JPS6360735B2 - - Google Patents
Info
- Publication number
- JPS6360735B2 JPS6360735B2 JP56056115A JP5611581A JPS6360735B2 JP S6360735 B2 JPS6360735 B2 JP S6360735B2 JP 56056115 A JP56056115 A JP 56056115A JP 5611581 A JP5611581 A JP 5611581A JP S6360735 B2 JPS6360735 B2 JP S6360735B2
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- crystals
- paragraph
- solution
- item
- 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
- 239000013078 crystal Substances 0.000 claims description 102
- 239000002904 solvent Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 15
- 230000001476 alcoholic effect Effects 0.000 claims description 13
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 239000012452 mother liquor Substances 0.000 claims description 13
- -1 alicyclic hydrocarbons Chemical class 0.000 claims description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 230000001066 destructive effect Effects 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Chemical group 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 22
- 238000002425 crystallisation Methods 0.000 description 20
- 230000008025 crystallization Effects 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 238000010992 reflux Methods 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- NYPJDWWKZLNGGM-UHFFFAOYSA-N fenvalerate Chemical compound C=1C=C(Cl)C=CC=1C(C(C)C)C(=O)OC(C#N)C(C=1)=CC=CC=1OC1=CC=CC=C1 NYPJDWWKZLNGGM-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000000638 stimulation Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- APTDTYOUWLWKGP-UHFFFAOYSA-N [cyano-[3-(4-fluorophenoxy)phenyl]methyl] 2-(4-chlorophenyl)-3-methylbutanoate Chemical compound C=1C=C(Cl)C=CC=1C(C(C)C)C(=O)OC(C#N)C(C=1)=CC=CC=1OC1=CC=C(F)C=C1 APTDTYOUWLWKGP-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は一般式（）
（式中、Ｘは水素原子またはフツ素原子を表わ
し、＊は不整炭素を表わす。）
で示され、その酸側およびアルコール側共に
（Ｓ）配置を有する異性体またはそれに富む混合
物の製造法に関する。
α−シアノ−３−フエノキシベンジル２−（４
−クロルフエニル）イソバレレート（以下、フエ
ンバレレート称する。）およびα−シアノ−３−
（４−フルオロフエノキシ）ベンジル２−（４−ク
ロルフエニル）イソバレレート（以下、ｐ−Ｆ−
フエンバレレートと称する。）は、それぞれ特開
昭49−26425号公報および特開昭52−125145号公
報に示された優れた殺虫性化合物である。
これらカルボン酸エステルは酸側、アルコール
側に各々１個ずつ不整炭素原子を有するので、４
つの立体異性体が存在しうる。以下表１のごと
く、各立体異性体およびその混合物を呼ぶ。
The present invention is based on the general formula () (In the formula, X represents a hydrogen atom or a fluorine atom, and * represents an asymmetric carbon.) Relating to a method for producing an isomer or a mixture rich in it, which is represented by . α-cyano-3-phenoxybenzyl 2-(4
-chlorophenyl)isovalerate (hereinafter referred to as fenvalerate) and α-cyano-3-
(4-fluorophenoxy)benzyl 2-(4-chlorophenyl)isovalerate (hereinafter p-F-
It is called fuenvalerate. ) are excellent insecticidal compounds disclosed in JP-A-49-26425 and JP-A-52-125145, respectively. These carboxylic acid esters have one asymmetric carbon atom on the acid side and one on the alcohol side, so 4
Two stereoisomers can exist. As shown in Table 1 below, each stereoisomer and its mixture are called.
【表】
また〔Aα〕，〔Aβ〕に富む異性体混合物をそれ
ぞれ〔Aα〕リツチ、〔Aβ〕リツチと呼ぶ。
前記一般式（）で示されるカルボン酸エステ
ルの〔Ａ〕および〔Aα〕はそれぞれ〔ラセミ体〕
の約２倍および４倍の殺虫活性を有することが知
られている。（特開昭53−24019号公報、特開昭55
−104249号公報）
また、その〔Ａ〕から〔Aα〕を選択的に晶析
する方法としては、特開昭54−16444号公報、同
54−55546号公報、同54−59248号公報、同54−
109945号公報および同55−104249号公報の方法が
知られている。
これらの方法は、一旦〔Ａ〕を得さえすれば極
めて単純な工程で〔Aα〕に変換できる点で有利
な方法である。
ところが上記のフエンバレレート〔Ａ〕から
〔Aα〕の取得方法につきさらに検討していく中
で、所期の目的を達せられない事実がまま見ら
れ、本発明者らはこれにつき種々検討した結果、
意外にも〔Aα〕と〔Aβ〕の混合物である〔Ａ〕
が結晶すること（融点：48.5〜49.5℃）を見出
し、さらにｐ−Ｆ−フエンバレレートにおいても
同様に〔Ａ〕が結晶すること（融点：52.0〜55.5
℃）を最近見出した。
本発明者らはさらに鋭意検討を続けた結果晶析
系内に実質的に純粋な〔Aα〕の結晶を存在させ
ることにより、即ち〔Ａ〕の結晶を系内に実質的
に存在させることなく、実質的に純粋な〔Aα〕
の結晶を存在させることにより、〔Ａ〕の溶液か
ら〔Aα〕の晶析がより再現性よく実施できるこ
とを見出した。このことは〔Ａ〕の溶液中に、
〔Ａ〕の結晶および〔Aα〕の結晶が実質的に存在
しなければ、溶解度の点から〔Ａ〕または〔Aα〕
の結晶が析出するような条件下であつても比較的
安定に過飽和状態が保たれ、そこに〔Aα〕のみ
の結晶を存在させることにより、〔Ａ〕の結晶が
析出することなく、〔Aα〕の結晶のみを析出させ
ることができることによる。
ところが、この方法においても、時として、所
期の目的を達し得ない事実があることが判明し、
本発明者らはこれについて種々検討した結果、た
とえば鉄さびの混入などの物理的刺激によつて
〔Ａ〕の溶液の過飽和安定性が破壊されることに
より、自然発生的に〔Ａ〕の結晶が析出し得るこ
とを見出した。
本発明者らは、このような現象につきさらに鋭
意検討を続けた結果、以下に述べるような方法に
より、〔Ａ〕の溶液の過飽和安定性が保持できる
温度−〔Ａ〕の濃度の領域が事前に測定でき、こ
の範囲内では〔Ａ〕の溶液から〔Aα〕の晶析が、
より一層再現性よく実施できることを見出し、こ
