WO2012123328A1 - Procédé pour la préparation d'amides primaires aromatiques - Google Patents

Procédé pour la préparation d'amides primaires aromatiques Download PDF

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Publication number
WO2012123328A1
WO2012123328A1 PCT/EP2012/054005 EP2012054005W WO2012123328A1 WO 2012123328 A1 WO2012123328 A1 WO 2012123328A1 EP 2012054005 W EP2012054005 W EP 2012054005W WO 2012123328 A1 WO2012123328 A1 WO 2012123328A1
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process according
liquid ammonia
ammonia
oxide
lewis acid
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George Robert Hodges
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Syngenta Ltd
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Syngenta Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • 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

  • the present invention relates to a novel process for preparing aromatic primary amides.
  • aromatic primary amides may be prepared from aromatic esters and liquid ammonia in the presence of a solid Lewis acid catalyst.
  • Ar is an aromatic moiety and R 1 is an organic radical, is reacted with liquid ammonia in the presence of a solid Lewis acid catalyst.
  • the solid Lewis acid catalyst should at least partially not dissolve in the reaction mixture at room temperature and pressure, or under the reaction conditions.
  • Preferred solid Lewis acid catalysts comprise a metal salt, a metal oxide or a metalloid oxide.
  • Elements generally considered to be metalloids are boron, silicon, germanium, arsenic, antimony, tellurium and polonium.
  • the metalloid is silicon.
  • the solid Lewis acid catalyst comprises a transition metal salt, or an oxide of a transition metal, an oxide of aluminium or an oxide of silicon.
  • the transition metal should belong to group 4, group 5, group 11 or group 12 of the periodic table.
  • the catalyst may comprise one or more of the above salts and oxides.
  • solid Lewis acid catalysts examples include:
  • copper (I) chloride copper (I) acetate; copper (II) acetate; copper (II) oxide; zinc oxide; niobium oxides; titanium oxides; aluminium oxide; Silica.
  • Niobium oxides include niobium monoxide, niobium dioxide, niobium pentoxide,
  • n ranges from 5 - 8 inclusive, e.g. NbsOig), Nbi 2 0 2 9 and Nb 47 0 116 .
  • Preferred examples of solid Lewis acid catalysts include:
  • copper (I) chloride copper (I) acetate; copper (II) acetate; copper (II) oxide; zinc oxide; niobium pentoxide; titanium dioxide; silica; alumina (aluminium oxide).
  • Preferred solid Lewis acid catalysts are metal oxides.
  • the solid Lewis acid catalyst comprises titanium dioxide and/or alumina (aluminium oxide), and preferably the solid Lewis acid catalyst is titanium dioxide or alumina (aluminium oxide).
  • preferred solid Lewis acid catalysts comprise one or more of the following:
  • solid Lewis acid catalysts are metal oxides and most preferably, the solid Lewis acid catalyst comprises titanium dioxide and/or alumina
  • the solid Lewis acid catalyst is titanium dioxide or alumina (aluminium oxide).
  • titanium dioxide means anatase.
  • the solid Lewis acid catalyst may be used in stoichiometric amounts relative to the compound of formula (II), or in super- or sub-stoichiometric amounts.
  • the process is conveniently carried out using liquid ammonia as solvent.
  • Other inert solvents may or may not be present. It may be advantageous to include an additional solvent to aid solubility of the starting material or products and to help processing e.g. it may be easier to remove the ammonia leaving a liquid rather than a solid.
  • Suitable inert solvents include aromatic or halogenated aromatic solvents such as toluene, xylene and chlorobenzene; and alkanes such as hexanes or ethers such as THF.
  • water may or may not be present. Typically, no more than 50% v/v of water may be present compared to the volume of ammonia. Preferably, no more than 40% v/v of water may be present. More preferably, no more than 20% v/v or less of water may be present. Even more preferably, the reaction should be conducted substantially in the absence of water. Reducing the amount of water can reduce the competing and detrimental hydrolysis of the compounds of formula (II) to the corresponding carboxylic acids.
