EP2683682A1 - Procédé de synthèse d'aminobiphényles - Google Patents

Procédé de synthèse d'aminobiphényles

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Publication number
EP2683682A1
EP2683682A1 EP12706867.4A EP12706867A EP2683682A1 EP 2683682 A1 EP2683682 A1 EP 2683682A1 EP 12706867 A EP12706867 A EP 12706867A EP 2683682 A1 EP2683682 A1 EP 2683682A1
Authority
EP
European Patent Office
Prior art keywords
compound
formula
alkyl
reaction
aryl
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Withdrawn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
EP12706867.4A
Other languages
German (de)
English (en)
Inventor
Markus Heinrich
Gerald PRATSCH
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.)
BASF SE
Original Assignee
BASF SE
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 EP11005807A external-priority patent/EP2546229A1/fr
Application filed by BASF SE filed Critical BASF SE
Priority to EP12706867.4A priority Critical patent/EP2683682A1/fr
Publication of EP2683682A1 publication Critical patent/EP2683682A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

Definitions

  • R 5 is each independently hydrogen, alkyl, cycloalkyl, haloalkyl, arylalkyl, het- roarylalkyl, aryl or heteroaryl;
  • R 11 is hydrogen, -OH, -SH, -alkyl, -Shaloalkyl, -SCycloalkyl, -S- (CH 2 ) q -aryl,
  • the cycloalkyl radicals may carry 1, 2 or 3 substituents selected from alkyl, alkoxy or halogen. Preferred are cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • arylalkyl denotes aryl radicals which are bonded via an alkyl group, preferably a C 1 -C 4 -alkyl group (aryl-C 1 -C 4 -alkyl), in particular a C 1 -C 2 -alkyl group (aryl C 1 -C 2 -alkyl), wherein the alkyl radical optionally carries 1, 2 or 3 substituents which are selected from halogen, cycloalkyl, alkoxy and haloalkoxy, and wherein the aryl group optionally bears 1, 2, 3, 4 or 5 substituents which are selected from halogen, alkyl, haloalkyl , Alkoxy and haloalkoxy. Examples thereof are 4-methoxybenzyl, benzyl, 2-phenylethyl (phenethyl) and the like; preferably benzyl and phenethyl.
  • heteroarylalkyl refers to heteroaryl groups having a C1-C4 alkyl group (aryl-Ci-C4-alkyl), in particular a Ci-C 2 through an alkyl group, preferably - alkyl (aryl-Ci-C 2 alkyl) bound wherein the alkyl radical optionally carries 1, 2 or 3 substituents which are selected from halogen, cycloalkyl, alkoxy, haloalkoxy, and where the heteroaryl group optionally carries 1, 2, 3 or 4 substituents which are selected from halogen, alkyl , Haloalkyl, alkoxy and haloalkoxy.
  • heteroaryloxycarbonyl denotes heteroaryloxy radicals having 1 to 4 heteroatoms bonded via a carbonyl group and selected from O, N, S and SO 2, the heteroaryl group optionally carrying 1, 2, 3 or 4 substituents selected from halogen, alkyl , Haloalkyl, alkoxy and haloalkoxy.
  • cycloalkylcarbonyloxy denotes cycloalkyl radicals having 3 to 10 carbon atoms attached via a carbonyloxy group as ring members, the cycloalkyl radical optionally carrying 1, 2 or 3 substituents selected from halogen, alkyl, haloalkyl, cycloalkyl, alkoxy and haloalkoxy.
  • arylalkylcarbonyloxy denotes arylalkyl radicals bonded via a carbonyloxy group, the alkyl radical optionally bearing 1, 2 or 3 substituents selected from halogen, cycloalkyl, alkoxy, haloalkoxy and the
  • Trifluoroethylthio 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, 1,1,2,2-tetrafluoroethylthio, 1 - Chloro-1, 2,2-trifluoroethylthio, pentafluoroethylthio, 3,3,3-trifluoroprop-1-ylthio, 1,1,1-trifluoroprop-2-ylthio, 3,3,3-trichloroprop-1-ylthio, 1 - Chlorobutylthio, 2-chlorobutylthio, 3-chlorobutylthio, 4- Chlorobutylthio, 1-fluorobutylthio, 2-fluorobutylthio, 3-fluorobutylthio, 4-fluorobuty
  • R 10 is preferably hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cycloalkyl, aryl or heteroaryl.
  • R 10 particularly preferably represents hydrogen, halogen, C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl.
  • R 10 is preferably hydrogen.
  • the process according to the invention is carried out in the "basic range"; ie the reaction medium in which the reaction of 1 and 2 takes place is basic.
  • the reaction is carried out at a pH of at least 9.1 (eg 9.1 to 14 or higher, eg to 14.5 or to 15), more preferably at least 9.5 (eg 9.5 to 14 or higher, eg to 14.5 or to 15), more preferably at least 10 (eg 10 to 14 or higher, eg to 14.5 or to 15), even more preferably at least 12 (eg 12 to 14 or higher, eg to 14.5 or to 15), in particular at least 13 (eg 13 to 14 or higher, eg to 14.5 or to 15), and especially at least 14 (eg 14 to 14.5 or 14 to 15).
  • Preferred organic solvents are short-chain nitriles, such as acetonitrile or propionitrile, amides, such as ⁇ , ⁇ -dimethylformamide or ⁇ , ⁇ -dimethylacetamide, short-chain monohydric or polyhydric alcohols, such as methanol, ethanol, propanol, ethylene glycol or trifluoroethanol, dimethyl sulfoxide and mixtures of these solvents , Particularly preferred is acetonitrile.
  • Ethyl acetate, propyl acetate or ethyl propionate open-chain ethers, such as diethyl ether, dipropyl ether, dibutyl ether, methyl isobutyl ether and methyl tert-butyl ether, aliphatic hydrocarbons, such as pentane, hexane, heptane and octane, and petroleum ethers, halogenated aliphatic hydrocarbons, such as methylene chloride, trichloromethane , Dichloroethane and trichloroethane, cycloaliphatic hydrocarbons, such as cyclopentane and cyclohexane, and aromatic hydrocarbons, such as benzene, toluene, xylenes, chlorobenzene, dichlorobenzenes and mesitylene.
