WO1994000423A1 - Procede de couplage croise d'acides boriques avec des composes halogenes - Google Patents

Procede de couplage croise d'acides boriques avec des composes halogenes Download PDF

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Publication number
WO1994000423A1
WO1994000423A1 PCT/EP1993/001432 EP9301432W WO9400423A1 WO 1994000423 A1 WO1994000423 A1 WO 1994000423A1 EP 9301432 W EP9301432 W EP 9301432W WO 9400423 A1 WO9400423 A1 WO 9400423A1
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WO
WIPO (PCT)
Prior art keywords
independently
general formula
diyl
radical
boronic
Prior art date
Application number
PCT/EP1993/001432
Other languages
German (de)
English (en)
Inventor
Kay-Uwe Klabunde
Hans Witzel
Volker Meyer
Eike Poetsch
Original Assignee
Merck Patent 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 Merck Patent Gmbh filed Critical Merck Patent Gmbh
Priority to KR1019940700482A priority Critical patent/KR100266113B1/ko
Priority to EP93912904A priority patent/EP0601156A1/fr
Priority to JP50198094A priority patent/JP3833698B2/ja
Publication of WO1994000423A1 publication Critical patent/WO1994000423A1/fr

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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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

Definitions

  • the invention relates to a method for cross-coupling boronic acids with halogen compounds using a metallic palladium catalyst for the preparation of compounds of general formula I.
  • R 1 and R 2 each independently of one another are an unsubstituted or at least one halogen-substituted alkyl, alkoxy or alkenyl radical having 1 to 15 carbon atoms, one or more CH 2 groups in these radicals also being each independently O-, -S-, .
  • R 2 also -H, -CN, -NCS, - Cl, -F, -CF 3 , -OCF 3 , -OCF 2 H or -OC 2 F 5 , -NH 2 , -COOH, -OH or -OCH 2 Ph, A 1 , A 2 and
  • a 3 each independently
  • x 3 and x 4 mean independently of one another R 1 or R 2 .
  • Z 1 and Z 2 each independently of one another -CO-O-, -O-CO-,
  • a difluorobenzene is reacted with butyllithium or lithium diisopropylamide in the presence of trimethyl borate and in a second stage the boronic acid obtained with a difluorobromobenzene in the presence of tetrakis (triphenylphosphine) palladium - (o) and an aqueous sodium carbonate solution mixed with toluene converted into a compound according to general formula I.
  • a difluorobenzene is lithiated with butyllithium at -78 ° C and then iodized at the same temperature.
  • the difluoroiodobenzene obtained is then reacted with a boronic acid in the presence of tetrakis (triphenylphosphine) palladium - (O) and an aqueous sodium carbonate solution in a mixture with toluene.
  • the object of the invention is to provide a method for cross-coupling boronic acids or boric acids with olefinic or aromatic halogen compounds, which does not have the disadvantages of the previously used method and can be carried out on a large scale on an economical and risk-free basis. This object was achieved according to the invention by a process for the preparation of compounds of the general formula I.
  • R 1 and R 2 each independently of one another are an unsubstituted or at least one halogen-substituted alkyl, alkoxy or alkylene radical having 1 to 15 carbon atoms, one or more CH 2 groups in these radicals each being independently of one another by —O -, -S-,
  • R 2 also -H, -CN, -NCS, -NH 2 , -Cl, -F, -CF 3 , -OCF 3 , -OCF 2 H or
  • Z 1 and Z 2 each independently of one another -CO-O-, -O-CO-,
  • x 1 , x 2 , x 3 , x 4 , R 1 , R 2 , A 1 , Z 1 and n have the meaning given above and a chlorine, bromine or iodine compound general formula III wherein
  • Y is Cl, Br or J and A 2 , Z 2 , R 2 , x 1 , x 2 , x 3 , x 4 and m have the meaning given above, in a solvent-water mixture in the presence of a transition metal catalyst and a water-soluble one Promoter implemented.
  • Suitable as a promoter are all compounds that formally form a mixed boronic or boric anhydride of the general formula ⁇
  • Y is a central atom or a molecular unit that is able to create bonds to both boronic acid and palladium via oxygen.
  • the central atom can be - boron, for example as H 3 BO 3 or polyboric acid,
  • Silicon for example as Na 2 SiO 3 ,
  • Sulfur for example as Na 2 SO 4 , Na 2 SO 3 , Na 2 S 2 O 3 , phosphorus, for example as H 3 PO 4 and H 3 PO 3 and their
  • Carbon for example as mono- or dicarboxylic acid, - an alkaline earth metal, titanium or aluminum, for example as a hydroxide or ester.
  • Preferred additives are magnesium hydroxide, calcium hydroxide, sodium sulfate, sodium silicate and borates.
  • Water-soluble borates such as borax and boron compounds that form borates in water such as NaBH 4 can be used. It is useful to have one
  • buffer solution pH 8 Borate-hydrochloric acid buffer, for example "buffer solution pH 8", manufactured by E. MERCK, Darmstadt.
  • the buffer solution can, for example, be placed in the reaction vessel and metered in during the reaction while maintaining the above-mentioned pH.
  • the cross coupling is carried out at a pH of 5 to 14, preferably in the range from 5.5 to 9.
  • Transition metal catalysts for example tetrakis (triphenylphosphine) palladium (II) chloride, 1,1'-bis (diphenylphosphino) -ferrocene-palladium (II) chloride or bis (tricyclohexylphosphine) palladium (II) chloride, the latter two optionally also as catalysts NaBH 4 pre-reduced, can be used.