れに種々の検討を加え本発明を完成するに至つ
た。
以下に本発明方法について具体的に説明する。
先ず、〔Ａ〕溶液の過飽和安定性が保持できる
温度−〔Ａ〕の濃度の領域を測定する方法を図１
に基づいて述べる。
曲線は使用する溶媒に対する〔Ａ〕の結晶の
溶解度曲線である。曲線は〔Ａ〕の溶液に対す
る〔Aα〕の結晶の溶解限界曲線で、これは所定
濃度の〔Ａ〕の溶液を一旦加熱した後、所定温度
に保温し、この系内に〔Aα〕の結晶を添加し
〔Aα〕の結晶の溶解の有無を調べることにより求
められる。曲線は過飽和破壊要素、たとえば鉄
さび、鉄粉、ガラス粉、ガラスビーズなどを含む
所定濃度の〔Ａ〕の溶液を一旦加熱した後、所定
温度で24時間以上保温撹拌した際の〔Ａ〕の結晶
の晶出の有無を観察して求められる〔Ａ〕晶出の
限界曲線である。曲線′は所定濃度の〔Ａ〕の
溶液を一旦加熱した後、所定温度に保温し、その
後これに上記のような過飽和破壊要素を添加して
24時間以上保温撹拌した際の〔Ａ〕の結晶の晶出
の有無を観察して求められる〔Ａ〕晶出の限界曲
線である。
上記方法により求められた４つの曲線は一般に
図１のような関係になる。曲線と曲線′とは
一致することもあるが、一般的に曲線′は図１
のように上に位置することが多い。図１において
曲線より上の領域は〔Ａ〕および〔Aα〕の結
晶が溶解する安定域であり、曲線と曲線へに
囲まれた領域は〔Aα〕の結晶は溶解するが、
〔Ａ〕の結晶が存在すれば〔Ａ〕の結晶が晶出す
る領域である。また曲線より下の領域が物理的
刺激によつて〔Ａ〕の結晶が晶出する不安定域で
ある。
本発明方法において、〔Ａ〕の溶液の過飽和安
定性が保持できる温度−〔Ａ〕の濃度の領域、即
ち〔Ａ〕の溶液から〔Aα〕の晶析が極めて再現
性よく実施できる領域とは、曲線と曲線とに
囲まれた領域であり、より好ましくは曲線と曲
線′とに囲まれた領域である。
また本発明で言う物理的刺激即ち過飽和破壊要
素としては、当該溶液中に存在しうる固体、たと
えば鉄粉などの金属粉、またはこれら金属のさ
び、ガラス粉、食塩、ポリマーの屑などが挙げら
れるが、そのほか放射線、機械的衝撃、極端な高
温または低温物質による温度刺激、あるいは該溶
液に不溶な液滴による刺激などが考えられる。
また、上記図１の曲線あるいは曲線′を求
めるには簡便な鉄さび、鉄粉、ガラス粉などが用
いられる。
本発明は図１における曲線と曲線とに囲ま
れた領域内より好ましくは曲線と曲線′とに
囲まれた領域内において、〔Ａ〕の溶液から
〔Aα〕の晶析を実施することを特徴とし、その領
域内においては物理的刺激に対しても、過飽和安
定性は保持され、このような晶析系内に実質的に
純粋な〔Aα〕の結晶を存在させることにより、
即ち〔Ａ〕の結晶を系内に実質的に存在させるこ
となく、実質的な純粋な〔Aα〕の結晶を存在さ
せることにより、〔Ａ〕の溶液から〔Aα〕の晶析
が極めて再現性よく実施できることになる。
また、本発明方法により〔Ａ〕の溶液から
〔Aα〕の晶析を行なう場合、〔Aα〕の結晶の晶出
に伴ない、晶析温度を徐々に下げていくことによ
り、〔Aα〕の結晶をより高収率に取得することが
できる。
本発明において晶析系から〔Ａ〕の結晶を実質
的に消失させるには、たとえば一旦系内を40℃以
上、通常〔Ａ〕の融点以上に加熱する方法により
達せられる。より好ましくは〔Ａ〕の融点以上の
沸点を有する溶媒を用いて還流することが望まし
い。
〔Ａ〕の溶液から〔Aα〕の晶析を行なう溶媒
としてはアルコール系溶媒、脂肪族炭化水素また
は脂環式炭化水素あるいはこれらの混合溶媒が例
示される。あるいはこれらの溶媒と芳香族炭化水
素、ケトン系溶媒、エステル系溶媒、エーテル系
溶媒、塩素系溶媒、フエノール系溶媒などとの混
合溶媒を用いることもできる。より好ましくは、
アルコール系溶媒単独もしくはこれと脂肪族炭化
水素および／または、芳香族炭化水素の混合溶媒
が挙げられる。アルコール系溶媒としては炭素数
１〜５のアルコールが好ましい、脂肪族炭化水
素、脂環式炭化水素としては炭素数５〜12の炭化
水素が好ましい。たとえば、ヘキサン、ヘプタ
ン、オクタン、石油エーテル、リグロイン、メチ
ルシクロヘキサンなどを挙げることができる。芳
香族溶媒としてはベンゼン、トルエン、キシレン
などを挙げることとができる。
これらの溶媒の使用量は溶媒の種類、晶析を行
なう温度によつて最適量が異なり、一概には限定
されるものではないが、通常、原料の〔Ａ〕に対
して0.5倍から30倍量（重量）程度が用いられる。
本発明において塩基性試剤の使用量は必須では
なく、塩基性触媒を加えることなく晶析分離を行
なう場合には母液部よりエステルを回収し、母液
部の〔Aβ〕の多くなつたエステルを塩基性触媒
と接触させて、アルコール部分のエピ化を行なわ
せ、〔Aα〕と〔Aβ〕の比率を平衡まで回復させ
た後、再び晶析操作を行なうことにより、結晶
〔Ａ〕をほぼ定量的に〔Aα〕に変換させることが
可能となる。塩基性触媒の存在下に晶析分離を行
なう場合には、原料の〔Ａ〕中に当初含まれてい
た〔Aα〕（通常は約50％）よりも多くの〔Aα〕
の結晶を取得することが可能になる。この時、母
液部のエステルは回収して、必要ならば精製した
のち繰り返し使用することも可能である。
また、〔Ａ〕から塩基性触媒の存在下に〔Aα〕
の結晶を晶析させた後、結晶を母液と分離せずに
塩基性触媒を除去ないし不活性化（中和）した
後、全量濃縮するなどして〔Aα〕の結晶と共に
母液部の〔Ａ〕をも回収することにより〔Aα〕
に富む〔Ａ〕を取得することができる。
この場合は、母液中に残存する〔Aα〕を失う
ことなくそのまま有効に利用できることになり、
また操作もより簡便になるので工業的生産上およ
び経済的により有利となる。
晶析の際に用いられる塩基性試剤としてはアン
モニア、ヒドラジン、メチルアミン、エチルアミ
ン、ｎ−プロピルアミン、イソプロピルアミン、
ｎ−ブチルアミン、ジメチルアミン、ジエチルア
ミン、ジ−ｎ−プロピルアミン、ジ−ｎ−ブチル
アミン、トリメチルアミン、トリエチルアミン、
シクロヘキシルアミン、エチレンジアミン、エタ
ノールアミン、ピロリジン、ピペリジン、モルホ
リン、アニリン、１−ナフチルアミン、ピリジ
ン、キノリン、１，５−ジアザビシクロ〔４，
３，０〕−ノン−５−エン等の窒素塩基、トリフ
エニルホスフイン、トリ−ｎ−ブチルホスフイン
等のリン塩基、テトラメチルアンモニウムハイド
ロオキサイド、テトラ−ｎ−ブチルアンモニウム
ハイドロオキサイド等の４級アンモニウムハイド
ロオキサイド等の４級アンモニウムハイドロオキ
サイド、水酸化ナトリウム、水酸化カリウム、炭
酸ナトリウム、シアン化ナトリウム、ナトリウム
メチラート、水素化ナトリウム、ナトリウムアミ
ド等の含金属塩基などを挙げることができ、より
好ましくはアンモニア、トリエチルアミンなどを
挙げることができる。
触媒の使用量は、触媒の種類、溶媒の種類、そ
の使用量および温度によつて変わるが、通常
0.001〜200モル％の範囲であり、アンモニアおよ
びトリエチルアミンでは通常５〜100モル％の範
囲で使用される。
種晶の〔Aα〕は実質的に〔Ａ〕結晶を含まな
いものが必要で、通常得られる結晶状の〔Aα〕
または〔Aα〕リツチは〔Aβ〕が存在し、〔Ａ〕
結晶が生成している可能性があるので、１回また
は２回以上再結晶操作を施したものを用いること
が好ましい。
また〔Aα〕の再結晶時に、析出する結晶を単
離することなく、母液と共に原料の〔Ａ〕の溶液
と混合してもよい。
再結晶の際に用いられる溶媒は〔Ａ〕溶液から
の〔Aα〕の晶析に用いられる溶媒と同一であつ
ても異なつていてもよく、アルコール系溶媒、脂
肪族炭化水素または脂環式炭化水素あるいはこれ
らの混合溶媒が例示される。あるいはこれらの溶
媒と芳香族炭化水素、ケトン系溶媒、エステル系
溶媒、エーテル系溶媒、塩素系溶媒、フエノール
系溶媒などとの混合溶媒も用いられうる。より好
ましくは、アルコール系溶媒、もしくはこれと脂
肪族炭化水素および／または芳香族炭化水素の混
合溶媒、脂肪族炭化水素もしくはこれと芳香族炭
化水素の混合溶媒が挙げられる。アルコール系溶
媒としては炭素数１〜５のアルコールが好まし
い。脂肪族炭化水素、脂環式炭化水素としては炭
素数５〜12の炭化水素が好ましい。たとえば、ヘ
キサン、ヘプタン、オクタン、石油エーテル、リ
グロイン、メチルシクロヘキサンなどを挙げるこ
とができる。芳香族炭化水素としてはベンゼン、
トルエン、キシレンなどを挙げることができる。
これらの溶媒の使用量は溶媒の種類によつては
最適量が異なり、一概には限定されるものではな
いが通常0.5〜50倍量（重量）の範囲で用いられ、
より好ましくは３倍量（重量）以上用いるのが望
ましい。
以下、実施例、参考例、比較例をもつて本発明
を説明する。
参考例 １
フエンバレレートの〔Ａ〕（液状、〔Aα〕／
〔Aβ〕＝46.9／53.1）のメチルアルコール溶液につ
いて、以下に述べる方法により、〔Ａ〕の溶液の
過飽和安定性が保持できる温度−〔Ａ〕濃度の領
域を測定し、図２に示されるグラフを得た。
先ず〔Ａ〕の結晶（上記の〔Ａ〕を全量結晶化
したもの）を用いて、メチルアルコールに対する
溶解度を測定した（曲線）。次に所定濃度の
〔Ａ〕のメチルアルコール溶液を一旦加熱した後、
所定温度に保温し、これに〔Aα〕の結晶
