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WO1992002492A1 - Procede de preparation de derives de pyrethroides - Google Patents

Procede de preparation de derives de pyrethroides Download PDF

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Publication number
WO1992002492A1
WO1992002492A1 PCT/HU1990/000053 HU9000053W WO9202492A1 WO 1992002492 A1 WO1992002492 A1 WO 1992002492A1 HU 9000053 W HU9000053 W HU 9000053W WO 9202492 A1 WO9202492 A1 WO 9202492A1
Authority
WO
WIPO (PCT)
Prior art keywords
general formula
acid chloride
reaction
cyanhydride
trans
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/HU1990/000053
Other languages
English (en)
Inventor
Sándor Botár
István Székely
Béla BERTÓK
Antal GAJÁRY
György HIDASI
Sándor Zoltán
Janis Hajimichael
András RAPI
Ferenc Lindwurm
László CSÍZ
Ágnes HEGEDÜS
István LAK
Mária TARY
Péterné MAGYAR
Lajos Nagy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chinoin Private Co Ltd
Original Assignee
Chinoin Gyogyszer es Vegyeszeti Termekek Gyara Zrt
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chinoin Gyogyszer es Vegyeszeti Termekek Gyara Zrt filed Critical Chinoin Gyogyszer es Vegyeszeti Termekek Gyara Zrt
Priority to PCT/HU1990/000053 priority Critical patent/WO1992002492A1/fr
Priority to HK98103147.9A priority patent/HK1003993B/xx
Publication of WO1992002492A1 publication Critical patent/WO1992002492A1/fr
Priority to GB9205920A priority patent/GB2251621B/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/38—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups
    • C07C255/39—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups with hydroxy groups esterified by derivatives of 2,2-dimethylcyclopropane carboxylic acids, e.g. of chrysanthemumic acids

Definitions

  • the invention relates to the preparation of pyrethroide derivatives in a great purity suitable for controlled crystallization. of the general formula (I),
  • - A is a chlorine atom, a bromine atom or a methyl group
  • Y is a hydrogen, a fluor or a chlorine atom
  • the wave line means an R respectively S configura ⁇ tion.
  • the o--cyano-esters of the general formula (I) are effective insecticides (Hungarian Pat. Specification No. 170 866).
  • phase-transfer-catalysts Disadvantage of the applied phase-transfer-catalysts is, that they accelarate the reaction, but they are accelarati ⁇ g the side reactions in a similar extent, and this way they further the hydrolysis of the acid chloride of the general formula (III) and in a small extent that of the cypermetrine too. But without these catalysts the reaction can be realised only with a yield of 64% and the quality of the product obtained is very poor too and requires chromatographic purification (US. Pat. Spec. No. 3 835 176 1). As phase-tra ⁇ sfer-catalysts "onium" e.g. quaternary ammonium compounds (Hungarian Pat. Spec. No.
  • secondary or tertiary amines advantageously - trietyl-amine or imidazole are applied in a quantity of 0.15-0.25 mol-equivalents calculated on the aldehyde of the general formula (IV).
  • the alkali-cyanide is applied expediently in a 7-9 mol% aqueous solution. It is advantageous to carry out the acylatio ⁇ reaction at a temperature of 5-15°C in the course of 2-3 hours. Using a suitable equipment, reacting the components in a shorter time even a higher temperature is not damaging the reaction.
  • Substantial advantage of the process is that because of using an aqueous medium a much more diluted cyanide solution can be applied, which makes the controlability of the pH value much easier.
  • the preparation and the mood of reacting on the cyanhydride takes a very important place.
  • the suitable aldehyde is reacted in a diluted aqueous solution with cyanide, to avoid the Canizzaro-reaction in the presence of at most 0.3 moles amine (calculated on aldehyde) .
  • the cyanhydride formed in the equilibrium reaction is reacted in statu nascens, in the aqueous medium, quickly - and accordingly at a suitable temperature - with the added acid chloride parallel to its formation.
  • the amine catalyst is selective, that is it catalyses only the main reaction, while the ionic phase- -transfer catalysts are not selective: but decreasing the surface tension they are catalysing in the same degree the undesirable e.g. hydrolytic side processes, as the main reaction.
  • the process according to the invention thus differs from the simple phase-transfer-catalysis.
  • the symptoms are: a) A very quick reaction, b) A very pure product (a 97% purity, usual in the laboratory) and this way: c) Cipermetrine is crystallized with a nearly quantitative yield (91%) even in case of 8 isomers - while a crystalline product was not known up to the present.
  • the active ingredient content of the product is 97%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention se rapporte à la préparation de dérivés de pyréthroïdes de pureté élevée, appropriés pour une cristallisation contrôlée. Les pyréthroïdes de la formule générale (I), dans laquelle: A représente un atome de chlore ou de brome ou un groupe méthyle, Y représente un atome d'hydrogène, de fluor ou de chlore, la ligne ondulée représente une configuration respectivement en R ou en S, s'obtiennent au moyen d'une réaction au cours de laquelle le cyanohydrure de la formule générale (II) est acylé avec un chlorure d'acide de la formule générale (III), et le cyanohydrure de la formule générale (II) se prépare à partir de benzaldéhyde de la formule générale (IV) par réaction avec un cyanure alcalin et de l'eau en utilisant une amine comme catalyseur; l'invention est caractérisée par le fait que, dans la solution aqueuse de cyanure de 7-9 mol %, on ajoute un benzaldéhyde en présence de 0,15-0,25 mol équivalents d'amine, on acyle le cyanohydrure formé dans le mélange réactionnel, à l'état naissant (statu nascens) parallèlement à la formation de cyanohydrure avec un chlorure d'acide et on extrait l'émulsion de cypermétrine obtenue avec un solvant apolaire.
PCT/HU1990/000053 1990-07-27 1990-07-27 Procede de preparation de derives de pyrethroides Ceased WO1992002492A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/HU1990/000053 WO1992002492A1 (fr) 1990-07-27 1990-07-27 Procede de preparation de derives de pyrethroides
HK98103147.9A HK1003993B (en) 1990-07-27 Process for the preparation of pyrethroid derivatives
GB9205920A GB2251621B (en) 1990-07-27 1992-03-18 Process for the preparation of pyrethroid derivatives

