WO2018210616A1 - Procédé pour la préparation de (4-halogéno-2,6-dialkylphényl)malononitriles - Google Patents

Procédé pour la préparation de (4-halogéno-2,6-dialkylphényl)malononitriles Download PDF

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Publication number
WO2018210616A1
WO2018210616A1 PCT/EP2018/061800 EP2018061800W WO2018210616A1 WO 2018210616 A1 WO2018210616 A1 WO 2018210616A1 EP 2018061800 W EP2018061800 W EP 2018061800W WO 2018210616 A1 WO2018210616 A1 WO 2018210616A1
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WO
WIPO (PCT)
Prior art keywords
formula
palladium
malononitrile
preparation
phosphine
Prior art date
Application number
PCT/EP2018/061800
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German (de)
English (en)
Inventor
Thomas Himmler
Christian Funke
Matthias Beller
Anahit PEWS-DAVTYAN
Helfried Neumann
Original Assignee
Bayer Cropscience Aktiengesellschaft
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Filing date
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Application filed by Bayer Cropscience Aktiengesellschaft filed Critical Bayer Cropscience Aktiengesellschaft
Publication of WO2018210616A1 publication Critical patent/WO2018210616A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • 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
    • C07C255/35—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 halogen atoms, or by nitro or nitroso groups

