WO2010043311A1 - Procédé de production de dérivés spirocycliques d'acide tétronique - Google Patents

Procédé de production de dérivés spirocycliques d'acide tétronique Download PDF

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Publication number
WO2010043311A1
WO2010043311A1 PCT/EP2009/007019 EP2009007019W WO2010043311A1 WO 2010043311 A1 WO2010043311 A1 WO 2010043311A1 EP 2009007019 W EP2009007019 W EP 2009007019W WO 2010043311 A1 WO2010043311 A1 WO 2010043311A1
Authority
WO
WIPO (PCT)
Prior art keywords
general formula
alkyl
spirocyclic tetronic
tetronic acid
hydrogen
Prior art date
Application number
PCT/EP2009/007019
Other languages
German (de)
English (en)
Inventor
Richard Breitschuh
Original Assignee
Richard Breitschuh
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 Richard Breitschuh filed Critical Richard Breitschuh
Priority to CN200980137126.0A priority Critical patent/CN102171201B/zh
Priority to BRPI0914370A priority patent/BRPI0914370A2/pt
Publication of WO2010043311A1 publication Critical patent/WO2010043311A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins

Definitions

  • the present invention relates to a novel process for preparing known spirocyclic tetronic acid derivatives.
  • Spirocyclic tetronic acid derivatives as well as their possible uses as insecticidal or acaricidal agents are known inter alia from EP-A-0 528 156.
  • the required structure of the spirocyclic tetronic acid structure is carried out via esters of the general formula (I)
  • X is C 1 -C 6 -alkyl, halogen, C 1 -C 6 -alkoxy or C 1 -C 3 -
  • Haloalkyl Y represents hydrogen, C:. -C 6 alkyl, halogen, C 1 -C 6 -alkoxy or C 1 -
  • Z stands for C 1 -C 6 -alkyl, halogen, C 1 -C 6 -alkoxy and n stands for a number 0-3 R 1 for alkyl and A and B together with the carbon atom to which they are bonded for a saturated or unsaturated, optionally substituted carbocycle or heterocycle
  • A, B, X, Y, Z and n are as defined above and G is hydrogen, a metal equivalent, an optionally substituted ammonium or a group -CO-R 4 in which R 4 is alkyl.
  • A, B, X, Y, Z and n are as defined above and R 5 is alkyl.
  • the spirocyclic tetronic acids initially form in the form of their anionic salts under the basic reaction conditions, but can also be obtained by subsequent acidification into their free acids or by addition of an acylating agent of the general formula (VI)
  • R 4 has the abovementioned meaning
  • LG stands for chlorine or any other leaving group
  • Suitable bases are all customary proton acceptors or combinations thereof, for example alkali metal or alkaline earth metal oxides, hydroxides, amides, hydrides or alkoxides, alkali metals or tertiary amine bases, for example 1,8-diazabicyclo [5.4.0 ] undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-2-ene (DBN) or 1, 4-diazabicyclo [2.2.2] octane (DABCO).
  • DBU 1,8-diazabicyclo [5.4.0 ] undec-7-ene
  • DBN 1,5-diazabicyclo [4.3.0] non-2-ene
  • DABCO 4-diazabicyclo [2.2.2] octane
  • diluents it is possible to use alcohols and all solvents which are inert under the reaction conditions or combinations thereof, preferably polar solvents such as, for example, 1,2-dimethoxyethane (glyme), 1,4-dioxane or tetrahydrofuran (THF), N-methylpyrrolidone (NMP) or N , N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), sulfolane.
  • polar solvents such as, for example, 1,2-dimethoxyethane (glyme), 1,4-dioxane or tetrahydrofuran (THF), N-methylpyrrolidone (NMP) or N , N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), sulfolane.
  • phase transfer catalysts eg: Triethylbenzylammonium chloride or tetrabutylammonium bromide
  • the reaction can be carried out in the range of 0-200 0 C, preferably at 40-120 0 C.
  • reaction is carried out at atmospheric pressure, but can also be carried out in vacuo or under pressure. If, after the reaction, an acylation of the tetronic acid salt is to take place, it is advisable to remove the alcohols formed during the reaction by means of distillation under reduced pressure.
  • reaction components of the formulas (II) and (III) are generally used in approximately equimolar amounts. However, it is also possible to use one or the other component in a larger excess (up to 5 mol).
  • the base used is generally used in approximately equimolar amounts or in a slight excess, but can also be used in far greater excess (up to 20 mol).
  • the starting materials of the general formulas (II) and (III) are known and mostly commercially available compounds or can be prepared by generally customary processes of organic chemistry.