（〔Aα〕／〔Aβ〕＝99.9／0.1、酸側光学純度100.0
％）を添加して、その溶解有無を観察して曲線
を求めた。さらに過飽和破壊要素として酸化第二
鉄を選び、所定濃度の〔Ａ〕のメチルアルコール
溶液300c.c.に対して酸化第二鉄10mgを加え、これ
を一旦加熱した後、所定温度に保温し、24時間
〔Ａ〕の晶出の有無を観察することにより、曲線
を求めた。また、所定濃度の〔Ａ〕のメチルア
ルコール溶液300c.c.を一旦加熱した後、所定温度
に保温し、酸化第二鉄10mgを加え、24時間〔Ａ〕
の晶出の有無を観察することにより曲線′を求
めた。
参考例 ２
参考例１で用いた〔Ａ〕の結晶40ｇにメチルア
ルコール80ｇを加え加熱溶解し、−16℃まで冷却
したのち、〔Aα〕の結晶（〔Aα〕／〔Aβ〕＝
99.9／0.1、酸側光学純度100.0％）１mgを接種、
同時に8.4％アンモニア−メチルアルコール溶液
4.8c.c.を加えた。−16℃そのまま撹拌し１日後、酢
酸1.4c.c.を加えたのち過し、〔Aα〕の結晶
（〔Aα〕／〔Aβ〕＝96.8／3.2）33.56ｇを得た。
比較例 １
参考例１で用いた〔Ａ〕100ｇにメチルアルコ
ール100ｇおよび鉄さび10mgを加え、30分間加熱
還流したのち、−５℃まで冷却し、同温度で保温
撹拌した。約７時間後、結晶が多量析出し、一部
サンプリングして結晶を分析してみたところ、
〔Ａ〕の結晶（〔Aα〕／〔Aβ〕＝46.5／53.5）であ
つた。
比較例 ２
参考例１で用いた〔Ａ〕100ｇにｎ−ヘプタン
117ｇ、トルエン13ｇ、メチルアルコール70ｇを
加え、30分間還流したのち、−15℃まで冷却し、
同温度で保温撹拌した。次に鉄さび５mgを添加し
たところ約５時間後、結晶が多量析出し、一部サ
ンプリングして結晶を分析してみたところ、〔Ａ〕
の結晶（〔Aα〕／〔Aβ〕＝46.0／54.0）であつた。
さらにこれを再び30分間還流したのち、−15℃ま
で冷却し、同温度で保温撹拌したところ、約８時
間後、結晶が多量析出し、その結晶は〔Ａ〕の結
晶（〔Aα〕／〔Aβ〕＝45.8／54.2）であつた。
比較例 ３
参考例１で用いた〔Ａ〕100ｇにメチルアルコ
ール200ｇおよび鉄さび10mgを加え、30分間加熱
還流したのち、−15℃まで冷却し、同温度で保温
撹拌しておいた。
一方、〔Aα〕の結晶（〔Aα〕／〔Aβ〕＝97.6／
2.4）10ｇにｎ−ヘプタン27ｇ、トルエン３ｇを
加え、30分間加熱還流したのち、35℃まで冷却
し、同温度で上記〔Aα〕の結晶１mgを加え30分
間撹拌した。その後30℃まで冷却し１時間保温撹
拌すると〔Aα〕の結晶が析出した。次に、−15℃
で保温撹拌しておいた上記〔Ａ〕の溶液に、この
〔Aα〕の結晶をその母液と共に全量注加し、同時
に12.9％アンモニア−メチルアルコール溶液6.29
ｇ加え、−15℃で24時間撹拌した。次いでこれに
酢酸3.43ｇを加えたのち過し、103.7ｇの結晶
を得た。得られた結晶は〔Ａ〕の結晶（〔Aα〕／
〔Aβ〕＝45.1／54.9）であつた。
比較例 ４
参考例１で用いた〔Ａ〕の結晶40ｇメチルアル
コール80ｇおよび鉄さび10mgを加え加熱溶解し、
−16℃まで冷却したのと、〔Aα〕の結晶
（〔Aα〕／〔Aβ〕＝99.1／0.1、酸側光学純度100.0
％）１mgを接種、同時に8.4％アンモニア−メチ
ルアルコール溶液4.8c.c.を加えた。−16℃でそのま
ま撹拌し１日後、酢酸1.4c.c.を加えたのち過し、
38.07ｇの結晶を得た。得られた結晶は〔Ａ〕の
結晶（〔Aα〕／〔Aβ〕＝44.5／55.5）であつた。
実施例 １
フエンバレレートの〔Ａ〕（液状、〔Aα〕／
〔Aβ〕＝46.9／53.1）100ｇにメチルアルコール200
ｇおよび過飽和破壊要素として、鉄さび10mg、ガ
ラスビーズ（直径約１mm）10個を加え、30分間加
熱還流したのち、５℃まで冷却した。同温度で24
時間撹拌し、〔Ａ〕の結晶が晶出しないことを確
認した。
一方、〔Aα〕の結晶（〔Aα〕／〔Aβ〕＝98.0／
2.0）３ｇにｎ−ヘプタン8.1ｇ、トルエン0.9ｇを
加え、30分間加熱還流したのち、35℃まで冷却
し、同温度で上記〔Aα〕の結晶１mgを加え30分
間撹拌した。その後30℃まで冷却し１時間保温撹
拌すると〔Aα〕の結晶が析出した。次に５℃で
保温撹拌しておいた上記の〔Ａ〕の溶液に、この
〔Aα〕の結晶をその母液と共に種晶として全量注
加し、同時にトリエチルアミン2.41ｇを加え、５
℃で25時間撹拌した。次いでこれに35％塩酸2.98
ｇを加えたのち過し、〔Aα〕の結晶（〔Aα〕／
〔Aβ〕＝98.6／1.4）54.39ｇを得た。
実施例 ２
実施例１で用いた〔Ａ〕79.6ｇにメチルアルコ
ール185.7ｇおよび酸化第二鉄10mgを加え、30分
間加熱還流したのち15℃まで冷却した。同温度で
24時間撹拌し、〔Ａ〕の結晶が晶出しないことを
確認した。さらに該溶液に再び酸化第二鉄10mgを
加え、15℃で25時間撹拌しても〔Ａ〕の結晶の晶
出は認められなかつた。
一方、〔Aα〕の結晶（〔Aα〕／〔Aβ〕＝99.9／
0.1）3.98ｇにｎ−ヘプタン10.75ｇ、トルエン
1.19ｇを加え、30分間加熱還流したのち、35℃ま
で冷却し、同温度で上記〔Aα〕の結晶１mgを加
え30分間撹拌した。その後30℃まで冷却し１時間
保温撹拌すると〔Aα〕の結晶が析出した。次に
15℃で保温撹拌しておいた上記〔Ａ〕の溶液に、
この〔Aα〕の結晶をその母液と共に種晶として
全量注加し、同時にトリエチルアミン1.92ｇを加
え、15℃で20時間撹拌し、〔Aα〕の結晶を晶出さ
せた。次にこの反応液を徐々に10℃まで冷却し、
10℃で24時間撹拌し、さらに５℃まで冷却して、
５℃で４時間撹拌した。次いでこれに35％塩酸
2.96ｇを加えたのち過し、〔Aα〕の結晶
（〔Aα〕／〔Aβ〕＝98.3／1.7）28.18ｇを得た。
実施例 ３
実施例１で用いた〔Ａ〕150.0ｇにメチルアル
コール850.0ｇおよび酸化第二鉄50mgを加え、30
分間加熱還流したのち０℃まで冷却した。
一方、〔Aα〕の結晶（〔Aα〕／〔Aβ〕＝99.0／
0.1）7.50ｇにｎ−ヘプタン20.25ｇ、トルエン
2.25ｇを加え、30分間加熱還流したのち、35℃ま
で冷却し、同温度で上記〔Aα〕の結晶１mgを加
え30分間撹拌した。その後30℃まで冷却し１時間
保温撹拌すると〔Aα〕の結晶が析出した。
次に、０℃で保温しておいた上記〔Ａ〕の溶液
に、この〔Aα〕の結晶をその母液と共に種晶と
して全量注加し、０℃で24時間保温撹拌したのち
析出した結晶を過し、〔Aα〕の結晶（〔Aα〕／
〔Aβ〕＝99.2／0.8）37.57ｇを得た。
実施例 ４
実施例１で用いた〔Ａ〕60.0ｇにメチルアルコ
ール240.0ｇを加え、30分間加熱還流したのち10
℃まで冷却した。
一方、〔Aα〕の結晶（〔Aα〕／〔Aβ〕＝99.9／
0.1）3.0ｇにメチルアルコール12.0ｇ、酢酸0.06
ｇを加え、30分間加熱還流したのち、30℃まで冷
却し、同温度で上記〔Aα〕の結晶１mgを加え、
１時間撹拌すると〔Aα〕の結晶が析出した。
次に、10℃で保温しておいた上記〔Ａ〕の溶液
に、この〔Aα〕の結晶をその母液と共に種晶と
して全量注加し、10℃で24時間保温撹拌したのち
析出した結晶を過し、〔Aα〕の結晶（〔Aα〕／
〔Aβ〕＝99.0／1.0）9.62ｇを得た。
実施例 ５
実施例１で用いた〔Ａ〕60.0ｇにメチルアルコ
ール240.0ｇおよび酢酸1.2ｇを加え、30分間加熱
還流したのち10℃まで冷却した。
一方、〔Aα〕の結晶（〔Aα〕／〔Aβ〕＝98.3／
1.7）10.0ｇにｎ−ヘプタン27.0ｇ、トルエン3.0
ｇを加え、30分間加熱還流したのち、35℃まで冷
却し、同温度で上記〔Aα〕の結晶１mgを加え30
分間撹拌した。その後30℃まで冷却し１時間保温
撹拌すると〔Aα〕の結晶が析出した。
次いでこのようにして得られた〔Aα〕の再結
晶スラリーのうち約１c.c.をとり、先に10℃で保温
撹拌しておいた上記〔Ａ〕の溶液に種晶として注
加し、10℃で20時間保温撹拌したのち析出した結
晶を過し、〔Aα〕の結晶（〔Aα〕／〔Aβ〕＝
99.7／0.3）8.84ｇを得た。[Table] Also, isomer mixtures rich in [Aα] and [Aβ] are called [Aα]-rich and [Aβ]-rich, respectively. [A] and [Aα] of the carboxylic acid ester represented by the general formula () are each [racemate]
It is known to have about twice and four times the insecticidal activity of (Unexamined Japanese Patent Publication No. 53-24019, Unexamined Japanese Patent Publication No. 55
-104249 Publication) In addition, as a method for selectively crystallizing [Aα] from [A],
