EP1362025A2 - Acides cinnamiques et derives d'acides cinnamiques a substitution polyhalogene et leur procede de production - Google Patents

Acides cinnamiques et derives d'acides cinnamiques a substitution polyhalogene et leur procede de production

Info

Publication number
EP1362025A2
EP1362025A2 EP02712904A EP02712904A EP1362025A2 EP 1362025 A2 EP1362025 A2 EP 1362025A2 EP 02712904 A EP02712904 A EP 02712904A EP 02712904 A EP02712904 A EP 02712904A EP 1362025 A2 EP1362025 A2 EP 1362025A2
Authority
EP
European Patent Office
Prior art keywords
formula
chlorine
hydrogen
cinnamic
acid
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.)
Withdrawn
Application number
EP02712904A
Other languages
German (de)
English (en)
Inventor
Walter Lange
Joachim Komoschinski
Markus Eckert
Michael Dockner
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.)
Saltigo GmbH
Original Assignee
Bayer AG
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
Priority claimed from DE2001107151 external-priority patent/DE10107151A1/de
Priority claimed from DE2001115405 external-priority patent/DE10115405A1/de
Priority claimed from DE2001152789 external-priority patent/DE10152789A1/de
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1362025A2 publication Critical patent/EP1362025A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/52—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing halogen
    • C07C57/58—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings
    • C07C57/60—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings having unsaturation outside the rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/687—Unsaturated compounds containing a keto groups being part of a ring containing halogen
    • C07C49/697—Unsaturated compounds containing a keto groups being part of a ring containing halogen containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms

Definitions

  • the present invention relates to new polyhalogen-substituted cinnamic acids and cinnamic acid derivatives and a process for the production of known and new polyhalogen-substituted cinnamic acids and cinnamic acid derivatives.
  • Known halogen-substituted cinnamic acids and cinnamic acid derivatives are intermediates for the production of agrochemicals and pharmaceuticals (see DE-A 22 44 761, WO 95/30645, WO 94/26692, WO 94/7893, WO 94/26693 and US-A 5 753 655).
  • A OH or O-alkyl.
  • Another way of producing a halogen-substituted cinnamic acid derivative is based on 2,4-difluorobromobenzene and this with acrylic acid
  • EP-A-584264 describes a process similar to that of EP-A-584 043. However, the process is carried out in the additional presence of arylphosphines, which is associated with further costs and additional effort.
  • R 1 , R 2 , R 3 and R 4 are the same or different and each represents hydrogen, fluorine, chlorine or bromine, at least two of these radicals being different from hydrogen and
  • X represents OR 5 or N (R 6 ) (R 7 ), where
  • R 5 represents hydrogen, optionally substituted Ci-C j o-alkyl, optionally substituted phenyl or benzyl and
  • R 6 and R 7 are the same or different and each represents optionally substituted C j -C Q alkyl and
  • R 8 represents hydrogen, chlorine, bromine or optionally substituted C 1 -C 4 -alkyl
  • R 1 , R 2 , R 3 and R 4 have the meaning given for formula (III) and
  • a ⁇ stands for one equivalent of halide, hydrogen sulfate, nitrate, acetate or tetrafluoroborate ions or for V% equivalent of sulfate ions or for 3 equivalent of phosphate ions,
  • R 8 represents hydrogen, chlorine, bromine or optionally substituted -CC-alkyl
  • the method according to the invention is very particularly preferably carried out without the addition of a base.
  • 0.5 mol or less, preferably 0.1 mol or less and particularly preferably 0.05 mol of base per mol of diazonium salt of the formula (IV) can be used.
  • the process according to the invention is advantageously and very particularly preferably carried out without the addition of arylphosphines.
  • arylphosphines In general, 4 mol or less, preferably 1 mol or less and particularly preferably 0.1 mol or less arylphosphines can be used per mol of palladium.
  • radicals R 5 , R 6 , R 7 and R 8 are optionally substituted alkyl radicals
  • substituents such as halogen, hydroxyl or Cg-C 2 aryl radicals can be used. Of these substituents, 1 to 2 can be present, for example, per radical from the group R 5 , R 6 , R 7 and R 8 .
  • R 1 is preferably hydrogen or chlorine
  • R 2 is hydrogen, fluorine, chlorine or bromine
  • R 3 is hydrogen or chlorine
  • R 4 is fluorine or chlorine, at least one of the radicals R 1 , R 2 and R 3 being different from hydrogen is.
  • R 5 preferably represents hydrogen, methyl, ethyl, isopropyl or benzyl.
  • R 7 preferably represents methyl or ethyl.
  • R 8 preferably represents hydrogen or methyl.
  • A® preferably represents one equivalent of chloride, hydrogen sulfate or acetate or 1/2 equivalent of sulfate.
  • homogeneous, palladium-containing catalysts examples include Palladium (II) - and
  • Palladium (O) compounds in question such as PdCl 2 , PdBr 2 , Pd (NO 3 ) 2 , H 2 PdCl 4 , Pd (CH 3 COO) 2 , Na 2 PdCl 4 , K 2 PdCl 4 , Pd (II) - acetylacetonate, tetra (triphenylphosphine) Pd and tris (dibenzylidene acetone) Pd 2 in question.
  • PdCl 2 , Pd (CH 3 COO) 2 and Pd (II) acetylacetonate are preferred.
  • the respective palladium-containing catalyst can be used, for example, in an amount of 0.001 to 10 mol%, preferably on the diazonium salt of the formula (IN).
  • Preferred reaction temperatures are those from +20 to + 80 ° C, especially those from +40 to + 65 ° C.
  • Suitable simple solvents are, for example, water, alcohols such as e.g. Ci-Cö-alkyl alcohols, carboxylic acids such as e.g. Formic acid, ethers such as e.g. Tetrahydrofuran and nitriles, e.g. Acetonitrile.
  • the diazonium salts of the formula (IV) can be prepared in a manner known per se (see, for example, Houben-Weyl, volume X / 3, pages 7 to 113) from the corresponding anilines by reaction with sodium nitrite in an acidic aqueous solution or by reaction of methyl nitrite in acidic methanol
  • the diazonium salts can be in
  • Form of the reaction mixture obtained in their preparation can be used in the process according to the invention, preferably after the destruction of any nitrite which may still be present. Isolation of the diazonium salts is not necessary.
  • Preferred compounds of the formula (V) are acrylic acid, methacrylic acid, acrylamide and methacrylamide.
  • the process according to the invention can be carried out, for example, by first starting from an aniline of the formula in the
  • R 1 , R 2 , R 3 and R 4 have the meaning given for formula (III),
  • nitrite in sulfuric acid aqueous solution or with an alkyl nitrite such as methyl, ethyl, butyl or amyl nitrite, preferably methyl nitrite in acid, e.g.