  • open-chain ethers such as diethyl ether, dipropyl ether
  • the reaction of the compound of formula 1 with the compound of formula 2 is generally carried out at a temperature in the range of -100 ° C to the boiling point of the reaction mixture, e.g. from -78 ° C to 200 ° C or from 0 ° C to 150 ° C.
  • the reaction at elevated temperature, preferably from 50 ° C to 130 ° C and in particular from 60 to 1 10 ° C. These temperatures are for solution in solution; If, on the other hand, the test is carried out in bulk and the melting point of the compound of the formula 2 is above room temperature, the reaction temperature will of course be at least equal to the temperature of the melt of the reaction mixture.
  • the reactants can in principle be brought into contact with each other in a different order.
  • the compound of formula 2 optionally dissolved or dispersed in a solvent or solvent system or optionally dissolved or dispersed in an alkaline medium
  • the compound of formula 1 optionally dissolved or dispersed in a solvent or solvent system or optionally dissolved or dispersed in an alkaline medium
  • the mixing of the components takes place at a temperature of preferably at most 50 ° C., e.g. -20 to 50 ° C or 0 to 50 ° C, or at a temperature of preferably at most 30 ° C, e.g. -20 to 30 ° C or 0 to 30 ° C, or at a temperature of preferably at most 25 ° C, e.g. -20 to 25 ° C or 0 to 25 ° C, or at a
  • the rate of addition is determined by several factors, such as batch size, temperature, reactivity of the reactants and the nature of the reaction conditions chosen, which causes decomposition of the compound of formula 1 a, 1 b and / or 1 c in nitrogen and an aryl radical , and can be determined by the person skilled in the individual case, for example by means of suitable preliminary tests.
  • a low reactivity of the educts requires a slower rate of addition, but at least partially compensated, for example by a higher temperature and / or by the choice of reaction conditions that accelerate decomposition of the compound of formula 1 a, 1 b and / or 1 c can.
  • the compounds 1 and 2 are used in a molar ratio of preferably 1: 1000 to 5: 1, for example from 1: 500 to 1: 1.
  • the compound 1 is particularly preferably used in deficit with respect to the compound 2.
  • compounds 1 and 2 are used in a molar ratio of from 1: 2 to 1:50, more preferably from 1: 3 to 1:20, and even more preferably from 1: 5 to 1:20.
  • the two preferred measures ie the use of the compound of formula 1 in the deficit (with respect to the compound of formula 2) and their gradual addition, cause an advantageous reaction course, since they suppress the homocoupling of the compound of formula 1.
  • the base is preferably used in at least an equimolar amount to compound 1.
  • the compound of formula 2 is initially charged in an alkaline medium and the compound of formula 1 is added.
  • the compound of the formula 2 is preferably initially introduced in the form of an aqueous dispersion which contains a base, and the compound of the formula 1 is added to this dispersion.
  • Compound 1 can be used in substance or in the form of a dispersion, in particular in the form of the solution as formed in the preparation of compound 1.
  • the dispersion of compound 1 can also be acidic, but the basicity of the template must be so high that, despite the addition of the acidic dispersion of compound 1, the required pH value is maintained during the reaction, ie the pH does not fall below the desired value after addition of the acidic dispersion.
  • the template is preferably heated before adding the compound of formula 1; preferably at a temperature of 50 to 130 ° C, in particular from 60 ° C to 1 10 ° C.
  • the compound of formula 1 in a first step, is first reacted in aqueous medium with a base, and in a second step, the dispersion obtained is added to the compound of formula 2.
  • compound 1 reacts at least partially to compounds 1 a, 1 b and / or 1 c. It is believed that these intermediates too in the first implementation variant (addition of compound 1 to the compound 2 introduced in alkaline medium) are carried out in situ.
  • the workup of the resulting reaction mixtures and the isolation of the compounds of formula 3 is carried out in the usual manner, for example by an extractive workup, by removing the solvent, for. B. under reduced pressure, or by a combination of these measures. Further purification can be carried out, for example, by crystallization, distillation or by chromatography.
  • the 5- or 6-membered hetaryl radical having 1, 2 or 3 nitrogen atoms as ring members is, for example, pyrrolyl, such as 1-, 2- or 3-pyrrolyl, pyrazolyl, such as 1-, 3-, 4- or 5- (1 H) -pyrazolyl, imidazolyl, such as 1-, 3-, 4- or 5- (1H) -imidazolyl, triazolyl, such as 1-, 4- or 5- [1,2,3] - (1H) - Triazolyl, 2- or 4- [1,2,3] - (2H) -triazolyl, pyridyl such as 2-, 3- or 4-pyridyl, pyrazinyl such as 2-pyrazinyl, pyrimidinyl such as 2-, 4- or 5-pyrimidinyl, pyridazinyl, such as 3- or 4-pyridazinyl, or triazinyl, such as 2- [1,3,5] triazinyl.
  • pyrrolyl such as