  • the reaction temperature is in the range from 20 ° C to 150 ° C. It is preferably set to a range from 60 ° C to 100 ° C.
  • Suitable solvents are hydrocarbons, such as toluene and ethereal solvents, for example
  • Tetrahydrofuran halogenated hydrocarbons and acidic solvents are unsuitable as solvents for the reaction. It is preferred to work in a solvent-water mixture. The tetrahydrofuran-water mixture is particularly preferred.
  • boronic acids according to the general formula II can be used as boronic acids, the advantage of the process being particularly clear in the case of ortho-substituted boronic acids, since these are very easily proton-deboronized under the usual coupling conditions.
  • vinyl boronic acids are also of the general formula
  • the corresponding boric acids, organyl 2 -B-OH, and the corresponding boronic anhydrides can also be used.
  • the halogen compounds of the general formula III can be used as halogen compounds.
  • aliphatic phosphines are used as ligands, such as tricyclohexylphosphines.
  • Suitable monodentate antimony compounds are
  • Suitable bidentate ligands are
  • R 1 is each independently straight-chain or
  • R 2 straight-chain or branched C 1-6 alkyl, C 1 _ 6 alkoxy,
  • the process according to the invention has the advantage that all synthesis steps can be carried out in a temperature range which can be mastered without technical difficulties.
  • Lithiation of fluoroaromatics at -78 ° C with subsequent iodination at the same temperature can be saved by the previous method. Furthermore, the range of compounds that can be used is higher, since sterically hindered boronic acid compounds, such as the so-called
  • Form fluoroboronic acids (2, 6-difluoroarylboronic acids) can be implemented. Compared to the previous process, there is no CO 2 development, which further improves the feasibility of the process on an industrial scale, especially with regard to safety.
  • the synthesis sequence according to the invention achieves a time saving of up to 90%. While two days are required for the synthesis in the classic process, the reaction in the process according to the invention is completed in 3 to 4 hours. It is also advantageous that yields of up to 90% can be achieved by the process according to the invention and the unreacted boronic acid can be recovered from the reaction mixture by simple crystallization. The competitive reaction of proton deboronization is largely suppressed.
  • pH 8 buffer 40 ml of pH 8 buffer (manufactured by E. MERCK, Darmstadt) were added and the mixture was heated to 50 ° C. The pH meter showed a pH of 9.
  • Example 2 2.4 g of NaOH (0.06 mol) were placed in 75 ml of water in the reaction vessel and 1.75 g of Mg (OH) 2 (0.03 mol) were added as a promoter. Then 75 ml of toluene and 7.4 g of 4- (4-propylcyclohexyl) phenylboronic acid (0.03 mol) were added. After a stirring time of 5 min. 4.2 g (0.03 mol) of 4-chlorobenzonitrile and 0.18 g of PdCl 2 (2 mol%) and 0.34 g were added to the mixture
  • Tricylohexylphosphin (4 mol%) added as a catalyst.
  • the mixture was heated to boiling temperature, refluxed for 2 hours, cooled to room temperature, suction filtered through a filter, the filter was washed with toluene and water and the organic phase was separated off. After the aqueous phase had been extracted again with toluene, the organic phases were combined, washed twice with water, dried, filtered and the toluene was distilled off. 10.1 g of crude product containing 95.4% of 4- (4-propylcyclohexyl) biphenyl-4'-carbonitrile were obtained. The yield was more than 95%.
  • Example 3 Example 3
  • Example 2 treated further.
  • the relatively low yield can be explained by the fact that a crude boronic acid mixture was used.
  • Example 2 4- (4-propylcyclohexyl) phenylboronic acid and 4-chlorobenzonitrile were converted to 4- (4-propylcyclohexyl) biphenyl-4'-carbonitrile (designated B in Table 1).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation de composés répondant à la formule générale (I), par couplage croisé d'acides boriques, d'acides boriniques ou d'anhydrides boriques dérivés de ces acides et répondant à la formule générale (II), dans laquelle x1, x2, x3 et x4 représentent indépendamment les uns des autres H, F, Cl, CF3, OCF3, OCF2H, OC2F5, COOH, OH, NH2, CN, NCS, R1 ou R2, avec un composé de chlore, de brome ou d'iode répondant à la formule générale (III), dans laquelle Y désigne Cl, Br ou J et x¿1?, x2, x3 et x4 ont indépendamment les uns des autres la signification susmentionnée, dans un mélange de solvant et d'eau en présence d'un métal de transition catalyseur et d'un borate soluble dans l'eau. Dans les formules, R?1, R2, A1, A2, Z1, Z2¿, m et n ont la signification donnée dans la première revendication.
PCT/EP1993/001432 1992-06-19 1993-06-07 Procede de couplage croise d'acides boriques avec des composes halogenes WO1994000423A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1019940700482A KR100266113B1 (ko) 1992-06-19 1993-06-07 보론산과할로겐화합물의교차커플링방법
EP93912904A EP0601156A1 (fr) 1992-06-19 1993-06-07 Procede de couplage croise d'acides boriques avec des composes halogenes
JP50198094A JP3833698B2 (ja) 1992-06-19 1993-06-07 硼酸とハロゲン化合物とのクロスカップリングの方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE4220082A DE4220082C2 (de) 1992-06-19 1992-06-19 Verfahren zur Kreuzkopplung von Boronsäuren mit Halogenverbindungen
DEP4220082.2 1992-06-19
EP93107956.0 1993-05-15
EP93107956 1993-05-15

