EP4028390A1 - Procédé amélioré de préparation d'époxydes à partir d'aldéhydes ou de cétones - Google Patents

Procédé amélioré de préparation d'époxydes à partir d'aldéhydes ou de cétones

Info

Publication number
EP4028390A1
EP4028390A1 EP20775207.2A EP20775207A EP4028390A1 EP 4028390 A1 EP4028390 A1 EP 4028390A1 EP 20775207 A EP20775207 A EP 20775207A EP 4028390 A1 EP4028390 A1 EP 4028390A1
Authority
EP
European Patent Office
Prior art keywords
formula
sulfonium salt
ketone
compound
iii
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.)
Pending
Application number
EP20775207.2A
Other languages
German (de)
English (en)
Inventor
Andre GROSSMANN
Björn SCHLUMMER
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.)
Syngenta Crop Protection AG Switzerland
Original Assignee
Saltigo GmbH
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 Saltigo GmbH filed Critical Saltigo GmbH
Publication of EP4028390A1 publication Critical patent/EP4028390A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/02—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms
    • C07C317/04—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/32—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms

Definitions

  • the invention relates to an improved process for the production of epoxides from aldehydes or ketones by reacting a ketone or aldehyde with at least one sulfonium salt, as well as sulfonium salts which are used in the process according to the invention.
  • Reactions of this type are also known under the name reactions Corey-Chaykovsky reaction (L. Kurti, B. Czako, “Strategy Applications of Named Reactions in Organic Synthesis”).
  • the epoxidation of the ketone or aldehyde takes place via a sulfur ylide intermediate, which can be generated from a sulfonium salt.
  • the sulfonium salts used for this are usually produced from a dialkyl sulfide and an alkylating agent such as dimethyl sulfate or alkyl halides.
  • the invention also relates to sulfonium salts which can be used in the process according to the invention.
  • the epoxides produced by the process according to the invention are, for example, intermediate or final stages for various commercial applications, such as, for example, agrochemicals.
  • the compound of the formula (IV) is, for example, an intermediate for the azole fungicide cyproconazole (DE 3406993 A1).
  • 2- (4-chloropheny) -2- (1-cyclopropyl-ethyl) -oxirane from 1 - (4-chlorophenyl) -2-cyclopropyl-propanone-1 in the presence of dodecyldimethylsulfonium methyl sulfate and potassium hydroxide in one yield described by 25% of theory.
  • EP 0205400 A2 describes the preparation of 2-propyloxirane from butyraldehyde in the presence of hexyldimethylsulfonium methyl sulfate and sodium hydroxide in yields of 70 to 80% of theory.
  • dialkyl sulfides e.g. dodecyl methyl sulfide or hexyl methyl sulfide
  • dialkyl sulfides e.g. dodecyl methyl sulfide or hexyl methyl sulfide
  • dialkyl sulfides such as dimethyl sulfide
  • the disadvantage that they have a significantly lower reactivity in this type of reaction which has significant economic disadvantages.
  • X 2 SY + Z- (II) is reacted, wherein in formula (I) and formula (II) X for methyl and Y for linear C2 to Cu -alkyl, preferably for n-ethyl, n-propyl, n-butyl , n-pentyl, n-heptyl, n-octyl, n-nonyl, n-decyl and n-undecyl, and in which in formula (II) Z is chloride, bromide, iodide or carbonate, in the presence of a base, preferably alkali metal hydroxide, particularly preferably sodium hydroxide or potassium hydroxide.
  • a base preferably alkali metal hydroxide, particularly preferably sodium hydroxide or potassium hydroxide.
  • the aldehydes or ketones used in the context of the invention are organic compounds which have at least one carbon-oxygen double bond.
  • the aldehydes or ketones can be linear, branched or cyclic.
  • the aldehydes or ketones used in the process according to the invention can carry further substituents such as further aliphatic or aromatic radicals, which in turn may or may not also be substituted.
  • the ketone is the compound of the formula (III),
  • the sulfonium salt of the formula (I) is usually in situ, i.e. during the process, by the reaction of a dialkyl sulfide of the formula (V),
  • the dialkyl sulfide of the formula (V) is usually used in a slight molar excess, for example from 1.01 to 1.2 mol, preferably from 1.01 to 1.15 mol of dialkyl sulfide, based on 1.00 mol of dimethyl sulfate. Since this reaction is exothermic, the temperature of the initially charged dialkyl sulfide of the formula (I) and / or that of the reaction mixture can also be below 50 ° C. at the beginning of the reaction. The addition of dimethyl sulfate increases the temperature of the reaction mixture even without additional heat being supplied.
  • the sulfonium salt obtained in this way can either be used directly in the process according to the invention or can also be stored.
  • the sulfonium salt of the formula (II) is also usually in situ, ie during the process, by the reaction of a dialkyl sulfide of the formula (V) in which X and Y have the same meaning as in formula (I) and Z is chloride, bromide or iodide is generated with a methyl halide, for example methyl chloride, methyl bromide or methyl iodide.
  • the dialkyl sulfide is usually used in a slight molar excess, for example from 1.01 to 1.2 mol, preferably from 1.01 to 1.15 mol of dialkyl sulfide, based on 1.00 mol of methyl halide.
  • the sulfonium salt of the formula (II), in which X and Y have the same meaning as in formula (I) and Z stands for carbonate, is also usually in situ, ie during the process, by the reaction of a dialkyl sulfide of the formula (V) with Dimethyl carbonate generated.
  • the dialkyl sulfide is usually used in a slight molar excess, for example from 1.01 to 1.2 mol, preferably from 1.01 to 1.15 mol of dialkyl sulfide, based on 1.00 mol of dimethyl carbonate.
  • the sulfonium salts of the formula (I) or of the formula (II) are preferably prepared in a separate reactor, preferably the first reactor (A), particularly preferably in the amount required for the respective reaction of the aldehyde or ketone, preferably the compound of Formula (III) is required.
  • the sulfonium salt of the formula (I) or of the formula (II) is therefore used as a melt or as a solution.
  • the ketone or aldehyde preferably the compound of the formula (III)
  • the process according to the invention is preferably carried out at least in the presence of the dialkyl sulfide of the formula (V) as solvent.
