WO2002004436A1 - Procedes relatifs a l'elaboration de composes a base de pyrone - Google Patents

Procedes relatifs a l'elaboration de composes a base de pyrone Download PDF

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Publication number
WO2002004436A1
WO2002004436A1 PCT/JP2001/005681 JP0105681W WO0204436A1 WO 2002004436 A1 WO2002004436 A1 WO 2002004436A1 JP 0105681 W JP0105681 W JP 0105681W WO 0204436 A1 WO0204436 A1 WO 0204436A1
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WO
WIPO (PCT)
Prior art keywords
methyl
pyrone
hydroxy
secondary amine
reaction
Prior art date
Application number
PCT/JP2001/005681
Other languages
English (en)
Japanese (ja)
Inventor
Tatsuya Mori
Noritada Matsuo
Original Assignee
Sumitomo Chemical Company, Limited
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 Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Priority to AU2001266362A priority Critical patent/AU2001266362A1/en
Publication of WO2002004436A1 publication Critical patent/WO2002004436A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
    • C07D309/38—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms one oxygen atom in position 2 or 4, e.g. pyrones

Definitions

  • the present invention relates to a process for producing 4-hydroxy-6-methyl-1- (4-methyl-12-pentenyl) -1-pyrone and 4-hydroxy-6-methyl-13- (4-methylpentanoyl) -12-pyrone.
  • Background art 4-hydroxy-6-methyl-1- (4-methyl-12-pentenyl) -1-pyrone and 4-hydroxy-6-methyl-13- (4-methylpentanoyl) -12-pyrone.
  • 4-Hydroxy-6-methyl-1- (4-methylpentanoyl) -12-pyrone represented by is a compound that can be used as an active ingredient of an insecticide as shown in Reference Examples below. .
  • dehydroacetic acid (3-acetyl-4-hydroxy) is disclosed in JP-B-41-20720.
  • a method is described in which (6-methyl-2-pyrone) and isobutyraldehyde are heated for several hours in the presence of a few drops of piperidine in chloroform.
  • the present invention relates to 4-hydroxy-16-methyl-13- (4-methyl-12-pentenyl) -12-pyrone represented by the above formula (2) from 3-acetyl-14-hydroxy-6-methyl-1-pyrone. Is produced in high yield, and is further converted to 4-hydroxy-6-methyl-13- (4-methylpentanoyl) -12-pyrone represented by the formula (1), whereby the active ingredient of the insecticide is obtained.
  • An object of the present invention is to provide a method for industrially and advantageously producing the compound 4-hydroxy-16-methyl-3- (4-methylpentanoyl) -1-pyrone.
  • the 3-acetyl-4-hydroxy-6-methyl-1-pyrone and isobutyl aldehyde represented by the formula are represented by the formula R 1 R 2 NH (wherein R 1 and R 2 each represent a linear C1-C4 alkyl group).
  • molecular sieves 3A powder is preferably used as the molecular sieve.
  • the amount of molecular sieves used in the reaction is usually 0.5 to 4 parts by weight, preferably 0.5 to 3 parts by weight, based on 1 part by weight of 3-acetyl-14-hydroxy-6-methyl-2-pyrone. Is the ratio of
  • Examples of the secondary amine which can be used in the reaction include getylamine, methylethylamine, dipropylamine and dibutylamine.
  • the reaction temperature of the reaction is set at a low temperature, which requires a longer time to complete the first process.
  • the temperature is set at a high temperature, the yield of the desired product tends to decrease. It is in the range of 5-25 ° C, preferably in the range of 15-20 ° C, more preferably in the range of 0-10 ° C.
  • the reaction between 3-acetyl-4-hydroxy-16-methyl-1-pyrone and isobutyraldehyde can be carried out without a solvent, but is usually carried out in a solvent.
  • the solvent used in the reaction is not particularly limited as long as it is a solvent inert to the reaction, but the use of tetrahydrofuran, methyl isobutyl ketone or acetone is preferred from the viewpoint of yield.
  • the reaction time required for the first process is usually 0.5 to 24 hours.
  • the molecular sieves are removed by filtration, and the filtrate is subjected to a normal post-treatment operation such as extraction of an organic solvent and concentration to obtain 4-hydroxy-16-methyl-3-.
  • (4-Methyl-2-pentyl) -1-pyrone can be isolated. Further, if necessary, it can be purified by recrystallization, chromatography or the like.
  • the reduction reaction of the second process is usually carried out in a solvent in the presence of a transition metal catalyst, in a solvent, with 4-hydroxy-16-methyl-1- (4-methyl-12-pentenyl) -12-pyrone and hydrogen.
  • the reaction is carried out.
  • the solvent used in the reaction is a solvent inert to the reduction reaction, and examples thereof include esters such as ethyl acetate and butyl acetate, ketones such as methyl isobutyl ketone, and aromatic hydrocarbons such as toluene. .