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/HU1990/000053 WO1992002492A1 (fr) 1990-07-27 1990-07-27 Procede de preparation de derives de pyrethroides

Publications (1)

Publication Number Publication Date
WO1992002492A1 true WO1992002492A1 (fr) 1992-02-20

Family

ID=10980904

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/HU1990/000053 Ceased WO1992002492A1 (fr) 1990-07-27 1990-07-27 Procede de preparation de derives de pyrethroides

Country Status (2)

Country Link
GB (1) GB2251621B (fr)
WO (1) WO1992002492A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LV12032B (en) 1995-04-24 1998-09-20 ARGO-CHEMIE Novenyvedoszer Gyarto Ertekesito es Forgalmazo Kft. METHODS OF PESTICIDE COMPOSITIONS AND THEIR ACQUISITION

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH589051A5 (fr) * 1971-06-29 1977-06-30 Sumitomo Chemical Co
EP0039173A1 (fr) * 1980-04-21 1981-11-04 Ici Americas Inc. Préparation d'insecticides d'esters cyano-benzyliques
US4323685A (en) * 1980-06-13 1982-04-06 Fmc Corporation Preparation of esters
US4382894A (en) * 1981-06-22 1983-05-10 Ciba-Geigy Corporation Production of α-cyanobenzyl esters

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH589051A5 (fr) * 1971-06-29 1977-06-30 Sumitomo Chemical Co
EP0039173A1 (fr) * 1980-04-21 1981-11-04 Ici Americas Inc. Préparation d'insecticides d'esters cyano-benzyliques
US4323685A (en) * 1980-06-13 1982-04-06 Fmc Corporation Preparation of esters
US4382894A (en) * 1981-06-22 1983-05-10 Ciba-Geigy Corporation Production of α-cyanobenzyl esters

Also Published As

Publication number Publication date
HK1003993A1 (en) 1998-11-13
GB2251621A (en) 1992-07-15
GB2251621B (en) 1994-04-06
GB9205920D0 (en) 1992-04-29

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