  • dialkyl sulfide of the formula (V) are used as the solvent, based on the ketone or the aldehyde, preferably based on the compound of the formula (III) .
  • the process according to the invention can also be carried out in the presence of other solvents, for example toluene, xylene, chlorobenzene, water, preferably xylene, mixtures thereof or mixtures of these solvents with dialkyl sulfide of the formula (V).
  • solvents for example toluene, xylene, chlorobenzene, water, preferably xylene, mixtures thereof or mixtures of these solvents with dialkyl sulfide of the formula (V).
  • the process according to the invention is carried out in the presence of a base, preferably in the presence of alkali metal hydroxide, furthermore preferably in the presence of sodium hydroxide or potassium hydroxide.
  • a base preferably in the presence of alkali metal hydroxide, furthermore preferably in the presence of sodium hydroxide or potassium hydroxide.
  • Potassium hydroxide is particularly preferably used as the base.
  • This can, for example, be potassium hydroxide in solid form, preferably as flakes, powder, or as a solution, particularly preferably as flakes.
  • base preferably alkali metal hydroxide, furthermore preferably sodium hydroxide or preferably potassium hydroxide, based on the aldehyde or the ketone, preferably based on the compound of the formula (III), are used.
  • per mole of ketone or aldehyde preferably per mole of the compound of the formula (III), from 1.0 to 2 mol, preferably from 1.0 to 1.3 mol, of the sulfonium salt of the formula (I) or (II) used.
  • the reaction is usually carried out at temperatures from 20 to 100.degree. C., preferably from 30 to 60.degree.
  • reaction of the aldehyde or ketone, preferably the compound of the formula (III), with the sulfonium salt of the formula (I) or the formula (II) takes place in a second reactor (B).
  • the reaction of the aldehyde or ketone, preferably the compound of the formula (III) is carried out in the presence of a solvent
  • the solvent preferably the dialkyl sulfide of the formula (V)
  • from 0.05 to 0.2 mol of water per mole of aldehyde or ketone, preferably per mole of the compound of the formula (III) may be added.
  • the alkali metal hydroxide preferably potassium hydroxide or sodium hydroxide
  • the reaction mixture preferably the reaction mixture in the second reactor (B)
  • the reaction mixture preferably the reaction mixture in the second reactor (B)
  • the reactor preferably the second reactor (B)
  • the sulfonium salt of the formula (I) or the formula (II) is then added, preferably from the first reactor (A), to the reaction mixture, preferably to the reaction mixture in the second reactor (B).
  • the addition is usually carried out within 0.5 to 3 hours, preferably from 0.75 to 2 hours.
  • the temperature of the reaction mixture is kept in a range from 30 to 50.degree. C., preferably from 35 to 45.degree.
  • the reaction mixture preferably the reaction mixture in the second reactor (B) is after the addition of the amount of the sulfonium salt of the formula (I) or the formula (II), usually from 1 to 4 hours at a temperature of the reaction mixture of 30 to 50 ° C, preferably from 35 to 45 ° C held.
  • the reaction mixture is preferably mixed mechanically or hydraulically during and after the addition of the sulfonium salt of the formula (I) or of the formula (II) in such a way that the result is as homogeneous a mixture as possible.
  • the progress of the reaction can be determined by analyzing samples that have been worked up like the reaction mixture.
  • the content of educt and product can usually be determined by means of HPLC or gas chromatography, either as a percentage by area without an external standard or as a percentage by weight with an external standard.
  • the reaction mixture is preferably hydrolyzed with water.
  • a third reactor (C) 1 to 2 kg, preferably 1.2 to 1.5 kg, of water based on 1 kg of aldehyde or ketone used, preferably based on 1 kg of compound of the formula ( III), are mixed with the reaction mixture, preferably with the reaction mixture in the second reactor (B).
  • Mixing is preferably carried out with mechanical and / or hydraulic mixing.
  • the water is particularly preferably initially taken, preferably in the third reactor (C), and the reaction mixture is added, preferably from the second reactor (B).
  • the lower aqueous phase can then be drained, preferably from the second reactor (B), and then the upper organic phase, preferably from the second reactor (B), can be transferred into a further reactor, preferably into the third reactor (C) .
  • Low-boiling portions of the reaction mixture can then be separated off by distillation from the upper organic phase. This is preferably done at a pressure of 5 to 20 hPa, particularly preferably 7 to 12 hPa.
  • a low-boiling fraction for example up to a bottom temperature of 91 ° C. at 10 hPa, is first distilled off.
  • n-butyl methyl sulfide is then distilled off, for example up to a bottom temperature of 91 ° C. at 10 hPa. This recovered n-butyl methyl sulfide can be reused in a next reaction of the same type.
  • the fraction remaining as the bottom of the distillation contains, as reaction product, the epoxide, preferably the epoxide of the formula (IV), usually with a content of greater than 85% by weight, preferably with a content of at least 90% by weight, in yields of 93 to 100 % of theory.
  • the product can usually be used as a starting material in a chemical reaction without further purification or work-up.
  • the epoxide of the formula (IV) is usually used in an epoxide opening with triazole to form cyproconazole.
  • epoxides preferably the compound of formula (IV)
  • an aldehyde or ketone preferably from the compound of the formula (III).
  • the invention also relates to the sulfonium salts of the formula (I) and of the formula (II) which are used in the process according to the invention.
  • the invention further relates to the use of the sulfonium salts of the formula (I) and of the formula (II) in the process according to the invention for the preparation of epoxides.
  • n-butyl methyl sulfide content: at least 90% by weight
  • 3157 g of 2- (4-chloropheny) -2- (1-cyclopropyl-ethyl) oxirane compound of Formula (IV)] (content: 90% by weight, yield: 96.6% of theory) remained in the bottom.
  • the recovered n-butyl methyl sulfide can be reused in a next reaction for the production of 2- (4-chloropheny) -2- (1-cyclopropyl-ethyl) -oxirane.