Abstract

L'invention concerne un procédé de production de dérivés spirocycliques d'acide tétronique. Des dérivés spirocycliques d'acide tétronique sont produits par l'intermédiaire d'esters de la formule générale (I). Selon l'invention, on fait réagir des esters d'acide hydroxycarboxylique et des esters d'acide arylacétique en présence d'une base, éventuellement d'un agent de dilution et éventuellement d'autres additifs, et l'acide tétronique spirocyclique formé est récupéré soit sous la forme de son sel, soit comme acide libre par acidification, soit transformé en un dérivé O-acylé par ajout d'un agent d'acylation. Les produits ainsi obtenus trouvent entre autres une utilisation comme agent insecticide ou acaricide.
PCT/EP2009/007019 2008-10-15 2009-09-30 Procédé de production de dérivés spirocycliques d'acide tétronique WO2010043311A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN200980137126.0A CN102171201B (zh) 2008-10-15 2009-09-30 螺环季酮酸衍生物的制备方法
BRPI0914370A BRPI0914370A2 (pt) 2008-10-15 2009-09-30 processo de preparação de derivados de ácido tetrônico espirocíclico

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200810051690 DE102008051690B3 (de) 2008-10-15 2008-10-15 Verfahren zur Herstellung von spirocyclischen Tetronsäurederivaten
DE102008051690.2 2008-10-15

Publications (1)

Publication Number Publication Date
WO2010043311A1 true WO2010043311A1 (fr) 2010-04-22

Family

ID=41633871

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/007019 WO2010043311A1 (fr) 2008-10-15 2009-09-30 Procédé de production de dérivés spirocycliques d'acide tétronique

Country Status (4)

Country Link
CN (1) CN102171201B (fr)
BR (1) BRPI0914370A2 (fr)
DE (1) DE102008051690B3 (fr)
WO (1) WO2010043311A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108658913A (zh) * 2018-06-13 2018-10-16 石家庄市绿丰化工有限公司 一种合成农药螺螨酯关键中间体的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4216814A1 (de) * 1991-07-16 1993-01-21 Bayer Ag 3-aryl-4-hydroxy-(delta)(pfeil hoch)3(pfeil hoch)-dihydrofuranon- und 3-aryl-4-hydroxy-(delta)(pfeil hoch)3(pfeil hoch)-dihydrothiophenon-derivate
DE10012825B4 (de) * 2000-03-16 2004-04-15 Bayer Corp. Verfahren zur Herstellung von spirocyclischen Tetronsäurederivaten

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BRETSCHNEIDER, T. ET AL.: "Spirodiclofen and Spiromesifen - Novel Acaricidal and Insecticidal Tetronic Acid Derivatives with a New Mode of Action", CHIMIA INTERNATIONAL JOURNAL FOR CHEMISTRY, vol. 57, no. 11, November 2003 (2003-11-01), pages 697 - 701, XP002567718, ISSN: 0009-4293, DOI: 10.2533/000942903777678588 *
MALLINGER A ET AL: "3-Aryltetronic acids: Efficient preparation and use as precursors for vulpinic acids", JOURNAL OF ORGANIC CHEMISTRY, vol. 74, no. 3, 22 December 2008 (2008-12-22), pages 1124 - 1129, XP002567720, ISSN: 0022-3263 *
MALLINGER A ET AL: "One-pot synthesis of tetronic acids from esters", SYNLETT, no. 3, 12 February 2008 (2008-02-12), pages 386 - 388, XP002567719, ISSN: 0936-5214 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108658913A (zh) * 2018-06-13 2018-10-16 石家庄市绿丰化工有限公司 一种合成农药螺螨酯关键中间体的方法

Also Published As

Publication number Publication date
DE102008051690B3 (de) 2010-04-22
BRPI0914370A2 (pt) 2016-07-26
CN102171201B (zh) 2014-03-26
CN102171201A (zh) 2011-08-31

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