  • any nitrite present in the reaction mixture obtained was destroyed by adding amidosulfonic acid, the reaction mixture thus treated to a mixture of acrylic acid or an acrylic acid derivative of the formula (V) with a homogeneous, palladium-containing catalyst and optionally a simple solvent such as water, methanol, ethanol or isopropanol is added dropwise at the reaction temperature and, if appropriate after a subsequent stirring time, the product of the formula (III) is removed, if appropriate after cooling and / or dilution with water, for example by filtration, distillation or phase separation.
  • a simple solvent such as water, methanol, ethanol or isopropanol
  • the process according to the invention has the advantages that it is simple, at low temperatures, in short reaction times, without large amounts and preferably without base additions without large amounts and preferably without absolutely necessary
  • the present invention further relates to new polyhalogenated cinnamic acids and
  • polyhalogenated cinnamic acids and cinnamic acid derivatives of the formula (III) including those of the formula (IIP) can be obtained by hydrogenation of the double bond (step 1) and subsequent cyclization (step 2) in indanone derivatives of the formula
  • R 1 to R 4 have the meaning given for formula (III) and
  • R 8 is hydrogen, bromine, chlorine or optionally substituted C ⁇ Q Ci -alkyl, are converted.
  • Compounds of the general formula (VIIa) in which R 8 represents hydrogen can be converted in a manner known per se by halogenation into the corresponding compounds of the general formula (VIIa) in which R 8 represents bromine or chlorine.
  • Ner compounds of the general formula (VIIa) in which R 8 is bromine or chlorine can be converted in a manner known per se, for example by palladium-catalyzed carbonylation reactions with carbon monoxide and a suitable nucleophile, into indanone derivatives of the formula (VIIIb),
  • R 1 to R 4 have the meaning given for formula (III) and
  • R 9 represents COOH, CO ⁇ H 2 or COOR 10 , where
  • R 10 is C r C 4 alkyl.
  • the new compounds of the formula (IIP) broaden the range of available indanones and thus potential active ingredients in the agricultural and pharmaceutical fields and in the field of liquid-crystalline substances.
  • Gaseous methyl nitrite was prepared from 35 g of sodium nitrite in a methanol (20 ml) / water (60 ml) mixture by adding 30 ml of 50% sulfuric acid (30 ml), which at 0 ° C. was mixed into a mixture of 250 ml of water, 60 ml conc. Sulfuric acid and 53.5 g of 2,4-dichloroaniline was introduced. The mixture was stirred for 1 hour. Excess methyl nitrite was removed by passing a stream of nitrogen and adding 3 g of amidosulfonic acid.
  • Example 5 The procedure was as in Example 5, but the 2,4-difluorocinnamic acid obtained was not isolated.
  • the aqueous-acidic product suspension obtained was made alkaline with sodium hydroxide solution and, with further stirring at 50 ° C., 2 g of Pd / C (5% strength) were added and the mixture was heated to 100 ° C. Hydrogen was then injected up to 5 bar.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des acides cinnamiques et des dérivés d'acides cinnamiques polyhalogénés que l'on produit en faisant réagir des sels de diazonium, accessibles à partir d'anilines polyhalogénées, avec de l'acide acrylique ou des dérivés d'acide acrylique en présence d'un catalyseur homogène contenant du palladium, à des températures comprises entre -5 et +100 °C. Une partie des acides cinnamiques et des dérivés d'acides cinnamiques ainsi obtenus est nouvelle. Les acides cinnamiques et les dérivés d'acides cinnamiques produits selon l'invention peuvent servir à la production d'indanones, qui constituent des précurseurs de produits chimiques agricoles et pharmaceutiques ainsi que de substances à propriétés cristallines liquides.
EP02712904A 2001-02-16 2002-02-13 Acides cinnamiques et derives d'acides cinnamiques a substitution polyhalogene et leur procede de production Withdrawn EP1362025A2 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE10107151 2001-02-16
DE2001107151 DE10107151A1 (de) 2001-02-16 2001-02-16 Polyhalogensubstituierte Zimtsäuren und Zimtsäurederivate und ein Verfahren zur Herstellung von polyhalogensubstituierten Zimtsäuren und Zimtsäurederivaten
DE2001115405 DE10115405A1 (de) 2001-03-29 2001-03-29 Polyhalogensubstituierte Zimtsäuren und Zimtsäurederivate und ein Verfahren zur Herstellung von polyhalogensubstituierten Zimtsäuren und Zimtsäurederivaten
DE10115405 2001-03-29
DE10152789 2001-10-25
DE2001152789 DE10152789A1 (de) 2001-10-25 2001-10-25 Polyhalogensubstituierte Zimtsäure und Zimtsäurederivate und ein Verfahren zur Herstellung von polyhalogensubstituierten Zimtsäuren und Zimtsäurederivaten
PCT/EP2002/001462 WO2002066411A2 (fr) 2001-02-16 2002-02-13 Acides cinnamiques et derives d'acides cinnamiques a substitution polyhalogene et leur procede de production