Definitions

  • the present invention relates to a process for the preparation of (4-halo-2,6-dialkylphenyl) malononitriles of the general formula (I).
  • (4-Halogen-2,6-dialkylphenyl) malononitriles of the general formula (I) are important intermediates for the preparation of bioactive compounds which can be used especially for the control of pests in plant protection.
  • they are used for the preparation of insecticidal, acaricidal or herbicidal cyclic ketoenols (for example WO2006 / 089633), from these (4-halo-2,6-dialkylphenyl) malononitriles the corresponding (4-halo-2,6-dialkylphenyl) acetic acids and from them the (4-halo-2,6-dialkylphenyl) acetic acid chlorides are produced.
  • the present invention therefore includes a novel process for the preparation of (4-halo-2,6-dialkylphenyl) malononitriles of the formula (I)
  • R 1 and R 2 independently of one another are C 1 -C 6 -alkyl and
  • R 1 and R 2 independently of one another are C 1 -C 6 -alkyl and Hal is chlorine.
  • R 1 and R 2 are independently methyl or ethyl and Hal is chloro.
  • Suitable solvents and diluents in the preparation of the compounds of the formula (I) are, for example: nitriles, for example acetonitrile, propionitrile, butyronitrile or benzonitrile; Ethers such as, for example, methyl tert-butyl ether, cyclopentyl methyl ether, tert-amyl methyl ether, 1,2-dimethoxyethane, diethylene glycol diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane; N-substituted lactams such as N-methyl-pyrrolidone (NMP); Amides such as ⁇ , ⁇ -dimethylformamide (DMF) or ⁇ , ⁇ -dimethylacetamide (DMAC); Sulfoxides such as dimethylsulfoxide (DMSO); Sulfones such as sulfolane; or mixtures of these solvents and
  • Preferred solvents and diluents are nitriles, for example acetonitrile, propionitrile, butyronitrile or benzonitrile; N-substituted lactams such as N-methyl-pyrrolidone (NMP); Amides such as ⁇ , ⁇ -dimethylformamide (DMF) or ⁇ , ⁇ -dimethylacetamide (DMAC); Sulfoxides such as dimethylsulfoxide (DMSO); or mixtures of these solvents and diluents.
  • NMP N-substituted lactams
  • NMP N-methyl-pyrrolidone
  • Amides such as ⁇ , ⁇ -dimethylformamide (DMF) or ⁇ , ⁇ -dimethylacetamide (DMAC)
  • Sulfoxides such as dimethylsulfoxide (DMSO); or mixtures of these solvents and diluents.
  • NMP N-methyl-pyrrolidone
  • DMSO Dimethyl sulfoxide
  • DMAC ⁇ , ⁇ -dimethylacetamide
  • the base used is an alkali metal hydroxide LiOH, NaOH, KOH, RbOH or CsOH. Preference is given to using NaOH or KOH; especially preferred is NaOH.
  • the alkali metal hydroxide can be used as a solid or as an aqueous solution.
  • an aqueous solution the water must be removed from the reaction mixture, for example by distillation. Preference is therefore given to the use of the alkali metal hydroxide as a preferably water-poor solid, for example in the case of NaOH in the form of so-called microprills.
  • the amount of alkali metal hydroxide relative to malononitrile is between 1 and 5 moles per mole; preferably between 1.5 and 5 moles per mole.
  • the reaction temperature in the first step of the process according to the invention is between 50 and 200.degree. C., preferably between 75 and 150.degree.
  • the reaction water resulting from the reaction of malononitrile with the alkali metal hydroxide is removed in a second step of the process according to the invention.
  • This removal of water can be done in different ways; For example, by adding water-binding agents such as dried molecular sieve, or by distilling off the water alone or in admixture with the solvent.
  • the water is removed by distillation.
  • Particularly preferred is a Distilled off amount of solvent / W ater mixture corresponding to between 40 and 70% of the original amount of solvent.
  • Suitable palladium catalysts for the reaction of the anion of the malononitrile generated with the base with the bromoaromatic compound of the formula (II) are both palladium precatalysts in combination with suitable phosphine ligands and already preformed palladium-ligand complexes.
  • Suitable catalysts are, for example, bis (triphenylphosphine) palladium (II) chloride, bis (tri-para-tolylphosphine) palladium (II) chloride, bis (tri-para-anisylphosphine) palladium (II) chloride, tetrakis ( triphenylphosphine) palladium (0), palladium (II) chloride, palladium (II) acetate, palladium (II) nitrate, palladium (II) sulfate, palladium (II) acetylacetonate, bis (dibenzylideneacetone) palladium (O) or complex of the formula (III).
  • palladium (II) chloride palladium (II) acetate, palladium (II) nitrate, palladium (II) acetylacetonate, tetrakis (triphenylphosphine) palladium (0), bis (tri-para-anisylphosphine) palladium (II) chloride or complex of formula (III).
  • Particularly preferred are palladium (II) nitrate, palladium (II) acetylacetonate, bis (tri-para-anisylphosphine) palladium (II) chloride or complex of the formula (III).
  • Emphasized are palladium (II) nitrate, palladium (II) acetylacetonate or complex of the formula (III).
  • L is triphenylphosphine, tri (para-tolyl) phosphine or tri (para-anisyl) phosphine; preferably L is triphenylphosphine or tri (para-anisyl) phosphine; most preferably L is tri (para-anisyl) phosphine (P (p-anisyl) 3 ).
  • the palladium catalyst from a precatalyst and a phosphine ligand in particular the combinations of palladium (II) chloride, Palladium (II) acetate, palladium (II) nitrate, palladium (II) sulfate, palladium (II) acetylacetonate, bis (dibenzylideneacetone) palladium (O) or complex of the formula (III) with the phosphine ligands triphenylphosphine, tri (para -tolyl) phosphine or tri (para-anisyl) phosphine in question.
  • the molar ratios of phosphine ligand to palladium are usually in the range between 1 and 20; preferably between 1 and 10.
  • the molar ratio of malononitrile to bromoaromatic compound of the formula (II) is usually between 0.9 and 2; preferably between 1 and 1.5.
  • the reaction temperature in the third process step of the invention is between 50 and 200 ° C; preferably between 75 and 150 ° C.
  • the reaction time in the third process step is between 1 and 24 hours.
  • the entire process is preferably carried out in an inert atmosphere, this being preferably prepared by inerting with nitrogen or argon.
  • reaction mixtures The work-up of the reaction mixtures is carried out by customary and known methods of organic chemistry.
  • a mixture of 1.52 g (23 mmol) of malononitrile and 2 g (50 mmol) of NaOH (in the form of microprills) in 24 ml of DMAC is heated at 90 ° C. for 1 hour. Subsequently, about 17 ml of DMAC / water mixture are distilled off at 25-30 mbar and replaced with fresh DMAC. Thereafter, 4.39 g (20 mmol) of 4-chloro-2,6-dimethylbromobenzene, 3.05 mg (0.05 mol%) of pdacac 2 and 28.2 mg (0.4 mol%) of tri (para -anisyl) phosphine. The mixture is heated for 11 hours at 125 ° C and then analyzed by gas chromatography. The yield of the target compound is 89% of theory.
  • Example 7 (4-Chloro-2,6-dimethylphenyl) malononitrile