No. 54-55546, No. 54-59248, No. 54-
The methods disclosed in Japanese Patent No. 109945 and Japanese Patent No. 55-104249 are known. These methods are advantageous in that once [A] is obtained, it can be converted to [Aα] in an extremely simple process. However, as we further investigated the method for obtaining [Aα] from Fuenvalerate [A] mentioned above, we found that the intended purpose could not be achieved.As a result of various studies, the inventors of the present invention ,
Surprisingly, [A] is a mixture of [Aα] and [Aβ].
It was discovered that [A] crystallized (melting point: 48.5-49.5°C), and that [A] also crystallized in p-F-fuenvalerate (melting point: 52.0-55.5).
℃) was recently discovered. As a result of further intensive studies, the present inventors found that by allowing substantially pure crystals of [Aα] to exist in the crystallization system, that is, without substantially allowing crystals of [A] to exist in the system. , substantially pure [Aα]
It has been found that crystallization of [Aα] from a solution of [A] can be carried out with better reproducibility by the presence of crystals of [A]. This means that in the solution [A],
If crystals of [A] and crystals of [Aα] are substantially absent, [A] or [Aα] from the viewpoint of solubility
The supersaturated state is maintained relatively stably even under conditions where crystals of This is because only the crystals of ] can be precipitated. However, it has been discovered that even with this method, there are times when the intended purpose cannot be achieved.
As a result of various studies on this issue, the present inventors found that crystals of [A] spontaneously form when the supersaturation stability of the solution of [A] is destroyed by physical stimulation such as the mixing of iron rust. It has been found that it can be precipitated. As a result of further intensive studies on this phenomenon, the present inventors determined that the range of temperature and concentration of [A] in which the supersaturation stability of the solution of [A] can be maintained can be determined in advance by the method described below. Within this range, the crystallization of [Aα] from the solution of [A] is
It was discovered that the method could be carried out with even better reproducibility, and by adding various studies to this, the present invention was completed. The method of the present invention will be specifically explained below. First, Figure 1 shows how to measure the temperature range where the supersaturation stability of the [A] solution can be maintained - the concentration range of [A].
Based on this. The curve is a solubility curve of the crystals of [A] in the solvent used. The curve is the solubility limit curve of crystals of [Aα] in a solution of [A]. This curve shows the solubility limit curve of crystals of [Aα] in a solution of [A], which is obtained by heating a solution of [A] at a predetermined concentration, keeping it at a predetermined temperature, and adding crystals of [Aα] into the system. It is determined by adding [Aα] and checking whether the crystals of [Aα] are dissolved. The curve shows the crystals of [A] when a solution of [A] with a predetermined concentration containing supersaturated destructive elements such as iron rust, iron powder, glass powder, glass beads, etc. is heated and then stirred at a predetermined temperature for 24 hours or more. [A] This is the crystallization limit curve obtained by observing the presence or absence of crystallization. Curve ′ is obtained by heating a solution of [A] at a predetermined concentration, keeping it at a predetermined temperature, and then adding the supersaturation destruction element as described above.
This is a limit curve for crystallization of [A] obtained by observing the presence or absence of crystallization of [A] when the product is kept warm and stirred for 24 hours or more. The four curves obtained by the above method generally have a relationship as shown in FIG. Although the curve and the curve ′ may coincide, generally the curve ′ is shown in Figure 1.