Publications (1)

Publication Number Publication Date
EP1362025A2 true EP1362025A2 (fr) 2003-11-19

Family

ID=27214295

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02712904A Withdrawn EP1362025A2 (fr) 2001-02-16 2002-02-13 Acides cinnamiques et derives d'acides cinnamiques a substitution polyhalogene et leur procede de production

Country Status (4)

Country Link
US (3) US6956129B2 (fr)
EP (1) EP1362025A2 (fr)
CN (1) CN1246280C (fr)
WO (1) WO2002066411A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6956129B2 (en) * 2001-02-16 2005-10-18 Bayer Aktiengesellschaft Polyhalogen-substituted cinnamic acids and cinnamic acid derivatives and a process for the preparation of polyhalogen-substituted cinnamic acids and cinnamic acid derivatives
US7673240B2 (en) * 2005-12-30 2010-03-02 Polaroid Labs, Llc Ubiquitous navbar user interface across multiple heterogeneous digital media devices

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SE349768B (fr) * 1963-06-28 1972-10-09 Kockums Ind Ab
DE2244761A1 (de) 1972-09-09 1974-03-14 Schering Ag Indan- und tetralinderivate
EP0401166B1 (fr) 1989-06-01 1995-02-22 Ciba-Geigy Ag Titanocènes contenant de l'azote et leur emploi
US4979982A (en) * 1990-02-02 1990-12-25 Uniroyal Chemical Company, Inc. Herbicidal cinnamic ester uracils
US6066501A (en) 1991-05-16 2000-05-23 Cold Spring Harbor Laboratory D-type cyclin and uses related thereto
US5998582A (en) 1991-05-16 1999-12-07 Cold Spring Harbor Laboratory D-type cyclins and uses related thereto
US5889169A (en) 1991-05-16 1999-03-30 Cold Spring Harbor Laboratory Cell cycle regulatory protein p16 gene
US6156876A (en) 1991-05-16 2000-12-05 Cold Spring Harbor Laboratory D-type cyclin and uses related thereto
IL99759A (en) 1991-10-16 1997-06-10 Teva Pharma Mono-fluorinated derivatives of n-propargyl-1-aminoindan, their preparation and pharmaceutical compositions containing them
US5508402A (en) 1992-08-18 1996-04-16 Ciba-Geigy Corporation Process for the preparation of N,N'-substituted ureas
FR2696466B1 (fr) 1992-10-02 1994-11-25 Rhone Poulenc Rorer Sa Dérivés de 5H,10H-imidazo[1,2-a]indeno[1,2-e]pyrazine-4-one, leur préparation et les médicaments les contenant.
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GB9309621D0 (en) 1993-05-11 1993-06-23 Wellcome Found Amide derivatives and their therapeutic use
CN101391953B (zh) 1994-04-20 2012-06-06 纳幕尔杜邦公司 用于制备*二嗪的中间体
NZ283961A (en) 1994-04-20 1997-11-24 Du Pont Preparation of arthropodicidal oxadiazines, precursors, and non-heterocyclic intermediates
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US5972118A (en) * 1995-10-27 1999-10-26 Tennessee Valley Authority Concentrated sulfuric acid hydrolysis of lignocellulosics
US5753655A (en) 1996-10-10 1998-05-19 Ortho Pharmaceutical Corporation 1-arylsulphonyl, arylcarbonyl and arylthiocarbonyl pyridazino derivatives and methods of preparation
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See references of WO02066411A2 *

Also Published As

Publication number Publication date
WO2002066411A3 (fr) 2002-11-21
CN1246280C (zh) 2006-03-22
US20080200731A1 (en) 2008-08-21
US20020115885A1 (en) 2002-08-22
US20050234264A1 (en) 2005-10-20
US6956129B2 (en) 2005-10-18
WO2002066411A2 (fr) 2002-08-29
US7381832B2 (en) 2008-06-03
CN1491201A (zh) 2004-04-21

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