  • the liquid ammonia is usually employed in an excess, for example from 10 to in excess of 1000 equivalents relative to the compounds of formula (II).
  • the liquid ammonia may be employed with an excess of 1000 equivalents relative to the compounds of formula (II), for example, up to 1000 equivalents relative to the compounds of formula (II).
  • the ammonia is employed with at least 10 equivalents of ammonia relative to the compounds of formula (II).
  • the process is conveniently carried out at a temperature in the range of 25°C to 175°C, for example, from 50°C to 150°C, and typically from 75°C to 140°C.
  • the process may be carried out at a temperature of at least 25°C, for example at least 50°C, and typically at least 75°C.
  • the process is conveniently carried out at a temperature up to 175°C, for example, up to 150°C, and typically up to 140°C.
  • the time the process takes will depend upon, inter alia, the catalyst: substrate ratio and the temperature at which the reaction is carried out.
  • the process may be performed for 1 minute to 24 hours, usually 10 minutes to 6 hours, typically 10 minutes to 1 hour.
  • the process may be performed for at least 1 minute, usually at least 10 minutes.
  • the process may be performed for up to 24 hours, usually up to 6 hours, typically no more than 1 hour.
  • the skilled person will be able to optimise the time needed for the reaction to provide a desired conversion to product.
  • the reaction can be performed either as a batch reaction or a flow reaction, wherein a mobile phase mixture comprising the liquid ammonia and the aromatic ester is contacted with a stationary phase comprising the solid Lewis acid catalyst, e.g. by passing the mobile phase over the stationary phase.
  • the flow reaction may be continuous or intermittent. Preferably, continuous flow conditions are used.
  • preferably 0.1-10 molar equivalents of the solid Lewis acid catalyst compared to the compounds of formula (II) are used, typically between 1-5 molar equivalents.
  • the flow process may be carried out in the presence of at least 0.1 molar equivalents of the solid Lewis acid catalyst compared to the compounds of formula (II), typically in the presence of at least 1 molar equivalent.
  • the process may be carried out in the presence of up to 10 molar equivalents of the solid Lewis acid catalyst compared to the compounds of formula (II), typically in the presence of up to 5 molar equivalents.
  • the person skilled in the art will understand that it is important to ensure a suitable contact time between the reagents and the catalyst in these cases.
  • liquid ammonia is employed in a large excess in a flow system where an excess of 1000 molar equivalents of the compound of formula (II) is not
  • a peristaltic pump (2) may be used to pump the reaction mixture through the packed bed reactor (3), through to a collecting vessel (6). It may be preferential to use the first chamber of one pump head (2b) as a pre-cooling chamber. For greater control of the reaction conditions, an oven (4) and back-pressure regulator (5) may also be used. Higher conversions can be readily achieved with multiple passes. Typically this would involve connecting the outlet back to the feed vessel or feedline although the product maybe optionally removed first.
  • R 1 , Ar, and their optional substituents are set out below, which may be combined in any combination.
  • R 1 is a branched or unbranched alkyl group containing from 1 to 6 carbon atoms and is, for example, methyl, ethyl, ⁇ -propyl, «-butyl, zso-propyl, sec-butyl, /so-butyl, tert-butyl, //-pentyl or /z-hexyl. Conveniently it is methyl or ethyl.
  • Ar is an optionally substituted phenyl, naphthyl or 5-6 membered
  • heterocyclic ring containing 1-3 atoms selected from nitrogen, sulphur and oxygen. Any such ring should not contain sulphur or oxygen atoms adjacent to another sulphur or oxygen atom.
  • Ar is an optionally substituted phenyl ring or an optionally substituted pyrazole group.