It is often located at the top, as in In Figure 1, the region above the curve is the stable region where the crystals of [A] and [Aα] dissolve, and the region surrounded by the curves is the region where the crystals of [Aα] dissolve, but
If crystals of [A] exist, this is a region where crystals of [A] will crystallize. The region below the curve is an unstable region where the crystals of [A] crystallize due to physical stimulation. In the method of the present invention, what is the range between the temperature and the concentration of [A] where the supersaturation stability of the solution of [A] can be maintained, that is, the range where crystallization of [Aα] from the solution of [A] can be carried out with extremely good reproducibility? , an area surrounded by two curved lines, and more preferably an area surrounded by two curved lines. In addition, the physical stimulus or supersaturation destructive element referred to in the present invention includes solids that may exist in the solution, such as metal powder such as iron powder, rust of these metals, glass powder, common salt, and polymer scraps. However, other possible causes include radiation, mechanical shock, temperature stimulation due to extremely high or low temperature substances, or stimulation due to droplets insoluble in the solution. Further, in order to obtain the curve or curve ' of FIG. 1, simple iron rust, iron powder, glass powder, etc. are used. The present invention is characterized in that [Aα] is crystallized from a solution of [A] in the region surrounded by the curves in FIG. Within this region, supersaturation stability is maintained even against physical stimulation, and by having substantially pure [Aα] crystals in such a crystallization system,
In other words, by allowing substantially pure crystals of [Aα] to exist in the system without substantially having crystals of [A] in the system, crystallization of [Aα] from a solution of [A] is extremely reproducible. It can be implemented well. In addition, when crystallizing [Aα] from a solution of [A] by the method of the present invention, the crystallization temperature is gradually lowered as the crystals of [Aα] crystallize. Crystals can be obtained in higher yield. In the present invention, substantially eliminating the crystals of [A] from the crystallization system can be achieved, for example, by once heating the system to 40° C. or higher, usually higher than the melting point of [A]. More preferably, it is desirable to reflux using a solvent having a boiling point higher than the melting point of [A]. Examples of the solvent for crystallizing [Aα] from the solution of [A] include alcoholic solvents, aliphatic hydrocarbons, alicyclic hydrocarbons, and mixed solvents thereof. Alternatively, a mixed solvent of these solvents and aromatic hydrocarbons, ketone solvents, ester solvents, ether solvents, chlorine solvents, phenolic solvents, etc. can also be used. More preferably,
Examples include alcoholic solvents alone or mixed solvents of alcoholic solvents and aliphatic hydrocarbons and/or aromatic hydrocarbons. The alcohol solvent is preferably an alcohol having 1 to 5 carbon atoms, and the aliphatic hydrocarbon or alicyclic hydrocarbon is preferably a hydrocarbon having 5 to 12 carbon atoms. Examples include hexane, heptane, octane, petroleum ether, ligroin, methylcyclohexane, and the like. Examples of aromatic solvents include benzene, toluene, and xylene. The optimal amount of these solvents to be used varies depending on the type of solvent and the temperature at which crystallization is performed, and is not strictly limited, but it is usually 0.5 to 30 times the amount of [A] in the raw material. The amount (weight) degree is used. In the present invention, the amount of the basic reagent used is not essential, and when performing crystallization separation without adding a basic catalyst, the ester is recovered from the mother liquor, and the ester with an increased amount of [Aβ] in the mother liquor is converted into a base. After bringing the alcohol moiety into contact with a chemical catalyst to epitomize the alcohol moiety and restoring the ratio of [Aα] and [Aβ] to equilibrium, the crystal [A] is almost quantitatively recovered by performing the crystallization operation again. can be converted to [Aα]. When performing crystallization separation in the presence of a basic catalyst, more [Aα] than the [Aα] originally contained in the raw material [A] (usually about 50%)
It becomes possible to obtain crystals. At this time, the ester in the mother liquor can be recovered and used repeatedly after being purified if necessary. In addition, in the presence of a basic catalyst from [A], [Aα]
After crystallizing the crystals of [Aα], remove or inactivate (neutralize) the basic catalyst without separating the crystals from the mother liquor, and then concentrate the entire amount to remove [A ] By also collecting [Aα]
[A] can be obtained. In this case, the [Aα] remaining in the mother liquor can be used effectively without being lost.
Moreover, since the operation becomes simpler, it becomes more advantageous in terms of industrial production and economy. Basic reagents used during crystallization include ammonia, hydrazine, methylamine, ethylamine, n-propylamine, isopropylamine,
n-butylamine, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, trimethylamine, triethylamine,
Cyclohexylamine, ethylenediamine, ethanolamine, pyrrolidine, piperidine, morpholine, aniline, 1-naphthylamine, pyridine, quinoline, 1,5-diazabicyclo[4,
Nitrogen bases such as 3,0]-non-5-ene, phosphorus bases such as triphenylphosphine and tri-n-butylphosphine, and quaternary bases such as tetramethylammonium hydroxide and tetra-n-butylammonium hydroxide. Preferred examples include quaternary ammonium hydroxide such as ammonium hydroxide, metal-containing bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium cyanide, sodium methylate, sodium hydride, and sodium amide. Examples include ammonia and triethylamine. The amount of catalyst used varies depending on the type of catalyst, type of solvent, amount used, and temperature, but is usually
It ranges from 0.001 to 200 mol%, and for ammonia and triethylamine, it is usually used in the range of 5 to 100 mol%. The seed crystal [Aα] must be substantially free of [A] crystals, and the usually obtained crystalline [Aα]
Or [Aα] rich exists [Aβ] and [A]
Since crystals may have formed, it is preferable to use one that has been recrystallized once or twice or more. Furthermore, during the recrystallization of [Aα], the precipitated crystals may be mixed with the solution of the raw material [A] together with the mother liquor without isolating them. The solvent used during recrystallization may be the same as or different from the solvent used for crystallizing [Aα] from the [A] solution, and may be an alcoholic solvent, an aliphatic hydrocarbon, or an alicyclic solvent. Examples include hydrocarbons and mixed solvents thereof. Alternatively, a mixed solvent of these solvents and aromatic hydrocarbons, ketone solvents, ester solvents, ether solvents, chlorine solvents, phenol solvents, etc. may also be used. More preferred are alcoholic solvents or mixed solvents of alcoholic solvents and aliphatic hydrocarbons and/or aromatic hydrocarbons, and mixed solvents of aliphatic hydrocarbons or alcoholic hydrocarbons and aromatic hydrocarbons. As the alcohol solvent, alcohol having 1 to 5 carbon atoms is preferable. The aliphatic hydrocarbons and alicyclic hydrocarbons are preferably hydrocarbons having 5 to 12 carbon atoms. Examples include hexane, heptane, octane, petroleum ether, ligroin, methylcyclohexane, and the like. Aromatic hydrocarbons include benzene,
Examples include toluene and xylene. The optimal amount of these solvents to be used differs depending on the type of solvent, and although it is not absolutely limited, it is usually used in the range of 0.5 to 50 times the amount (weight),
It is more preferable to use 3 times the amount (weight) or more. The present invention will be explained below with reference to Examples, Reference Examples, and Comparative Examples. Reference example 1 Fuenvalerate [A] (liquid, [Aα]/
For the methyl alcohol solution of [Aβ] = 46.9/53.1), the temperature-[A] concentration region where the supersaturation stability of the [A] solution can be maintained was measured using the method described below, and the graph shown in Figure 2 was obtained. I got it. First, the solubility in methyl alcohol was measured using crystals of [A] (all of the above [A] was crystallized) (curve). Next, after heating the methyl alcohol solution of [A] at a predetermined concentration,
Insulated at a specified temperature, crystals of [Aα] ([Aα]/[Aβ] = 99.9/0.1, acid side optical purity 100.0
%) was added, and the presence or absence of dissolution was observed to obtain a curve. Further, ferric oxide was selected as the supersaturation destruction element, 10 mg of ferric oxide was added to 300 c.c. of methyl alcohol solution of [A] with a predetermined concentration, and after heating it, it was kept at a predetermined temperature. A curve was determined by observing the presence or absence of crystallization for 24 hours [A]. In addition, after heating 300 c.c. of methyl alcohol solution of [A] with a specified concentration, keep it at the specified temperature, add 10 mg of ferric oxide, and heat it for 24 hours [A].