Landscapes

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

Abstract

L'invention concerne un procédé amélioré de préparation d'époxydes à partir d'aldéhydes ou de cétones par réaction d'une cétone ou d'un aldéhyde avec au moins un sel de sulfonium, et des sels de sulfonium qui peuvent être utilisés dans le procédé selon l'invention.
EP20775207.2A 2019-09-12 2020-09-09 Procédé amélioré de préparation d'époxydes à partir d'aldéhydes ou de cétones Pending EP4028390A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19196907 2019-09-12
PCT/EP2020/075210 WO2021048212A1 (fr) 2019-09-12 2020-09-09 Procédé amélioré de préparation d'époxydes à partir d'aldéhydes ou de cétones

Publications (1)

Publication Number Publication Date
EP4028390A1 true EP4028390A1 (fr) 2022-07-20

Family

ID=67953613

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20775207.2A Pending EP4028390A1 (fr) 2019-09-12 2020-09-09 Procédé amélioré de préparation d'époxydes à partir d'aldéhydes ou de cétones

Country Status (6)

Country Link
US (1) US20220332691A1 (fr)
EP (1) EP4028390A1 (fr)
CN (1) CN114401950A (fr)
CA (1) CA3153841A1 (fr)
MX (1) MX2022002846A (fr)
WO (1) WO2021048212A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2023002804A (es) * 2022-03-09 2023-09-11 Upl Ltd Un proceso para la preparación de compuesto de triazol.

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998856A (en) * 1975-04-10 1976-12-21 Hoffmann-La Roche Inc. Preparation of epoxides
EP0079972B1 (fr) * 1981-11-19 1985-05-02 C.F. Spiess & Sohn GmbH & Co. Chemische Fabrik Procédé pour la production de montmorrillonites tertiaires de sulfonium et leur utilisation
CH658654A5 (de) 1983-03-04 1986-11-28 Sandoz Ag Azolderivate, verfahren zu ihrer herstellung und mittel die diese verbindungen enthalten.
EP0205400A3 (fr) * 1985-06-03 1987-10-14 Ciba-Geigy Ag Procédé pour la préparation d'alcoyloxirannes
WO2010142779A1 (fr) * 2009-06-12 2010-12-16 Basf Se Dérivés antifongiques de 1,2,4-triazolyle ayant un substituant soufré en 5

Also Published As

Publication number Publication date
WO2021048212A1 (fr) 2021-03-18
US20220332691A1 (en) 2022-10-20
BR112022004259A2 (pt) 2022-05-31
CN114401950A (zh) 2022-04-26
CA3153841A1 (fr) 2021-03-18
MX2022002846A (es) 2022-04-06

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