  • typical substituents include halogen, CN, NO 2 , OH, NH 2 , Ci-C 8 alkyl, d-C 8 alkoxy, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, CO(Ci-C 8 alkyl), COH, SH, C C 8 alkylthio, Ci-C 8 alkylsulphinyl, C C 8 alkylsulphonyl, alkylamine, dialkylamine, C0 2 H, C0 2 (Ci-C 8 alkyl), 0(CO)Ci-C 8 alkyl, 0(CO)H, CON(Ci-C 8 alkyl) 2 , CONH(Ci-C 8 alkyl), HCO(Ci-C 8 alkyl), HCOH, N(d-C 8 alkyl)CO(C,-C 8 alkyl) or HCO
  • Preferred optional substituents include halogen, CN, N0 2 , OH, NH 2 , C 1 -C4 alkyl, C1-C4 alkoxy, C 3 -C6 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, wherein the alkyl, alkoxy, cycloalkyl, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, CN, NH 2 , N0 2 , OH, C1-C4 alkyl, Ci C 4 -haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy.
  • Even more preferred optional substituents include hydrogen, halogen, CN, N0 2 , OH, NH 2 , C 1 -C4 alkyl, C 1 -C4 alkoxy, C3-C6 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C4 alkynyl, wherein the alkyl, alkoxy, cycloalkyl, alkenyl and alkynyl are optionally substituted by one or more groups independently selected from halogen, methyl, CN, methoxy, halomethyl and halomethoxy.
  • Optional substituents which are again more preferred include halogen, C 1 -C4 alkyl, CN, C 1 -C4 alkoxy, C 1 -C4 haloalkyl and C 1 -C4 haloalkoxy.
  • substituents include halogen, methyl, CN, methoxy, halomethyl and halomethoxy.
  • Ar represents cycle A-1
  • R 2 represents C 1 -C4 haloalkyl, preferably difluoromethyl or trifluoromethyl, most preferably difluoromethyl
  • R 3 represents C 1 -C4 alkyl, preferably methyl or ethyl, most preferably methyl.
  • Figure 1 shows a schematic diagram illustrating a typical set up for a continuous flow reactor:
  • the continuous reaction apparatus schematically represented in fig. 1 was used.
  • a peristaltic pump (2; Agilent peristaltic water cooled pump 1200 binary) was used throughout.
  • the feed went from the feed vessel (1) through to the first chamber of pump head 2b. This was used as a pre-cooling chamber.
  • the feed then passed to pump head 2a and through a packed bed reactor (3) located in an oven (4), followed by a back pressure regulator (5), leading to a collecting vessel (6).
  • the flow rate through the apparatus was 0.3mL min "1 .
  • Comparative Example 2 Preparation of benzamide Methyl benzoate (1.5mL) was dissolved in liquid ammonia (lOmL). A column was placed in the oven and the temperature was raised to 100°C before pure liquid ammonia was pumped through. The pressure was adjusted to 100 bar via adjustable back pressure regulator after pure liquid ammonia start pumping. The column was first flushed by pure liquid ammonia for 10 min. Then the reaction mixture was fed through for 30 min at 0.3mL min "1 . Finally, the column was rinsed with pure liquid ammonia (80 min) at the same flow rate. No sample was been taken during the reaction, after the run was finished, sample was heated at 80°C to free ammonia and methanol. After that, the mass balance was recorded by weighing and purity was checked by HPLC. No conversion to amide was observed.
  • Methyl benzoate (1.193 mL) was dissolved in liquid ammonia (10 mL).
  • a column packed with aluminium oxide (2.16 g) was placed in the oven and the temperature was raised to 100°C before pure liquid ammonia was pumped through at 0.3mL min "1 .
  • the pressure was adjusted to 100 bar via adjustable back pressure regulator after pure liquid ammonia started pumping.
  • the column was first flushed by pure liquid ammonia for 10 min. Then the reaction mixture was fed through for 30 min at 0.3mL min "1 . Finally, the column was rinsed with pure liquid ammonia (80 min) at the same flow rate. No sample was taken during the reaction. After the run was finished, a sample was heated at 80°C to free ammonia and methanol. After that, the mass balance was recorded by weighing and purity was checked by FIPLC (36% yield, no visible impurities).
  • Methyl benzoate (1.193 mL) was dissolved in liquid ammonia (10 mL).
  • the pressure was adjusted to 100 bar via adjustable back pressure regulator after the pure liquid ammonia started pumping.