The curve ' was determined by observing the presence or absence of crystallization. Reference Example 2 80 g of methyl alcohol was added to 40 g of crystals of [A] used in Reference Example 1, dissolved by heating, cooled to -16°C, and then crystals of [Aα] ([Aα] / [Aβ] =
99.9/0.1, acid side optical purity 100.0%) 1mg inoculated,
At the same time, 8.4% ammonia-methyl alcohol solution
Added 4.8cc. The mixture was stirred at -16°C, and after one day, 1.4 cc of acetic acid was added and filtered to obtain 33.56 g of [Aα] crystals ([Aα]/[Aβ] = 96.8/3.2). Comparative Example 1 100 g of methyl alcohol and 10 mg of iron rust were added to 100 g of [A] used in Reference Example 1, heated under reflux for 30 minutes, cooled to -5°C, and stirred at the same temperature. After about 7 hours, a large amount of crystals precipitated, and when we sampled some and analyzed the crystals, we found that
It was a crystal of [A] ([Aα]/[Aβ] = 46.5/53.5). Comparative Example 2 Add n-heptane to 100 g of [A] used in Reference Example 1.
After adding 117 g, toluene 13 g, and methyl alcohol 70 g, refluxing for 30 minutes, cooling to -15℃,
The mixture was kept stirred at the same temperature. Next, when 5 mg of iron rust was added, a large amount of crystals precipitated after about 5 hours, and when we sampled some and analyzed the crystals, we found that [A]
The crystals were ([Aα]/[Aβ] = 46.0/54.0).
After refluxing this again for 30 minutes, it was cooled to -15°C and stirred at the same temperature. After about 8 hours, a large amount of crystals precipitated, and the crystals were [A] crystals ([Aα]/[ Aβ] = 45.8/54.2). Comparative Example 3 200 g of methyl alcohol and 10 mg of iron rust were added to 100 g of [A] used in Reference Example 1, heated under reflux for 30 minutes, cooled to -15°C, and stirred at the same temperature. On the other hand, the crystal of [Aα] ([Aα] / [Aβ] = 97.6 /
2.4) 27 g of n-heptane and 3 g of toluene were added to 10 g, and the mixture was heated under reflux for 30 minutes, then cooled to 35° C. At the same temperature, 1 mg of the crystals of [Aα] above were added and stirred for 30 minutes. Thereafter, the mixture was cooled to 30°C and stirred for 1 hour while keeping it warm to precipitate crystals of [Aα]. Next, −15℃
Add the entire amount of the crystals of [Aα] together with the mother liquor to the solution of [A] above, which had been kept warm and stirred at 200°C, and at the same time add 12.9% ammonia-methyl alcohol solution 6.29
g was added thereto, and the mixture was stirred at -15°C for 24 hours. Next, 3.43 g of acetic acid was added thereto and filtered to obtain 103.7 g of crystals. The obtained crystal is a crystal of [A] ([Aα]/
[Aβ] = 45.1/54.9). Comparative Example 4 Add 40 g of crystals of [A] used in Reference Example 1, 80 g of methyl alcohol, and 10 mg of iron rust, and dissolve by heating.
When cooled to -16℃, [Aα] crystal ([Aα]/[Aβ] = 99.1/0.1, acid side optical purity 100.0
%) was inoculated, and at the same time 4.8 cc of 8.4% ammonia-methyl alcohol solution was added. After stirring at -16℃ for 1 day, 1.4cc of acetic acid was added and filtered.
38.07g of crystals were obtained. The obtained crystals were crystals of [A] ([Aα]/[Aβ]=44.5/55.5). Example 1 Fuenvalerate [A] (liquid, [Aα]/
[Aβ] = 46.9/53.1) 200 methyl alcohol per 100g
10 mg of iron rust and 10 glass beads (about 1 mm in diameter) were added as a supersaturation breaking element, heated under reflux for 30 minutes, and then cooled to 5°C. 24 at the same temperature
After stirring for an hour, it was confirmed that crystals of [A] did not crystallize. On the other hand, the crystal of [Aα] ([Aα] / [Aβ] = 98.0 /
2.0) 8.1 g of n-heptane and 0.9 g of toluene were added to 3 g, and the mixture was heated under reflux for 30 minutes, then cooled to 35° C. At the same temperature, 1 mg of crystals of the above [Aα] were added and stirred for 30 minutes. Thereafter, the mixture was cooled to 30°C and stirred for 1 hour while keeping it warm to precipitate crystals of [Aα]. Next, all of the crystals of [Aα] were added as seed crystals together with the mother liquor to the above solution of [A] which had been stirred at 5°C, and 2.41 g of triethylamine was added at the same time.
Stirred at ℃ for 25 hours. Then add 35% hydrochloric acid 2.98
After adding g, the crystal of [Aα] ([Aα]/
[Aβ]=98.6/1.4) 54.39 g was obtained. Example 2 185.7 g of methyl alcohol and 10 mg of ferric oxide were added to 79.6 g of [A] used in Example 1, heated under reflux for 30 minutes, and then cooled to 15°C. at the same temperature
After stirring for 24 hours, it was confirmed that crystals of [A] did not crystallize. Furthermore, even after adding 10 mg of ferric oxide to the solution and stirring at 15° C. for 25 hours, no crystallization of [A] was observed. On the other hand, the crystal of [Aα] ([Aα] / [Aβ] = 99.9 /
0.1) 3.98g, n-heptane 10.75g, toluene
After adding 1.19 g and heating under reflux for 30 minutes, the mixture was cooled to 35° C. At the same temperature, 1 mg of the crystals of [Aα] above were added and stirred for 30 minutes. Thereafter, the mixture was cooled to 30°C and stirred for 1 hour while keeping it warm to precipitate crystals of [Aα]. next
Add to the above solution [A] which has been stirred while keeping warm at 15℃.
The entire amount of the [Aα] crystals together with the mother liquor were added as seed crystals, and at the same time, 1.92 g of triethylamine was added and stirred at 15°C for 20 hours to crystallize [Aα] crystals. Next, this reaction solution was gradually cooled to 10°C.
Stir at 10°C for 24 hours, further cool to 5°C,
The mixture was stirred at 5°C for 4 hours. Then add 35% hydrochloric acid to this
After adding 2.96 g, it was filtered to obtain 28.18 g of crystals of [Aα] ([Aα]/[Aβ] = 98.3/1.7). Example 3 850.0 g of methyl alcohol and 50 mg of ferric oxide were added to 150.0 g of [A] used in Example 1, and 30
After heating under reflux for a minute, the mixture was cooled to 0°C. On the other hand, the crystal of [Aα] ([Aα] / [Aβ] = 99.0 /
0.1) 7.50g, n-heptane 20.25g, toluene
After adding 2.25 g and heating under reflux for 30 minutes, the mixture was cooled to 35°C, and at the same temperature, 1 mg of the above [Aα] crystals were added and stirred for 30 minutes. Thereafter, the mixture was cooled to 30° C. and stirred for 1 hour to precipitate crystals of [Aα]. Next, the entire amount of the crystals of [Aα] were added as seed crystals together with the mother liquor to the solution of [A] kept at 0℃, and the precipitated crystals were stirred at 0℃ for 24 hours. Then, the crystal of [Aα] ([Aα]/
[Aβ]=99.2/0.8) 37.57 g was obtained. Example 4 240.0 g of methyl alcohol was added to 60.0 g of [A] used in Example 1, and after heating under reflux for 30 minutes,
Cooled to ℃. On the other hand, the crystal of [Aα] ([Aα] / [Aβ] = 99.9 /
0.1) 3.0g, 12.0g of methyl alcohol, 0.06 of acetic acid
g was added, heated under reflux for 30 minutes, cooled to 30°C, and added 1 mg of the above [Aα] crystals at the same temperature.