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

Abstract

L'invention concerne un procédé de synthèse de 2-aminobiphényles ainsi que de dérivés de ce composé par réaction d'un sel de benzènediazonium avec un composé d'aniline dans des conditions réactionnelles basiques.
EP12706867.4A 2011-03-07 2012-03-06 Procédé de synthèse d'aminobiphényles Withdrawn EP2683682A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12706867.4A EP2683682A1 (fr) 2011-03-07 2012-03-06 Procédé de synthèse d'aminobiphényles

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP11001877 2011-03-07
EP11005807A EP2546229A1 (fr) 2011-07-15 2011-07-15 Procédé de synthèse d'aminobiphényles
PCT/EP2012/053798 WO2012120003A1 (fr) 2011-03-07 2012-03-06 Procédé de synthèse d'aminobiphényles
EP12706867.4A EP2683682A1 (fr) 2011-03-07 2012-03-06 Procédé de synthèse d'aminobiphényles

Publications (1)

Publication Number Publication Date
EP2683682A1 true EP2683682A1 (fr) 2014-01-15

Family

ID=45787222

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12706867.4A Withdrawn EP2683682A1 (fr) 2011-03-07 2012-03-06 Procédé de synthèse d'aminobiphényles

Country Status (5)

Country Link
US (1) US20130338369A1 (fr)
EP (1) EP2683682A1 (fr)
CN (1) CN103517893A (fr)
BR (1) BR112013022613A2 (fr)
WO (1) WO2012120003A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2968371T3 (es) 2013-10-10 2024-05-09 Eastern Virginia Medical School Derivados de 4-((2-hidroxi-3-metoxibencil)amino) bencenosulfonamida como inhibidores de la 12-lipoxigenasa
CN106366002B (zh) * 2016-08-30 2019-01-22 京博农化科技股份有限公司 一种啶酰菌胺中间体4′-氯-2-氨基联苯的合成方法
CN110117256B (zh) * 2019-06-25 2023-06-30 芮城县斯普伦迪生物工程有限公司 一种联苯吡菌胺的合成方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA007106B1 (ru) 2001-11-02 2006-06-30 Басф Акциенгезельшафт Способ получения амидов 2-галогенпиридинкарбоновых кислот
DE102004041531A1 (de) 2004-08-27 2006-03-02 Bayer Cropscience Ag Verfahren zum Herstellen von Biphenylaminen
DE102004045242A1 (de) 2004-09-17 2006-03-23 Bayer Cropscience Ag Synergistische fungizide Wirkstoffkombinationen
CA2636695A1 (fr) 2006-06-01 2007-12-06 Basf Se Procede de preparation des biphenyls substitues
CA2666746C (fr) 2006-11-03 2014-10-14 Basf Se Procede de fabrication de difluoromethylpyrazolylcarboxylates
PL2164831T3 (pl) 2007-06-01 2013-12-31 Basf Se Sposób wytwarzania n-podstawionych (3-difluorowcometylopirazol-4-ilo)karboksyamidów
EP2008991A1 (fr) 2007-06-29 2008-12-31 Bayer CropScience AG Procédé destiné à la fabrication de bi-aryles
KR20110027834A (ko) * 2008-07-03 2011-03-16 바스프 에스이 아미노비페닐렌의 제조 방법
DE102008049675A1 (de) 2008-09-30 2010-04-01 Markus Dr. Heinrich Verfahren zur Herstellung von 3-Aminobiphenylen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012120003A1 *

Also Published As

Publication number Publication date
CN103517893A (zh) 2014-01-15
US20130338369A1 (en) 2013-12-19
BR112013022613A2 (pt) 2016-12-06
WO2012120003A1 (fr) 2012-09-13

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