  • the column was first flushed by pure liquid ammonia (10 min). Then the reaction mixture was fed for 30 min at 0.3mL min "1 . Finally, the column was rinsed with pure liquid ammonia (80 min) at the same flow rate. No sample was taken during the reaction. After the run was finished, a sample was heated at 80°C to free ammonia and methanol. After that, the mass balance was recorded by weighting and purity was checked by HPLC (15% yield, no visible impurities).
  • Methyl benzoate (46 ⁇ .) was dissolved in liquid ammonia (10 mL). A column packed with aluminium oxide (4.4 g) was placed the oven and the temperature was raised to 120°C before pure liquid ammonia was pumped through. Then pure liquid ammonia was pumped through the system at 0.3 mL min "1 and the pressure adjusted to 120 bar using an adjustable back pressure regulator.
  • Example 6 Preparation of 3 -difluoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid amide 3-Difluoromethyl-l-methyl-lH-pyrazole-4-carboxylic acid ethyl ester (511.3 mg) was dissolved in liquid ammonia (10 mL). A column packed with Ti0 2 (anatase modification; 2.16 g) was placed in the oven and the temperature was raised to 100°C before pure liquid ammonia was pumped through at 0.3mL min "1 . The pressure was adjusted to 100 bar via adjustable back pressure regulator after the pure liquid ammonia started pumping.
  • Example 1 Preparation of 3 -difluoromethyl-1 -methyl- lH-pyrazole-4-carboxylic acid amide
  • Example 13 Preparation of benzamide Methyl benzoate (1.5mL) and biphenyl (trace) were dissolved in liquid ammonia (lOmL).
  • reaction mixture was fed to the pump. Pure liquid ammonia was fed through again after the reaction mixture was finished and samples were collected every 10 minutes. Once the samples were ammonia free, they were dissolved in methanol and analysed by HPLC.
  • Methyl benzoate (1.5mL) and biphenyl (trace) were dissolved in liquid ammonia (lOmL).
  • a column packed with zinc oxide (1.79g) was placed in the oven and the temperature was raised to 100°C before pure liquid ammonia was pumped through. The pressure was adjusted to 100 bar via adjustable back pressure regulator after pure liquid ammonia started pumping. Timing was started once the system was filled with the ammonia. After 10 minutes the first sample (column pre-flush) was collected and sampled by HPLC. Then the reaction mixture was fed to the pump. Pure liquid ammonia was fed through again after the reaction mixture was finished and samples were collected every 10 minutes. Once the samples were ammonia free, they were dissolved in methanol and analysed by HPLC. Mean conversion between 10-40 minutes: 1%
  • Methyl benzoate (1.5mL) and biphenyl (trace) were dissolved in liquid ammonia (lOmL).
  • a column packed with niobium pentoxide (1.13g) was placed in the oven and the temperature was raised to 100°C before pure liquid ammonia was pumped through. The pressure was adjusted to 100 bar via adjustable back pressure regulator after pure liquid ammonia started pumping. Timing was started once the system was filled with the ammonia. After 10 minutes the first sample (column pre-flush) was collected and sampled by HPLC. Then the reaction mixture was fed to the pump. Pure liquid ammonia was fed through again after the reaction mixture was finished and samples were collected every 10 minutes. Once the samples were ammonia free, they were dissolved in methanol and analysed by HPLC. Mean conversion between 10-40 minutes: 1%
  • Methyl benzoate (1.5mL) and biphenyl (trace) were dissolved in liquid ammonia (lOmL).
  • a column packed with silica gel (1.24g) was placed in the oven and the temperature was raised to 100°C before pure liquid ammonia was pumped through. The pressure was adjusted to 100 bar via adjustable back pressure regulator after pure liquid ammonia started pumping. Timing was started once the system was filled with the ammonia. After 10 minutes the first sample (column pre-flush) was collected and sampled by HPLC. Then the reaction mixture was fed to the pump. Pure liquid ammonia was fed through again after the reaction mixture was finished and samples were collected every 10 minutes. Once the samples were ammonia free, they were dissolved in methanol and analysed by HPLC. Mean conversion between 10-40 minutes: 5%
