. The optical resolution method according to claim 1, 2, 3, or 4, wherein the reaction is carried out at temperature. (6) Claims 1, 2, and 3 using optically active α-phenyl-β-paratolylethylamine,
The optical resolution method according to item 4 or 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18124986A JPH0667871B2 (en) | 1986-07-31 | 1986-07-31 | Optical resolution of primary chrysanthemic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18124986A JPH0667871B2 (en) | 1986-07-31 | 1986-07-31 | Optical resolution of primary chrysanthemic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6335540A true JPS6335540A (en) | 1988-02-16 |
| JPH0667871B2 JPH0667871B2 (en) | 1994-08-31 |
Family
ID=16097401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18124986A Expired - Lifetime JPH0667871B2 (en) | 1986-07-31 | 1986-07-31 | Optical resolution of primary chrysanthemic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0667871B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0374347A (en) * | 1989-08-11 | 1991-03-28 | Kuraray Co Ltd | Optical resolution of cis-trans-mixed chrysanthemumic acids |
| US5298660A (en) * | 1991-04-08 | 1994-03-29 | Sumitomo Chemical Company, Limited | Optically active secondary amine compound, process for producing optically active secondary amine compound and process for producing optically active carboxylic acid by using said compound |
| JPH11279111A (en) * | 1998-01-29 | 1999-10-12 | Sumitomo Chem Co Ltd | Production of optically active chrysanthemumic acid |
-
1986
- 1986-07-31 JP JP18124986A patent/JPH0667871B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0374347A (en) * | 1989-08-11 | 1991-03-28 | Kuraray Co Ltd | Optical resolution of cis-trans-mixed chrysanthemumic acids |
| US5298660A (en) * | 1991-04-08 | 1994-03-29 | Sumitomo Chemical Company, Limited | Optically active secondary amine compound, process for producing optically active secondary amine compound and process for producing optically active carboxylic acid by using said compound |
| US5510519A (en) * | 1991-04-08 | 1996-04-23 | Sumitomo Chemical Company, Limited | Optically active secondary amine compound, process for producing optically active secondary amine compound and process for producing optically active carboxylic acid by using said compound |
| JPH11279111A (en) * | 1998-01-29 | 1999-10-12 | Sumitomo Chem Co Ltd | Production of optically active chrysanthemumic acid |
| JP4576642B2 (en) * | 1998-01-29 | 2010-11-10 | 住友化学株式会社 | Process for producing optically active chrysanthemic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0667871B2 (en) | 1994-08-31 |
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