After stirring for 1 hour, crystals of [Aα] precipitated. Next, the entire amount of the crystals of [Aα] were added as seed crystals together with the mother liquor to the solution of [A] kept at 10°C, and the precipitated crystals were stirred at 10°C for 24 hours. Then, the crystal of [Aα] ([Aα]/
[Aβ]=99.0/1.0) 9.62 g was obtained. Example 5 240.0 g of methyl alcohol and 1.2 g of acetic acid were added to 60.0 g of [A] used in Example 1, heated under reflux for 30 minutes, and then cooled to 10°C. On the other hand, the crystal of [Aα] ([Aα] / [Aβ] = 98.3 /
1.7) 10.0g, n-heptane 27.0g, toluene 3.0
After heating under reflux for 30 minutes, the mixture was cooled to 35°C, and at the same temperature, 1 mg of the above [Aα] crystals was added to the mixture for 30 minutes.
Stir for a minute. Thereafter, the mixture was cooled to 30°C and stirred for 1 hour while keeping it warm to precipitate crystals of [Aα]. Next, about 1 c.c. of the recrystallized slurry of [Aα] obtained in this way was taken and added as a seed crystal to the solution of [A] above, which had been stirred while keeping warm at 10°C. After stirring at 10°C for 20 hours, the precipitated crystals were filtered and the [Aα] crystals ([Aα]/[Aβ] =
99.7/0.3) 8.84g was obtained.
図１は〔Ａ〕の溶液の過飽和安定性が保持でき
る温度−〔Ａ〕の濃度の領域について示した概略
図である。図２はフエンバレレートの〔Ａ〕のメ
チルアルコール溶液について、参考例１に記した
方法により測定した、過飽和安定性が保持できる
温度−〔Ａ〕の濃度の領域図である。
図１および図２において横軸は〔Ａ〕の濃度
（重量％）を表わし、縦軸は温度（℃）を表わす。
FIG. 1 is a schematic diagram showing the range of temperature and concentration of [A] in which the supersaturation stability of the solution of [A] can be maintained. FIG. 2 is a diagram showing the range of the temperature at which supersaturation stability can be maintained - the concentration of [A], measured by the method described in Reference Example 1 for a methyl alcohol solution of [A] of fenvalerate. In FIGS. 1 and 2, the horizontal axis represents the concentration (% by weight) of [A], and the vertical axis represents the temperature (° C.).
Claims (1)
し、＊は不整炭素を表わす。） で示され、その酸側がＳ体であるカルボン酸エス
テル（以下、〔Ａ〕と称する。）の溶液から、塩基
性試剤の存在下または非存在下に、その酸側およ
びアルコール側が共に（Ｓ）体である当該カルボ
ン酸エステル（以下、〔Aα〕と称する。）の結晶
を晶析する際に、新たな〔Aα〕が溶解せず、か
つ、過飽和破壊要素の存在により〔Ａ〕の結晶の
晶出が見られない温度および濃度の領域内の
〔Ａ〕の過飽和溶液に、実質的に純粋な〔Aα〕の
結晶を種晶として加え、〔Aα〕の結晶を晶析させ
ることを特徴とする〔Aα〕または〔Aα〕に富む
前記一般式（）で示されるカルボン酸エステル
の製造法。 ２ 〔Ａ〕の溶液から〔Aα〕を晶析させるに先
だち、一旦〔Ａ〕の溶液を40℃以上に加熱してお
くことを特徴とする特許請求の範囲第１項に記載
の方法。 ３ 種晶として、再結晶操作を施した〔Aα〕を
用いる特許請求の範囲第１項または第２項に記載
の方法。 ４ 〔Aα〕を溶媒中で再結晶し、結晶を単離す
ることなく母液と共に、種晶として、〔Ａ〕の溶
液と混合する特許請求の範囲第３項に記載の方
法。 ５ 再結晶溶媒として、アルコール系溶媒、脂肪
族炭化水素および脂環式炭化水素からなる群より
選ばれる単独溶媒、混合溶媒またはそれらを含む
溶媒を使用する特許請求の範囲第３項または第４
項に記載の方法。 ６ 再結晶溶媒として、アルコール系溶媒、脂肪
族炭化水素および脂環式炭化水素からなる群より
選ばれる単独溶媒、混合溶媒と芳香族炭化水素と
の混合溶媒を使用する特許請求の範囲第３項、第
４項または第５項に記載の方法。 ７ 再結晶溶媒として、アルコール系溶媒、脂肪
族炭化水素および脂環式炭化水素からなる群より
選ばれる単独溶媒、混合溶媒またはそれらを含む
溶媒を、用いる〔Aα〕に対して0.5〜50倍量（重
量）使用する特許請求の範囲第３項、第４項また
は第５項に記載の方法。 ８ 再結晶溶媒として、アルコール系溶媒、脂肪
族炭化水素および脂環式炭化水素からなる群より
選ばれる単独溶媒、混合溶媒と芳香族炭化水素と
の混合溶媒を、用いる〔Aα〕に対して0.5〜50倍
量（重量）使用する特許請求の範囲第３項、第４
項、第５項、第６項または第７項に記載の方法。 ９ 〔Ａ〕の溶液から〔Aα〕を晶析させる際の
溶媒としてアルコール系溶媒、脂肪族炭化水素お
よび脂環式炭化水素からなる群より選ばれる単独
溶媒、混合溶媒またはそれらを含む溶媒を用いる
特許請求の範囲第１項、第２項、第３項または第
４項に記載の方法。 １０ 〔Ａ〕の溶液から〔Aα〕を晶析させる際
の溶媒としてアルコール系溶媒を用いる特許請求
の範囲第１項、第２項、第３項、第４項または第
９項に記載の方法。 １１ 〔Ａ〕の溶液から〔Aα〕を晶析させる際
の溶媒として脂肪族炭化水素、脂環式炭化水素お
よび芳香族炭化水素からなる群より選ばれる１種
または２種以上の溶媒とアルコール系溶媒との混
合溶媒を用いる特許請求の範囲第１項、第２項、
第３項、第４項、第９項または第１０項に記載の
方法。 １２ 塩基性試剤の存在下に〔Aα〕の結晶を晶
析させる特許請求の範囲第１項、第２項、第３
項、第４項、第９項、第１０項または第１１項に
記載の方法。 １３ 塩基性試剤の存在下に〔Aα〕の結晶を晶
析させ、析出した〔Aα〕を母液中の〔Ａ〕と共
に回収して〔Aα〕に富む〔Ａ〕を取得する特許
請求の範囲第１項、第２項、第３項、第４項、第
９項、第１０項、第１１項または第１２項に記載
の方法。 １４ 塩基性試剤がアンモニアまたはトリエチル
アミンである特許請求の範囲第１２項または第１
３項に記載の方法。 １５ 前記一般式（）においてＸが水素原子で
ある特許請求の範囲第１項、第２項、第３項、第
４項、第５項、第６項、第７項、第８項、第９
項、第１０項、第１１項、第１２項、第１３項ま
たは第１４項に記載の方法。[Claims] 1 General formula () (In the formula, X represents a hydrogen atom or a fluorine atom, and * represents an asymmetric carbon.) From a solution of a carboxylic acid ester (hereinafter referred to as [A]) whose acid side is in the S form. , in the presence or absence of a basic reagent, when crystallizing the carboxylic acid ester (hereinafter referred to as [Aα]) whose acid side and alcohol side are both (S) form, new Substantially pure [A] is added to a supersaturated solution of [A] within a temperature and concentration range where [Aα] does not dissolve and crystals of [A] do not crystallize due to the presence of supersaturation destructive elements. A method for producing a carboxylic acid ester rich in [Aα] or [Aα] represented by the general formula (), which comprises adding crystals of [Aα] as seed crystals and crystallizing the crystals of [Aα]. 2. The method according to claim 1, wherein the solution of [A] is heated to 40° C. or higher before crystallizing [Aα] from the solution of [A]. 3. The method according to claim 1 or 2, in which recrystallized [Aα] is used as a seed crystal. 4. The method according to claim 3, wherein [Aα] is recrystallized in a solvent and mixed with the solution of [A] together with the mother liquor as a seed crystal without isolating the crystals. 5. Claims 3 or 4 in which a single solvent, a mixed solvent, or a solvent containing them selected from the group consisting of alcoholic solvents, aliphatic hydrocarbons, and alicyclic hydrocarbons is used as the recrystallization solvent.