  • Example 20 Preparation of benzamide
  • Methyl benzoate (1.5mL) and biphenyl (trace) were dissolved in liquid ammonia (l OmL).
  • a column packed with acid clay (1.24g) was placed in the oven and the temperature was raised to 100°C before pure liquid ammonia was pumped through. The pressure was adjusted to 100 bar via adjustable back pressure regulator after pure liquid ammonia started pumping. Timing was started once the system was filled with the ammonia. After 10 minutes the first sample (column pre-flush) was collected and sampled by HPLC. Then the reaction mixture was fed to the pump. Pure liquid ammonia was fed through again after the reaction mixture was finished and samples were collected every 10 minutes. Once the samples were ammonia free, they were dissolved in methanol and analysed by HPLC. Mean conversion between 10-40 minutes: 3%
  • Example 21 Preparation of benzamide
  • Methyl benzoate (1.5mL) and biphenyl (trace) were dissolved in liquid ammonia (lOmL).
  • Two columns in series, both packed with aluminium oxide (1.30g and 1.23g) were placed in the oven and the temperature was raised to 100°C before pure liquid ammonia was pumped through. The pressure was adjusted to 100 bar via adjustable back pressure regulator after pure liquid ammonia started pumping. Timing was started once the system was filled with the ammonia. After 10 minutes the first sample (column pre-flush) was collected and sampled by HPLC. Then the reaction mixture was fed to the pump. Pure liquid ammonia was fed through again after the reaction mixture was finished and samples were collected every 10 minutes. Once the samples were ammonia free, they were dissolved in methanol and analysed by HPLC. Mean conversion between 10-40 minutes: 35%. Reaction is not equilibrium.
  • Methyl benzoate (1.2mL) and biphenyl (trace) were dissolved in liquid ammonia (l OmL).
  • a column packed with aluminium oxide (1.13g) was placed in the oven and the temperature was raised to 125°C before pure liquid ammonia was pumped through. The pressure was adjusted to 100 bar via adjustable back pressure regulator after pure liquid ammonia started pumping. Timing was started once the system was filled with the ammonia. After 10 minutes the first sample (column pre-flush) was collected and sampled by HPLC. Then the reaction mixture was fed to the pump. Pure liquid ammonia was fed through again after the reaction mixture was finished and samples were collected every 10 minutes. Once the samples were ammonia free, they were dissolved in methanol and analysed by HPLC. Mean conversion between 10-40 minutes: 28%
  • Methyl benzoate (1.2mL) and biphenyl (trace) were dissolved in liquid ammonia (l OmL).
  • a column packed with aluminium oxide (1.13g) was placed in the oven and the temperature was raised to 125°C before pure liquid ammonia was pumped through. The pressure was adjusted to 100 bar via adjustable back pressure regulator after pure liquid ammonia started pumping. Timing was started once the system was filled with the ammonia. After 10 minutes the first sample (column pre-flush) was collected and sampled by HPLC. Then the reaction mixture was fed to the pump. Pure liquid ammonia was fed through again after the reaction mixture was finished and samples were collected every 10 minutes. Once the samples were ammonia free, they were dissolved in methanol and analysed by HPLC. Mean conversion between 10-40 minutes: 24%
  • reaction mixture was fed to the pump. Pure liquid ammonia was fed through again after the reaction mixture was finished and samples were collected every 10 minutes. Once the samples were ammonia free, they were dissolved in methanol and analysed by HPLC.
  • Methyl benzoate (596 L) and methanol (193 ⁇ ⁇ ) were dissolved in liquid ammonia (l OmL).
  • a column packed with aluminium oxide (2.14g) was placed the oven and the temperature was raised to 100°C before pure liquid ammonia was pumped through. Then pure liquid ammonia was pumped through the system at 0.3 mL min "1 and the pressure adjusted to lOObar using an adjustable back pressure regulator.
  • Solvent A water 50mM Na 2 HP0 3 PH adjusted to 2.6 by H 3 P0 4
  • Solvent A water 50mM Na 2 HP0 3 PH adjusted to 2.6 by H 3 P0 4