  • transition metal catalyst examples include a palladium catalyst and a platinum catalyst, and more specific examples include palladium-carbon and platinum oxide.
  • the amount of the transition metal catalyst to be used is usually a ratio of 100 parts by weight to 100 parts by weight of 4-hydroxy-16-methyl-13- (4-methyl-2-pentenyl) -12-pyrone.
  • the reaction time required for the second process is usually 0.5 to 24 hours.
  • reaction mixture is filtered to remove the catalyst, and the filtrate is subjected to ordinary post-treatment operations such as extraction with an organic solvent and concentration to give 4-hydroxy-6-methyl-3- (4-methylpentanoyl).
  • ordinary post-treatment operations such as extraction with an organic solvent and concentration to give 4-hydroxy-6-methyl-3- (4-methylpentanoyl).
  • L) It is possible to isolate 1-2-pyrone. Further, if necessary, it can be purified by distillation, chromatography, crystallization, amine salt crystallization, or the like.
  • 3-acetyl-4-hydroxy-6-methyl-1-pyrone 3.Og, isobutyraldehyde 1.9g and molecular sieves 3A powder 3.Og were added to 15ml of dry tetrahydrofuran 15ml, and getylamine at 0-5 ° C under stirring. 0.53 g of a 1 Oml solution of dry tetrahydrofuran was added dropwise over about 1 hour. After the dropwise addition, the mixture was further stirred at 0 to 5 ° C for 2 hours. Thereafter, the reaction mixture was filtered through celite, and the celite was washed with 50 ml of ethyl acetate.
  • House flies (M / sca io / 7? Esi / a) 10 adults (5 males and 5 females) were released into a cubic glass chamber (0.34 m 3 in volume) with a side of 70 cm. 0.7 ml of the oil was sprayed into the chamber at a pressure of 0.9 kgZcm 2 with a spray gun from a small window on one side of the chamber. Fifteen minutes later, the state of the housefly knockdown was observed. As a result of two replicate tests, the knockdown rate was 95%.
  • the present invention advantageously produces 4-hydroxy-6-methyl-1- (4-methyl-2-pentanoyl) -12-pyrone and 4-hydroxy-16-methyl-3- (4-methylpentenyl) -12-pyrone. These compounds are useful as an active ingredient of an insecticide or an intermediate in the production thereof.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé relatif à l'élaboration de 4-hydroxy-6-méthyl-3-(4-méthyl-2-penténoyl)-2-pyrone par réaction entre 3-acétyl-4-hydroxy-6-méthyl-2-pyrone et isobutyraldéhyde, en présence d'amine secondaire de formule générale R?1R2NH (R1 et R2¿ étant chacun alkyle C¿1-4? linéaire) et d'un tamis moléculaire à une température comprise entre -5 et 25 ° C. L'invention concerne également un procédé relatif à l'élaboration de 4-hydroxy-6-méthyl-3-(4-méthylpentanoyl)-2-pyrone par réduction de 4-hydroxy-6-méthyl-3-(4-méthyl-2-penténoyl)-2-pyrone. On peut ainsi préparer avantageusement des principes actifs d'insecticides ou des intermédiaires pour l'élaboration de ces produits.
PCT/JP2001/005681 2000-07-12 2001-06-29 Procedes relatifs a l'elaboration de composes a base de pyrone WO2002004436A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001266362A AU2001266362A1 (en) 2000-07-12 2001-06-29 Processes for the preparation of pyrone compounds

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2000211001 2000-07-12
JP2000337153 2000-11-06
JP2000-337153 2000-11-06
JP2000-211001 2000-11-06

Publications (1)

Publication Number Publication Date
WO2002004436A1 true WO2002004436A1 (fr) 2002-01-17

Family

ID=26595866

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2001/005681 WO2002004436A1 (fr) 2000-07-12 2001-06-29 Procedes relatifs a l'elaboration de composes a base de pyrone

Country Status (2)

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AU (1) AU2001266362A1 (fr)
WO (1) WO2002004436A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8090341B2 (en) 2005-07-18 2012-01-03 Telecommunication Systems, Inc. Integrated services user part (ISUP) /session initiation protocol (SIP) gateway for unlicensed mobile access (UMA) emergency services call flow

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS411412B1 (fr) * 1963-02-27 1966-02-03

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS411412B1 (fr) * 1963-02-27 1966-02-03

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8090341B2 (en) 2005-07-18 2012-01-03 Telecommunication Systems, Inc. Integrated services user part (ISUP) /session initiation protocol (SIP) gateway for unlicensed mobile access (UMA) emergency services call flow

Also Published As

Publication number Publication date
AU2001266362A1 (en) 2002-01-21

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