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 PDFInfo
- 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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- WIPO (PCT)
- Prior art keywords
- formula
- palladium
- malononitrile
- preparation
- phosphine
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 37
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 35
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- QORFOTVNIVMCMZ-UHFFFAOYSA-N 2-(4-chloro-2,6-dimethylphenyl)propanedinitrile Chemical compound ClC1=CC(=C(C(=C1)C)C(C#N)C#N)C QORFOTVNIVMCMZ-UHFFFAOYSA-N 0.000 claims description 17
- RAVACSWYIIPFFV-UHFFFAOYSA-N tris[(4-methoxyphenyl)methyl]phosphane Chemical compound C1=CC(OC)=CC=C1CP(CC=1C=CC(OC)=CC=1)CC1=CC=C(OC)C=C1 RAVACSWYIIPFFV-UHFFFAOYSA-N 0.000 claims description 17
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 16
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 10
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- -1 p-anisyl Chemical group 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- NNWUVWYOMJOQCI-UHFFFAOYSA-N 2-(4-chloro-2,6-diethylphenyl)propanedinitrile Chemical compound ClC1=CC(=C(C(=C1)CC)C(C#N)C#N)CC NNWUVWYOMJOQCI-UHFFFAOYSA-N 0.000 claims description 4
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 claims description 4
- 241000251730 Chondrichthyes Species 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- CFMPIQSLDJXNPD-UHFFFAOYSA-N 2-bromo-5-chloro-1,3-dimethylbenzene Chemical compound CC1=CC(Cl)=CC(C)=C1Br CFMPIQSLDJXNPD-UHFFFAOYSA-N 0.000 description 3
- 0 C*1(c(c(C)c2)c(C)cc2Cl)Br*(C)(c(c(C)c2)c(C)cc2Cl)Br1 Chemical compound C*1(c(c(C)c2)c(C)cc2Cl)Br*(C)(c(c(C)c2)c(C)cc2Cl)Br1 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 3
- 229910000364 palladium(II) sulfate Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000012041 precatalyst Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- RUKJCCIJLIMGEP-ONEGZZNKSA-N 4-dimethylaminocinnamaldehyde Chemical compound CN(C)C1=CC=C(\C=C\C=O)C=C1 RUKJCCIJLIMGEP-ONEGZZNKSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical class CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 150000004768 bromobenzenes Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical class C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 description 1
- BSFVCIYREAMMOJ-UHFFFAOYSA-N tris[(2-methoxyphenyl)methyl]phosphane Chemical compound COC1=CC=CC=C1CP(CC=1C(=CC=CC=1)OC)CC1=CC=CC=C1OC BSFVCIYREAMMOJ-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- 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.
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 |
Family
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PCT/EP2018/061800 WO2018210616A1 (fr) | 2017-05-15 | 2018-05-08 | Procédé pour la préparation de (4-halogéno-2,6-dialkylphényl)malononitriles |
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TW (1) | TW201904936A (fr) |
WO (1) | WO2018210616A1 (fr) |
Citations (5)
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 |
-
2018
- 2018-05-08 WO PCT/EP2018/061800 patent/WO2018210616A1/fr active Application Filing
- 2018-05-11 TW TW107116041A patent/TW201904936A/zh unknown
Patent Citations (5)
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)
Title |
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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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