Publications (1)

Publication Number Publication Date
WO1994000423A1 true WO1994000423A1 (fr) 1994-01-06

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Application Number Title Priority Date Filing Date
PCT/EP1993/001432 WO1994000423A1 (fr) 1992-06-19 1993-06-07 Procede de couplage croise d'acides boriques avec des composes halogenes

Country Status (5)

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EP (1) EP0601156A1 (fr)
JP (1) JP3833698B2 (fr)
KR (1) KR100266113B1 (fr)
DE (1) DE4220082C2 (fr)
WO (1) WO1994000423A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0679619A2 (fr) * 1994-04-26 1995-11-02 Hoechst Aktiengesellschaft Procédé de couplage croisé de composés aromatiques du bore avec des composés aromatiques halogénés ou de sulphates de peralkyle
WO1995031461A1 (fr) * 1994-05-17 1995-11-23 Merck & Co., Inc. Preparation de 2-aryle carbapenemes
EP0690046A1 (fr) * 1994-07-01 1996-01-03 Hoechst Aktiengesellschaft Procédé pour la préparation des biphényles avec palladacyclen comme catalysateur
EP0694530A2 (fr) * 1994-07-28 1996-01-31 Hoechst Aktiengesellschaft Procédé de couplage croisé de composés aromatiques du bore avec des composés aromatiques halogénés ou de sulphates de peralkyl
WO1998016486A1 (fr) * 1996-10-11 1998-04-23 Zeneca Limited Procede pour la preparation de composes aromatiques substitues
US5922646A (en) * 1994-04-29 1999-07-13 Hoechst Schering Agrevo Gmbh Acylated aminophenylsulfonylureas, processes for their preparation and their use as herbicides and plant growth regulators
CN109704914A (zh) * 2019-01-19 2019-05-03 山东理工大学 一种1,1-二氟乙基芳香化合物的简易合成新方法
CN111533649A (zh) * 2020-06-01 2020-08-14 南京工业大学 一种酸类化合物的合成方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19527118A1 (de) * 1995-07-25 1997-01-30 Hoechst Ag Verfahren zur Durchführung von Kreuzkupplungsreaktionen
DE10211597A1 (de) * 2002-03-15 2003-10-02 Merck Patent Gmbh Verfahren zur Herstellung von Ringverbindungen
JP5975081B2 (ja) * 2013-09-30 2016-08-23 ダイキン工業株式会社 含フッ素ビアリール化合物の製造方法
JP7231389B2 (ja) * 2018-11-26 2023-03-01 帝人株式会社 フルオレン骨格を有する化合物の製造方法および不純物の少ないフルオレン骨格を有する化合物