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

Abstract

L'invention concerne un procédé pour la préparation de (4-halogéno-2,6-dialkylphényl)malononitriles de formule (I) par transformation d'aromatiques bromés de formule (II) avec du malononitrile en présence d'une base, d'un composé à base de palladium et d'un ligand de type phosphine, dans lequel, dans une première étape de procédé, on transforme d'abord l'un avec l'autre, uniquement, le malononitrile et la base et ensuite, dans une deuxième étape de procédé, on élimine par distillation l'eau de réaction le cas échéant formée conjointement avec une partie du solvant ou du diluant avant d'ajouter, dans la troisième étape de procédé, l'aromatique bromé de formule (II), le catalyseur à base de palladium et le ligand de type phosphine. En outre, l'invention concerne de nouveaux (4-halogéno-2,6-dialkylphényl)malononitriles de formule (I) et un nouveau complexe à base de palladium de formule (III) et son utilisation comme catalyseur.
PCT/EP2018/061800 2017-05-15 2018-05-08 Procédé pour la préparation de (4-halogéno-2,6-dialkylphényl)malononitriles WO2018210616A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17171024 2017-05-15
EP17171024.7 2017-05-15

Publications (1)

Publication Number Publication Date
WO2018210616A1 true WO2018210616A1 (fr) 2018-11-22

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TW (1) TW201904936A (fr)
WO (1) WO2018210616A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000078712A1 (fr) 1999-06-16 2000-12-28 Syngenta Participations Ag Dinitriles d'acide arylmalonique substitue comme intermediaires de preparation d'herbicides
WO2004050607A1 (fr) 2002-12-05 2004-06-17 Syngenta Participations Ag Procede de preparation de dinitriles d'acide phenylmalonique
WO2006089633A2 (fr) 2005-02-22 2006-08-31 Bayer Cropscience Ag Cetoenols cycliques substitues par spirocetal
WO2015161224A1 (fr) * 2014-04-17 2015-10-22 Merial, Inc. Utilisation de composés de malononitrile pour protéger des animaux contre les parasites
WO2018015489A1 (fr) 2016-07-22 2018-01-25 Syngenta Participations Ag Procédé pour la préparation d'acide phenylmalonic dinitriles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000078712A1 (fr) 1999-06-16 2000-12-28 Syngenta Participations Ag Dinitriles d'acide arylmalonique substitue comme intermediaires de preparation d'herbicides
WO2004050607A1 (fr) 2002-12-05 2004-06-17 Syngenta Participations Ag Procede de preparation de dinitriles d'acide phenylmalonique
WO2006089633A2 (fr) 2005-02-22 2006-08-31 Bayer Cropscience Ag Cetoenols cycliques substitues par spirocetal
WO2015161224A1 (fr) * 2014-04-17 2015-10-22 Merial, Inc. Utilisation de composés de malononitrile pour protéger des animaux contre les parasites
WO2018015489A1 (fr) 2016-07-22 2018-01-25 Syngenta Participations Ag Procédé pour la préparation d'acide phenylmalonic dinitriles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PAUL F ET AL: "structural charachterization and simple synthesis of {Pd[P(o-Tol)3]2},dimeric Palladium(II) complexes obtained by oxidative addition of aryl bromides, and corresponding monometallic amine complexes", ORGANOMETALLICS, AMERICAN CHEMICAL SOCIETY, US, vol. 14, 1 January 1995 (1995-01-01), pages 3030 - 3039, XP002358606, ISSN: 0276-7333, DOI: 10.1021/OM00006A053 *

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