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

Abstract

L'invention concerne un nouveau procédé chimique pour préparer des amides primaires aromatiques. Le procédé consiste à faire réagir un composé de formule (II) avec de l'ammoniaque liquide en présence d'un catalyseur acide de Lewis solide pour former un composé de formule (I) dans laquelle Ar et R1 sont tels définis dans les revendications.
PCT/EP2012/054005 2011-03-11 2012-03-08 Procédé pour la préparation d'amides primaires aromatiques Ceased WO2012123328A1 (fr)

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GB201104203A GB201104203D0 (en) 2011-03-11 2011-03-11 Chemical process
GB1104203.3 2011-03-11

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WO2012123328A1 true WO2012123328A1 (fr) 2012-09-20

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103145580A (zh) * 2013-03-11 2013-06-12 黄河三角洲京博化工研究院有限公司 一种2-(4-氟代苯甲酰基)苯甲酰胺的制备方法
WO2014166885A1 (fr) * 2013-04-11 2014-10-16 Bayer Cropscience Ag Procédé de synthèse d'amides carboxyliques
CN104193645A (zh) * 2014-07-15 2014-12-10 上海应用技术学院 一种手性二甲基环丙甲酰胺的制备方法
EP3553179A1 (fr) 2018-04-12 2019-10-16 Universität Bielefeld Préparation de biocatalytique énantiosélective de 4-cyano-substitué 1-aminoindane et d'ozanimod
CN111362822A (zh) * 2020-02-18 2020-07-03 中国平煤神马能源化工集团有限责任公司 一种芳酰胺类化合物的制备方法

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WO2009063813A1 (fr) * 2007-11-12 2009-05-22 Kao Corporation Procédé de production d'un amide d'acide carboxylique aliphatique
WO2010072631A1 (fr) 2008-12-24 2010-07-01 Syngenta Limited Procedes de preparation de fongicides

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WO2009063813A1 (fr) * 2007-11-12 2009-05-22 Kao Corporation Procédé de production d'un amide d'acide carboxylique aliphatique
WO2010072631A1 (fr) 2008-12-24 2010-07-01 Syngenta Limited Procedes de preparation de fongicides
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103145580A (zh) * 2013-03-11 2013-06-12 黄河三角洲京博化工研究院有限公司 一种2-(4-氟代苯甲酰基)苯甲酰胺的制备方法
CN103145580B (zh) * 2013-03-11 2015-04-08 黄河三角洲京博化工研究院有限公司 一种2-(4-氟代苯甲酰基)苯甲酰胺的制备方法
WO2014166885A1 (fr) * 2013-04-11 2014-10-16 Bayer Cropscience Ag Procédé de synthèse d'amides carboxyliques
CN104193645A (zh) * 2014-07-15 2014-12-10 上海应用技术学院 一种手性二甲基环丙甲酰胺的制备方法
EP3553179A1 (fr) 2018-04-12 2019-10-16 Universität Bielefeld Préparation de biocatalytique énantiosélective de 4-cyano-substitué 1-aminoindane et d'ozanimod
WO2019197571A1 (fr) 2018-04-12 2019-10-17 Universität Bielefeld Préparation biocatalytique énantiosélective de 1-aminoindane 4-cyano-substituté et d'ozanimod
CN111362822A (zh) * 2020-02-18 2020-07-03 中国平煤神马能源化工集团有限责任公司 一种芳酰胺类化合物的制备方法

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