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991008184A2 (fr) * 1989-12-06 1991-06-13 MERCK Patent Gesellschaft mit beschränkter Haftung Composes de 2,6-difluorobenzol 1,4-disubstitues et milieux a cristaux liquides

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
WO1991008184A2 (fr) * 1989-12-06 1991-06-13 MERCK Patent Gesellschaft mit beschränkter Haftung Composes de 2,6-difluorobenzol 1,4-disubstitues et milieux a cristaux liquides

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 115, no. 15, 14. Oktober 1991, Columbus, Ohio, US; abstract no. 158650q, N. A. BUMAGIN ET AL. 'Palladium-catalyzed cross-coupling of arylboric acids and sodium tetraphenylborate with arylhalides in aqueous solutions' Seite 889 ; *
CHEMISTRY LETTERS 1989, TOKYO JP Seiten 1404 - 1408 A. SUZUKI ET AL. 'Cross-Coupling Reaction of Alkyl- or Arylboronic Acid Esters with Organic Halides Induced by Thallium(I) Salts and Palladium-Catalysts' in der Anmeldung erwähnt *
MOLECULAR CRYSTALS AND LIQUID CRYSTALS (INC. NONLINEAR OPTICS ) Bd. 206, 1991, READING GB Seiten 187 - 204 M. HIRD ET AL. 'Cross-Coupling Reactions in the Synthesis of Liquid Crystals' in der Anmeldung erwähnt *
SYNLETT Bd. 221, 1990, STUTTGART DE Seiten 221 - 223 A. SUZUKI ET AL. 'Palladium-Catalyzed Cross-Coupling Reaction of Aryl or Vinyl Triflates with Organoboron Compounds' *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0679619A3 (fr) * 1994-04-26 1996-01-03 Hoechst Ag Procédé de couplage croisé de composés aromatiques du bore avec des composés aromatiques halogénés ou de sulphates de peralkyle.
EP0679619A2 (fr) * 1994-04-26 1995-11-02 Hoechst Aktiengesellschaft Procédé de couplage croisé de composés aromatiques du bore avec des composés aromatiques halogénés ou de sulphates de peralkyle
US5922646A (en) * 1994-04-29 1999-07-13 Hoechst Schering Agrevo Gmbh Acylated aminophenylsulfonylureas, processes for their preparation and their use as herbicides and plant growth regulators
US6498253B1 (en) 1994-04-29 2002-12-24 Hoechst Schering Agrevo Gmbh Acylated aminophenylsulfonylureas, processes for their preparation and their use as herbicides and plant growth regulators
WO1995031461A1 (fr) * 1994-05-17 1995-11-23 Merck & Co., Inc. Preparation de 2-aryle carbapenemes
EP0690046A1 (fr) * 1994-07-01 1996-01-03 Hoechst Aktiengesellschaft Procédé pour la préparation des biphényles avec palladacyclen comme catalysateur
US5559277A (en) * 1994-07-01 1996-09-24 Hoechst Ag Process for preparing biphenyls using palladacycles as catalysts
EP0694530A2 (fr) * 1994-07-28 1996-01-31 Hoechst Aktiengesellschaft Procédé de couplage croisé de composés aromatiques du bore avec des composés aromatiques halogénés ou de sulphates de peralkyl
EP0694530A3 (fr) * 1994-07-28 1996-05-15 Hoechst Ag Procédé de couplage croisé de composés aromatiques du bore avec des composés aromatiques halogénés ou de sulphates de peralkyl
US5919930A (en) * 1994-07-28 1999-07-06 Hoechst Aktiengesellschaft Process for cross-coupling aromatic boron compounds with aromatic halogen compounds or perfluoroalkylsulfonates
WO1998016486A1 (fr) * 1996-10-11 1998-04-23 Zeneca Limited Procede pour la preparation de composes aromatiques substitues
US6218564B1 (en) 1996-10-11 2001-04-17 Zeneca Limited Process for the preparation of substituted aromatic compounds
CN109704914A (zh) * 2019-01-19 2019-05-03 山东理工大学 一种1,1-二氟乙基芳香化合物的简易合成新方法
CN111533649A (zh) * 2020-06-01 2020-08-14 南京工业大学 一种酸类化合物的合成方法
CN111533649B (zh) * 2020-06-01 2023-03-21 南京工业大学 一种酸类化合物的合成方法

Also Published As

Publication number Publication date
JP3833698B2 (ja) 2006-10-18
KR100266113B1 (ko) 2000-09-15
EP0601156A1 (fr) 1994-06-15
JPH07502751A (ja) 1995-03-23
DE4220082C2 (de) 1994-09-15
DE4220082A1 (de) 1993-12-23

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