The method described in section. 6. Claim 3, in which a single solvent selected from the group consisting of alcoholic solvents, aliphatic hydrocarbons, and alicyclic hydrocarbons, a mixed solvent of a mixed solvent, and an aromatic hydrocarbon are used as the recrystallization solvent. , the method according to paragraph 4 or paragraph 5. 7 As the recrystallization solvent, a single solvent, a mixed solvent, or a solvent containing them selected from the group consisting of alcoholic solvents, aliphatic hydrocarbons, and alicyclic hydrocarbons is used in an amount of 0.5 to 50 times the amount of [Aα] used. (Weight) The method according to claim 3, 4 or 5 used. 8 As the recrystallization solvent, a single solvent selected from the group consisting of alcoholic solvents, aliphatic hydrocarbons, and alicyclic hydrocarbons, a mixed solvent of a mixed solvent, and an aromatic hydrocarbon are used. 0.5 for [Aα] ~50 times the amount (weight) of claims 3 and 4
The method according to paragraph 5, paragraph 6 or paragraph 7. 9. As a solvent for crystallizing [Aα] from a solution of [A], a single solvent, a mixed solvent, or a solvent containing them selected from the group consisting of alcoholic solvents, aliphatic hydrocarbons, and alicyclic hydrocarbons is used. A method according to claim 1, 2, 3 or 4. 10. The method according to claim 1, 2, 3, 4, or 9, in which an alcoholic solvent is used as a solvent when crystallizing [Aα] from a solution of [A]. . 11 One or more solvents selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons and an alcohol system as a solvent for crystallizing [Aα] from a solution of [A] Claims 1 and 2 using a mixed solvent with a solvent,
The method according to paragraph 3, paragraph 4, paragraph 9 or paragraph 10. 12 Claims 1, 2, and 3, which involve crystallizing [Aα] in the presence of a basic reagent.
10. The method according to paragraph 4, paragraph 9, paragraph 10 or paragraph 11. 13 Claim No. 1, in which crystals of [Aα] are crystallized in the presence of a basic reagent, and the precipitated [Aα] is recovered together with [A] in the mother liquor to obtain [A] rich in [Aα]. The method according to item 1, item 2, item 3, item 4, item 9, item 10, item 11 or item 12. 14 Claim 12 or 1, wherein the basic reagent is ammonia or triethylamine
The method described in Section 3. 15 Claims 1, 2, 3, 4, 5, 6, 7, 8, and 8, wherein in the general formula (), X is a hydrogen atom. 9
10, 11, 12, 13, or 14.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5611581A JPS57169453A (en) | 1981-04-13 | 1981-04-13 | Preparation of optically active carboxylic ester |
| EP81304922A EP0050521B1 (en) | 1980-10-20 | 1981-10-20 | Preparation of insecticidal optically active isovalerate esters |
| DE8181304922T DE3167334D1 (en) | 1980-10-20 | 1981-10-20 | Preparation of insecticidal optically active isovalerate esters |
| US06/313,089 US4422978A (en) | 1980-10-20 | 1981-10-20 | Method for preparing optically active carboxylic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5611581A JPS57169453A (en) | 1981-04-13 | 1981-04-13 | Preparation of optically active carboxylic ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57169453A JPS57169453A (en) | 1982-10-19 |
| JPS6360735B2 true JPS6360735B2 (en) | 1988-11-25 |
Family
ID=13018070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5611581A Granted JPS57169453A (en) | 1980-10-20 | 1981-04-13 | Preparation of optically active carboxylic ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57169453A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5416444A (en) * | 1977-07-07 | 1979-02-07 | Sumitomo Chem Co Ltd | Optically active alpha-cyano-3-phenoxybenzyl 2-(4-chlorophenyl)-isovalerate and its preparation |
| JPS5455546A (en) * | 1977-10-07 | 1979-05-02 | Sumitomo Chem Co Ltd | Preparation of optically active alpha-cyano-3-phenoxy-benzyl 2-(4-chlorophenyl)-isovalerate |
| JPS54109945A (en) * | 1978-01-31 | 1979-08-29 | Roussel Uclaf | Insecticidal ester of photoactive substituted acetic acid and racemic or photoactive substituted benzylalcohol* its manufacture and insecticide composition containing it |
-
1981
- 1981-04-13 JP JP5611581A patent/JPS57169453A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5416444A (en) * | 1977-07-07 | 1979-02-07 | Sumitomo Chem Co Ltd | Optically active alpha-cyano-3-phenoxybenzyl 2-(4-chlorophenyl)-isovalerate and its preparation |
| JPS5455546A (en) * | 1977-10-07 | 1979-05-02 | Sumitomo Chem Co Ltd | Preparation of optically active alpha-cyano-3-phenoxy-benzyl 2-(4-chlorophenyl)-isovalerate |
| JPS54109945A (en) * | 1978-01-31 | 1979-08-29 | Roussel Uclaf | Insecticidal ester of photoactive substituted acetic acid and racemic or photoactive substituted benzylalcohol* its manufacture and insecticide composition containing it |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57169453A (en) | 1982-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1334964B1 (en) | Process for producing b-form nateglinide crystal | |
| US6384227B2 (en) | Racemisation process for use in the manufacture of levobupivacaine and related piperidinecarboxanilide anaesthetic agents | |
| JPS6360735B2 (en) | ||
| EP1474392A1 (en) | Polymorphic form xvi of fexofenadine hydrochloride | |
| JP2005120024A (en) | Method for producing 4'-cyano-3-[(4-fluorophenyl)sulfonyl]-2-hydroxy-2-methyl-3'-trifluoromethylpropionanilide | |
| EP0050521B1 (en) | Preparation of insecticidal optically active isovalerate esters | |
| US20060258705A1 (en) | Process for making crystalline donepezil hydrochloride monohydrate | |
| US4661625A (en) | Synthesis and purification of d-propoxyphene hydrochloride | |
| JPH0330588B2 (en) | ||
| JPH09176115A (en) | Production of optically active n-benzyl-3-aminopyrrolidine | |
| WO2002068391A1 (en) | Process for resolving racemic mixtures of piperidine derivatives | |
| US20110046416A1 (en) | Process for preparation of benzphetamine and its pharmaceutically acceptable salts | |
| EP0090203B1 (en) | Process for preparing p.chlorophenoxyacetyl-piperonylpiperazine | |
| JPH0342266B2 (en) | ||
| JP3422080B2 (en) | Method for producing long-chain carboxylic acid lactate | |
| US5130490A (en) | Purification of 3,5-diaminobenzotrifluoride by selective precipitation of the hydrochloride salt | |
| JP2947492B2 (en) | Theanine manufacturing method | |
| JPS6360019B2 (en) | ||
| JP3251722B2 (en) | Method for producing N-substituted-3-piperidinol | |
| US20040039206A1 (en) | Process for resolving racemic mixtures of piperidine derivatives | |
| US4350642A (en) | Process for preparation of a pesticidal phenylacetate enantiomer pair | |
| JPS62263135A (en) | Separation of m-cresol | |
| US20230107889A1 (en) | Process for producing acylthiourea compound | |
| JP3235232B2 (en) | Method for producing thiocarbamate | |
| JPH0439448B2 (en) |